TWI862695B - Curable resin composition containing siloxane resin, cured film thereof, and producing process of siloxane resin - Google Patents

Abstract

The present invention provides a curable resin composition containing a siloxane resin, a cured product thereof, and a method for producing the siloxane resin. A curable resin composition, characterized in that it contains a siloxane resin satisfying the following (i) to (iii), and a curing agent and/or a photocation ion initiator. (i) It has the following structure T1 showing a signal at -47 ppm to -52 ppm, the following structure T2 showing a signal at -55 ppm to -61 ppm, and the following structure T3 showing a signal at -62 ppm to -72 ppm in a ²⁹ Si-NMR spectrum, and the area ratio of the signals is T1:T2:T3=0 to 1:1 to 10:1 to 100. (ii) The weight average molecular weight is 750 to 20,000. (iii) The molecular weight of each reactive group is less than 350.

Description

Curable resin composition containing silicone resin and cured product thereof, and method for producing silicone resin

The present invention relates to a curable resin composition using a siloxane resin containing a reactive group such as a 3,4-epoxyepoxyhexyl group, and a cured film formed by curing the composition.

In display elements such as liquid crystal display elements, organic electroluminescent elements (organic EL (electroluminescence) elements), and electronic paper elements, hardened films such as protective films for preventing degradation or damage of electronic parts such as touch screens, interlayer insulation films for maintaining insulation between wiring arranged in layers, and flattening films for increasing the aperture ratio are provided. Conventionally, a transparent hardened film (hereinafter also referred to as a protective film) is formed on the surface of a color filter used in the manufacture of a color liquid crystal display (LCD) as a protective layer. The protective film of the color filter can be formed for the following purposes: to flatten the unevenness generated between pixels of the color filter, to improve the durability of the color filter against heat treatment or chemical treatment in a later step, to improve the reliability of the color liquid crystal display, etc. As a protective film for color filters, it is required to have excellent flatness, heat resistance, chemical resistance, adhesion, hardness, electrical reliability, and transparency.

For example, in terms of flatness, it is required to flatten the unevenness of about 1 μm to 2 μm in height caused by repeated coating of the coloring composition when forming pixels to less than 0.1 μm. In terms of heat resistance, there is a situation where a high temperature of about 200°C to 270°C is applied to the protective film when a transparent electrode such as indium tin oxide (ITO) is made by sputtering, and the protective film is required to be stable under the above temperature conditions. In terms of chemical resistance, the protective film is required to be stable to acids, alkalis, and solvents used in subsequent steps. In terms of adhesion, when manufacturing a liquid crystal display panel, a substrate is sometimes bonded to the protective film, and it is required that the protective film in the above position does not peel off from the substrate. In terms of hardness, from the perspective of the durability of the protective film, high hardness is required. As for electrical reliability, it is required that the insulation of the protective film be maintained, or that impurities contained in the protective film do not contaminate the liquid crystal. As for transparency, it is required that the protective film does not absorb light in the visible wavelength region and does not damage the color characteristics of the color filter.

In addition to the above-mentioned requirements for the protective film, as LCD panels become more functional, wide viewing angles and high-speed responses are also required. In the process of using display methods such as in-plane switching (IPS) mode, the requirements for the protective film are becoming more stringent. In display methods such as IPS mode, if gaseous or liquid components or water generated or bleeds out from the color filter layer enters the liquid crystal layer through the protective layer, the concentration of water or ionic impurities in the liquid crystal layer increases, or bubbles are formed in the liquid crystal, which will cause poor display. Therefore, in terms of preventing the passage of the impurity components, and in terms of the fact that the gas generation from the protective film in direct contact with the liquid crystal layer is directly related to poor display, low gas generation is particularly important. In recent years, there has been a demand for thinner LCD panels, so there has been a demand for thinner protective films, and the flatness requirements for achieving flatness in thin films have also become stricter. In other words, a new issue has arisen: balancing low gas generation and flatness.

As a material for a protective film of a color filter, a large number of epoxy or acrylic compound compositions have been proposed so far (Patent Documents 1 to 5, etc.), but no material has been found that satisfies the required properties of low gas generation and flatness at the same time. On the other hand, a siloxane epoxy resin having a 3,4-cyclohexyl group (Patent Document 6) or a material for forming a cured film using the material or a form of a color filter material (Patent Documents 7 to 9, etc.) has been proposed, but no attention has been paid to the siloxane structure in detail, and no discussion has been conducted on low gas generation or flatness (Patent Documents 7 to 8, etc.). [Prior Art Documents] [Patent Documents]

[Patent Document 1] International Publication No. 96/34303 [Patent Document 2] Japanese Patent Publication No. 2000-103937 [Patent Document 3] Japanese Patent Publication No. 2000-143772 [Patent Document 4] Japanese Patent Publication No. 2001-091732 [Patent Document 5] Japanese Patent Publication 2004-069930 Publication [Patent Document 6] WO2015/151957 [Patent Document 7] Japanese Patent Publication No. 2005-338790 [Patent Document 8] Japanese Patent Publication No. 2012-241118 [Patent Document 9] Japanese Patent Publication No. 2017-171748

[Problem to be solved by the invention] The present invention is a curable resin composition containing a siloxane resin having flatness, extremely good low moisture absorption, low gas generation, and excellent heat resistance, light resistance, chemical resistance, electrical reliability and transparency.

As described above, the protective film for a color filter must have the required properties of low moisture absorption, low gas generation, and flatness while maintaining high heat resistance, chemical resistance, hardness, electrical reliability, and transparency, and the range of applications of protective film materials that can meet the above requirements as a composition is narrowing.

Furthermore, in recent years, color filters (RGBW method) have been developed that have white (W) pixels that are not coated with color filters in addition to red, green, and blue (RGB), and the protective film is also required to fill the W space that is not coated with the color composition and satisfy the flatness. In other words, in addition to the conventional 1 μm to 2 μm bumps on the pixels, the larger 2 μm to 3 μm concave spaces are required to be flattened using a thin film with a thickness of 2 μm or less on the colored pixel formation portion.

The present invention is made in view of the above-mentioned problems, and aims to provide a curable resin composition that can form a protective film that satisfies the required properties of flatness, low moisture absorption, and low gas generation, and is also excellent in heat resistance, chemical resistance, adhesion, hardness, electrical reliability, and transparency, a cured film formed by curing the composition, and a method for producing a siloxane resin used therein. [Technical means for solving the problem]

The inventors of the present invention have conducted research to solve the problems required for the protective film of the color filter described above, and have found that the problems can be solved by formulating a curable resin composition of a silicone resin having a specific structure, thereby completing the present invention.

That is, the gist of the present invention is as follows. [1] A curable resin composition comprising a siloxane resin satisfying the following (i) to (iii), and a curing agent and/or a photocation initiator. (i) Having the following structure T1 showing a signal at -47 ppm to -52 ppm, the following structure T2 showing a signal at -55 ppm to -61 ppm, and the following structure T3 showing a signal at -62 ppm to -72 ppm in a ²⁹ Si-nuclear magnetic resonance (NMR) spectrum, and the area ratio of the signals is T1:T2:T3=0 to 1:1 to 10:1 to 100. (ii) The weight average molecular weight is 750 to 20,000. (iii) The molecular weight of each reactive group contained in the following (a) is less than 350. [Chemistry 1] [In Structures T1 to T3, R is a hydrogen group, a methyl group, an ethyl group or a phenyl group, and X is (a) or (b) below, which may be the same or different, and at least one X in each structure is (a). (a) Any reactive group selected from glycidyl, 3,4-epoxycyclohexyl, vinyl, acryl and methacryl, or a group having the reactive group at the end of an organic group having 1 to 6 carbon atoms; (b) An organic group having 1 to 6 carbon atoms] [2] The curable resin composition according to [1], wherein X includes a group having a 3,4-epoxycyclohexyl group at the end of an organic group having 1 to 6 carbon atoms. [3] The curable resin composition according to [1] or [2], wherein the siloxane resin contains the following structure D1 showing a signal at -9 ppm to -13 ppm and the following structure D2 showing a signal at -15 ppm to -24 ppm in the ²⁹ Si-NMR spectrum. [Chemistry 2] [In Structure D1 to Structure D2, R is a hydrogen group, a methyl group, an ethyl group or a phenyl group, and Y is (a) or (b) described above, and may be the same or different in each structure.] [4] The curable resin composition according to any one of [1] to [3], wherein the curing agent is one or more selected from the group consisting of polycarboxylic acids, polycarboxylic acid anhydrides, and polycarboxylic acid thermally decomposable esters. [5] The curable resin composition according to any one of [1] to [4], wherein the solid content of the siloxane resin is 3 mass % or more and 99 mass % or less relative to the total mass of the solid content. [6] The curable resin composition according to any one of [1] to [5], comprising a non-silicone compound having no siloxane skeleton and having an epoxy group or a polymerizable unsaturated bond. [7] The curable resin composition according to [6], wherein the non-silicone compound having no siloxane skeleton and having an epoxy group or a polymerizable unsaturated bond is an epoxy compound represented by the following formula (4). [In formula (4), Ar is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. In addition, a portion of the hydrogen atoms of the divalent aromatic hydrocarbon group represented by Ar may be substituted by a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. The average value of l is 0 to 2.] [8] A cured product obtained by curing the curable resin composition according to any one of [1] to [7]. [9] A method for producing a siloxane resin, which is a method for producing a siloxane resin that satisfies the following (i) to (iii), wherein Si(X ₁ )(OR ₁ ) ₃ is hydrolyzed or hydrolytically condensed, or Si(X ₁ )(OR ₁ ) ₃ and Si(X ₂ ) ₂ (OR ₄ ) ₂ are hydrolyzed or hydrolytically condensed. [Wherein, X ₁ is a group represented by (a) below, which may be the same or different, but at least contains a group having a 3,4-epoxycyclohexyl group at the end of an organic group having 1 to 6 carbon atoms. X ₂ is a group represented by (a) or (b) below, which may be the same or different, but at least contains a group represented by (b). R ₁ and R ₄ are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group. 〕 (i) Having the following structure T1 showing a signal at -47 ppm to -52 ppm, the following structure T2 showing a signal at -55 ppm to -61 ppm, and the following structure T3 showing a signal at -62 ppm to -72 ppm in the ²⁹ Si-NMR spectrum, and the area ratio of the signals is T1:T2:T3 = 0 to 1:1 to 10:1 to 100. (ii) The weight average molecular weight is 750 to 20,000. (iii) The molecular weight of each reactive group contained in the following (a) is less than 350. [Chemistry 4] [In structures T1 to T3, R is hydrogen, methyl, ethyl or phenyl, X is (a) or (b) below, which may be the same or different, and at least one X in each structure is (a). (a) any reactive group selected from glycidyl, 3,4-epoxycyclohexyl, vinyl, acryl and methacryl, or a group having the reactive group at the end of an organic group having 1 to 6 carbon atoms; (b) an organic group having 1 to 6 carbon atoms] [Effects of the invention]

The curable resin composition of the present invention can form a cured film that satisfies the required properties of flatness, extremely good low moisture absorption, and low gas generation, and is also excellent in heat resistance, chemical resistance, electrical reliability, and transparency, and can improve the display performance of a display element, a display element including the cured film, and the cured film. The curable resin composition of the present invention can be used as a protective film for a color filter of an LCD including an RGBW method, and can also be used in a display device that requires a transparent cured film with excellent flatness and low gas generation. That is, it can be preferably used as a structural element of organic EL display devices other than LCD, micro-light emitting diode (μLED) display devices, and display devices using quantum dots, especially in the case of a transparent film that needs to flatten unevenness or steps. Furthermore, it can also be applied to sensors such as complementary metal oxide semiconductor (CMOS) equipped with a color filter layer. In addition, it can also be used universally as an insulating film layer of semiconductor devices, multi-layer printed wiring substrates, or touch screens, especially in the case of requiring flatness. Furthermore, it is widely used in various applications such as optical applications requiring transparency, heat resistance, low moisture absorption, etc., optical device applications, mechanical parts materials, electrical and electronic parts materials, automotive parts materials, civil engineering materials, molding materials, coatings, adhesives, etc.

The curable resin composition of the present invention contains a siloxane resin and a curing agent and/or a photo-ion initiator. In addition, the curable resin composition may contain a surfactant, a solvent, etc. Here, the so-called siloxane resin refers to a resin having a siloxane bond (-Si-O-Si-), and the present invention contains a siloxane resin having the following structure.

<Siloxane resin> The chemical shifts of the silicon-bonded units T and D in the ²⁹ Si-NMR spectrum are observed in the ranges of -45 ppm to -80 ppm for T unit and 0 ppm to -40 ppm for D unit. In the siloxane resin of the present invention, signals are shown in the ranges of -47 ppm to -52 ppm, -55 ppm to -61 ppm, and -62 ppm to -72 ppm as T unit. These signals respectively indicate signals originating from silicon-bonded units of the following structures T1 (-47 ppm to -52 ppm), T2 (-55 ppm to -61 ppm), and T3 (-62 ppm to -72 ppm).

[Chemistry 5] [Wherein, R is hydrogen, methyl, ethyl, or phenyl, and X is (a) or (b) below, which may be the same or different, and at least one X in each structure is (a). The X will be described later. (a) any reactive group selected from glycidyl, 3,4-epoxycyclohexyl, vinyl, acryl, and methacryl, or a group having the reactive group at the end of an organic group having 1 to 6 carbon atoms; (b) an organic group having 1 to 6 carbon atoms]

The silicone resin of the present invention is characterized in that it contains not only a signal indicating a T3 structure that can be observed in a general silicone resin, but also the T2 structure and the T1 structure. By having not only a T3 structure but also such a T2 structure and a T1 structure, it has heat resistance or chemical resistance derived from the T3 structure, and can improve solubility in organic solvents or compatibility when used with other resins, and can widely design the required characteristics of the cured product, and can also be applied to various processing processes used for curable resin compositions. Moreover, for these structures T1 to T3, the area ratio of the signals is preferably T1:T2:T3=0~1:1~10:1~100, preferably 0~1:1~10:1~50.

Furthermore, the siloxane resin of the present invention preferably contains not only the T structure but also the following structure D1 showing a signal at -9 ppm to -13 ppm and the following structure D2 showing a signal at -15 ppm to -24 ppm in the ²⁹ Si-NMR spectrum. By having such a specified structure D1 and structure D2, compatibility with organic solvents or other epoxy resins etc. becomes good, which is preferred in terms of the above aspect. [Chemistry 6] [In Structure D1 and Structure D2, R is hydrogen, methyl, ethyl or phenyl, and Y is (a) or (b) described above, and may be the same or different in each structure.]

Furthermore, the area ratio of the signal of the T structure and the D structure is preferably (T1+T2+T3): (D1+D2) = 10~1: 5~0. From the viewpoint of low hygroscopicity of the cured product, it is more preferably (T1+T2+T3): (D1+D2) = 10~1: 2~0. For example, if there is a need to improve heat resistance (low gas generation), it is necessary to design the siloxane resin in such a way that a large amount of T structure is introduced. In addition, for example, if there is a need to control various physical properties of the cured product and it is necessary to improve compatibility with other epoxy resins, it is necessary to design a siloxane resin containing a certain amount of D structure or more.

The representative structure of the siloxane resin of the present invention has a group represented by the following formula (1) or (2) in the molecule.

In the above formula (1) and formula (2), j, k, m, and n satisfy 1≦j+k≦7   (j≧0, k≧1)···(i) 2≦m+n≦100   (m≧1, n≧1)···(ii) Here, from the viewpoint of compatibility with other compounds, j+k is preferably 1 or more, and from the viewpoint of chemical resistance and adhesion of the coating film, j+k is preferably 7 or less. That is, it is preferable to have a ring structure of an appropriate size that can satisfy such characteristics. j+k is more preferably 1 to 6, and further preferably 1 to 4. In addition, from the viewpoint of molecular weight control and compatibility with other compounds, m+n is preferably 2 or more and 100 or less. That is, it is preferably a compound in which a ring structure and a chain structure are bonded at an appropriate ratio, and the m+n is more preferably 2 to 99, and further preferably 3 to 75. * represents a bond, and when linked, it forms a Si-O-Si bond.

In formula (1) and formula (2), X is (a) or (b), which may be the same or different, and includes more than one (a). Furthermore, (a) only needs to be present somewhere in X in the T structure or Y in the D structure, and preferably, there are multiple (a)s, and they are present in both the T structure and the D structure.

Among the groups having the reactive group described in (a) at the end of the organic group having 1 to 6 carbon atoms, the "organic group having 1 to 6 carbon atoms" may include branchable alkyl groups, cycloalkyl groups, phenyl groups, etc. The number of carbon atoms is preferably 1 to 4, and more preferably 1 to 3. Examples of such organic groups include alkyl groups such as methyl, ethyl, various propyl groups, various butyl groups, and cycloalkyl groups such as cyclopropyl groups. Furthermore, the term "various" refers to various isomers including normal-, secondary-, tertiary-, and iso-.

In the formula (1) and the formula (2), when X is a alkyl group having 1 to 3 carbon atoms, preferably, X is a methyl group or an ethyl group.

A plurality of Xs may be the same or different. From the viewpoint of curability, it is preferred that at least one reactive group in (a) is included, wherein the reactive groups include a group having a 3,4-epoxycyclohexyl group at the end of an organic group having 1 to 6 carbon atoms, and more preferably, the group having a 3,4-epoxycyclohexyl group at the end of an organic group having 1 to 6 carbon atoms is 15 mol% or more, and more preferably 30 mol% or more, relative to 100 mol% of Si. The group having a 3,4-epoxycyclohexyl group at the end of an organic group having 1 to 6 carbon atoms is preferably β-(3,4-epoxycyclohexyl)ethyl.

On the other hand, R' in formula (1) and formula (2) is a hydroxyl group, a carbonyl group having 1 to 3 carbon atoms, a phenyl group, a methoxy group, an ethoxy group, or a group represented by the following formula (3). Here, RX in formula (3) is a hydroxyl group, a alkyl group having 1 to 3 carbon atoms, a phenyl group, a methoxy group, or an ethoxy group, and X is (a) or (b) above. Preferably, * represents a bond, and when linked, it forms a Si-O-Si bond, and the number of repeating units is 0 to 15,000.

R' in formula (1) and formula (2) may be the same or different. When all R' are hydroxyl groups, the storage stability is poor and the low hygroscopicity of the cured film may be impaired depending on the formulation composition. Therefore, it is preferred that the content of hydroxyl groups is 30 mol% or less relative to 100 mol% of Si, and groups other than hydroxyl groups are more preferred.

In the above R' and RX, the alkyl group having 1 to 3 carbon atoms is more preferably a methyl group or an ethyl group, whereby a cured film having high heat resistance can be obtained.

Furthermore, the weight average molecular weight of the siloxane resin is 750 to 20,000, and the molecular weight of each reactive group contained in (a) is less than 350 g/eq.

The weight average molecular weight is expressed as the polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC). Siloxane resins with an Mw of less than 750 form films (cured products) with low crosslinking density and poor chemical resistance. They are also likely to remain in the coating as unreacted products, which deteriorates the degassing properties of the coating. When the Mw is greater than 20,000, there is a tendency for the flatness of the film (cured product) to deteriorate, or for the compatibility with other compounds to deteriorate. The preferred Mw is 1,000 to 15,000.

In addition, when the molecular weight per reactive group contained in (a) is 350 g/eq or more, the content of the reactive group decreases, the curability is insufficient, and there is a tendency for the crosslinking density to decrease, so that the properties of the cured film such as chemical resistance deteriorate. Preferably, the molecular weight is 150 or more and less than 350. In addition, assuming that all reactive groups include epoxy groups, the molecular weight is equivalent to epoxy equivalent.

The curable resin composition of the present invention can obtain a cured film with low hygroscopicity by containing the above-mentioned siloxane resin, the siloxane epoxy resin among them, and particularly the siloxane epoxy resin containing 3,4-epoxyepoxyhexyl group. The details of the reason are not certain, but it is estimated that the epoxy group of the conventional general siloxane epoxy resin is a structural unit derived from a glycidyl group with high hydrophilicity, while the siloxane epoxy resin containing 3,4-epoxyepoxyhexyl group is a cyclohexyl epoxy group with high hydrophobicity. It is further speculated that the reason is that conventional general siloxane epoxy resins, when produced by hydrolysis condensation or the like, tend to generate or retain silanol groups (groups representing hydroxyl groups in R' in the above formula (1) and formula (2)), whereas the siloxane epoxy resin containing 3,4-epoxyepoxyhexyl groups in the present invention has fewer silanol groups.

The siloxane resin of the present invention can be produced, for example, by the following method (A) or (B). That is, it can be produced by a known method such as (A) a method of hydrolyzing and condensing an alkoxysilane compound having a specific organic group or a mixture of an alkoxysilane having a specific organic group and other silane compounds in the presence of an appropriate organic solvent, acid and water, or (B) a method of adding a compound having a specific organic group and a double bond group to a polysiloxane having a hydrosilane structure, but the method (A) is general and easy, and is therefore preferred.

In the case of production by method (A), examples include: using a trialkoxysilane represented by the general formula Si(X ₁ )(OR ₁ ) ₃ as an alkoxysilane compound and hydrolyzing or hydrolytically condensing it, or hydrolyzing or hydrolytically condensing the Si(X ₁ )(OR ₁ ) ₃ and a dialkoxysilane represented by the general formula Si(X ₂ ) ₂ (OR ₄ ) _2. Wherein, X ₁ is a group represented by (a) or (b) and may be the same or different, but preferably one or more of (a) is included, wherein (a) contains a group having a 3,4-epoxycyclohexyl group at the end of an organic group having 1 to 6 carbon atoms. X ₂ is a group represented by (a) or (b) and may be the same or different, but one or more of (b) is included. _R1 and _R4 are independently an alkyl group having 1 to 3 carbon atoms or a phenyl group.

For this reaction, it is preferable to carry out hydrolysis condensation under acidic conditions, for example. Organic or inorganic acids such as hydrogen fluoride, hydrochloric acid, nitric acid, formic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, methanesulfonic acid, and toluenesulfonic acid can be used. The presence of water is required for the hydrolysis condensation, and the amount of water can be sufficient to hydrolyze the hydrolyzable groups of the silane compound, but it is preferably added in an amount of 0.3 to 1.5 times the molar amount of the hydrolyzable groups (theoretical amount).

Examples of the trialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, isobutyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, p-phenylenetrimethoxysilane, p-phenylenetriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 8-octenyltrimethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, Trialkoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 3,4-epoxycyclohexylmethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)methyltripropoxysilane are used. Among these, trialkoxysilanes having a 3,4-epoxycyclohexyl group are preferably used.

Examples of the dialkoxysilane include dimethyldimethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, Dialkoxysilane compounds such as 2-(4-epoxycyclohexyl)ethylmethyldipropoxysilane, 2-(3,4-epoxycyclohexyl)diethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)diethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, ethylmethyldimethoxysilane, ethylmethyldiethoxysilane, ethylmethyldipropoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, etc. These trialkoxy or dialkoxy silane compounds may be used alone or in combination of two or more.

In the present invention, the content of the silicone resin in the solid component of the curable resin composition is preferably 3% by mass or more, more preferably 8% by mass or more. Within the above range, the low hygroscopicity of the cured product is sufficiently high. On the other hand, the upper limit is preferably 99% by mass or less, more preferably 95% by mass or less.

<Hardener, photocationic ion initiator> In the curable resin composition of the present invention, a curing agent (thermal curing agent) selected from the group consisting of polycarboxylic acids, polycarboxylic acid anhydrides and polycarboxylic acid thermally decomposable esters, or a photocationic ion initiator, or a combination thereof can be used together with the silicone resin. By using these curing agents and/or photocationic ion initiators, the curable resin composition of the present invention can be cured by heat, light irradiation, or a combination of heat and light irradiation to form a cured film.

Here, the polycarboxylic acid used as the hardener is a compound having two or more carboxyl groups in one molecule, and examples thereof include succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, phthalic acid, benzene-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, and butane-1,2,3,4-tetracarboxylic acid.

In addition, the anhydride of the polycarboxylic acid as the curing agent includes the anhydrides of the polycarboxylic acids exemplified above, and may be an intermolecular anhydride, and generally an anhydride that is ring-closed within the molecule is used. As a preferred anhydride, trimellitic anhydride can be exemplified.

Furthermore, the thermally decomposable ester of the polycarboxylic acid as the curing agent includes tert-butyl ester, 1-(alkyloxy)ethyl ester, 1-(alkylalkyl)ethyl ester of the polycarboxylic acid exemplified above (wherein the alkyl group described here represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a branched structure or a ring structure and may be substituted by any substituent), etc.

In addition, as a hardener, a polymer or copolymer having two or more carboxyl groups may be used. The carboxyl group of the polymer or copolymer may be an anhydride or a thermally decomposable ester. Examples of such polymers or copolymers include polymers or copolymers containing (meth)acrylic acid as a structural component, copolymers containing maleic anhydride as a structural component, compounds obtained by reacting tetracarboxylic dianhydride with diamine or diol and ring-opening the anhydride, and the like.

On the other hand, as the photopolymerization initiator, there can be listed acid generators such as diazonium salts, iodonium salts, coronium salts, phosphonium salts, selenium salts, oxonium salts, and ammonium salt compounds. Examples of the acid generator include San-Aid SI series of Sanshin Chemical Industry Co., Ltd., CPI series of San-Apro Co., Ltd., ADEKA ARKLS SP series of ADEKA Co., Ltd., and WPAG series of Fujifilm and Koshun Chemical Co., Ltd. In addition, an auxiliary agent or a sensitizer that exerts an effect in combination with the photopolymerization initiator can be used in combination.

In the curable resin composition of the present invention, the amount of such a curing agent and/or a photo-ion initiator is preferably 1 mass % to 40 mass %, more preferably 10 mass % to 30 mass %, and further preferably 10 mass % to 20 mass % relative to the total mass of the solid components of the composition. If it is less than 1 mass %, the curing reaction is not sufficiently advanced, and the heat resistance of the cured product is insufficient, and the physical properties of the cured product cannot be fully obtained. In particular, when the non-silicone type epoxy compound described later remains, the adverse effect on the gas generation property also becomes greater. On the other hand, if it exceeds 40 mass %, the remaining cured product that does not contribute to the curing reaction has an adverse effect on the gas generation property, and the characteristics as a cured product cannot be fully obtained.

<Non-silicone compound> The curable resin composition of the present invention may further include a non-silicone compound that does not include a siloxane structure. Such a non-silicone compound can be used without particular limitation as long as it is compatible with the silicone resin. By including the non-silicone compound, properties such as flatness or hardness can be further improved, or the viscosity can be adjusted, so it is preferred. As such a non-silicone compound, a compound that does not include a siloxane skeleton and has an epoxy group or a polymerizable unsaturated bond is used. In general, when a siloxane epoxy resin having an epoxy group is used as the siloxane resin of the present application, since the main combination is an epoxy compound that does not contain a siloxane skeleton, as long as the epoxy compound that does not contain a siloxane skeleton and is liquid at room temperature or solid at room temperature can be uniformly mixed with the addition of a solvent, it can be used without any particular restrictions. In addition, when a siloxane resin having a polymerizable unsaturated bond is used as the siloxane resin of the present application, as long as the compound that does not contain a siloxane skeleton and has a polymerizable unsaturated bond can be mainly uniformly mixed with the addition of a solvent, it can be used without any particular restrictions. Specific compounds are exemplified below.

Examples of chain aliphatic epoxy compounds that are liquid at room temperature include trihydroxymethylpropane triglycidyl ether, trihydroxymethylethane triglycidyl ether, monoglycidyl ether or diglycidyl ether of branched alkyl esters, and the FOLDI series manufactured by Nissan Chemical Co., Ltd. Such chain aliphatic epoxy compounds increase the crosslinking density by reacting with a hardener, thereby contributing to the improvement of heat resistance. In particular, epoxy compounds with a viscosity of 30 mPa·s to 500 mPa·s (25°C) are preferably used.

In addition, examples of aliphatic epoxy compounds that are liquid at room temperature include (3',4'-epoxycyclohexylmethyl)3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane or bis(3,4-epoxycyclohexylmethyl)adipate, hydrobisphenol A diglycidyl ether, 1,4-cyclohexanedimethanol-bis(3,4-epoxycyclohexanecarboxylate), and epoxy compounds having a viscosity of 50 mPa·s to 3500 mPa·s (25°C) are preferably used.

Examples of the aromatic epoxy compound that is liquid at room temperature include low molecular weight compounds such as bisphenol A type epoxy compound and bisphenol F type epoxy compound.

Examples of the epoxy compound having a triazine skeleton that is liquid at room temperature include polyfunctional epoxy compounds having a triazine skeleton (TEPIC-PAS, TEPIC-VL, TEPIC-UC, etc. manufactured by Nissan Chemical Co., Ltd.).

Among these epoxy compounds that are liquid at room temperature, low molecular weight liquid compounds such as (3',4'-epoxycyclohexylmethyl) 3,4-epoxycyclohexanecarboxylate and bisphenol A type epoxy resin are more preferably used.

By using these liquid epoxy resins, the flatness of the film (cured product) can be further improved.

On the other hand, as the epoxy compound which is solid at room temperature, alicyclic cyclohexane adducts such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, glycidyl ethers of polyols, glycidyl esters of polycarboxylic acids, 1,2-epoxy-4-(2-oxohexacyclopropyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (e.g., "EHPE3150" manufactured by Daicel Corporation) can be used without particular limitation. The epoxy compounds are known to be solid at room temperature, such as epoxy compounds, copolymers of (meth)acrylates containing glycidyl (meth)acrylate as an essential component, epoxidized polybutadiene (e.g., "NISSO-PB·JP-100" manufactured by Nippon Soda Co., Ltd.), trifunctional epoxy compounds having a triazine skeleton (e.g., TEPIC SC-G, TEPIC S, TEPIC SS, TEPIC SP, etc. manufactured by Nissan Chemical Co., Ltd.). In addition, epoxy compounds that are waxy or granular at room temperature and have a low melting point, i.e., ε-caprolactam-modified products of (3',4'-epoxycyclohexylmethyl) 3,4-epoxycyclohexanecarboxylate (TTA2081, TTA2083 manufactured by Tetrachem Co., Ltd.), etc. can also be used.

Among them, the copolymer of two or more (meth)acrylates having glycidyl (meth)acrylate as an essential component is, for example, a compound obtained by free radical copolymerization of glycidyl (meth)acrylate with (meth)acrylates and other polymerizable unsaturated compounds by a conventional method. In the free radical copolymerization, a known free radical polymerization initiator such as an azo compound or a peroxide can be used. In addition, the degree of polymerization can be controlled in such a way that the weight average molecular weight is 900 to 20,000 by using a known chain transfer agent or polymerization inhibitor.

(Meth)acrylates other than glycidyl (meth)acrylate and other polymerizable unsaturated compounds used in the copolymer are exemplified below, but are not limited to these.

(Meth)acrylates can be obtained by condensing (meth)acrylic acid (the so-called (meth)acrylic acid refers to acrylic acid or methacrylic acid) with an alcohol (R ¹ OH) component. As the (R ¹ OH) component, a known component can be used without particular limitation. Specific examples of ^R1 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclopentyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, adamantyl, isobornyl, dicyclopentanyl, dicyclopentenyl, vinyl, allyl, ethynyl, phenyl, tolyl, mesityl, naphthyl, anthracenyl, phenanthryl, benzyl, 2-phenylethyl, 2-phenylvinyl and the like saturated or unsaturated monovalent hydrocarbon groups, and pyridyl, piperidinyl, etc. The alkyl or heterocyclic group may be a structure in which a halogen atom, a carbonyl group, a thiocarbonyl group, a nitro group, a silyl group, an ether group, a thioether group, an ester group, a thioester group, a dithioester group, a carbamate group, a thiocarbamate group, a urea group, a thiourea group, or the like is introduced as a substituent at any position. Such a monovalent group can be appropriately selected according to the structure of the target (meth)acrylate copolymer. In terms of performance and economy, it is preferably a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms, and more preferably a saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon atoms. Furthermore, the saturated or unsaturated monovalent hydrocarbon group may be a hydrocarbon group having a branched structure or a ring structure, and may be further substituted by any substituent. Among them, the substituent preferably does not have a reactive structure such as an acidic group and an amide bond.

As other polymerizable unsaturated compounds, styrene and its derivatives can be cited. As specific compounds, compounds obtained by introducing an alkyl group, a halogen atom, a hydroxyl group, etc. into the aromatic ring of styrene, α-methylstyrene, or p-styrene can be used.

In addition to the above, polymerizable unsaturated compounds containing epoxy groups other than glycidyl methacrylate (for example, glycidyl acrylate, [4-(glycidyloxy)butyl](meth)acrylate, [(3,4-epoxycyclohexyl)methyl](meth)acrylate, and 4-(glycidyloxymethyl)styrene, etc.), and polymerizable unsaturated compounds containing alkoxysilyl groups (for example, [3-(trimethoxysilyl)propyl](meth)acrylate, [3-(triethoxysilyl)propyl](meth)acrylate, and 4-(trimethoxysilyl)styrene, etc.) can also be copolymerized.

Among the copolymers exemplified above, preferred examples include copolymers obtained by copolymerizing glycidyl methacrylate and alkyl methacrylate (C1 to C4 alkyl), or further copolymerizing styrene, and having a softening point (Tg) of 10 to 90° C. A more preferred range of Tg of the copolymer is 40 to 90° C.

Among the epoxy compounds that are solid at room temperature, from the viewpoint of further improving heat resistance and low gas generation, an epoxy compound represented by the following general formula (4) in which the average value of l is 0 to 2 is particularly preferred.

[Chemistry 9]

In the general formula (4), Ar is a divalent aromatic alkyl group having 6 to 12 carbon atoms. In addition, a part of the hydrogen atoms of the divalent aromatic alkyl group represented by Ar may be substituted with a alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group.

The epoxy compound of the general formula (4) may be a bisphenol fluorene epoxy compound or a bis-naphthol fluorene epoxy compound. The epoxy compound is a component that has a relatively small effect on the viscosity of the curable resin composition and is effective in imparting low gas generation or heat resistance. In particular, a bis-naphthol fluorene epoxy resin is more preferably used to impart low gas generation.

The average value of l in the general formula (4) may be 0 to 2. If it is 0 or more, the solubility can be improved, and if it exceeds 2, there is a tendency to affect the curability of the cured film. The average value of l is preferably 0.01 to 1. The average value of l can be calculated from the epoxy equivalent. For example, in the case of a bis-naphthol fluorene type epoxy compound, it can be calculated according to (epoxy equivalent) × 2 = (average value of l) × 506.6 + 562.7 , and in the case of a bis-phenol fluorene type epoxy compound, it can be calculated according to (epoxy equivalent) × 2 = (average value of l) × 406.5 + 462.5 .

The epoxy compound of the general formula (4) can be synthesized by a known method such as the method described in Japanese Patent Laid-Open No. 9-328534. Generally, the most preferred method is to condense 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis(4-hydroxynaphthyl)fluorene with epichlorohydrin in the presence of a base. The value of l can be set to a desired value by adjusting the molar ratio of the raw material compounds during synthesis or adjusting the reaction conditions.

Next, compounds having no siloxane skeleton and having polymerizable unsaturated bonds are exemplified. Any epoxy acrylate compound obtained by reacting a monocarboxylic acid compound having a polymerizable unsaturated bond, such as acrylic acid or methacrylic acid, with the exemplified epoxy compound having no siloxane skeleton can be used without particular limitation as long as it can be uniformly mixed with the solvent. Furthermore, as other examples of monocarboxylic acid compounds having polymerizable unsaturated bonds, when (meth)acrylate represents acrylate or methacrylate, there can be listed half ester of 2-hydroxyethyl (meth)acrylate and succinic anhydride, half ester of 2-hydroxyethyl (meth)acrylate and phthalic anhydride, half ester of 2-hydroxyethyl (meth)acrylate and cyclohexane-1,2-dicarboxylic anhydride, 4-vinylbenzoic acid, etc. In addition, polymerizable monomers having polymerizable unsaturated bonds can be used without particular limitation as long as they can be uniformly mixed under the addition of solvent. Examples of polymerizable monomers include (meth)acrylates having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, and the like. (Meth)acrylates such as propylene glycol (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxide-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and one or more thereof can be used.

<Other ingredients> In addition, a known curing accelerating compound known as a curing accelerator, curing catalyst or latent curing agent for epoxy compounds can be used in the curable resin composition of the present invention as needed. When the curing accelerating compound is used, it is preferably formulated in an amount of 0.01% to 2% by mass relative to the total mass of the solid components of the composition, and more preferably 0.05% to 1.5% by mass. If it is less than 0.01% by mass, it lacks the effect as an accelerator, and if it exceeds 2% by mass, sufficient storage stability cannot be obtained when the curable resin composition is made into a solution, or it has an adverse effect on coloring when heated.

Examples of the curing-promoting compound include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, and imidazoles, and particularly preferred are 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene or salts thereof.

Furthermore, the curable resin composition of the present invention may contain a solvent. As the solvent, known compounds may be used, for example, ester solvents (butyl acetate, cyclohexyl acetate, etc.), ketone solvents (methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, etc.), alcohol solvents (3-methoxybutanol, ethylene glycol mono-tert-butyl ether, etc.), aromatic solvents (toluene, xylene, etc.), aliphatic solvents, amine solvents, and amide solvents may be used without particular limitation. From the aspect of safety, ester or ether solvents having a propylene glycol skeleton are preferred, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol diacetate, etc. In addition, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, and 1,3-butanediol diacetate, etc., which have structures similar to these, are also preferred.

There is no particular limitation on the solid content concentration of the curable resin composition of the present invention. For example, when used as a protective film for a color filter, the total amount of components other than the solvent, i.e., the solid content concentration, is generally adjusted to be in the range of 10% to 30% by mass. In addition, in order to improve the flatness of the protective film for the color filter, it is preferred to control the drying property of the curable resin composition by using 40% to 90% by mass of a solvent having a boiling point of less than 150°C at normal pressure and 10% to 60% by mass of a solvent having a boiling point of 150°C or more at normal pressure.

The curable resin composition of the present invention preferably has a total content of the silicone resin and the non-silicone compound satisfying (i) to (iii), i.e., a curable resin content of 55% to 95% by mass, more preferably 60% to 80% by mass, relative to the total mass of the solid components. If the content of the curable resin is less than 55% by mass, the ratio of the curing agent to the curable resin becomes large, and the properties of the cured product as a curable resin cannot be fully obtained, or the excess cured product that does not contribute to the curing reaction has an adverse effect on gas generation. In addition, if the content of the curable resin exceeds 95% by mass, the ratio of the curing agent to the curable resin becomes extremely small, the curing reaction is not fully promoted, and the heat resistance of the cured product is insufficient.

The curable resin composition of the present invention may further contain other arbitrary components as needed, for example, it may contain a coloring material, a filler, a resin, an additive, etc. Here, as coloring materials, there can be listed dyes, organic pigments, inorganic pigments, carbon black pigments, etc., as fillers, there can be listed silica, talc, etc., as resins, there can be listed vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, melamine resins, etc., as additives, there can be listed dispersants, surfactants, silane coupling agents, viscosity adjusters, wetting agents, defoaming agents, antioxidants, ultraviolet absorbers, thermal radical initiators, etc. As these optional components, known compounds can be used without particular limitation. When used as a protective film for a color filter, a surfactant (fluorine-based surfactant, silicone-based surfactant, etc.) can be used, and the total content thereof is preferably set to 10 mass% in the solid content of the curable resin composition as the upper limit. As a coupling agent, for example, a silane coupling agent (3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane), a titanium-based coupling agent, and an aluminum-based coupling agent can be used. Examples of the thermal radical initiator include azo initiators such as 2,2-azobisisobutyronitrile, dimethyl 2,2-azobis-2-methylpropionate, and 1,1′-azobis(1-acetyloxy-1-phenylethane), and peroxides such as benzoyl peroxide.

As a method for producing the cured product of the curable resin composition of the present invention, a known method can be used. For example, after applying or injecting the curable resin composition to an appropriate substrate or mold corresponding to the purpose or use, the solvent can be removed and cured by heating. The solvent can also be removed by reduced pressure drying or the like.

The cured product of the curable resin composition of the present invention can be made into a film-like cured film. The cured film is applied to the surface of the pixel coloring composition applied on the substrate of the color filter and cured to produce a protective film for the color filter. At this time, when producing a color filter having white (W) pixels without a pixel coloring composition applied to the color filter in addition to RGB, if the curable resin composition of the present invention is applied and cured to produce a protective film, the W space with a depth of about 1.0 μm to 3.0 μm formed due to the non-application of the coloring composition can be filled, and at the same time, the flatness between the surface of the protective film formed on the RGB coloring composition applied on the substrate and the surface of the protective film formed on the W space can be satisfied.

The cured product of the curable resin composition of the present invention can be used as a protective film for color filters of LCDs including RGBW systems, and can also be used in display devices that require a transparent cured film with excellent flatness and low gas generation. That is, it can be preferably used as a structural element of organic EL display devices other than LCDs, μLED display devices, and display devices using quantum dots, especially in the case of a transparent film that needs to flatten unevenness or steps. Furthermore, it can also be applied to sensors such as CMOS equipped with a color filter layer. In addition, the hardened material of the curable resin composition of the present invention can fill the step portion as described above and improve the flatness of the surface, so it can also be used for anti-corrosion agent layers such as solder resist layers, anti-plating layers, anti-corrosion layers, interlayer insulation layers such as multilayer printed wiring boards, gas barrier films, sealing materials for semiconductor light-emitting elements such as lenses and light-emitting diodes (LEDs), top coatings of coatings or inks, plastic hard coatings, metal anti-rust films, etc. In addition, it can be used not only as a coating agent, but also by molding the curable resin composition itself and applying it to the production of films, substrates, plastic parts, optical lenses, etc., so it is extremely useful. [Example]

Hereinafter, embodiments of the present invention will be specifically described based on embodiments and comparative examples, but the present invention is not limited to these.

[Weight average molecular weight (Mw)] Mw was measured by gel permeation chromatography (GPC) under the following conditions. Apparatus: HLC-8020 manufactured by Tosoh Co., Ltd. Mobile phase: tetrahydrofuran Column temperature: 40°C Flow rate: 0.6 mL/min Sample concentration: 1.0 mass % Sample injection volume: 20 μL Detector: Differential refractometer Standard substance: Monodisperse polystyrene

[ ²⁹ Si-NMR measurement conditions] Apparatus name: JNM-ECA400 manufactured by JEOL Ltd. Observation nucleus: ²⁹ Si Observation frequency: 79.43 MHz Measurement temperature: Room temperature Measurement solvent: CDCl ₃ Pulse width: 8.75 μsec (90°) Pulse repetition time: 5.0 sec Accumulated times: 11000 times Sample concentration (sample/measurement solvent/buffering agent): 200 mg/0.7 ml/10 mg Buffering agent: Cr(acac) ₃

<Synthesis of Siloxane Epoxy Resin> [Synthesis Example 1] 25.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 150.0 g of toluene were placed in a reaction vessel including a stirring device, a dropping funnel, a thermometer and a stirrer. After complete dissolution, 1.25 g of p-toluenesulfonic acid monohydrate as an acid catalyst was further mixed and stirred at room temperature for 30 minutes. 3.3 g of water was then added dropwise and stirred for 24 hours. After the reaction was completed, the mixture was washed with an aqueous solution of NaHCO ₃ , the organic layer was dried and filtered with MgSO ₄ , and the volatiles were removed under reduced pressure to obtain 18.8 g of a transparent viscous resin. The epoxy equivalent of the obtained resin was 250 g/eq. Mw was 4100 (Silicone Epoxy Resin A-1).

[Synthesis Example 2] 20.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 5.0 g of 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, and 150.0 g of toluene were placed in a reaction container including a stirring device, a dropping funnel, a thermometer, and a stirrer. After complete dissolution, 1.25 g of p-toluenesulfonic acid monohydrate as an acidic catalyst was further mixed and stirred at room temperature for 30 minutes. 3.1 g of water was then added dropwise and stirred for 24 hours. After the reaction was completed, the mixture was washed with an aqueous solution of NaHCO ₃ , the organic layer was dried and filtered with MgSO ₄ , and the volatiles were removed under reduced pressure to obtain 20.3 g of a transparent viscous resin. The epoxy equivalent weight of the obtained resin was 270 g/eq. Mw was 3200 (Silicone Epoxy Resin A-2).

[Synthesis Example 3] 12.5 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 12.5 g of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 150.0 g of toluene were placed in a reaction container including a stirring device, a dropping funnel, a thermometer, and a stirrer. After complete dissolution, 1.25 g of p-toluenesulfonic acid monohydrate as an acidic catalyst was further mixed and stirred at room temperature for 30 minutes. 3.0 g of water was then added dropwise and stirred for 24 hours. After the reaction was completed, the mixture was washed with an aqueous solution of NaHCO ₃ , the organic layer was dried and filtered with MgSO ₄ , and the volatiles were removed under reduced pressure to obtain 19.7 g of a transparent viscous resin. The epoxy equivalent weight of the obtained resin was 230 g/eq. Mw was 5000 (Silicone Epoxy Resin A-3).

[Synthesis Example 4] 7.5 g of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 17.5 g of 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, and 150.0 g of toluene were placed in a reaction container including a stirring device, a dropping funnel, a thermometer, and a stirrer. After complete dissolution, 1.25 g of p-toluenesulfonic acid monohydrate as an acidic catalyst was further mixed and stirred at room temperature for 30 minutes. 2.6 g of water was then added dropwise and stirred for 24 hours. After the reaction was completed, the mixture was washed with an aqueous solution of NaHCO ₃ , the organic layer was dried and filtered with MgSO ₄ , and the volatiles were removed under reduced pressure to obtain 19.7 g of a transparent viscous resin. The epoxy equivalent weight of the obtained resin was 290 g/eq. Mw was 3800 (Silicone Epoxy Resin A-4).

[Synthesis Example 5] 25.0 g of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and 15.0 g of toluene are placed in a reaction container including a stirring device, a dropping funnel, a thermometer and a stirrer. After complete dissolution, 1.25 g of p-toluenesulfonic acid monohydrate as an acidic catalyst is further mixed and stirred at room temperature for 30 minutes. 2.8 g of water is then added dropwise and stirred for 24 hours. After the reaction is completed, the mixture is washed with an aqueous solution of NaHCO ₃ , the organic layer is dried and filtered with MgSO ₄ , and the volatiles are removed under reduced pressure to obtain 20.1 g of a transparent viscous resin. The epoxy equivalent of the obtained resin is 340 g/eq. Mw is 3500 (Silicone Epoxy Resin A-5).

[Synthesis Example 6] 12.5 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 12.5 g of dimethyldiethoxysilane, and 150.0 g of toluene were placed in a reaction container including a stirring device, a dropping funnel, a thermometer, and a stirrer. After complete dissolution, 1.25 g of p-toluenesulfonic acid monohydrate as an acid catalyst was further mixed and stirred at room temperature for 30 minutes. 3.7 g of water was then added dropwise and stirred for 24 hours. After the reaction was completed, the mixture was washed with an aqueous solution of NaHCO ₃ , the organic layer was dried and filtered with MgSO ₄ , and the volatiles were removed under reduced pressure to obtain 20.0 g of a transparent viscous resin. The epoxy equivalent weight of the obtained resin was 310 g/eq. Mw was 2900 (Silicone Epoxy Resin A-6).

[Synthesis Example 7] 15.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 5.0 g of dimethyldiethoxysilane, 5.0 g of methacryloyloxypropyltrimethoxysilane, and 150.0 g of toluene were placed in a reaction container including a stirring device, a dropping funnel, a thermometer, and a stirrer. After complete dissolution, 1.25 g of p-toluenesulfonic acid monohydrate as an acid catalyst was further mixed and stirred at room temperature for 30 minutes. 3.5 g of water was then added dropwise and stirred for 24 hours. After the reaction was completed, the mixture was washed with an aqueous solution of NaHCO ₃ , the organic layer was dried and filtered with MgSO ₄ , and the volatiles were removed under reduced pressure to obtain 20.0 g of a transparent viscous resin. The epoxy equivalent weight of the obtained resin was 260 g/eq. Mw was 2000 (Silicone Epoxy Resin A-7).

[Comparative Synthesis Example 1] 25.0 g of (3-glycidyloxypropyl)trimethoxysilane, 100.0 g of toluene, and 50.0 g of 2-propanol (isopropyl alcohol, IPA) were placed in a reaction container including a stirring device, a dropping funnel, a thermometer, and a stirrer. After complete dissolution, 7.5 g of a 5% tetramethylammonium hydroxide aqueous solution (TMAH (tetramethyl ammonium hydroxide) aqueous solution) as an alkaline catalyst was added and stirred at room temperature for 24 hours. After the reaction was completed, the mixture was washed with a citric acid aqueous solution, the organic layer was dried with MgSO ₄ and filtered, and the volatile matter was removed under reduced pressure to obtain 20.4 g of a transparent viscous resin. The epoxy equivalent of the obtained resin was 169 g/eq. Mw was 28,000 (Silicone Epoxy Resin a-1).

(Preparation of hardening resin composition) Prepare the compositions shown in Tables 1 to 5, stir and mix at room temperature for 3 hours, and dissolve the solid components in the solvent to prepare hardening resin compositions. The composition values are expressed as parts by mass, and the total of the solid components is 100 parts by mass.

As a curable resin composition, the components used in the formulation of the examples and comparative examples are shown below. <Silicone epoxy resin> A-1: Silicone epoxy resin prepared in Synthesis Example 1 A-2: Silicone epoxy resin prepared in Synthesis Example 2 A-3: Silicone epoxy resin prepared in Synthesis Example 3 A-4: Silicone epoxy resin prepared in Synthesis Example 4 A-5: Silicone epoxy resin prepared in Synthesis Example 5 Oxygen resin A-6: Siloxane epoxy resin prepared in Synthesis Example 6 A-7: Siloxane epoxy resin prepared in Synthesis Example 7 A-8: Condensate of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and dimethyldimethoxysilane ("6730D" manufactured by Hengqiao Industrial Co., Ltd., epoxy equivalent 295 g/eq, Mw: 4,500) a-1: Siloxane epoxy resin prepared in Comparative Synthesis Example 1 (epoxy equivalent 169 g/eq, Mw: 28,000) a-2: Siloxane epoxy resin having epoxy epoxyhexyl groups ("X-40-2669" manufactured by Shin-Etsu Chemical, epoxy equivalent 191 g/eq, Mw: 383) a-3: Siloxane epoxy resin having epoxy epoxyhexyl groups ("KR-470" manufactured by Shin-Etsu Chemical, epoxy equivalent 200 g/eq, Mw: 737) a-4: Siloxane epoxy resin having methoxy, ethoxy and glycidyl groups ("X-41-1059A" manufactured by Shin-Etsu Chemical, epoxy equivalent 350 g/eq, Mw: 2,500) a-5: Siloxane epoxy resin having epoxy cyclohexyl groups but no hydroxyl, methoxy, ethoxy or phenoxy groups ("Poly 200" manufactured by Arakawa Chemical Industries)

The silicone epoxy resin component used in the formulation was subjected to ²⁹ Si-NMR measurement under the above conditions using a nuclear magnetic resonance device (JNM-ECA 400 manufactured by JEOL Ltd.). As a result, signals were observed at -47 ppm to -52 ppm, -55 ppm to -61 ppm, and -62 ppm to -72 ppm in components A-1 to A-8, a-1, and a-4, which are derived from the structures T1, T2, and T3. In components A-2, A-4, A-6, and A-7, signals were observed at -6 ppm to -13 ppm and -15 ppm to -24 ppm, which are derived from the structures D1 and D2. For A-8, the area ratio of each signal is T1:T2:T3=1:7:15, D1:D2=4:26.

<Hardener, photocatalytic ion initiator> B-1: trimellitic anhydride B-2: cyclopentanetetracarboxylic dianhydride B-3: aromatic zirconia salt-based Adeka Optomer "SP-170" (manufactured by ADEKA Co., Ltd.)

<Non-silicone type epoxy compounds not containing silicone structure> C-1: Bisphenol A type epoxy resin [YD-011 manufactured by Nippon Steel Chemical Materials Co., Ltd., epoxy equivalent 450 g/eq to 500 g/eq] C-2: Fluorene type epoxy resin [ESF-300C manufactured by Nippon Steel Chemical Materials Co., Ltd., epoxy equivalent 220 g/eq to 240 g/eq] C-3: 1,2-epoxy-4-(2-oxacyclopropyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 manufactured by Daicel Co., Ltd., epoxy equivalent: 170 g/eq to 190 g/eq) g/eq) C-4: Glycidyl methacrylate copolymer with a copolymer composition of 5:3:2 of glyceryl methacrylate: methyl methacrylate: n-butyl methacrylate, epoxy equivalent: 295 g/eq

＜Hardening accelerator＞ E-1: 1,8-diazabicyclo[5.4.0]undec-7-ene octanoate

<Coupling agent> F-1: 3-(Glycidyloxy)propyltrimethoxysilane

<Other ingredients> S-1: Fluorine-based surfactant (manufactured by DIC Corporation, Megafac F-556) <Solvent> U-1: Propylene glycol monomethyl ether acetate (PGMEA) U-2: 3-methoxy propanoic acid methyl (MMP) U-3: Diethylene glycol ethyl methyl ether (EDM)

[Table 1] Embodiment 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Silicone Epoxy Resin A-1 70 35 A-2 70 35 A-3 70 35 A-4 70 35 A-5 70 35 A-6 70 35 A-7 70 A-8 70 35 Hardener B-1 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 B-2 B-3 Non-Silicone Epoxy Compounds C-1 twenty one twenty one twenty one twenty one twenty one twenty one twenty one C-2 C-3 C-4 14 14 14 14 14 14 14 Hardening accelerator E-1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Coupling agent F-1 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Surfactants S-1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Solvent U-1 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 U-2 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 U-3 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Total amount of epoxy resin 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 Total solid content 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Total amount of liquid ingredients 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500

[Table 2] Embodiment 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 30 Silicone Epoxy Resin A-1 twenty three A-2 30 12.5 A-3 30 twenty three 12.5 A-4 A-5 30 twenty three A-6 30 twenty three 12.5 A-7 A-8 30 twenty three 12.5 12.5 Hardener B-1 19 19 19 19 19 19 19 19 19 19 19 19 19 B-2 19 19 B-3 Non-Silicone Epoxy Compounds C-1 24.5 24.5 24.5 24.5 24.5 C-2 28 28 28 28 28 C-3 28 28 28 28 28 12 12 12 12 12 C-4 12 12 12 12 12 19 19 19 19 19 twenty one twenty one twenty one twenty one twenty one Hardening accelerator E-1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Coupling agent F-1 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Surfactants S-1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Solvent U-1 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 U-2 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 U-3 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Total amount of epoxy resin 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 Total solid content 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Total amount of liquid ingredients 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500

[Table 3] Embodiment 31 32 33 34 35 36 37 38 39 40 41 42 Silicone Epoxy Resin A-1 7 3.5 5.5 5.5 5.5 5.5 5.5 A-2 A-3 A-4 7 7 9 A-5 7 7 A-6 7 3.5 7 A-7 A-8 3.5 7 Hardener B-1 19 19 19 19 19 19 19 19 19 19 19 B-2 19 B-3 Non-Silicone Epoxy Compounds C-1 twenty one twenty one twenty one twenty one 28 28 28 24.5 24.5 24.5 24.5 14 C-2 20 C-3 28 28 28 28 24.5 24.5 24.5 12 12 14 14 9.5 C-4 14 14 14 14 14 14 14 twenty one 19 19 19 14 Hardening accelerator E-1 1 1 1 1 1 1 1 1 1 1 1 1 Coupling agent F-1 8 8 8 8 8 8 8 8 8 8 8 8 Surfactants S-1 2 2 2 2 2 2 2 2 2 2 2 2 Solvent U-1 300 300 300 300 300 300 300 300 300 300 300 300 U-2 150 150 150 150 150 150 150 150 150 150 150 150 U-3 50 50 50 50 50 50 50 50 50 50 50 50 Total amount of epoxy resin 70 70 70 70 70 70 70 70 70 70 70 70 Total solid content 100 100 100 100 100 100 100 100 100 100 100 100 Total amount of liquid ingredients 500 500 500 500 500 500 500 500 500 500 500 500

[Table 4] Embodiment 43 44 45 46 47 48 Silicone Epoxy Resin A-1 12.5 95 A-2 A-3 95 A-4 12.5 A-5 A-6 95 A-7 A-8 95 Hardener B-1 20 20 B-2 B-3 1 1 1 1 Non-Silicone Epoxy Compounds C-1 14 14 C-2 C-3 28 28 C-4 15.5 15.5 Hardening accelerator E-1 Coupling agent F-1 8 8 3 3 3 3 Surfactants S-1 2 2 1 1 1 1 Solvent U-1 300 300 300 300 300 300 U-2 150 150 150 150 150 150 U-3 50 50 50 50 50 50 Total amount of epoxy resin 70 70 95 95 95 95 Total solid content 100 100 100 100 100 100 Total amount of liquid ingredients 500 500 500 500 500 500

[Table 5] Comparison Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Silicone Epoxy Resin a-1 70 35 12.5 a-2 70 35 12.5 a-3 70 35 12.5 a-4 70 35 12.5 a-5 70 Hardener B-1 19 19 19 19 19 19 19 19 19 19 19 20 20 19 B-2 19 B-3 Non-Silicone Epoxy Compounds C-1 twenty one twenty one twenty one twenty one 24.5 24.5 14 14 35 C-2 12 12 C-3 28 28 35 C-4 14 14 14 14 twenty one twenty one 15.5 15.5 35 35 Hardening accelerator E-1 1 1 1 1 1 1 1 1 1 1 1 1 1 Coupling agent F-1 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Surfactants S-1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Solvent U-1 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 U-2 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 U-3 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Total amount of epoxy resin 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 Total solid content 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Total amount of liquid ingredients 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500

(Evaluation of curable resin composition: flatness) As a color filter substrate, a substrate having a black matrix and red/green/blue pixels and a mosaic pattern without blue pixels and having 2.5 μm high concave and convex surfaces on the pixels was prepared. The curable resin composition was applied to the color filter substrate using a spin coater and dried on a 90°C hot plate for 2 minutes to prepare a test piece. At this time, the coating conditions (rotation speed) were adjusted so that a cured film with a film thickness of 1.5 μm was obtained on the pixels. Next, the test piece was calcined in a hot air oven at 230°C for 30 minutes to obtain a cured film of the curable resin composition.

The height of the unevenness at two points randomly selected on the surface of the cured film formed in a protective pixel manner was measured using a contact surface roughness meter (trade name: Fine Shape Tester ET-4000A, manufactured by Kosaka Laboratory Co., Ltd.), and a three-stage evaluation was performed based on the following criteria. ◎ (Good): The height difference of the unevenness is 0.10 μm or less ○ (Slightly Good): The height difference of the unevenness exceeds 0.10 μm and is 0.15 μm or less △ (Slightly Poor): The height difference of the unevenness exceeds 0.15 μm and is 0.20 μm or less × (Poor): The height difference of the unevenness exceeds 0.2 μm

(Evaluation of curable resin composition: hygroscopicity) The curable resin composition was applied to an alkali-free glass substrate using a spin coater and dried on a hot plate at 90°C for 2 minutes to prepare a test piece. At this time, the coating conditions (rotation speed) were adjusted so as to obtain a cured film with a film thickness of 1.5 μm. Next, the test piece was calcined in a hot air oven at 230°C for 30 minutes to obtain a cured film of the curable resin composition. Next, the substrate with the cured film was placed in a constant temperature and humidity device (Espec Environmental Tester SH-221) at 85°C and 85%RH for 24 hours to allow it to absorb moisture. 10 mg of the cured film of the test piece was cut and sampled, and the temperature was raised from room temperature to 150°C at 10°C/min in a nitrogen environment and kept at 150°C for 20 minutes. The weight loss at this time was set as the weight change caused by moisture absorption of the film, and the weight was measured using a thermogravimetric analyzer (trade name: Rigaku Co., Ltd. differential thermal balance Thermo plus EVO2) and evaluated in three stages based on the following criteria. ◎    : Weight loss less than 0.5% ○: Weight loss of 0.5% or more and less than 2% △    : Weight loss of 2% or more and less than 3% ×: Weight loss of 3% or more

(Evaluation of curable resin composition: gas generation) The curable resin composition was applied to an alkali-free glass substrate using a spin coater and dried on a 90°C hot plate for 2 minutes to prepare a test piece. At this time, the coating conditions (rotation speed) were adjusted so that a cured film with a film thickness of 1.5 μm was obtained. Next, the test piece was calcined in a hot air oven at 230°C for 30 minutes to obtain a cured film of the curable resin composition. 10 mg of the cured film of the test piece was cut and sampled, and the temperature was raised from room temperature to 120°C at 10°C/min under atmospheric airflow and kept at 120°C for 30 minutes. Then, the temperature was raised from 120°C to 230°C at 10°C/min and kept at 230°C for 3 hours. The weight loss at this time was measured using a thermogravimetric analyzer (trade name: Rigaku Co., Ltd. differential thermal balance Thermo plus EVO2) and evaluated in three stages based on the following criteria. ◎    : Weight loss less than 5% ○: Weight loss of 5% or more and less than 7% △    : Weight loss of 7% or more and less than 10% ×: Weight loss of 10% or more

(Evaluation of curable resin composition: chemical resistance) The test piece formed with a cured film of a curable resin composition in the same manner as the above-mentioned evaluation of moisture absorption was immersed in N-methylpyrrolidone for 30 minutes at 40°C (NMP (N-methyl pyrrolidone) treatment), immersed in an 18% hydrochloric acid aqueous solution at 25°C for 60 minutes (acid treatment), or immersed in a 5 wt% sodium hydroxide aqueous solution at 25°C for 60 minutes (NaOH treatment), and the state of each cured film was observed and evaluated in three stages based on the following criteria. ○: No change in appearance and the film thickness change is within 2% △    : No change in appearance, but the film thickness change exceeds 2% ×: Change in appearance is observed

(Evaluation of curable resin composition: electrical reliability) A test piece with a cured film formed of a curable resin composition was prepared in the same manner as the gas generation evaluation. 40 mg of the cured film of the test piece was cut and sampled, and the sample was immersed in 1 g of liquid crystal ("MLC-6608" manufactured by Merck) and kept at 100°C for 72 hours. The voltage retention rate of the liquid crystal was measured and evaluated in three stages based on the following criteria. ○: The voltage retention rate is 95% or more △: The voltage retention rate is 90% or more and less than 95% ×: The voltage retention rate is less than 90%

(Evaluation of curable resin composition: transparency) A test piece with a cured film formed of a curable resin composition was prepared in the same manner as the gas generation evaluation. The transmittance of the cured film at a wavelength of 400 nm was measured using a spectrophotometer, and a three-stage evaluation was performed based on the following criteria. ○: Transmittance is 95% or more △: Transmittance is 93% or more and less than 95% ×: Transmittance is less than 93%

(Evaluation of curable resin composition: light resistance) The curable resin composition was applied to an alkali-free glass substrate using a spin coater and dried on a hot plate at 90°C for 2 minutes to prepare a test piece. The above operation was repeated multiple times, and the coating conditions (rotation speed) were adjusted in such a way that a cured film with a film thickness of 10 μm was obtained. Next, the test piece was calcined in a hot air oven at 230°C for 30 minutes to prepare a test piece having a cured film formed with the curable resin composition. Thereafter, light irradiation was performed using a Metalling Weather Meter (M6T: manufactured by Suga Test Instruments Co., Ltd.) with an irradiation intensity of 0.5 kW/m ² and 1500 MJ/m ² . The color change of the cured product after irradiation was visually evaluated in four stages according to the following criteria. ◎: No yellowing was observed visually. ○: Slight yellowing was observed visually. △: Yellowing was observed visually. ×: Obvious yellowing was observed visually.

The evaluation results of each curable resin composition are shown in Tables 6 to 10.

It can be seen that the curable resin composition (cured film) of each of Examples 1 to 48 satisfies the flatness, low moisture absorption, and low gas generation required for the protective film of the color filter, and is also excellent in chemical resistance, electrical reliability, transparency, and light resistance. On the other hand, in the composition of Comparative Example 1, since the siloxane epoxy resin a-1 with a high weight average molecular weight is used, the flatness is particularly poor, and the gas generation during moisture absorption and chemical resistance (NMP) are also poor, which is considered to be caused by the easy survival of reactive groups. In the compositions of Comparative Examples 2 to 3, since silicone epoxy resin a-2 or silicone epoxy resin a-3 with a low weight average molecular weight is used, the gas generation is particularly high and the chemical resistance (NMP, NaOH) is poor. In the composition of Comparative Example 4, since silicone epoxy resin a-4 with a high epoxy equivalent is used, it is estimated that the content of reactive groups is reduced and the curing property and/or crosslinking density are insufficient, resulting in particularly poor chemical resistance (NMP, NaOH). In the composition of Comparative Example 5, a siloxane epoxy resin a-5 having an epoxy epoxies but not having a hydroxyl, methoxy, ethoxy or phenoxy group is used. The resin does not have the specified T1 structure to T3 structure, so the flatness, transparency, and light resistance are particularly poor, and the chemical resistance (NaOH) is also poor. In the compositions of Comparative Examples 6 to 13, the amount of the resins a-1 to a-5 used in the above-mentioned comparative examples is reduced, and corresponding non-siloxane epoxy compounds C-1 to C-4 are used respectively, but each evaluation item cannot be fully satisfied. Furthermore, in the compositions of Comparative Examples 14 and 15, silicone epoxy resin was not used, and although non-silicone epoxy compounds of C-1, C-2 or C-3 were used as components equivalent to resins, the results showed that gas generation and light resistance were particularly poor.

[Table 6] Embodiment 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Flatness ○ ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ○ ◎ ◎ ◎ ◎ Low outgassing (moisture absorption) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Low outgassing ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Chemical resistance (NMP) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Acid resistance (hydrochloric acid solution) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Alkali resistance (NaOH solution) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Electrical reliability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Transparency ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ ○ Lightfastness ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ ○

[Table 7] Embodiment 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 30 Flatness ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Low outgassing (moisture absorption) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Low outgassing ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Chemical resistance (NMP) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Acid resistance (hydrochloric acid solution) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Alkali resistance (NaOH solution) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Electrical reliability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Lightfastness ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○

[Table 8] Embodiment 31 32 33 34 35 36 37 38 39 40 41 42 Flatness ◎ ◎ ◎ ◎ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ Low outgassing (moisture absorption) ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ Low outgassing ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ Chemical resistance (NMP) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Acid resistance (hydrochloric acid solution) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Alkali resistance (NaOH solution) ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Electrical reliability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Lightfastness ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

[Table 9] Embodiment 43 44 45 46 47 48 Flatness ○ ○ ○ ○ ○ ○ Low outgassing (moisture absorption) ◎ ◎ ◎ ◎ ◎ ◎ Low outgassing ○ ○ ○ ○ ○ ○ Chemical resistance (NMP) ○ ○ ○ ○ ○ ○ Acid resistance (hydrochloric acid solution) ○ ○ ○ ○ ○ ○ Alkali resistance (NaOH solution) ○ ○ ○ ○ ○ ○ Electrical reliability ○ ○ ○ ○ ○ ○ Transparency ○ ○ ◎ ◎ ◎ ◎ Lightfastness ○ ○ ◎ ◎ ◎ ◎

[Table 10] Comparison Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Flatness × △ ○ ○ × × ◎ ◎ △ △ △ ◎ ◎ ◎ ○ Low outgassing (moisture absorption) × × × △ △ × △ △ × × △ △ △ ○ × Low outgassing ○ × × ○ ○ ○ △ × × ○ × × × △ × Chemical resistance (NMP) × × △ △ ○ ○ △ △ × △ △ △ △ △ ○ Acid resistance (hydrochloric acid solution) ○ ○ ○ ○ ○ ○ ○ ○ △ ○ ○ × × ○ ○ Alkali resistance (NaOH solution) △ × △ △ △ △ △ × × △ × × × ○ ○ Electrical reliability ○ ○ △ ○ ○ ○ △ △ ○ ○ ○ ○ ○ ○ ○ Transparency ○ ○ ○ ○ × ○ ○ ○ × ○ ○ ○ ○ ○ ○ Lightfastness ○ ○ ○ ○ × △ △ △ × △ △ ○ ○ △ △

without.

without.

without.

Claims (8)

A curable resin composition, characterized in that: it contains a siloxane resin satisfying the following (i) to (iii), and a curing agent and/or a photocation ion initiator, (i) having the following structure T1 showing a signal at ^-47ppm to -52ppm, the following structure T2 showing a signal at -55ppm to -61ppm, and the following structure T3 showing a signal at -62ppm to -72ppm in a 29 Si-nuclear magnetic resonance spectrum, and the area ratio of the signals is T1:T2:T3=0~1:1~10:1~100; (ii) having a weight average molecular weight of 750 to 20,000; (iii) having a molecular weight of less than 350 for each reactive group contained in the following (a);

[In structures T1 to T3, R is hydrogen, methyl, ethyl or phenyl, X is (a) or (b) below, which may be the same or different, and at least one X in each structure is (a); (a) any reactive group selected from glycidyl, 3,4-epoxycyclohexyl, vinyl, acryl and methacryl, or a group having the reactive group at the end of an organic group having 1 to 6 carbon atoms; (b) an organic group having 1 to 6 carbon atoms], the siloxane resin contains the following structure D1 showing a signal at -9ppm to -13ppm in a ^29Si -nuclear magnetic resonance spectrum and the following structure D2 showing a signal at -15ppm to -24ppm,

[In Structure D1 and Structure D2, R is hydrogen, methyl, ethyl or phenyl, and Y is (a) or (b) as described above, which may be the same or different in each structure]. The curable resin composition as described in claim 1 is characterized in that: the X contains a group having a 3,4-epoxycyclohexyl group at the end of an organic group having 1 to 6 carbon atoms. The curable resin composition as described in claim 1 or claim 2 is characterized in that the curing agent is one or more selected from the group consisting of polycarboxylic acids, polycarboxylic acid anhydrides, and polycarboxylic acid thermally decomposable esters. The curable resin composition as described in claim 1 or claim 2 is characterized in that the solid content of the silicone resin is greater than 3% by mass and less than 99% by mass relative to the total mass of the solid components. The curable resin composition as described in claim 1 or claim 2 is characterized in that it contains a non-silicone compound that does not contain a siloxane skeleton and has an epoxy group or a polymerizable unsaturated bond. The curable resin composition according to claim 5 is characterized in that the non-silicone type compound having no silicone skeleton and having an epoxy group or a polymerizable unsaturated bond is an epoxy compound represented by the following formula (4):

[In formula (4), Ar is a divalent aromatic alkyl group having 6 to 12 carbon atoms; in addition, a portion of the hydrogen atoms of the divalent aromatic alkyl group represented by Ar may be substituted by a alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group; the average value of 1 is 0 to 2]. A hardened product, characterized in that it is formed by hardening the hardening resin composition as described in any one of claim 1 to claim 6. A method for producing a siloxane resin is a method for producing a siloxane resin that satisfies the following (i) to (iii). The method for producing a siloxane resin is characterized in that: Si(X ₁ )(OR ₁ ) ₃ is hydrolyzed or hydrolytically condensed, or Si(X ₁ )(OR ₁ ) ₃ and Si(X ₂ ) ₂ (OR ₄ ) ₂ are hydrolyzed or hydrolytically condensed, [wherein, X ₁ is a group shown in the following (a), which may be the same or different, but at least contains a group having a 3,4-epoxycyclohexyl group at the end of an organic group having 1 to 6 carbon atoms; X ₂ is a group shown in the following (a) or (b), which may be the same or different, but at least contains a group shown in (b); R ₁ and R ₄ are independently an alkyl group having 1 to 3 carbon atoms or a phenyl group;] (i) having ^{a 29} In the Si-NMR spectrum, the following structure T1 shows a signal at -47ppm~-52ppm, the following structure T2 shows a signal at -55ppm~-61ppm, and the following structure T3 shows a signal at -62ppm~-72ppm, and the area ratio of the signals is T1:T2:T3=0~1:1~10:1~100; (ii) the weight average molecular weight is 750~20000; (iii) the molecular weight of each reactive group contained in the following (a) is less than 350;

[In structures T1 to T3, R is hydrogen, methyl, ethyl or phenyl, X is (a) or (b) below, which may be the same or different, and at least one X in each structure is (a); (a) any reactive group selected from glycidyl, 3,4-epoxycyclohexyl, vinyl, acryl and methacryl, or a group having the reactive group at the end of an organic group having 1 to 6 carbon atoms; (b) an organic group having 1 to 6 carbon atoms], the siloxane resin contains the following structure D1 showing a signal at -9ppm to -13ppm in a ^29Si -nuclear magnetic resonance spectrum and the following structure D2 showing a signal at -15ppm to -24ppm,

[In Structure D1 and Structure D2, R is hydrogen, methyl, ethyl or phenyl, and Y is (a) or (b) as described above, which may be the same or different in each structure].