Cured transparent resin composition and various articles derived therefrom

Abstract

Embodiments of the present invention relate to a curable transparent resin composition and various articles derived therefrom. The curable transparent resin composition comprises: (A) a fluororesin containing one or more carboxyl groups; and (B) an epoxy resin. This curable transparent resin composition exhibits excellent dry film properties, heat resistance, transparency, adhesion, and discoloration resistance through the combination of the two components, and thus enables the formation of a thin film having an excellent adhesion and discoloration resistance while having a light transmittance at a similar level to that of a silicone resin composition that is commonly used for display applications. Thus, the curable transparent resin composition of the present invention can be used not only as a display component requiring excellent light transmittance, but also as a variety of applications such as an LED sealing material, a glass adhesive, a dry film, or a chip bonding material, which require excellent adhesion and discoloration resistance.

Description

Technical Field

[0001] This invention relates to curable transparent resin compositions and various articles derived therefrom. Specifically, the articles may be LED sealing material compositions, glass adhesive compositions, or chip bonding compositions comprising the curable transparent resin composition; or they may be display components having a cured product formed from the curable transparent resin composition on a substrate, LED devices encapsulating LED elements through a cured layer formed from the LED sealing material composition, or dry films having a cured transparent resin layer formed from the curable transparent resin composition on a thin film. Background Technology

[0002] Light-emitting diodes (LEDs) and other optical semiconductor devices have excellent low power consumption characteristics, so their application in outdoor lighting or vehicle applications is increasing.

[0003] Recently, vertical LED chips have been developed with the goal of further improving the luminous efficiency of optoelectronic semiconductor devices. In vertical LED chips, the electrodes are arranged in a vertical structure, and the current flows uniformly in the light-emitting layer. Compared with horizontal LED chips of the same size with horizontally arranged electrodes, the current can flow by tens of times, thus suppressing the temperature rise of the light-emitting layer and improving luminous efficiency.

[0004] Furthermore, since the electrodes in a vertical LED chip are configured in a vertical structure, when mounting a vertical LED chip on a wiring board, the electrodes on one side need to be electrically connected using the same wire bonding method as before, while the electrodes on the other side need to be electrically connected using a soldering process or conductive adhesive.

[0005] Currently, as adhesives for mounting vertical LED chips onto wiring boards, soldering processes or conductive adhesives incorporating conductive particles into epoxy resin compositions are widely used. However, in the case of soldering processes, the heat required to melt the solder during chip bonding can easily damage the light-emitting layer of the optoelectronic semiconductor, making it undesirable. Furthermore, the soldering process or conductive adhesives incorporating conductive particles into epoxy resin compositions cannot adequately reflect light, resulting in poor light extraction efficiency. Moreover, from the perspective of design freedom when used in optoelectronic semiconductor devices, high transparency of the chip bonding material is also required.

[0006] Furthermore, as an example of using conductive adhesives, Patent Document 1 discloses a conductive adhesive that combines bisphenol A type epoxy resin or bisphenol F type epoxy resin with an alicyclic epoxy resin, and further adds a benzotriazole derivative as an ultraviolet absorber, thereby improving lightfastness to light around 450–500 nm. However, the composition according to this invention contains a large amount of white titanium dioxide or colored conductive particles, and therefore cannot be a highly transparent adhesive.

[0007] Furthermore, light-emitting diodes (LEDs) are used after their internal chips are sealed with a sealant to protect their internal structure. Various resins are used as transparent sealants for LEDs; for example, epoxy resin compositions containing anhydride curing agents and curing accelerators are available. For instance, Patent Documents 2 and 3 disclose epoxy resin compositions in which thiophosphite compounds and thiophosphoric acid are added to improve transparency.

[0008] Prior technology literature

[0009] [Patent Documents]

[0010] (Patent Document 1) Japanese Patent Publication No. 3769152

[0011] (Patent Document 2) Japanese Patent No. Sho 59-062624

[0012] (Patent Document 3) Japanese Patent No. Sho 60-140884 Summary of the Invention

[0013] Technical issues

[0014] Devices that mount optical semiconductor elements require cured surfaces to protect the semiconductor elements, electrodes, substrates, etc., from the external environment. Currently, thermosetting liquid silicone resins are used to form cured surfaces. Silicone resins have the advantages of forming cured surfaces with excellent rubber-like properties such as weather resistance, heat resistance, hardness, and elongation. However, cured surfaces formed from silicone resins have high permeability. When such cured surfaces are used in high-light and high-heat-generating high-grayscale LEDs, discoloration of the sealing material may occur due to corrosive gases, and grayscale reduction may occur due to corrosion of the silver plating on the electrodes or substrate. To solve these problems, the present invention provides a curable transparent resin composition that does not use silicone resin, but rather a composition (A) using a fluororesin containing one or more carboxyl groups as the main component, and (B) containing epoxy resin.

[0015] The present invention provides a curable transparent resin composition that exhibits excellent dry film properties, heat resistance, transparency, adhesion, color change and shape retention.

[0016] Furthermore, the present invention is used to provide a display component, an LED sealing material composition, a glass adhesive composition, a dry film or chip bonding composition utilizing the aforementioned curable transparent resin composition.

[0017] Technical solution

[0018] One embodiment of the present invention relates to a curable transparent resin composition comprising (A) a fluoropolymer containing one or more carboxyl groups and (B) an epoxy resin.

[0019] In one implementation, the fluororesin may, in addition to the carboxyl group, contain one or more functional groups selected from the group consisting of hydroxyl, aldehyde, peroxyhydroxyl, amino, amine, carbonyl, acrylic, acryloyl, nitrile, vinyl, halogenated, polyurethane, and ester groups.

[0020] In one implementation, the fluoropolymer may contain one or more hydroxyl groups as functional groups in addition to carboxyl groups.

[0021] In one implementation, the molar equivalent % of the carboxyl group relative to the total functional groups contained in the fluoropolymer can be from 1 to 100%.

[0022] In one implementation, the fluoropolymer can be a polymer of reaction units represented by chemical formula (I) and reaction units represented by chemical formula (II).

[0023] Chemical formula (I)

[0024]

[0025] The molar ratio of a, b, c, and d in the chemical formula (I) is a:b:c:d = 1-3:0-1:1:0-10.

[0026] Chemical formula (II)

[0027]

[0028] In the chemical formula (II), e, f, and g can be independently selected from integers greater than 0 and less than 10, and A1, A2, and A3 can be hydroxyl groups or hydroxyl groups substituted with carboxylic acids.

[0029] In one implementation example, the epoxy resin may be a silicone epoxy resin.

[0030] In one implementation example, the epoxy resin may be in a liquid state at room temperature.

[0031] In one implementation, the epoxy resin may not have an aromatic ring or carbon double bond.

[0032] In one implementation, the main chain of the epoxy resin may contain siloxane (Si-O) groups.

[0033] In one implementation, the epoxy resin may not contain fluorine.

[0034] In one implementation example, the epoxy resin may be tetra[(epoxycyclohexyl)ethyl]tetramethylcyclotetrasiloxane, glycidoxymethyltrimethoxysilane, 3-glycidoxypropyltrihydroxysilane, 3-glycidoxypropyldimethylhydroxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltributoxysilane, 1-bis(glycidoxypropyl)tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)tetramethoxydisiloxane, Alkane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)-1,3-dimethyl-1,3-dimethoxydisiloxane, 2,3-epoxypropyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 6,7-epoxyheptyltrimethoxysilane, 1,3-bis(2,3-epoxypropyl)tetramethoxydisiloxane, 1,3-bis(6,7-epoxyethynyl)tetramethoxydisiloxane, 2-(3,4-epoxycyclohexyl)ethyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, or combinations thereof.

[0035] In one implementation, the curable transparent resin composition may further comprise (C) a thixotropic agent.

[0036] In one implementation example, the (C) thixotropic agent may be hydrophilic calcined silica or hydrophobic calcined silica.

[0037] In one implementation example, the BET surface area of ​​the hydrophilic or hydrophobic calcined silica can be 150 m². 2 / g or more and 200m 2 / g or more or 250m 2 / g or more.

[0038] Another embodiment of the present invention relates to a display component characterized by having a cured material formed from the above-described curable transparent resin composition on a substrate.

[0039] Another embodiment of the present invention relates to a sealing material composition for LEDs comprising the above-described curable transparent resin composition.

[0040] Another embodiment of the present invention relates to an LED device in which an LED element is encapsulated by a curing layer formed from the LED sealing material composition.

[0041] Another embodiment of the present invention relates to a glass adhesive composition comprising the above-described curable transparent resin composition.

[0042] Another embodiment of the present invention relates to a dry film having a curable resin layer formed from the above-described curable transparent resin composition on a thin film.

[0043] Another embodiment of the present invention relates to a chip bonding composition comprising the above-described curable transparent resin composition.

[0044] Technical effect

[0045] The curable transparent resin composition according to one embodiment of the present invention exhibits excellent dry film properties, heat resistance, transparency, adhesion, color change, and shape retention. Therefore, it possesses light transmittance similar to that of existing silicone resin compositions widely used in displays, while also being able to form cured products (e.g., thin films) with excellent adhesion. Thus, the curable transparent resin composition of the present invention can be used not only for display components requiring excellent light transmittance, but also for various other applications such as LED sealing materials, glass adhesives, dry films, and chip bonding materials requiring excellent adhesion. Attached Figure Description

[0046] Figures 1a to 1f The diagram shows the droplets of the compositions of Examples 1, 7, 13, 1, 3, and 5, respectively.

[0047] Figures 2a to 2c Images of droplets of the compositions of Examples 1, 7, and 13 are shown, respectively. Detailed Implementation

[0048] The various embodiments or examples described in this specification are intended to illustrate the technical concept of the present invention. The technical concept of the present invention includes various modifications, equivalents, alternatives, and embodiments or examples selectively combined from all or part of the various embodiments or examples described in this specification. Furthermore, the technical concept of the present invention is not limited to the various embodiments or examples provided below, or their specific descriptions.

[0049] The terms used in this specification, including technical or scientific terms, shall, unless otherwise defined, have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains. Terms such as those defined in a general dictionary shall be interpreted as having meanings consistent with their meanings in the context of the relevant art, and shall not be construed as having ideal or overly formal meanings unless explicitly defined in this invention.

[0050] As used in this specification, expressions such as "comprising," "may contain," "have," and "may have" indicate the presence of features (e.g., functions, actions, or constituent elements) as an object, rather than excluding the existence of other additional features. That is, such expressions should be understood as open-ended terms that encompass the possibility of other implementations.

[0051] The singular expressions used in this specification may also have a plural meaning unless otherwise specified in the context, and this also applies to the singular expressions recited in the claims.

[0052] The expressions “A, B and C”, “A, B or C”, “A, B and / or C”, “at least one of A, B and C”, “at least one of A, B or C”, “at least one of A, B and / or C”, “selected from at least one of A, B and C”, “selected from at least one of A, B or C”, “selected from at least one of A, B and / or C”, etc., used in this specification may refer to the listed items or all possible combinations of the listed items.

[0053] The term "about" as used in this invention can refer to a general range of error for various values, as is well known to those skilled in the art. In the context of the numerical values ​​or ranges described herein, this can mean ±20%, ±15%, ±10%, ±9%, ±8%, ±7%, ±6%, ±5%, ±4%, ±3%, ±2%, or ±1% of a numerical value or range mentioned or claimed in one embodiment.

[0054] The dimensions, values ​​and ranges used in this specification are not limited to those dimensions, values ​​and ranges unless otherwise specified in the context, but may refer to equivalent ranges including them.

[0055] The following describes various embodiments of the present invention.

[0056] [Cureable transparent resin composition]

[0057] One embodiment of the present invention relates to a curable transparent resin composition.

[0058] Currently, compositions containing thermosetting liquid silicone resins are generally used as curable transparent resin compositions for applications such as displays. However, while these silicone resins exhibit excellent weather resistance due to minimal degradation from light or heat, their very high permeability can shorten device lifespan. To address this issue, compositions containing aromatic epoxy resins, such as bisphenol A or bisphenol F epoxy resins, have been used. However, compositions containing epoxy resins suffer from low transmittance and yellowing.

[0059] In one embodiment, the curable transparent resin composition comprises (A) a fluoropolymer having one or more carboxyl groups and (B) an epoxy resin. The curable transparent resin composition may further comprise (C) a thixotropic agent. The curable transparent resin composition, through this combination of two or more components, for example, three components, exhibits excellent dry film properties, heat resistance, transparency, adhesion, color change, and shape retention. When these two or more components are included in a specific mixing ratio, even better effects can be achieved. Thus, not only does it possess light transmittance similar to that of silicone resin compositions currently commonly used in displays, but it can also form a film with excellent adhesion.

[0060] Fluororesin

[0061] In one embodiment, fluororesins can be used without particular restriction, as long as they contain one or more carboxyl groups. Because of the carboxyl groups, these fluororesins exhibit excellent heat resistance, adhesion, and color-changing effects through chemical reaction with epoxy groups. If, unlike the fluororesins, they do not contain carboxyl groups but other reactive groups such as hydroxyl groups, they do not chemically react with epoxy groups, making curing difficult. Even if a reaction occurs, it must be performed at high temperatures or require an additional catalyst, thus increasing the likelihood of yellowing (color change). Furthermore, the presence of amine or aromatic functional groups can lead to yellowing due to chemical reaction with epoxy groups.

[0062] The fluororesin may include two or more carboxyl groups. The fluororesin may also contain only carboxyl groups as functional groups.

[0063] The fluororesin may contain one or more functional groups in addition to the carboxyl group. Besides the carboxyl group, the fluororesin may also contain one or more functional groups selected from the group consisting of hydroxyl, aldehyde, peroxide hydroxyl, amino, amine, carbonyl, acrylate, acryloyl, nitrile, vinyl, halogen, polyurethane, and ester groups. For example, the fluororesin may contain one or more hydroxyl groups in addition to the carboxyl group, but is not limited thereto. For example, the fluororesin may contain both carboxyl and hydroxyl groups.

[0064] The molar equivalent percentage of the carboxyl group relative to the total functional groups contained in the fluoropolymer can be from 1 to 100%.

[0065] For example, the fluoropolymer may contain one or more functional groups in the main chain or side chain. For example, the fluoropolymer may contain one or more functional groups in the main chain. For example, the fluoropolymer may contain one or more functional groups in the side chain. For example, the fluoropolymer may contain one or more functional groups in both the main chain and side chain.

[0066] The fluoropolymer can be a block copolymer of two or more fluorinated monomers with different structures, but is not limited thereto. For example, the fluorinated monomers may include monomers of polyvinylidene fluoride, fluoroelastomer, or polytetrafluoroethylene (PTFE), but are not limited thereto. For example, at least one of the fluorinated monomers may be tetrafluoroethylene or ethylene tetrafluoroethylene (ETFE), but is not limited thereto. For example, at least one of the fluorinated monomers may have a structure of the following chemical formula 1B, but is not limited thereto.

[0067] [Chemical Formula 1B]

[0068]

[0069] In the chemical formula 1B, y is 0 ≤ y ≤ 10.

[0070] For example, the fluoropolymer may be a random copolymer of ETFE and a fluorinated monomer having the structure of the chemical formula 1B, or a random copolymer containing ETFE and a fluorinated monomer having the structure of the chemical formula 1B as the reaction unit, but is not limited thereto.

[0071] For example, the fluoropolymer may be a polymer of reaction units represented by chemical formula (I) and reaction units represented by chemical formula (II), but is not limited thereto.

[0072] Chemical formula (I)

[0073]

[0074] In the chemical formula (I), the molar ratio of a, b, and c, a:b:c, can be 1–3:0–1:1, and d can be 0–10. For example, in the chemical formula (I), the molar ratio of a, b, c, and d, a:b:c:d, can be 1–3:0–1:1:0–10.

[0075] Chemical formula (II)

[0076]

[0077] In the chemical formula (II), e, f and g can be independently selected from integers above 0 and below 10, and A1, A2 and A3 can be hydroxyl groups or hydroxyl groups substituted with carboxylic acids.

[0078] Among them, carboxylic acids are not specifically limited as long as they are organic compounds with -COOH groups. For example, they can contain one -COOH group, or they can be polycarboxylic acids containing two or more -COOH groups.

[0079] The polycarboxylic acid may be, for example, succinic acid, glutaric acid, adipic acid, phthalic acid, trimellitic acid, etc., but is not limited to these.

[0080] The reaction unit represented by the chemical formula (II) can be, for example, the structure described below, but is not limited thereto.

[0081]

[0082] The fluoropolymer can be commercially available, such as GK series resins (manufactured by Daikin Industries, Ltd., trade names) including GK-570, GK-500, GK-510, GK-580, GK-581, etc., and LUMIFLON series resins (manufactured by Asahi Glass Co., Ltd., trade names) including LF200, LF400, LF552E, LF600X, LF800, LF810, LF810Y, LF910LM, LF936, LF9010, LF200MEK, LF9716, LF9721, etc.

[0083] Based on the total weight of the composition of the present invention, the fluorine content can exceed 30% by weight, for example, it can be 31-50% by weight, for example, it can be 32-50% by weight, for example, it can be 33-55% by weight, for example, it can be 35-50% by weight, for example, it can be 38-47% by weight.

[0084] The fluorine content in fluoropolymers can be, for example, 1 to 50% by weight, for example, 3 to 45% by weight, for example, 5 to 40% by weight.

[0085] When the fluorine content is 1% by weight or more, it can have sufficient flame retardancy. When it is less than 50% by weight, the proportion of fluorine in the fluoropolymer is not too large, so sufficient adhesion can be obtained.

[0086] The carboxyl equivalent of the fluoropolymer can be, for example, 500–7000 g / equivalent, 550–6500 g / equivalent, or 600–6000 g / equivalent. When the carboxyl equivalent meets the above range, the appropriate amount of reactive groups provides sufficient reactivity, thus improving the stability and reliability over time while shortening the process time and achieving full curing.

[0087] The hydroxyl equivalent of fluoropolymers can be, for example, 300–5500 g / equivalent, 450–3500 g / equivalent, or 550–3000 g / equivalent. When the hydroxyl equivalent is below 5500 g / equivalent, sufficient crosslinking density can improve the heat resistance of the solder. When the hydroxyl equivalent is above 300 g / equivalent, the hygroscopicity and water absorption can be reduced by decreasing the content of residual hydroxyl groups, thereby improving the heat resistance of the solder. Furthermore, due to the appropriate crosslinking points, reactivity is reduced and storage stability is improved at room temperature.

[0088] The weight-average molecular weight of fluoropolymers can be, for example, 5,000–150,000, 10,000–120,000, or 15,000–100,000. The weight-average molecular weight is measured using the GPC method and converted from a calibration curve prepared using standard polystyrene.

[0089] The fluororesin can be used alone or in combination of two or more.

[0090] [Epoxy Resin]

[0091] In one embodiment, the curable transparent resin composition comprises an epoxy resin. The curable transparent resin composition comprises an epoxy resin, such as a silicone epoxy resin, thus enabling the film using the composition to exhibit improved transparency and adhesion to a glass substrate.

[0092] The epoxy resin is a resin with epoxy groups, such as a difunctional epoxy resin having two epoxy groups in the molecule, or a polyfunctional epoxy resin having three or more epoxy groups in the molecule.

[0093] The epoxy resin may be fluorine-free.

[0094] The epoxy equivalent in the epoxy resin can be from 0.1 to 50 mol equivalents, but is not limited to this.

[0095] The epoxy resin may not contain aromatic rings or carbon double bonds. When the epoxy resin does not contain aromatic rings or carbon double bonds, its transparency is improved by the principle of not forming free radicals, and it will not yellow. The curable transparent resin composition containing it can exhibit excellent dry film properties, heat resistance, transparency, and adhesion. Furthermore, the curable transparent resin composition can exhibit excellent shape retention and color change stability through its heat resistance.

[0096] The epoxy resin may have at least one of aliphatic or alicyclic backbone.

[0097] The epoxy resin can be liquid at room temperature, but is not limited thereto. Room temperature refers to approximately 20°C. That is, the epoxy resin can be a liquid epoxy resin. The determination of liquid state is based on the "Method for Confirmation of Liquid State" in Annex 2 of the Ministry Ordinance concerning the Testing and Properties of Hazardous Substances (Ministry of Housing and Urban-Rural Development Ordinance No. 1 of 1989). For example, it is performed by the method described in paragraphs 23-25 ​​of Japanese Patent Application Publication No. 2016-079384. By including liquid epoxy resin, the dry film formed from the composition exhibits excellent flexibility.

[0098] The epoxy resin may contain siloxane (Si-O) groups in its main chain, but is not limited thereto. When the main chain of the epoxy resin contains siloxane groups, it is possible to produce cured products with excellent rubber properties such as weather resistance, heat resistance, hardness, or elongation.

[0099] The epoxy resin may be a hydrogen-added epoxy resin, but is not limited thereto.

[0100] The epoxy resin may be tetra[(epoxycyclohexyl)ethyl]tetramethylcyclotetrasiloxane, glycidoxymethyltrimethoxysilane, 3-glycidoxypropyltrihydroxysilane, 3-glycidoxypropyldimethylhydroxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltributoxysilane, 1-bis(glycidoxypropyl)tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)tetramethoxydisiloxane, 1,3- Bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)-1,3-dimethyl-1,3-dimethoxydisiloxane, 2,3-epoxypropyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 6,7-epoxyheptyltrimethoxysilane, 1,3-bis(2,3-epoxypropyl)tetramethoxydisiloxane, 1,3-bis(6,7-epoxyethynyl)tetramethoxydisiloxane, 2-(3,4-epoxycyclohexyl)ethyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, or combinations thereof, but not limited thereto.

[0101] The epoxy resin may be represented by one of the following chemical formulas 3-1, 3-2, or 3-3, but is not limited thereto.

[0102] [Chemical Formula 3-1]

[0103]

[0104] [Chemical Formula 3-2]

[0105]

[0106] [Chemical Formula 3-3]

[0107]

[0108] In the chemical formula 3-2, n is 0 ≤ n ≤ 100.

[0109] Examples of epoxy resins include silicone epoxy resins, alicyclic epoxy resins, and multifunctional epoxy resins. For example, the epoxy resin may be a silicone epoxy resin. Furthermore, the silicone epoxy resin, alicyclic epoxy resin, or multifunctional epoxy resin may contain aromatic compounds to a limit that does not impair the cured transparency.

[0110] Commercially available silicone epoxy resins include, but are not limited to, KR-470 manufactured by Shin-Etsu, TSR-104 manufactured by Isung Materials, and TSR-194 manufactured by Hansol E&C.

[0111] Examples of alicyclic epoxy resins include 3,4,3',4'-diepoxybiscyclohexyl, 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis(3,4-epoxycyclohexyl)-1,3-hexafluoropropane, bis(3,4-epoxycyclohexyl)methane, bis(3,4-epoxycyclohexyl)adipic acid, 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexane carboxylate, (3,4-epoxy-6-methylcyclohexyl)methyl-3',4'-epoxy-6-methylcyclohexane carboxylate, ethylene-1,2-bis(3,4-epoxycyclohexane carboxylate), 3,4-epoxycyclohexylmethanol, or 3,4-epoxycyclohexylethyltrimethoxysilane, etc., which are alicyclic epoxy resins with epoxy groups, but are not limited to these. Examples of commercially available products include CELOXIDE2000, CELOXIDE 2021, CELOXIDE 3000, and EHPE3150 manufactured by Daicel Chemical Industries, Ltd.; Epomic VG-3101 manufactured by Mitsui Chemicals, Ltd.; E-1031S manufactured by Emulsion Shell Epoxy Resin Co., Ltd.; TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd.; and EPB-13 and EPB-27 manufactured by SODA Corporation of Japan, etc., but are not limited to these.

[0112] Examples of multifunctional epoxy compounds include linear epoxy resins such as YED216D manufactured by Mitsubishi Chemical Corporation; brominated epoxy resins such as jERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclone 152 and Epiclone 165 manufactured by DIC Corporation, Epototte YDB-400 and YDB-500 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., DER542 manufactured by Dow Chemical, carbide epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and AER711 and AER714 manufactured by Asahi Chemical Co., Ltd.; and Epototte manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy resins such as ST-2004, ST-2007, and ST-3000 (trade names); glycidyl amine type epoxy resins such as JER604 manufactured by Mitsubishi Chemical Corporation; Epototte YH-434 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; and SUMI epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names); hydantoin-type epoxy resins; and CELOXIDE manufactured by Daicel Co., Ltd. Alicyclic epoxy resins such as 2021P (trade name); trihydroxybenzane-type epoxy resins such as YL-933 manufactured by Mitsubishi Chemical Corporation, and TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Dow Chemical Corporation; non-xylenol or non-phenolic epoxy resins or mixtures thereof such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; tetraphenylethane-type epoxy resins such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; heterocyclic epoxy resins such as TEPIC (trade name) manufactured by Nissan Chemical Industries, Ltd.; glycidyl methacrylate copolymer epoxy resins such as CP-50S, CP-50M, etc. manufactured by Nippon Yushi Co., Ltd.; and copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, etc., but not limited to these. These epoxy resins can be used alone or in combination of two or more.

[0113] [Thixotropic agent]

[0114] In one embodiment, the curable transparent resin composition may further include a thixotropic agent.

[0115] As a thixotropic agent, silica or other organic or inorganic substances can be used. As silica, hydrophilic silica or hydrophobic silica can be used, for example, hydrophilic calcined silica or hydrophobic calcined silica, such as polydimethylsiloxane-treated silica and hexamethyldisilazane-treated silica.

[0116] For example, silicon dioxide may have the structure described below, but is not limited thereto.

[0117]

[0118] As an organic material, saturated or unsaturated organic materials can be used. As an inorganic material, metals or non-metals can be used, such as alumina, silicon nitride, and aluminum nitride. In particular, using hydrophilic or hydrophobic calcined silica is advantageous for achieving the effects of this disclosure, with a BET surface area of ​​150 m². 2 / g or more, 200m 2 / g or more or 250m 2 When the concentration is above / g, it is particularly beneficial to achieve the effects of this disclosure.

[0119] [Content of each component]

[0120] In one embodiment, the content of fluoropolymer (A) may be approximately 60% to 99% by weight, approximately 60% to 98% by weight, approximately 62% to 97% by weight, approximately 64% to 96.5% by weight, approximately 66% to 96% by weight, approximately 68% to 95.5% by weight, approximately 70% to 95% by weight, approximately 72% to 94.5% by weight, approximately 74% to 94% by weight, approximately 76% to 93.5% by weight, or approximately 78% to 93% by weight, based on the total weight of the composition of the present invention. When the content of fluoropolymer (A) is above the aforementioned minimum value, the dry film properties, heat resistance, transparency, adhesion, color change, and shape retention desired by the curable transparent resin composition of the present invention can be achieved more superiorly; when the content is below the aforementioned maximum value, the dry film properties, heat resistance, transparency, adhesion, color change, and shape retention desired by the present invention can be achieved.

[0121] In one embodiment, the content of epoxy resin (B) may be from about 0.9 wt% to about 20 wt%, from about 1 wt% to about 20 wt%, from about 1.1 wt% to about 19 wt%, from about 1.2 wt% to about 18 wt%, from about 1.3 wt% to about 17 wt%, from about 1.4 wt% to about 16 wt%, from about 1.5 wt% to about 15 wt%, from about 1.6 wt% to about 14 wt%, from about 1.7 wt% to about 13 wt%, from about 1.8 wt% to about 12 wt%, from about 1.9 wt% to about 11 wt%, from about 2 wt% to about 10 wt%, from about 2.5 to about 9 wt%, from about 3 to about 8 wt%, or from about 3.5 to about 7 wt%, based on the total weight of the composition of the present invention. When the content of epoxy resin (B) is above the minimum value, the dry film properties, heat resistance, transparency, adhesion, color change and shape retention of the curable transparent resin composition of the present invention can be achieved; when the content is below the maximum value, the dry film properties, heat resistance, transparency, adhesion, color change and shape retention of the present invention can be achieved.

[0122] In one embodiment, the thixotropic agent content may be from about 0.1 to about 20% by weight, from about 0.1 to about 18% by weight, from about 0.2 to about 15% by weight, or from about 0.2 to about 12% by weight, based on the total weight of the composition of the present invention. When the thixotropic agent content is above the stated minimum value, the dry film properties, heat resistance, transparency, adhesion, color change, and shape retention desired by the present invention can be sufficiently achieved; when the content is below the stated maximum value, the dry film properties, heat resistance, transparency, adhesion, color change, and shape retention desired by the present invention can be sufficiently achieved.

[0123] [Other Additives]

[0124] In one embodiment, the curable transparent resin composition may include at least one of a thermosetting agent, a multifunctional monomer, a free radical photoinitiator, a dispersant, a thermosetting polymerization inhibitor, a solvent, and a leveling agent.

[0125] Thermosetting agents can be imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; and hexylene oxide. Hydrazine compounds such as diacid hydrazide and sebacic hydrazide; phosphorus compounds such as triphenylphosphine; S-triazine derivatives of guanidineamine, acetylguanidineamine, benzoguanidineamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct or 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct, etc., but not limited to these.

[0126] Multifunctional monomers can be any known monomer having two or more functional groups without special restrictions, such as trimethylolpropane triacrylate, trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, or pentaerythritol tri(meth)acrylate, but are not limited thereto. Such multifunctional monomers can improve the pencil hardness and chemical resistance of the cured transparent resin composition of the present invention.

[0127] The free radical photoinitiator can be any known type without particular restriction, and may include one or more of the following: benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides, or oxime esters. More specifically, for example, acetyl, benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1-methylethyl-phenol ketone, p-isopropyl-α-hydroxyisobutylacetophenone, N,N-dimethylaminoacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, ethyl p-dimethylaminobenzoate, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2- Aminoanthraquinone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzyl dimethyl ketal, benzophenone, methyl benzophenone, trimethyl benzophenone (TZT), 4-benzoyl4'-methyldiphenyl sulfide, 4,4'-dichlorobenzophenone, diethylthioxanthone (DETX), 2-isopropylthioxanthone (ITX), 4,4'-bis(diethylamino)benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1 (IRGACURE907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (IRGACURE) 369), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butanone-1 (IRGACURE 379), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (OMNIRAD 819 or IRGACURE 819), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (Mosaphoto 348), bis(ethanolamine 5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl]titanium, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-indan-5-yl}-2-methyl-propane-1-one (ESACURE) ONE), 1-propanone, 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl] (ESACURE 1001M), bis-N,N-[4-dimethylaminobenzoyl)oxyethylene-1-yl]-methylamine (ESACUREA198), or mixtures of two or more thereof, but not limited thereto.

[0128] As a dispersant, there are no particular limitations on the use of well-known, commercially available BYK products such as DISPERBYK-111, DISPERBYK-110, DISPERBYK-118, DISPERBYK-140, DISPERBYK-142, DISPERBYK-163, DISPERBYK-2150, DISPERBYK-2200, DISPERBYK-2205, and DISPERBYK-2163. One or more of the following, but not limited to: DISPERBYK-2013, DISPERBYK-180, DISPERBYK-2155, DISPERBYK-2009, DISPERBYK-168, DISPERBYK-2164, DISPERBYK-2118, DISPERBYK-2008, DISPERBYK-9076, DISPERBYK-9077, and DISPERBYK-2055.

[0129] The content of the dispersant may be 0.1 to 5% by weight, 0.5 to 2% by weight, 0.7 to 1.5% by weight, 0.9 to 1.3% by weight, or 0.9 to 1.1% by weight, based on the total weight of the composition of the present invention.

[0130] Thermosetting polymerization inhibitors can be used without particular restriction, as long as they can be used to maintain the storage stability of the composition. The curable transparent resin composition of the present invention contains a thermosetting compound, such as a capped isocyanate. This thermosetting compound remains stable after capping and before heating, but at room temperature or moderate temperature (about 30°C to about 60°C), some of the thermosetting compound reacts, thereby reducing storage stability. To prevent this reduction in storage stability and maintain the storage stability of the curable transparent resin composition, a thermosetting polymerization inhibitor can be used. Examples include, but not limited to, one or more of phenols such as hydroquinone, tert-butylcatechol, and butylated hydroxyanisole; quinones such as p-benzoquinone; amines such as nitrohydroxylamine and phenylenediamine; thiols; and dithiocarbamates. Thermosetting polymerization inhibitors can be tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminium or aluminum nitrohydroxyamine (Q-1301; Wako).

[0131] The content of the thermosetting polymerization inhibitor can be 0.01 to 0.5% by weight, 0.01 to 0.3% by weight, 0.05 to 0.2% by weight, 0.05 to 0.15% by weight, or 0.05 to 0.1% by weight, based on the total weight of the composition of the present invention. When the content of the thermosetting polymerization inhibitor is above the aforementioned minimum value, sufficient storage stability of the curable transparent resin composition can be achieved; when the content is below the aforementioned maximum value, the desired degree of curing can be achieved by heating.

[0132] Furthermore, the curable transparent resin composition of the present invention can use a solvent, such as an organic solvent, as a diluent to dilute the composition or adjust the viscosity for coating onto a substrate or carrier film.

[0133] Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, ethylene glycol ethyl ether acetates, ethers, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, examples include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethylene glycol ethers such as cellosolves, methyl cellosolves, butyl cellosolves, carbitol, methyl carbitol, butyl carbitol, propylene glycol monoether, dipropylene glycol monoether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ethers, naphtha, hydrogenated naphtha, and solvent naphtha. Such organic solvents can be used alone or in mixtures of two or more. There is no particular limit to the amount of organic solvent used; it can be added as needed.

[0134] The curable transparent resin composition of the present invention is, for example, adjusted to a viscosity suitable for a coating method by means of the organic solvent, coated onto a substrate by means of dip coating, flow coating, roller coating, bar coating, screen printing, curtain coating, etc., and the organic solvent contained in the composition is evaporated and dried (temporarily dried) at a temperature of about 50 to 300°C, thereby forming a non-stick coating film.

[0135] Leveling agents can be used without particular restriction as long as they are used to increase adhesion to the finally cured PSR substrate and solve sagging problems (pinholes). For example, from the perspective of the leveling properties suitable for the compositions of the present invention, commercially available silicone or non-silicone leveling agents from BYK can be used, and combinations of two or more can be used. Silicone leveling agents can be BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, B YK-325N, BYK-326, BYK-327, BYK-329, BYK-331, BYK-333, BYK-342, BYK-346, BYK-345, BYK-348, BYK-349, BY The following are at least one of BYK-370, BYK-377, BYK-378, BYK-3455, BYK-3456, BYK-3450, BYK-3451, BYK-3480, BYK-3481, BYK-3760, BYK-UV-3500, BYK-UV-3505, BYK-UV-3530, BYK-UV-3535, BYK-UV-3570, BYK-UV-3575 and BYK-UV-3576, but not limited to these. The non-silicone leveling agent may be at least one of BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-381, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYK-3560, and BYK-3566, but is not limited thereto.

[0136] The leveling agent content can be 0.1 to 1.0 wt%, 0.2 to 0.8 wt%, 0.3 to 0.7 wt%, or 0.4 to 0.6 wt% based on the total weight of the composition of the present invention. When the leveling agent content is above the minimum value, a curable transparent resin composition that achieves the desired adhesion or is free from sagging problems (pinholes) can be manufactured. When the content is above the maximum value, reactivity decreases, or if it is present in the lower layer of the marking ink coating, adhesion may decrease.

[0137] In one embodiment, the curable transparent resin composition may additionally include at least one of a dispersant, defoamer, flow modifier, foaming agent, surfactant, antioxidant, antistatic agent, and gloss agent, in which case it may be added in small amounts relative to the total weight of the curable transparent resin composition.

[0138] In one embodiment, the curable transparent resin composition may be characterized by not containing a cationic photoinitiator. The curable transparent resin composition of the present invention is characterized in that, even without or using a cationic photoinitiator, the heteropolymer monomers and monomers having functional groups capable of forming crosslinks with cationic curable functional groups are cured by active energy rays. Through this feature, the curable transparent resin composition of the present invention can exhibit excellent viscosity or storage stability and excellent surface curing properties.

[0139] In one embodiment, the average light transmittance of the curable transparent resin composition may be 95% or more, for example, 98% or more. The average light transmittance is measured using the following method:

[0140] The composition (curable resin composition) printed on a TORAY XD-500P (50µm) PET film was laminated onto a 2000µm thick glass substrate at 60°C for 40 seconds. After removing the PET film laminated onto the glass substrate, the glass substrate was cured at 150°C for 1 hour in a hot air circulating drying oven, and 50µm thick test pieces were used for evaluation. The transmittance of each test piece in the wavelength range of 350–800nm ​​was measured using a JASCO V-670 spectrophotometer and evaluated according to a standard. Transmittance was taken as 100% transmittance of the glass substrate. The transmittance was measured by contacting the spectrophotometer with the cured coating of the composition on the glass substrate and expressed as a relative value compared to the transmittance of the glass substrate. Higher transmittance indicates higher transparency of the cured composition.

[0141] In one embodiment, regarding the color difference b-value of the curable transparent resin composition, for test pieces prepared using the same method as those prepared with average light transmittance, 80gsm of Double A A4 paper was placed under a glass substrate, and the color difference b-value of each test piece was measured using a Konica Minolta CM-700D color meter. The lower the b-value, the closer it is to achromatic. That is, since a lower b-value indicates a smaller color difference, it means that the composition can adequately prevent discoloration. In one embodiment, the color difference b-value of the curable transparent resin composition may be 2.9 or less, for example, 1.5 or less.

[0142] In one embodiment, the haze value of the curable transparent resin composition was measured using a glass substrate cut to 50mm x 50mm size, with the composition facing upwards, on a test piece prepared using the same method as for preparing a test piece with average transmittance. The measurement was performed on a MURAKAMI HM-150 haze measuring instrument with a light source (halogen lamp A), incident area (14mmΦ), and incident aperture (20mmΦ) according to test method ASTM D1003. A haze value closer to 0 indicates higher transmittance. In one embodiment, the haze value of the curable transparent resin composition may be 5.0% or less, for example, 3.0% or less.

[0143] [thing]

[0144] Another embodiment of the invention relates to various articles derived from curable transparent resin compositions. These curable transparent resin compositions may be contained in or formed into various articles. Descriptions of the various articles are provided below.

[0145] [Components for displays]

[0146] In one embodiment, the display component is characterized by having a cured product formed from the aforementioned curable transparent resin composition on a substrate.

[0147] The substrate used in this invention can be, for example, a resin film such as polyimide film or PET film, a glass substrate, a ceramic substrate, a metal substrate, or a wafer. In particular, resin films such as polyimide film or PET film, or glass substrates, can be used. The material and shape of the substrate can be selected according to the intended use or performance of the target molded article, and two or more materials and shapes can be selected individually or in combination as needed. Furthermore, from the viewpoint of adhesion, the substrate can be a glass substrate.

[0148] After preparing the aforementioned curable transparent resin composition with predetermined components, the viscosity can be adjusted to a suitable coating method, for example, by using an organic solvent, and then coated on the substrate by methods such as dip coating, flow coating, roller coating, bar coating, screen printing, or screen coating. Flow coating, roller coating, bar coating, or screen printing are particularly suitable.

[0149] [LED device]

[0150] By thick-film coating of a curable transparent resin composition or by pouring it into a predetermined mold and then heat-curing or UV-curing, a molded material encapsulated in a transparent cured product can be obtained. This material is particularly suitable for optical components such as LEDs, light-receiving elements, photoelectric conversion elements, or light transmission-related components.

[0151] In one embodiment, the sealing material composition for LEDs includes the aforementioned curable transparent resin composition.

[0152] In one embodiment, the LED element in the LED device is encapsulated by a cured layer formed from the LED sealing material composition.

[0153] [Glass adhesive compositions and chip bonding compositions]

[0154] In one embodiment, the glass adhesive composition comprises the aforementioned curable transparent resin composition.

[0155] The cured transparent resin composition exhibits excellent adhesion to glass, making it suitable for use as a glass fixing application in vehicles.

[0156] In another embodiment, the chip bonding composition includes the aforementioned curable transparent resin composition.

[0157] The curable transparent resin composition exhibits excellent adhesion to the wafer substrate, making it suitable for use as a chip bonding material.

[0158] [Dry film]

[0159] In one embodiment, the dry film has a thin film (e.g., a support (carrier) film) and a resin layer formed on the film using the aforementioned curable transparent resin composition. Furthermore, the dry film may also have a protective film (so-called a protective film) on the resin layer formed on the film.

[0160] The film is not particularly limited, and for example, films containing thermoplastic resins such as polyester films (e.g., polyethylene terephthalate and polyethylene naphthalate), polyimide films, polyamide-imide films, polypropylene films, and polystyrene films can be used. From the viewpoints of heat resistance, mechanical strength, and operability, polyethylene terephthalate is particularly suitable. Furthermore, laminates of these films can also be used as films.

[0161] Furthermore, regarding the thermoplastic resin film mentioned above, from the viewpoint of improving mechanical strength, it can be a film extending in the 1-axis direction or the 2-axis direction.

[0162] There is no particular limitation on the thickness of the film, but it can be, for example, 10 to 150 μm.

[0163] The resin layer is formed using the curable transparent resin composition, and its thickness is not particularly limited, but is preferably varied according to the application, but for example it can be more than 1 μm and less than 150 μm.

[0164] The curable transparent resin composition can be uniformly coated onto a film and dried to form a resin layer using a comma coating machine, doctor blade coating machine, lip coating machine, rod coating machine, extrusion coating machine, reverse coating machine, transfer roller coating machine, gravure coating machine, and spray coating machine.

[0165] Regarding the dry film, in order to prevent dust from adhering to the surface of the resin layer, a peelable protective film can be laminated on the surface of the resin layer.

[0166] As a peelable protective film, it is not particularly limited as long as the adhesion between the resin layer and the protective film is less than the adhesion between the resin layer and the film when the protective film is peeled off. For example, polyethylene film, polytetrafluoroethylene film, polypropylene film, and surface-treated paper can be used.

[0167] The thickness of the protective film is not particularly limited, but can be, for example, greater than 10 μm and less than 150 μm.

[0168] The present invention will become clearer through the foregoing embodiments and the following examples. The embodiments described below with reference to the table below will be described in detail to facilitate understanding and implementation by those skilled in the art. However, these embodiments are for illustrative purposes only, and the scope of the invention is not limited to these embodiments.

[0169] [Example]

[0170] I. Preparation of Curable Transparent Resin Composition

[0171] Reactants having the components and amounts listed in Table 1 below, and propylene glycol monomethyl ether as a solvent at a content of 20% by weight based on the total weight of the reactants, were mixed in a mixer at 2,000 rpm and 45°C for 0.5 hours. Pigments and dispersants were then added, and the mixture was dispersed using 0.2 μm zirconia beads for 3 hours. The resulting curable transparent resin composition was then prepared by filtration through a 1 μm filter.

[0172] The components listed in Table 1 are as follows:

[0173] 1) Resin A (a fluoropolymer resin having one or more carboxyl groups):

[0174] Purchase (a:b:c:d = 3:1:1:8) and The polymer (GK-570, obtained from Daikin) is a polymer synthesized using succinic anhydride.

[0175] 2) Epoxy Resin A (an epoxy resin (liquid) containing siloxane (Si-O) groups in its main chain): Purchased from: Shin-Etsu, Product name: KR-470

[0176] 3) Silica A: BET surface area is 250m² 2 Hydrophilic calcined silica of / g or higher, source: EVONIK, product name: AEROSIL380

[0177] 4) Silica B: BET surface area is 200-250 m² 2 / g of hydrophilic calcined silica, source: EVONIK, product name: AEROSIL200

[0178] 5) Silica C: BET surface area is 150-200 m² 2 / g of hydrophilic calcined silica, source: EVONIK, product name: AEROSIL150

[0179] 6) Silica D: BET surface area is 150m² 2 Hydrophilic calcined silica (below g / g) can be found at: EVONIK, product name: AEROSIL130.

[0180] 7) Silica E: BET surface area is 250m² 2 Hydrophobic calcined silica of / g or higher, source: EVONIK, product name: AEROSIL R106

[0181] 8) Silica F: BET surface area is 150-200 m² 2 / g of hydrophobic calcined silica, source: EVONIK, product name: AEROSIL R974

[0182] 9) Silica G: BET surface area is 150m² 2 Hydrophobic calcined silica (below / g) can be sourced from: EVONIK, product name: AEROSIL R208.

[0183] II. Characteristic Tests

[0184] The compositions of the examples and comparative examples prepared as described above were evaluated as follows. The evaluation results are shown in... Figures 1a to 1f , Figures 2a to 2c Table 1 and Table 2.

[0185] 1. Dry film properties (DF properties)

[0186] (1) 50μm standard: A curable transparent resin composition was applied to a TORAY XD-500P (50μm) PET film using an applicator at a speed of 1.0 m / min. After drying in four chambers at 60°C, 80°C, 105°C, and 105°C for 30 minutes, respectively, a 50μm thickness was printed. After drying in a hot air circulating drying oven at 80°C for 30 minutes, the dry film was evaluated according to the following standard.

[0187] (2) 200μm Standard: A curable transparent resin composition was applied to a TORAY XD-500P (200μm) PET film using an applicator at a speed of 0.7 m / min. After drying in four chambers at 60°C, 80°C, 130°C, and 135°C for 30 minutes each, a 200μm thickness was achieved. The dried film was then dried in a hot air circulating drying oven at 80°C for 30 minutes and evaluated according to the following standard. (Cross cut was performed using the ASTM D3359 test method, at a specification of 10 / 10, 1 mm.)

[0188] ○: Slit (film cross cut & tape peel test), bending (90°), and tacky are all good (OK).

[0189] △: When cut open (slit; film cross-section & tape peel test, bent at 90°), cracks are visible.

[0190] X: Slit (film cross-section & tape peel test, bent at 90°), poor adhesion (NG).

[0191] 2. Transparency

[0192] A curable transparent resin composition was laminated onto a TORAY XD-500P (50µm) PET film on a glass substrate for 40 seconds at 60°C. After removing the laminated PET film from the glass substrate, the glass substrate was cured at 150°C for 2 hours in a hot air circulating drying oven to obtain test pieces. The transmittance of each test piece in the wavelength range of 350–800 nm was measured using a JASCO V-670 spectrophotometer and evaluated according to a standard. For transmittance, the transmittance of the glass substrate was set as 100%, and the transmittance was measured by contacting the spectrophotometer on the cured coating of the glass substrate composition and expressed as a relative value compared with the transmittance of the glass substrate.

[0193] ○: The average light transmittance is over 98%.

[0194] △: The average light transmittance is above 95% but less than 98%.

[0195] X: Unable to be measured due to lack of curing.

[0196] The specific measurement results of the average transmittance are shown in Table 2. Specifically, Table 2 shows the average transmittance of the compositions of Example 1 and Comparative Examples 1 to 7 in the visible light region (wavelength range of 350 to 800 nm).

[0197] Referring to Table 1, when using the compositions of Examples 1 to 13, excellent transmittance is achieved in the visible light region.

[0198] 3. Heat resistance

[0199] Heat resistance was evaluated on specimens prepared using the same method as those prepared in the transparency evaluation, after being placed at 85°C / 85% humidity for 1000 hours, according to the following criteria.

[0200] ◎: After being placed at 85℃ / 85% humidity for 1000 hours, 100% of the product remained after cross-section and tape peel test.

[0201] ○: After being placed at 85℃ / 85% humidity for 1000 hours, a cross-section and tape peel test was performed, and 70-90% of the material remained.

[0202] △: After being placed at 85℃ / 85% humidity for 1000 hours, 50-70% of the material remained after cross-section and tape peeling tests.

[0203] X: Unable to be evaluated due to incomplete or insufficient curing.

[0204] 4. Adhesion

[0205] The following criteria were used to evaluate specimens prepared using the same method as those prepared in the transparency evaluation, which were immersed in H2O and boiled for 1000 hours at 85°C / 85% humidity.

[0206] ◎: After boiling, the cross-section and tape peeling tests are OK.

[0207] ○: OK after boiling.

[0208] △: Slightly peeling off after boiling.

[0209] X: Unable to be evaluated due to incomplete or insufficient curing.

[0210] 5. Color-changing property

[0211] For test pieces prepared using the same method as those prepared in the transparency evaluation, 80gsm A4 paper from DoubleA was placed under a glass substrate, and the b value (Yellow to Blue) of L, a, and b values ​​was measured using a Konica Minolta CM-700D (colorimeter). The evaluation was performed according to the following criteria: +b represents the yellow series, -b represents the blue series, and the lower the b value, the closer it is to achromatic.

[0212] ○: Color difference b value is less than 1.5%

[0213] △: Color difference b value exceeds 1.5%

[0214] X: Color difference b value is 3.0% or more, or cannot be evaluated due to insufficient curing.

[0215] The excellent color-changing properties of the composition in this specification indicate that the color difference is small, and therefore the composition can effectively prevent color change.

[0216] 6. Shape retention

[0217] A sample was prepared by dripping 0.1 mL of the composition onto a glass substrate using a syringe (1 mL) from HWAJIN Pharmaceuticals, drying it at 90 °C for 15 minutes in a hot air circulating drying oven, and then curing it at 150 °C for 2 hours.

[0218] The thickness and diameter of each specimen were measured using a KEYENCE VHX-5000 three-dimensional microscope, and the specimens were evaluated according to the following criteria.

[0219] ◎: Diameter less than 2500μm, thickness greater than 1000μm

[0220] ○: Diameter 2500–3000 μm, thickness 800–1000 μm

[0221] △: Diameter 3000–3500 μm, thickness 600–800 μm

[0222] X: Diameter exceeding 3500μm, thickness less than 600μm

[0223] Table 1

[0224]

[0225]

[0226]

[0227] Table 2

[0228]

[0229] See Table 1 and Table 2. Figures 1a to 1f and Figures 2a to 2c According to Examples 1 to 13, a curable transparent resin composition according to one embodiment of the present invention comprises (A) a combination of a fluoropolymer containing one or more carboxyl groups and (B) an epoxy resin, thereby exhibiting excellent dry film properties, heat resistance, transparency, adhesion, color change and shape retention.

[0230] In particular, the compositions of Examples 1 to 12, which contain silica (especially hydrophilic calcined silica or hydrophobic calcined silica) as a thixotropic agent, can achieve superior dry film properties, heat resistance, transparency, adhesion, color change and shape retention.

Claims

1. A curable transparent resin composition, characterized in that, Based on the total weight of the curable transparent resin composition, it comprises: (A) Fluoropolymers containing one or more carboxyl groups, accounting for more than 60% by weight; and (B) Less than 20% by weight of epoxy resin; The epoxy resin does not have an aromatic ring or carbon double bond; The color difference b value is below 2.

9.

2. The curable transparent resin composition according to claim 1, characterized in that: In addition to the carboxyl group, the fluororesin also contains one or more functional groups selected from the group consisting of hydroxyl, aldehyde, peroxyhydroxyl, amino, amine, carbonyl, acrylic, acryloyl, nitrile, vinyl, halogen, polyurethane, and ester groups.

3. The curable transparent resin composition according to claim 1, characterized in that: In addition to carboxyl groups, the fluoropolymer contains one or more hydroxyl groups as functional groups.

4. The curable transparent resin composition according to claim 1, characterized in that: The molar equivalent percentage of the carboxyl group relative to the total functional groups contained in the fluoropolymer is 1 to 100%.

5. The curable transparent resin composition according to claim 1, characterized in that: The fluororesin is a polymer of reactive units represented by chemical formula (I) and reactive units represented by chemical formula (II). Chemical formula (I) In the chemical formula (I), the molar ratio of a:b:c:d is 1~3:0~1:1:0~10. Chemical formula (II) In the chemical formula (II), e, f, and g are independently selected from integers greater than 0 and less than 10, and A1, A2, and A3 are independently hydroxyl groups or hydroxyl groups substituted with carboxylic acids.

6. The curable transparent resin composition according to claim 1, characterized in that: The epoxy resin is a silicone epoxy resin.

7. The curable transparent resin composition according to claim 1, characterized in that: The epoxy resin is liquid at room temperature.

8. The curable transparent resin composition according to claim 1, characterized in that: The epoxy resin backbone contains siloxane (Si-O) groups.

9. The curable transparent resin composition according to claim 1, characterized in that: The epoxy resin does not contain fluorine.

10. The curable transparent resin composition according to claim 1, characterized in that: The epoxy resin is tetratetramethylcyclotetrasiloxane, glycidoxymethyltrimethoxysilane, 3-glycidoxypropyltrihydroxysilane, 3-glycidoxypropyldimethylhydroxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltributoxysilane, 1-bis(glycidoxypropyl)tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)tetramethoxydisiloxane, 1, 3-Bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)-1,3-dimethyl-1,3-dimethoxydisiloxane, 2,3-epoxypropyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 6,7-epoxyheptyltrimethoxysilane, 1,3-bis(2,3-epoxypropyl)tetramethoxydisiloxane, 1,3-bis(6,7-epoxyethynyl)tetramethoxydisiloxane, 2-(3,4-epoxycyclohexyl)ethyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, or combinations thereof.

11. The curable transparent resin composition according to claim 1, characterized in that: The curable transparent resin composition also contains (C) a thixotropic agent.

12. The curable transparent resin composition according to claim 11, characterized in that: The thixotropic agent (C) is either hydrophilic calcined silica or hydrophobic calcined silica.

13. The curable transparent resin composition according to claim 12, characterized in that: The BET surface area of ​​the hydrophilic or hydrophobic calcined silica is 150 m². 2 / g or more, 200m 2 / g or more or 250m 2 / g or more.

14. A component for a display, characterized in that, The substrate has a cured product formed from the curable transparent resin composition according to any one of claims 1-13.

15. A sealing material composition for LEDs, characterized in that, Include: The curable transparent resin composition according to any one of claims 1-13.

16. An LED device, characterized in that: The LED element is encapsulated by a cured layer formed from the LED sealing material composition according to claim 15.

17. A glass adhesive composition, characterized in that, Include: The curable transparent resin composition according to any one of claims 1-13.

18. A dry film, characterized in that: The film has a cured resin layer formed from the cured transparent resin composition according to any one of claims 1-13.

19. A composition for chip bonding, characterized in that, Include: The curable transparent resin composition according to any one of claims 1-13.

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