CN116004149A - Curable transparent resin composition and various articles derived therefrom - Google Patents

Abstract

Embodiments of the present invention relate to curable transparent resin compositions and various articles derived therefrom. The curable transparent resin composition comprises: (A) a fluororesin having at least one carboxyl group; and (B) an epoxy resin. The curable transparent resin composition exhibits excellent dry film properties, heat resistance, transparency, adhesion and discoloration properties by a combination of two components, and thus can form a film having excellent adhesion and discoloration properties while having light transmittance at a level similar to that of a silicone resin composition currently in common use for display applications. Therefore, the curable transparent resin composition of the present invention can be used not only as a member for a display that requires excellent light transmittance but also for various applications such as LE D sealing materials, glass adhesives, dry films, or die bonding materials that require excellent adhesion and discoloration.

Description

Curable transparent resin composition and various articles derived therefrom

Technical Field

The present invention relates to a curable transparent resin composition and various articles derived therefrom. Specifically, the article may be a sealing material composition for LEDs, a glass adhesive composition, or a die bonding composition comprising the curable transparent resin composition, or may be a display component having a cured product formed from the curable transparent resin composition on a substrate, an LED device encapsulating an LED element with a cured layer formed from the LED sealing material composition, or a dry film having a curable transparent resin layer formed from the curable transparent resin composition on a film.

Background Art

Optical semiconductor elements such as light emitting diodes (LEDs) have the excellent characteristic of low power consumption, and therefore their application in optical semiconductor devices for outdoor lighting and vehicle use is increasing.

Recently, vertical LED chips are being developed with the goal of further improving the luminous efficiency of optical semiconductor elements. In vertical LED chips, electrodes are arranged in a vertical structure, and current flows evenly in the light-emitting layer. Compared with horizontal LED chips of the same size with electrodes arranged horizontally, dozens of times more current can flow, thereby suppressing the temperature rise of the light-emitting layer and improving the luminous efficiency.

In addition, since the electrodes in the vertical LED chip are configured in a vertical structure, when the vertical LED chip is installed on a wiring board, the electrodes on one side need to be electrically connected using the same wire bonding method as in the past, and the electrodes on the other side need to be electrically connected using a welding process or a conductive adhesive.

At present, as an adhesive for mounting a vertical LED chip on a wiring board, a conductive adhesive obtained by mixing conductive particles in a welding process or an epoxy resin composition is widely used. However, in the case of a welding process, the heat required to melt the solder required for chip bonding can easily damage the light-emitting layer of the optical semiconductor, so it is not preferred. In addition, since the welding process or the conductive adhesive obtained by mixing conductive particles in an epoxy resin composition cannot fully reflect light, there is a problem of poor light extraction efficiency. Furthermore, from the perspective of design freedom when used as an optical semiconductor device, the chip bonding material is also required to have high transparency.

In addition, as an example of using a conductive adhesive, for example, Patent Document 1 proposes a conductive adhesive that uses a bisphenol A type epoxy resin or a bisphenol F type epoxy resin and an alicyclic epoxy resin, and further adds a benzotriazole derivative as an ultraviolet absorber to improve the light resistance to light near 450 to 500 nm. However, the composition according to the invention contains a large amount of white titanium oxide or colored conductive particles, and therefore cannot be a highly transparent adhesive.

In addition, light-emitting diodes are used after sealing the chip inside with a sealant to protect the inside. Various resins are used as transparent sealants for light-emitting diodes, for example, epoxy resin compositions containing an acid anhydride curing agent and a curing accelerator. For example, Patent Documents 2 and 3 disclose epoxy resin compositions to which thiophosphite compounds and thiophosphoric acid are added in order to improve transparency.

[Prior technical literature]

[Patent Literature]

(Patent Document 1) Japanese Patent Publication No. 3769152

(Patent Document 2) Japanese Patent No. 59-062624

(Patent Document 3) Japanese Patent No. Sho 60-140884

Summary of the invention

Technical issues

In order to protect the optical semiconductor elements, electrodes, substrates, etc. from the external environment, the device on which the optical semiconductor elements are mounted needs a cured product to protect the surfaces of these structures. Currently, cured products are formed using thermosetting liquid silicone resins, which have the advantage of forming cured products with excellent rubber properties such as weather resistance, heat resistance, hardness, and elongation. However, the cured product formed by silicone resin has high air permeability. When such a cured product is used for high-grayscale LEDs with strong light and high heat generation, the sealing material may be discolored due to corrosive gases, and the grayscale may be reduced due to corrosion of the silver plating on the electrodes or substrates. In order to solve these problems, the present invention provides a composition that does not use silicone resin, but provides (A) a fluororesin containing one or more carboxyl groups as a main component, and (B) a curable transparent resin composition containing epoxy resin.

The present invention is used to provide a curable transparent resin composition, which can exhibit excellent dry film properties, heat resistance, transparency, adhesion, color changeability and shape retention.

Furthermore, the present invention is intended to provide a display component, an LED sealing material composition, a glass adhesive composition, a dry film, or a die bonding composition using the curable transparent resin composition.

Technical Solution

One embodiment of the present invention relates to a curable transparent resin composition including (A) a fluororesin having one or more carboxyl groups, and (B) an epoxy resin.

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

In one implementation example, the fluororesin may further include one or more hydroxyl groups as functional groups in addition to the carboxyl group.

In one implementation example, the molar equivalent % of the carboxyl group relative to the entire functional group contained in the fluororesin may be 1 to 100%.

In one implementation example, the fluororesin may be a polymer of a reaction unit represented by the following chemical formula (I) and a reaction unit represented by the following chemical formula (II).

Chemical formula (I)

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

Chemical formula (II)

In the chemical formula (II), e, f and g are independently selected from integers of 0 to 10, and A ₁ , A ₂ and A ₃ are independently hydroxyl groups or hydroxyl groups substituted with carboxylic acid.

In one implementation example, the epoxy resin may be silicon epoxy resin.

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

In one implementation example, the epoxy resin may not have an aromatic ring or a carbon double bond.

In one implementation example, the main chain of the epoxy resin may contain a siloxane (Si—O) group.

In one implementation example, the epoxy resin may not contain fluorine.

In one implementation example, the epoxy resin can be tetra[(epoxycyclohexyl)ethyl]tetramethylcyclotetrasiloxane, glycidyloxymethyltrimethoxysilane, 3-glycidyloxypropyltrihydroxysilane, 3-glycidyloxypropyldimethylhydroxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyldimethoxymethylsilane, 3-glycidyloxypropyldiethoxymethylsilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyltributoxysilane, 1-bis(glycidyloxypropyl)tetramethyldisiloxane, 1,3-bis(glycidyloxypropyl)tetramethoxydisiloxane, 1,3-bis(3-glycidyloxypropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(glycidyloxypropyl)-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 a combination thereof.

In one implementation example, the curable transparent resin composition may further include (C) a thixotropic agent.

In one implementation example, the (C) thixotropic agent may be hydrophilic fumed silica or hydrophobic fumed silica.

In one implementation example, the BET surface area of the hydrophilic fumed silica or the hydrophobic fumed silica may be greater than 150 m ² /g and greater than 200 m ² /g or greater than 250 ^{m 2} /g.

Another embodiment of the present invention relates to a display member characterized by having a cured product formed from the curable transparent resin composition on a substrate.

Another embodiment of the present invention relates to a sealing material composition for LEDs including the above-mentioned curable transparent resin composition.

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

Another embodiment of the present invention relates to a glass adhesive composition including the above-mentioned curable transparent resin composition.

Another embodiment of the present invention relates to a dry film characterized by comprising a curable resin layer formed from the above-mentioned curable transparent resin composition on a thin film.

Another embodiment of the present invention relates to a die bonding composition including the above-mentioned curable transparent resin composition.

Technical Effects

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, and thus has a light transmittance similar to that of the existing silicone resin composition widely used for display applications, and can also form a cured product (such as a film) with excellent adhesion. Therefore, 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 LED sealing material, glass adhesive, dry film, chip bonding material, etc. requiring excellent adhesion.

BRIEF DESCRIPTION OF THE DRAWINGS

1a to 1f are schematic diagrams showing droplets of the compositions of Example 1, Example 7, Example 13, Comparative Example 1, Comparative Example 3, and Comparative Example 5, respectively;

2a to 2c are pictures showing droplets of the compositions of Example 1, Example 7, and Example 13, respectively.

DETAILED DESCRIPTION

The various embodiments or examples described in this specification are intended to be illustrated to clearly explain the technical idea of the present invention. The technical idea of the present invention includes various modifications, equivalents, alternatives, and embodiments or examples selectively combined from all or part of each embodiment or example described in this specification. In addition, the technical idea of the present invention is not limited to the various embodiments or examples provided below, or their specific descriptions.

The terms used in this specification, including technical or scientific terms, shall have the meanings commonly understood by those skilled in the art to which the present invention belongs unless otherwise defined. Terms such as those defined in general dictionaries shall be interpreted as having the meanings consistent with the meanings in the context of the relevant technology, and shall not be interpreted as having ideal or overly formal meanings if not clearly defined in the present invention.

The expressions "including", "may include", "have", "may have" and the like used in this specification indicate the existence of the features (e.g., functions, actions or constituent elements) as the object, but do not exclude the existence of other additional features. That is, such expressions should be understood as open-ended terms that include the possibility of other implementations.

Singular expressions used in this specification may include plural meanings unless otherwise specified in the context, and the same applies to singular expressions recorded in the claims.

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

The term "about" used in the present invention can represent the conventional error range for each value as known to those skilled in the art. This can represent ±20%, ±15%, ±10%, ±9%, ±8%, ±7%, ±6%, ±5%, ±4%, ±3%, ±2% or ±1% of the numerical value or range mentioned or required in one embodiment in the context of the numerical value or range recorded in this specification.

Unless otherwise specified in the context, the dimensions, values, and ranges thereof used in the present specification are not limited to the dimensions, values, and ranges thereof, but may indicate an equivalent range thereof.

Various embodiments of the present invention are described below.

[Curable transparent resin composition]

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

At present, compositions containing thermosetting liquid silicone resins are generally used as curable transparent resin compositions for display applications and the like. However, in the case of the known silicone resins, since they are less degraded by light or heat, they have excellent weather resistance, but have the problem of shortening the life of the equipment due to their very high air permeability. In order to solve this problem, compositions containing aromatic epoxy resins such as bisphenol A epoxy resins or bisphenol F epoxy resins are used, but compositions containing epoxy resins have problems of low transmittance and yellowing.

In one embodiment, the curable transparent resin composition comprises (A) a fluororesin 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 exhibits excellent dry film properties, heat resistance, transparency, adhesion, color changeability and morphology retention through a combination of two or more components, for example, three components. When these two or more components are included in a specific mixing ratio, a more excellent effect can be exhibited. Thus, not only a light transmittance at a similar level to that of the silicone resin composition currently commonly used for display purposes can be formed, but also a film with excellent adhesion can be formed.

[Fluororesin]

In one embodiment, the fluororesin can be used without special restrictions, as long as it contains one or more carboxyl groups. Since the fluororesin has a carboxyl group, it can exert excellent heat resistance, adhesion and color change effects through a chemical reaction with an epoxy group. If it does not contain a carboxyl group like the fluororesin, but contains other reactive groups such as a hydroxyl group, it does not react chemically with the epoxy group, so it may be difficult to cure, and even if it reacts, it must react in a high temperature environment or require another catalyst, so the possibility of yellowing (discoloration) is high, and in the case of containing an amine or aromatic functional group, there is a problem of yellowing due to a chemical reaction with an epoxy group.

The fluororesin may include two or more carboxyl groups. The fluororesin may include only a carboxyl group as a functional group.

The fluororesin may contain one or more functional groups in addition to the carboxyl group. The fluororesin may contain one or more functional groups selected from the group consisting of hydroxyl, aldehyde, peroxyhydroxyl, amino, amine, carbonyl, acrylic, acryl, nitrile, vinyl, halogen, polyurethane and ester groups as functional groups in addition to the carboxyl group. 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 a carboxyl group and a hydroxyl group.

The molar equivalent % of the carboxyl group with respect to the entire functional groups included in the fluororesin may be 1 to 100%.

For example, the fluororesin may contain one or more functional groups in the main chain or the side chain. For example, the fluororesin may contain one or more functional groups in the main chain. For example, the fluororesin may contain one or more functional groups in the side chain. For example, the fluororesin may contain one or more functional groups in the main chain and the side chain.

The fluororesin may be a block copolymer of two or more fluorine-containing monomers with different structures, but is not limited thereto. For example, the fluorine-containing monomer may include a monomer of polyvinylidene fluoride, a fluoroelastomer, or polytetrafluoroethylene (PTFE), but is not limited thereto. For example, at least one of the fluorine-containing monomers may be tetrafluoroethylene or ethylene tetrafluoroethylene (ETFE), but is not limited thereto. For example, at least one of the fluorine-containing monomers may have the structure of the following chemical formula 1B, but is not limited thereto.

[Chemical formula 1B]

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

For example, the fluororesin may be a random copolymer of the ETFE and a fluorine-containing monomer having the structure of Chemical Formula 1B, or a random copolymer including the ETFE and a fluorine-containing monomer having the structure of Chemical Formula 1B as reaction units, but is not limited thereto.

For example, the fluororesin may be a polymer of a reaction unit represented by the following chemical formula (I) and a reaction unit represented by the following chemical formula (II), but is not limited thereto.

Chemical formula (I)

In the chemical formula (I), the molar ratio of a, b, and c (a:b:c) may be 1 to 3:0 to 1:1, and d may be 0 to 10. For example, in the chemical formula (I), the molar ratio of a, b, c, and d (a:b:c:d) may be 1 to 3:0 to 1:1:0 to 10.

Chemical formula (II)

In the chemical formula (II), e, f and g are independently selected from integers of 0 to 10, and A ₁ , A ₂ and A ₃ are independently hydroxyl groups or hydroxyl groups substituted with carboxylic acid.

The carboxylic acid is not particularly limited as long as it is an organic compound having a -COOH group, and may contain, for example, one -COOH group, or may be a polycarboxylic acid containing two or more -COOH groups.

The polycarboxylic acid may be, for example, succinic acid, glutaric acid, adipic acid, phthalic acid, trimellitic acid, etc., but is not limited thereto.

The reaction unit represented by the chemical formula (II) may be, for example, the following structure, but is not limited thereto.

The fluororesin may be commercially available, for example, GK series resins such as GK-570, GK-500, GK-510, GK-580, and GK-581 (all manufactured by Daikin Corporation, trade names), LUMIFLON series such as LF200, LF400, LF552E, LF600X, LF800, LF810, LF810Y, LF910LM, LF936, LF9010, LF200MEK, LF9716, and LF9721 (all manufactured by Asahi Glass Co., Ltd., trade names), etc.

Based on the total weight of the composition of the present invention, the fluorine content may exceed 30 weight %, for example, 31 to 50 weight %, for example, 32 to 50 weight %, for example, 33 to 55 weight %, for example, 35 to 50 weight %, for example, 38 to 47 weight %.

The fluorine content in the fluororesin may be, for example, 1 to 50% by weight, for example, 3 to 45% by weight, for example, 5 to 40% by weight.

When the fluorine content is 1% by weight or more, sufficient flame retardancy can be obtained, and when it is 50% by weight or less, the proportion of fluorine present in the fluororesin is not too large, so sufficient adhesion can be obtained.

The carboxyl equivalent of the fluororesin may be, for example, 500 to 7000 g/equivalent, for example, 550 to 6500 g/equivalent, for example, 600 to 6000 g/equivalent. When the carboxyl equivalent satisfies the above range, the reactive groups have sufficient reactivity due to the appropriate content, thereby improving the stability and reliability over time, shortening the process time, and achieving sufficient curing.

The hydroxyl equivalent of the fluororesin can be, for example, 300 to 5500 g/equivalent, for example, 450 to 3500 g/equivalent, for example, 550 to 3000 g/equivalent. When the hydroxyl equivalent is 5500 g/equivalent or less, the solder heat resistance can be improved by sufficient crosslinking density. When the hydroxyl equivalent is 300 g/equivalent or more, the moisture absorption and water absorption can be reduced by reducing the content of the residual hydroxyl group, thereby improving the solder heat resistance. In addition, since it has appropriate crosslinking points, it also reduces reactivity at room temperature and improves storage stability.

The weight average molecular weight of the fluororesin may be, for example, 5000 to 150000, for example, 10000 to 120000, for example, 15000 to 100000. The weight average molecular weight is measured by GPC method and converted from a calibration curve prepared using standard polystyrene.

The fluororesins may be used alone or in combination of two or more.

[Epoxy resin]

In one embodiment, the curable transparent resin composition includes an epoxy resin. The curable transparent resin composition includes an epoxy resin, such as a silicon epoxy resin, and thus can improve the transparency of a film using the composition and the adhesion to a glass substrate.

The epoxy resin is a resin having an epoxy group, and examples thereof include a bifunctional epoxy resin having two epoxy groups in a molecule and a multifunctional epoxy resin having three or more epoxy groups in a molecule.

The epoxy resin may not contain fluorine.

The epoxy equivalent in the epoxy resin may be 0.1 to 50 mol equivalent %, but is not limited thereto.

The epoxy resin may not contain an aromatic ring or a carbon double bond. When the epoxy resin does not contain an aromatic ring or a carbon double bond, the transparency is improved by the principle of not forming free radicals, and yellowing does not occur. The curable transparent resin composition containing the epoxy resin can exhibit excellent dry film properties, heat resistance, transparency and adhesion. In addition, the curable transparent resin composition can exhibit excellent shape retention and color change stability through heat resistance.

The epoxy resin may have at least one of an aliphatic or alicyclic backbone.

The epoxy resin may be in liquid state at room temperature, but is not limited thereto. Wherein, room temperature refers to a temperature of about 20°C. That is, the epoxy resin may be a liquid epoxy resin. The judgment of the liquid state is based on the "liquid state confirmation method" in Annex 2 of the Ministerial Order on the Test and Properties of Dangerous Substances (Autonomous Ministry Order No. 1 of 1989). For example, it is carried out by the method described in paragraphs 23-25 of Japanese Patent Publication No. 2016-079384. By including a liquid epoxy resin, the dry film formed by the composition has excellent flexibility.

The epoxy resin may include a siloxane (Si—O) group in the main chain, but is not limited thereto. When the epoxy resin includes a siloxane group in the main chain, a cured product having excellent rubber properties such as weather resistance, heat resistance, hardness or elongation can be produced.

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

The epoxy resin may be tetrakis[(epoxycyclohexyl)ethyl]tetramethylcyclotetrasiloxane, glycidyloxymethyltrimethoxysilane, 3-glycidyloxypropyltrihydroxysilane, 3-glycidyloxypropyldimethylhydroxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyldimethoxymethylsilane, 3-glycidyloxypropyldiethoxymethylsilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyltributoxysilane, 1-bis(glycidyloxypropyl)tetramethyldisiloxane, 1,3-bis(glycidyloxypropyl)tetramethoxydisiloxane, 1,3- Bis(3-glycidyloxypropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(glycidyloxypropyl)-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 a combination thereof, but not limited thereto.

The epoxy resin may be represented by one of the following Chemical Formula 3-1, Chemical Formula 3-2 or Chemical Formula 3-3, but is not limited thereto.

[Chemical formula 3-1]

[Chemical formula 3-2]

[Chemical formula 3-3]

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

Examples of the epoxy resin include silicon epoxy resin, alicyclic epoxy resin, and multifunctional epoxy resin. For example, the epoxy resin may be silicon epoxy resin. Furthermore, the silicon epoxy resin, alicyclic epoxy resin, and multifunctional epoxy resin may contain aromatics within the limit of not damaging the cured transparency.

Examples of commercially available silicone epoxy resins include KR-470 manufactured by Shin-Etsu Co., Ltd., TSR-104 manufactured by Isung Materials, and TSR-194 manufactured by Hansol E&C, but are not limited thereto.

Examples of the alicyclic epoxy resin include, but are not limited to, 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)cyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl)methyl-3',4'-epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-bis(3,4-epoxycyclohexanecarboxylate), 3,4-epoxycyclohexylmethanol or 3,4-epoxycyclohexylethyltrimethoxysilane and the like. Examples of commercially available products include CELOXIDE 2000, CELOXIDE 2021, CELOXIDE 3000, and EHPE 3150 manufactured by Daicel Chemical Industries, Ltd.; Epomic VG-3101 manufactured by Mitsui Chemicals, Inc.; E-1031S manufactured by Emulsion Shell Epoxy Resin Co., Ltd.; TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd.; EPB-13 and EPB-27 manufactured by Nippon SODA Co., Ltd., but are not limited to these.

Examples of the polyfunctional epoxy compound include linear epoxy resins such as YED216D manufactured by Mitsubishi Chemical Corporation; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclone 152 and Epiclone 165 manufactured by DIC Corporation, Epototette YDB-400 and YDB-500 manufactured by Nippon Steel & Sumitomo Chemical Corporation, D.E.R.542 manufactured by Dow Chemical, carbocyclic ESB-400 and ESB-700 manufactured by Sumitomo Chemical Corporation, A.E.R.711 and A.E.R.714 manufactured by Asahi Chemical Co., Ltd. (all trade names) and brominated epoxy resins; Epototette manufactured by Nippon Steel & Sumitomo Chemical Corporation; Hydrogenated bisphenol A type epoxy resins such as ST-2004, ST-2007, and ST-3000 (trade names); jER604 manufactured by Mitsubishi Chemical Corporation; glycidylamine type epoxy resins such as Epototte YH-434 manufactured by Nippon Steel & Sumitomo Chemical Corporation and SUMI Epoxy ELM-120 manufactured by Sumitomo Chemical Corporation (all trade names); hydantoin type epoxy resins; CELOXIDE manufactured by Daicel Corporation Alicyclic epoxy resins such as 2021P (trade names); trihydroxyphenylmethane epoxy resins such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, EPPN-502 (all trade names) manufactured by Dow Chemical, etc.; non-xylenol-type or non-phenol-type epoxy resins such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation, or mixtures thereof tetraphenylethane type epoxy resins such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; heterocyclic epoxy resins such as TEPIC (trade names) manufactured by Nissan Chemical Industry Co., Ltd.; methacrylate glycidyl copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; and copolymer epoxy resins of cyclohexylmaleimide and methacrylate glycidyl, etc., but not limited thereto. These epoxy resins may be used alone or in combination of two or more.

[Thixotropic agent]

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

As the thixotropic agent, silica or an organic or inorganic substance other than silica can be used. As silica, hydrophilic silica or hydrophobic silica can be used, for example, hydrophilic fumed silica or hydrophobic fumed silica, for example, polydimethylsiloxane-treated silica, hexamethyldisilazane-treated silica.

For example, silicon dioxide may have a structure as described below, but is not limited thereto.

As the organic matter, a saturated organic matter or an unsaturated organic matter can be used. As the inorganic matter, a metal or a non-metal can be used, such as aluminum oxide, silicon nitride, aluminum nitride, etc. In particular, when hydrophilic fumed silica or hydrophobic fumed silica is used, it is beneficial to achieve the effects of the present disclosure, and when the BET surface area is 150 m ² /g or more, 200 m ² /g or more, or 250 m ² /g or more, it is particularly beneficial to achieve the effects of the present disclosure.

[Content of each component]

In one embodiment, the content of the fluororesin (A) may be about 60% to about 99% by weight, about 60% to about 98% by weight, about 62% to about 97% by weight, about 64% to about 96.5% by weight, about 66% to about 96% by weight, about 68% to about 95.5% by weight, about 70% to about 95% by weight, about 72% to about 94.5% by weight, about 74% to about 94% by weight, about 76% to about 93.5% by weight, or about 78% to about 93% by weight, based on the total weight of the composition of the present invention. When the content of the fluororesin (A) is greater than or equal to the minimum value, the dry film properties, heat resistance, transparency, adhesion, color changeability, and shape retention to be achieved by the curable transparent resin composition of the present invention can be more excellently achieved, and when it is less than or equal to the maximum value, the dry film properties, heat resistance, transparency, adhesion, color changeability, and shape retention to be achieved by the present invention can be achieved.

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

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

[Other additives]

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 inhibitor, a solvent, and a leveling agent.

The heat curing agent can be imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine; hexane Hydrazine compounds such as dicarboxylic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine; S-triazine derivatives such as guanamine, acetylguanamine, benzoguanamine, 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, but are not limited thereto.

As the multifunctional monomer, any known monomer having two or more or three functional groups can be used without particular limitation, and for example, trimethylolpropane triacrylate, trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate or pentaerythritol tri(meth)acrylate can be used, but the invention is not limited thereto. Such a multifunctional monomer can improve the pencil hardness and chemical resistance of the curable transparent resin composition of the present invention after curing.

The free radical photoinitiator can be any known one without particular limitation, and can include, for example, one or more selected from benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides or oxime esters. More specifically, for example, biacetyl, 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-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1-methylethyl-phenol ketone, p-isopropyl-α-hydroxyisobutyl benzophenone, 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-amylanthraquinone, 2- Aminoanthraquinone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzyl dimethyl ketal, benzophenone, methyl benzophenone, trimethyl benzophenone (TZT), 4-benzoyl 4'-methyl diphenyl sulfide, 4,4'-dichlorobenzophenone, diethyl thioxanthone (DETX), 2-isopropyl thioxanthone (ITX), 4,4'-bis(diethylamino)benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-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 (Mosaphoto348), bis(ethanolamine 5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-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-acetone, 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 a mixture of two or more thereof, but not limited thereto.

As the dispersant, a known one can be used without particular limitation. Commercially available ones include DISPERBYK-111, DISPERBYK-110, DISPERBYK-118, DISPERBYK-140, DISPERBYK-142, DISPERBYK-163, DISPERBYK-2150, DISPERBYK-2200, DISPERBYK-2205, and DISPERBYK-2163 manufactured by BYK. , DISPERBYK-2013, DISPERBYK-180, DISPERBYK-2155, DISPERBYK-2009, DISPERBYK-168, DISPERBYK-2164, DISPERBYK-2118, DISPERBYK-2008, DISPERBYK-9076, DISPERBYK-9077 and DISPERBYK-2055, but not limited thereto.

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

Thermosetting polymerization inhibitors can be used without special restrictions 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 thermosetting compounds, such as blocked isocyanates. This thermosetting compound remains in a stable state before heating after blocking, but under normal temperature or medium temperature (about 30°C to about 60°C), some of the thermosetting compounds react, which can reduce the storage stability. In order to prevent the reduction of this storage stability and maintain the storage stability of the curable transparent resin composition, a thermosetting polymerization inhibitor can be used. For example, phenols such as hydroquinone, tert-butylcatechol, butylhydroxyanisole, quinones such as p-benzoquinone, amines such as nitrohydroxylamine and phenylenediamine, thiols, and dithiocarbamates are one or more, but not limited to this. As the thermosetting polymerization inhibitor, an amine-based tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum (Tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum) or nitrohydroxyamine aluminum salt (Q-1301; Wako Co., Ltd.) can be used.

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

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

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol 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; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, 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 ether, naphtha, hydrogenated naphtha, and solvent naphtha. Such organic solvents may be used alone or as a mixture of two or more. The amount of the organic solvent used is not particularly limited, and it can be appropriately added as needed.

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

The leveling agent can be used without any particular limitation as long as it is used to increase the adhesion on the final cured PSR substrate and solve the sagging problem (pinhole phenomenon). For example, from the aspect of the leveling property suitable for the composition of the present invention, the leveling agent can use a silicone or non-silicone leveling agent of BYK Company which is commercially available, and a combination 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, BYK-325N, BYK-326, BYK-327, BYK-329, BYK-331, BYK-333, BYK-342, BYK-346, BYK-345, BYK-348, BYK-349, BY K-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-3 570, BYK-UV-3575 and BYK-UV-3576, but is not limited to this. 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.

The content of the leveling agent can be 0.1 to 1.0 weight %, 0.2 to 0.8 weight %, 0.3 to 0.7 weight % or 0.4 to 0.6 weight % based on the total weight of the composition of the present invention. When the content of the leveling agent is above the minimum value, a curable transparent resin composition having the desired adhesion or no sagging problem (pinhole phenomenon) can be manufactured, and when the content is greater than the maximum value, the reactivity is reduced, or when it exists in the lower layer of the marking ink coating, the adhesion may be reduced.

In one embodiment, the curable transparent resin composition may additionally include at least one of a dispersant, a defoamer, a fluidity regulator, a foaming agent, a surfactant, an antioxidant, an antistatic agent, and a brightener, in which case a small amount may be added relative to the total weight of the curable transparent resin composition.

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 in the absence or use of a cationic photoinitiator, the heteromonomer and the monomer having a functional group capable of forming a crosslinked bond with a cationic curable functional group are also 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 curability.

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 by the following method:

The composition (curable resin composition) printed on TORAY's XD-500P (50um) PET film was laminated (lamination) on a glass substrate with a thickness of 2000μm at a temperature of 60°C for 40 seconds. After removing the PET film laminated on the glass substrate, the glass substrate was heated and cured at a temperature of 150°C in a hot air circulation drying oven for 1 hour, and a test piece with a thickness of 50μm was evaluated. The transmittance of each test piece in the wavelength range of 350 to 800nm was measured using JASCO's V-670 spectrophotometer and evaluated according to the benchmark. The transmittance of the glass substrate is 100%, and the transmittance is measured by contacting the spectrophotometer on the cured coating of the composition on the glass substrate, and expressed as a relative value compared with the transmittance of the glass substrate. The higher the transmittance, the higher the transparency of the cured product of the composition.

In one embodiment, about the color difference b value of the curable transparent resin composition, for the test piece made by the same method as the test piece made into the average light transmittance, after placing A4 paper 80gsm of Double A company under the glass substrate, the color difference b value of each test piece was measured with the colorimeter (Color meter) of CM-700D of Konica Minolta (KONICA MINOLTA) company. The lower the b value, the closer to achromatic color. That is, because the lower the b value, the smaller the color difference, the composition can be appropriately prevented from discoloration. In one embodiment, the color difference b value of the curable transparent resin composition can be less than 2.9, for example, less than 1.5.

In one embodiment, regarding the haze value of the curable transparent resin composition, for a test piece made in the same way as a test piece made with average transmittance, a glass substrate was cut into a size of 50 mm * 50 mm, and the composition was facing upward, and the HM-150 haze measuring device of MURAKAMI was used to measure the light source (halogen lamp A), the incident area (14 mmΦ), and the incident opening (20 mmΦ) according to the test method ASTM D1003. The closer the haze value is to 0, the higher the transmittance. In one embodiment, the haze value of the curable transparent resin composition can be 5.0% or less, for example, it can be 3.0% or less.

[thing]

Another embodiment of the present invention relates to various articles derived from the curable transparent resin composition. The curable transparent resin composition can be contained in various articles, or can be formed into various articles. For descriptions of the various articles, see the following.

[Display components]

In one embodiment, a member for a display is characterized by comprising a cured product formed from the curable transparent resin composition on a substrate.

The substrate used in the present invention may be exemplified by resin films such as polyimide films and PET films, glass substrates, ceramic substrates, metal substrates or wafer plates. In particular, resin films such as polyimide films and PET films or glass substrates may be used. The material and shape of the substrate may be selected according to the purpose or performance of the target molded object, and two or more materials and shapes may be selected alone or in combination as required. Furthermore, from the perspective of adhesion, the substrate may be a glass substrate.

After the aforementioned curable transparent resin composition is prepared with a predetermined composition, it can be adjusted to a viscosity suitable for a coating method, for example, by an organic solvent, and coated on the substrate by a method such as dip coating, flow coating, roller coating, rod coating, screen printing, or curtain coating. In particular, flow coating, roller coating, rod coating, or screen printing can be used.

[LED device]

By thick-film coating of a curable transparent resin composition or pouring it into a predetermined mold and then performing heat curing or UV curing, a molding material encapsulated with 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.

In one embodiment, the LED sealing material composition includes the above-mentioned curable transparent resin composition.

In one embodiment, an LED element in an LED device is encapsulated by a cured layer formed of the LED encapsulating material composition.

[Glass adhesive composition and die bonding composition]

In one embodiment, a glass adhesive composition includes the aforementioned curable transparent resin composition.

The curable transparent resin composition has excellent adhesion to glass and is therefore suitable for use in fixing glass of vehicles.

In another embodiment, a die bonding composition includes the above-mentioned curable transparent resin composition.

The curable transparent resin composition has excellent adhesion to a wafer substrate and is therefore suitable for use as a die bonding material.

[Dry film]

In one embodiment, the dry film comprises a thin film (e.g., a support (carrier) film) and a resin layer formed on the thin film using the aforementioned curable transparent resin composition. In addition, the dry film may further comprise a thin film (so-called protective film) on the resin layer formed on the thin film to play a protective (covering) role.

The film is not particularly limited, and for example, films containing thermoplastic resins such as polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamide-imide films, polypropylene films, and polystyrene films can be used. Among them, polyethylene terephthalate can be particularly used from the viewpoints of heat resistance, mechanical strength, and handling properties. Furthermore, a laminate of these films can also be used as a film.

Furthermore, the thermoplastic resin film described above may be a film stretched in one axis direction or two axes direction from the viewpoint of improving mechanical strength.

The thickness of the film is not particularly limited, but may be, for example, 10 to 150 μm.

The resin layer is formed using the curable transparent resin composition. The thickness thereof is not particularly limited and is preferably appropriately changed according to the intended use. For example, the thickness may be 1 μm or more and 150 μm or less.

The curable transparent resin composition can be uniformly coated on a film by a comma coater, a knife coater, a lip coater, a rod coater, an extrusion coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc., and dried to form a resin layer.

The dry film may be provided with a peelable protective film on the surface of the resin layer in order to prevent dust from adhering to the surface of the resin layer.

The peelable protective film is not particularly limited as long as the adhesion between the resin layer and the protective film is smaller 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.

The thickness of the protective film is not particularly limited, but may be, for example, 10 μm or more and 150 μm or less.

The present invention will be more clearly understood through the aforementioned embodiments and the following examples. The following is described in detail with reference to the embodiments described in the following table so that those skilled in the art can easily understand and implement them. However, these embodiments are intended to illustrate the present invention in detail, and the scope of the present invention is not limited to these embodiments.

[Example]

I. Preparation of curable transparent resin composition

The reactants having the components and contents listed in Table 1 below and propylene glycol monomethyl ether as a solvent in an amount of 20% by weight based on the total weight of the reactants were mixed and mixed at 45° C. for 0.5 hours at a speed of 2,000 rpm using a stirrer, and then a pigment and a dispersant were added and dispersed for 3 hours using zirconium oxide beads having a particle size of 0.2 μm. Thereafter, the mixture was filtered using a 1 μm filter to prepare a curable transparent resin composition.

The components recorded in Table 1 are as follows:

1) Resin A (fluororesin having one or more carboxyl groups):

(a:b:c:d＝3:1:1:8)和

的聚合物(GK-570(入手处：大金)后，利用琥珀酸酐(succinic anhydride)合成的聚合物Purchase

(a:b:c:d=3:1:1:8) and

The polymer (GK-570 (source: Daikin) was then used to synthesize the polymer using succinic anhydride.

入手处：信越，产品名：KR-4702) Epoxy resin A (epoxy resin (liquid) containing siloxane (Si-O) groups in the main chain):

Purchased from: Shin-Etsu, Product name: KR-470

3) Silica A: hydrophilic fumed silica with a BET surface area of 250 m ² /g or more, source: EVONIK, product name: AEROSIL380

4) Silica B: hydrophilic fumed silica with a BET surface area of 200 to 250 m ² /g, source: EVONIK, product name: AEROSIL200

5) Silica C: hydrophilic fumed silica with a BET surface area of 150 to 200 m ² /g, source: EVONIK, product name: AEROSIL150

6) Silica D: hydrophilic fumed silica with a BET surface area of 150 m ² /g or less, source: EVONIK, product name: AEROSIL130

7) Silica E: hydrophobic fumed silica with a BET surface area of 250 m ² /g or more, source: EVONIK, product name: AEROSIL R106

8) Silica F: hydrophobic fumed silica with a BET surface area of 150 to 200 m ² /g, source: EVONIK, product name: AEROSIL R974

9) Silica G: hydrophobic fumed silica with a BET surface area of 150 m ² /g or less, source: EVONIK, product name: AEROSIL R208

II. Characteristic test

The following evaluations were performed on the compositions of Examples and Comparative Examples prepared as above. The evaluation results are shown in FIG. 1 a to FIG. 1 f , FIG. 2 a to FIG. 2 c , and Table 1 and Table 2, respectively.

1. Dry film properties (DF properties)

(1) 50 μm standard: The curable transparent resin composition was applied to the XD-500P (50 μm) PET film of TORAY Corporation at a speed of 1.0 m/min using an applicator, and then dried at 60°C, 80°C, 105°C, and 105°C for 30 minutes in four cavities, and then printed to a thickness of 50 μm. The film was dried at 80°C for 30 minutes in a hot air circulation drying oven to produce a dry film, and then evaluated according to the following standards.

(2) 200 μm benchmark: Use an applicator to apply a curable transparent resin composition on TORAY's XD-500P (200 μm) PET film at a speed of 0.7 m/min, and dry it in 4 cavities at 60°C, 80°C, 130°C, and 135°C for 30 minutes, and then print it to a thickness of 200 μm. Dry it in a hot air circulation drying oven at 80°C for 30 minutes. After the dry film is produced, it is evaluated according to the following benchmarks. (The cross cut is implemented by the test method ASTMD3359 with a specification of 10/10 and 1 mm.)

○: Slit (slit, film cross cut (10/10) & tape peel test, bending (90°) and tacky (tacky) are all good (OK).

△: Fragmentation was observed when slit (film cross-cut & tape peeling test, 90° bending).

Ⅹ: Slit (film cross-cut & tape peeling test, bending 90°), poor adhesion (NG).

2. Transparency

At a temperature of 60°C, a curable transparent resin composition printed on a XD-500P (50um) PET film of TORAY Corporation was laminated on a glass substrate for 40 seconds. After removing the laminated PET film on the glass substrate, the glass substrate was heated and cured in a hot air circulation drying oven at a temperature of 150°C for 2 hours and used as a test piece. The transmittance of each test piece in the wavelength range of 350 to 800nm was measured using a V-670 spectrophotometer from JASCO Corporation, and evaluated according to the benchmark. For the transmittance, the transmittance of the glass substrate was set to 100%, and the transmittance was measured on the cured coating of the glass substrate composition using a contact spectrophotometer, and expressed as a relative value compared with the transmittance of the glass substrate.

○: The average light transmittance is 98% or more.

△: The average light transmittance is 95% or more and less than 98%.

X: Unable to measure due to uncuring.

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

Referring to Table 1, when the compositions of Examples 1 to 13 are used, excellent light transmittance can be exhibited in the visible light region.

3. Heat resistance

The test piece produced in the same manner as the test piece produced in the transparency evaluation was left to stand at 85° C./85% humidity for 1000 hours, and then subjected to heat resistance evaluation. The evaluation was performed based on the following criteria.

◎: 100% of the film remains after cross-cutting and tape peeling test after being left at 85°C/85% humidity for 1000 hours.

○: 70 to 90% of the adhesive remained after cross-cutting and tape peeling test after being left at 85°C/85% humidity for 1000 hours.

△: After being left at 85°C/85% humidity for 1000 hours, 50-70% of the film remained after cross-cutting and tape peeling tests.

X: Unable to evaluate due to uncured or insufficiently cured.

4. Adhesion

A test piece prepared in the same manner as the test piece prepared in the transparency evaluation was immersed in H ₂ O and boiled at 85° C. and 85% humidity for 1000 hours, and evaluated according to the following criteria.

◎: Cross-cutting and tape peeling tests after boiling were OK.

○: OK after boiling.

△: Slightly peeled off after boiling.

X: Unable to evaluate due to uncured or insufficiently cured.

5. Color change

For the test piece prepared in the same manner as the test piece prepared in the transparency evaluation, 80 gsm A4 paper of DoubleA was placed under the glass substrate, and the b (Yellow to Blue) value among the L, a, and b values was measured using a CM-700D (colorimeter) of Konica Minolta, and the evaluation was performed according to the following criteria. The +b side represents the yellow series, and the -b side represents the blue series. The lower the b value, the closer to the achromatic color.

○: Color difference b value is 1.5% or less

△: Color difference b value exceeds 1.5%

Ⅹ: Color difference b value is 3.0% or more or cannot be evaluated due to insufficient curing

In the present specification, "the composition is excellent in color changeability" means that the color difference is not large, and thus the composition can well prevent color change.

6. Shape retention

0.1 mL of the composition was dropped onto a glass substrate using a syringe (1 mL) from HWAJIN Pharmaceutical Co., Ltd., and then dried at 90° C. for 15 minutes in a hot air circulation drying oven and heat-cured at 150° C. for 2 hours to prepare a test piece.

The thickness and diameter of each test piece were measured using a KEYENCE VHX-5000 three-dimensional microscope and evaluated according to the following criteria.

◎: Diameter is less than 2500μm, thickness is more than 1000μm

○: Diameter 2500-3000μm, thickness 800-1000μm

△: diameter 3000-3500μm, thickness 600-800μm

Ⅹ: Diameter exceeds 3500μm and thickness is less than 600μm

【Table 1】

【Table 2】

Referring to Table 1, Table 2, Figures 1a to 1f and Figures 2a to 2c and Examples 1 to 13, the curable transparent resin composition according to one embodiment of the present invention includes a combination of (A) a fluororesin containing one or more carboxyl groups and (B) an epoxy resin, thereby exhibiting excellent dry film properties, heat resistance, transparency, adhesion, color changeability and morphology retention.

In particular, the compositions of Examples 1 to 12 containing silica (especially, hydrophilic fumed silica or hydrophobic fumed silica) as a thixotropic agent can achieve more excellent dry film properties, heat resistance, transparency, adhesion, color changeability, and shape retention.

Claims (20)

1. A curable transparent resin composition comprising:

(A) A fluororesin having at least one carboxyl group; and

(B) An epoxy resin.

2. The curable transparent resin composition according to claim 1, wherein:

in addition to the carboxyl group, the fluororesin further comprises, as a functional group, one or more selected from the group consisting of a hydroxyl group, an aldehyde group, a hydroxyl peroxide, an amino group, an amine group, a carbonyl group, an acrylic group, an acryl group, a nitrile group, a vinyl group, a halogen group, a urethane group, and an ester group.

3. The curable transparent resin composition according to claim 1, wherein:

the fluororesin contains one or more hydroxyl groups as functional groups in addition to the carboxyl groups.

4. The curable transparent resin composition according to claim 1, wherein:

the molar equivalent% of carboxyl groups with respect to the entire functional groups contained in the fluororesin is 1 to 100%.

5. The curable transparent resin composition according to claim 1, wherein:

the fluororesin is a polymer having a reaction unit represented by the following chemical formula (I) and a reaction unit represented by the following chemical formula (II),

chemical formula (I)

The molar ratio a of a, b, c, d in the chemical formula (I): b: c: d is 1-3: 0 to 1:1:0 to 10 percent of the total weight of the composite,

Chemical formula (II)

In the chemical formula (II), e, f and g are independently selected from integers of 0 to 10, A ₁ 、A ₂ A is a ₃ Independently of each other, is a hydroxyl group or a form in which a hydroxyl group is substituted with a carboxylic acid.

6. The curable transparent resin composition according to claim 1, wherein:

the epoxy resin is silicon epoxy resin.

7. The curable transparent resin composition according to claim 1, wherein:

the epoxy resin is in a liquid state at normal temperature.

8. The curable transparent resin composition according to claim 1, wherein:

the epoxy resin does not have an aromatic ring or a carbon double bond.

9. The curable transparent resin composition according to claim 1, wherein:

the epoxy resin backbone contains siloxane (Si-O) groups therein.

10. The curable transparent resin composition according to claim 1, wherein:

the epoxy resin does not contain fluorine.

11. The curable transparent resin composition according to claim 1, wherein:

the epoxy resin is tetra [ (epoxycyclohexyl) ethyl ] tetramethyl cyclotetrasiloxane, glycidoxymethyl trimethoxysilane, 3-glycidoxypropyl trihydroxy silane, 3-glycidoxypropyl dimethylhydroxy silane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl dimethoxymethyl silane, 3-glycidoxypropyl diethoxymethyl silane, 3-glycidoxypropyl dimethylmethoxy silane, 3-glycidoxypropyl tributoxy silane, 1-bis (glycidoxypropyl) tetramethyl disiloxane, 1, 3-bis (glycidoxypropyl) tetramethoxy disiloxane, 1, 3-bis (3-glycidoxypropyl) tetramethoxy disiloxane, 1, 3-tetramethyl disiloxane, 1, 3-bis (glycidoxypropyl) -1, 3-dimethyl-1, 3-dimethoxy disiloxane, 2, 3-epoxypropyl trimethoxysilane, 3, 4-epoxybutyl trimethoxysilane, 7-epoxyheptyl-3-dimethoxy silane, 3- (2, 4-epoxyethyl) tetramethoxy silane, 2, 3-bis (glycidoxypropyl) tetramethoxy disiloxane, 1, 3-bis (glycidoxypropyl) silane, 3-dimethoxy disiloxane, 2, 3-epoxypropyl trimethoxy silane, 3-bis (4-glycidoxypropyl) silane, 6-dimethoxy silane, 4-bis (4-glycidoxypropyl) or 2-epoxypropyl) silane 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, or a combination thereof.

12. The curable transparent resin composition according to claim 1, wherein:

the curable transparent resin composition further comprises (C) a thixotropic agent.

13. The curable transparent resin composition according to claim 12, wherein:

the thixotropic agent (C) is a hydrophilic fumed silica or a hydrophobic fumed silica.

14. The curable transparent resin composition according to claim 13, wherein:

the BET surface area of the hydrophilic fumed silica or the hydrophobic fumed silica is 150m ² Over/g, 200m ² Above/g or 250m ² And/g.

15. A member for a display, characterized in that a substrate has thereon a cured product formed of the curable transparent resin composition according to any one of claims 1 to 14.

16. An encapsulating material composition for an LED, comprising: the curable transparent resin composition according to any one of claims 1 to 14.

17. An LED device, wherein:

the LED element is encapsulated by a cured layer formed from the sealing material composition for an LED according to claim 16.

18. A glass adhesive composition comprising:

The curable transparent resin composition according to any one of claims 1 to 14.

19. A dry film, wherein:

the film having thereon a curable resin layer formed of the curable transparent resin composition according to any one of claims 1 to 14.

20. A composition for chip bonding, comprising:

the curable transparent resin composition according to any one of claims 1 to 14.

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