Alkali-soluble silicone compound, photosensitive resin composition, cured resin film, semiconductor package, and display device

Abstract

To provide an alkali-soluble silicone compound and a photosensitive resin composition capable of forming a resin cured film having good light resistance in a high temperature environment and good durability in a high temperature and high humidity environment, and to provide a semiconductor package and a display device using the resin cured film.SOLUTION: The alkali-soluble silicone compound has a substituent represented by formula (3). Wherein R5 is independently H or methyl; R6 is independently C 4 - C 20 hydrocarbyl optionally containing a hetero atom; R7 is independently C 1 - C 20 hydrocarbyl optionally containing a hetero atom; and L is H or a carboxy group-containing substituent. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an alkali-soluble silicone compound, a photosensitive resin composition, a cured resin film, a semiconductor package, and a display device. [Background technology]

[0002] Silicone resins have excellent electrical properties, adhesiveness, heat resistance, low water absorption, and the like, and are used in many fields, including electronic materials. Semiconductor devices and image display devices may use protective films to seal and protect each element on a substrate, and silicone resins are sometimes used as such protective films. Silicone resins have superior weather resistance, light resistance, and heat resistance compared to acrylic resins, and are particularly useful as light-emitting diode (LED) encapsulants because they are less susceptible to deterioration and discoloration over time, even when exposed to light and heat emitted from blue light-emitting diodes (blue LEDs) for long periods of time.

[0003] Patent Document 1 discloses an organopolysiloxane containing an isocyanuric acid derivative group, which is a reaction product of an isocyanuric acid derivative having an aliphatic unsaturated group and an organopolysiloxane. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-099751 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, light-emitting elements using LED elements have come to be used in a variety of applications, and it is expected that LED elements will be used for long periods of time in harsh environments such as high-temperature environments. The cured resin film for the LED encapsulant used in such LED elements may be required to have light resistance in high-temperature environments and durability in high-temperature and high-humidity environments.

[0006] However, according to the investigations of the present inventors, the organopolysiloxane described in Patent Document 1 does not satisfy both the light resistance in a high-temperature environment and the durability in a high-temperature, high-humidity environment.

[0007] The present invention has been made in view of the above points, and has an object to provide an alkali-soluble silicone compound and a photosensitive resin composition capable of forming a cured resin film that has good light resistance in high-temperature environments and durability in high-temperature, high-humidity environments, as well as a semiconductor package and a display device that use the cured resin film. [Means for solving the problem]

[0008] One aspect of the present invention for solving the above problems relates to an alkali-soluble silicone compound described in the following [1] to [2].

[0009] [1] An alkali-soluble silicone compound represented by the following general formula (1) or (2):

[0010] [ka]

[0011] wherein R1 independently represents a hydrocarbon group having 1 to 10 carbon atoms. R2 independently represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. X independently represents a divalent substituent which may contain a heteroatom therein. Y independently represents a hydrogen atom or a substituent represented by the following general formula (3). Z independently represents a hydrogen atom or a substituent represented by the following general formula (3). General formula (1) contains at least one substituent represented by the following general formula (3). m and n each independently represent a number from 0 to 50, and p is a number from 0 to 200.

[0012] [ka]

[0013] wherein R3 independently represents a hydrocarbon group having 1 to 10 carbon atoms; R4 independently represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom; G independently represents a hydrogen atom or a substituent represented by general formula (3), and general formula (2) contains at least one substituent represented by the following general formula (3); and q represents a number from 3 to 6.

[0014] [ka]

[0015] wherein R5 independently represents a hydrogen atom or a methyl group. R6 independently represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a heteroatom. R7 independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. L represents a hydrogen atom or a substituent represented by the following general formula (4). General formula (3) contains at least one substituent represented by the following general formula (4). * represents a bonding site to R2 or a silicon atom.

[0016] [ka]

[0017] Here, M represents a di- or trivalent carboxylic acid residue, and r is 1 or 2. * represents the bonding site to the oxygen atom.

[0018] [2] X in the general formula (1) is a divalent substituent represented by general formula (5): [1] The alkali-soluble silicone compound according to [1].

[0019] [ka]

[0020] wherein R5 independently represents a hydrogen atom or a methyl group; R6 independently represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a heteroatom; R7 independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom; L represents a hydrogen atom or a substituent represented by general formula (4); * represents a bonding site to R2 or the silicon atom.

[0021] One aspect of the present invention for solving the above problems relates to a photosensitive resin composition described in the following [3] to [4].

[0022] [3] (A) the alkali-soluble silicone compound according to [1] or [2]; (B) an unsaturated group-containing polymerizable compound; (C) an epoxy compound; (D) a photopolymerization initiator; A photosensitive resin composition comprising:

[0023] [4] The epoxy equivalent of the component (C) is 80 g / eq to 500 g / eq, Neither the component (B) nor the component (C) contains an aromatic ring structure. The photosensitive resin composition according to [3].

[0024] One aspect of the present invention for solving the above problems relates to a cured resin film described in [5] below.

[0025] [5] A cured resin film formed from the photosensitive resin composition according to [3] or [4].

[0026] One aspect of the present invention for solving the above problem relates to a semiconductor package described in [6] below.

[0027] [6] A semiconductor package having the cured resin film according to [5].

[0028] One aspect of the present invention for solving the above problems relates to a display device described in [7] below.

[0029] [7] A display device having the cured resin film according to [5]. [Effects of the Invention]

[0030] According to the present invention, there are provided an alkali-soluble silicone compound and a photosensitive resin composition capable of forming a cured resin film that has good light resistance in high-temperature environments and durability in high-temperature, high-humidity environments, as well as a semiconductor package and a display device that use the cured resin film. DETAILED DESCRIPTION OF THE INVENTION

[0031] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[0032] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0033] 1. Alkali-soluble silicone compounds The alkali-soluble silicone compound according to this embodiment is a linear or cyclic silicone compound containing at least one substituent represented by general formula (3), and has an isocyanuric ring skeleton, a carboxy group, and a polymerizable unsaturated group in one molecule.

[0034] [ka]

[0035] In general formula (3), R5 independently represents a hydrogen atom or a methyl group. R6 independently represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a heteroatom. R7 independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. L independently represents a hydrogen atom or a substituent represented by the following general formula (4). General formula (3) contains at least one substituent represented by the following general formula (4). * represents a bonding site.

[0036] In the present application, a hydrocarbon group that may contain a heteroatom refers to a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom or a functional group containing a heteroatom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced with a heteroatom or a functional group containing a heteroatom. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms. Examples of functional groups containing heteroatoms include hydroxy groups, carboxy groups, carbonyl groups, ester groups, cyano groups, amino groups, imino groups, nitro groups, amide groups, thiol groups, urethane groups, and sulfo groups. Among these, oxygen atoms and ester groups are preferred as heteroatoms or functional groups containing heteroatoms that can replace carbon atoms or hydrogen atoms in the hydrocarbon group.

[0037] [ka]

[0038] In general formula (4), M represents a di- or trivalent carboxylic acid residue, and r is 1 or 2. * represents the bonding site to the oxygen atom.

[0039] Silicone compounds have silicon-oxygen bonds in the main chain of the compound. It is generally known that silicon-oxygen bonds have higher bond energy than carbon-carbon bonds, and the inclusion of silicone compounds with such silicon-oxygen bonds increases heat resistance.

[0040] Among these silicone compounds, those containing a monovalent substituent represented by general formula (3) in particular are capable of forming a cured resin film that has good light resistance in a high-temperature environment (hereinafter also simply referred to as "light resistance") and durability in a high-temperature, high-humidity environment (hereinafter also simply referred to as "durability"). The reason for this is not entirely clear, but is thought to be as follows.

[0041] In the alkali-soluble silicone compound according to this embodiment, the polymerizable unsaturated group is bonded to the siloxane main chain via an isocyanuric ring and a relatively long-chain (4 or more carbon atoms) hydrocarbon group as R6. The isocyanuric rings can form interactions such as hydrogen bonds between themselves, making it relatively easy for the alkali-soluble silicone compounds to come into close proximity with each other. Furthermore, the long-chain hydrocarbon group broadens the range of movement of the polymerizable unsaturated group, making it even easier for the polymerizable unsaturated groups to come into close proximity with each other. This significantly increases the sensitivity when the unsaturated group is polymerized by exposure to light, forming a three-dimensional crosslinked structure. When a cured resin film is formed, its mobility is suppressed in high-temperature and high-temperature / high-humidity environments. This suppresses resin degradation and discoloration over time, and improves light resistance in high-temperature environments and durability in high-temperature / high-humidity environments. Furthermore, by using a hydrocarbon group with a relatively long chain (four or more carbon atoms) as R6, the solubility of the alkali-soluble silicone compound in the alkaline developer is appropriately reduced, resulting in a solubility (dissolution rate) similar to that of the other monomer components in the resist. This allows for uniform dissolution in the alkaline solution, which is thought to result in good alkaline developability (development time and line shape).

[0042] Furthermore, by using a hydrocarbon group having 20 or fewer carbon atoms as R6, a dense crosslinked structure is formed, and the hydrophobicity is adjusted so as not to become too high. This makes it difficult to inhibit polar interactions due to hydrogen bonding between isocyanuric rings, etc., and this makes it easier for polymerizable unsaturated groups to come into close proximity with each other, thereby suppressing mobility in high temperature or high temperature / high humidity environments when the resin is cured.

[0043] R6 independently represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a heteroatom. Examples of R6 include alkylene groups such as butylene, hexylene, decylene, and dodecylene, and divalent substituents represented by the following general formula (6). Among these, R6 is preferably a divalent substituent represented by the following general formula (6). By linking R8 and N with an ester bond, raw materials are easily available, synthesis is facilitated, and further, since the bond is more rigid than a hydrocarbon chain, durability in a high-temperature, high-humidity environment is likely to be improved when three-dimensionally crosslinked. On the other hand, an alkylene group is preferred from the viewpoint of easily suppressing hydrolysis and easily improving durability in a high-humidity environment.

[0044] [ka]

[0045] In general formula (6), R8 represents a hydrocarbon group having 1 to 17 carbon atoms which may contain a heteroatom. N represents a divalent carboxylic acid residue. * represents a bonding site to an oxygen atom. ** represents a bonding site to a carbon atom.

[0046] Examples of R8 include alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, decylene, and dodecylene, as well as alkylene groups having an ether bond such as ethoxyethylene, propoxyethylene, propoxypropylene, and ethoxypropylene. From the viewpoint of ease of synthesis, an ethylene group or an ethoxyethylene group is preferred, and an ethylene group is more preferred.

[0047] Examples of dicarboxylic acids or dicarboxylic anhydrides used to form N include: aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; and alicyclic dicarboxylic acids in which a carboxy group is directly bonded to an alicyclic structure, such as 1,2-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 5-norbornene-2,3-dicarboxylic acid; and acid anhydrides thereof.

[0048] The dicarboxylic acid or dicarboxylic acid anhydride used to form N is preferably an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid or an acid anhydride thereof. By using such a compound, since it does not have an aromatic ring, the absorption of the alkali-soluble silicone compound is shifted to shorter wavelengths, and light resistance is likely to be improved.

[0049] Furthermore, the divalent carboxylic acid or divalent carboxylic acid anhydride used to form N is preferably an alicyclic dicarboxylic acid in which a carboxy group is directly bonded to an alicyclic structure, or an acid anhydride thereof, and even more preferably an alicyclic dicarboxylic acid in which carboxy groups are bonded to two adjacent carbon atoms forming the alicyclic structure, selected from the group consisting of 1,2-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 5-norbornene-2,3-dicarboxylic acid, or an acid anhydride thereof. Generally, under high temperature and high humidity, the carbonyl carbon of an ester bond may be attacked by water, hydroxide ions, or the like, resulting in hydrolysis, which contributes to deterioration of durability. The use of an alicyclic dicarboxylic acid in which a carboxy group is directly bonded to an alicyclic structure enhances hydrophobicity, making it easier to suppress water absorption, which causes hydrolysis, and also increases steric hindrance around the carbonyl carbon, making it easier to suppress hydrolysis by water, hydroxide ions, or the like. As a result, durability under high temperature and high humidity is likely to be improved. Furthermore, in the case of an alicyclic dicarboxylic acid in which carboxy groups are linked to two adjacent carbon atoms forming an alicyclic structure, the area around the carbonyl carbon is congested, which further inhibits hydrolysis by water, hydroxide ions, etc. As a result, durability under high temperature and high humidity conditions is further improved. Furthermore, in the case of 1,2-cyclohexanedicarboxylic acid or its anhydride, the same steric hindrance effect is further enhanced, which further improves durability under high temperature and high humidity conditions.

[0050] R5 independently represents a hydrogen atom or a methyl group. R5 is preferably a hydrogen atom. When R5 is a hydrogen atom, the reactivity of active species such as radicals generated in the polymerizable unsaturated group adjacent to R5 tends to increase, making it easier to form strong three-dimensional crosslinks when formed into a cured resin film. As a result, light resistance and durability tend to be improved.

[0051] R7 independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Examples of R7 include alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, decylene, and dodecylene, as well as alkylene groups having an ether bond such as ethoxyethylene, propoxyethylene, propoxypropylene, and ethoxypropylene. From the viewpoint of ease of synthesis, a methylene group is more preferable.

[0052] In general formula (3), L is a hydrogen atom or a substituent represented by general formula (4). The introduction rate of the substituent represented by general formula (4) is preferably 25 mol % to 100 mol %, and more preferably 50 mol % to 100 mol %, relative to the total moles of L (100 mol %). By setting the introduction rate of the substituent represented by general formula (3) to 25 mol % or more, alkali solubility is likely to be enhanced, resulting in excellent patterning properties. Furthermore, strong crosslinks are formed by reaction with an epoxy compound, which tends to enhance durability at high temperatures and high temperature and high humidity.

[0053] In general formula (4), M represents a dicarboxylic or tricarboxylic acid residue, and r is 1 or 2. Examples of dicarboxylic and tricarboxylic acids and their acid monoanhydrides that can be used to form M include aliphatic dicarboxylic acids, aliphatic tricarboxylic acids, alicyclic dicarboxylic acids, alicyclic tricarboxylic acids, aromatic dicarboxylic acids, aromatic tricarboxylic acids, and their acid monoanhydrides.

[0054] Examples of the aliphatic dicarboxylic acids and aliphatic tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, as well as dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0055] Examples of the alicyclic dicarboxylic acid and alicyclic tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, cyclohex-4-ene-1,2-dicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, 3-methylcyclohexane-1,2-dicarboxylic acid, methyl endomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, and norbornanedicarboxylic acid, as well as dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0056] Examples of the aromatic dicarboxylic acid and aromatic tricarboxylic acid include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid, as well as dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

[0057] The compound used to form M is preferably an aliphatic dicarboxylic acid, an aliphatic tricarboxylic acid, an alicyclic dicarboxylic acid, an alicyclic tricarboxylic acid, or an acid anhydride thereof. By using such a compound, the absorption of the alkali-soluble silicone compound is shifted to shorter wavelengths because it does not have an aromatic ring, and light resistance is likely to be improved.

[0058] Furthermore, the compound used to form M is preferably an alicyclic dicarboxylic acid or alicyclic tricarboxylic acid or an acid anhydride thereof, more preferably cyclohex-4-ene-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, or 4-methylcyclohexane-1,2-dicarboxylic acid or an acid anhydride thereof, and most preferably 4-methylcyclohexane-1,2-dicarboxylic acid or an acid anhydride thereof. Cyclohex-4-ene-1,2-dicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, or an acid anhydride thereof is an alicyclic dicarboxylic acid in which carboxy groups are bonded to two adjacent carbon atoms forming an alicyclic structure, resulting in significant steric hindrance around the carbonyl carbon. This effectively inhibits hydrolysis by water, hydroxide ions, and the like. As a result, durability under high temperature and high humidity conditions is likely to be improved. Furthermore, 4-methylcyclohexane-1,2-dicarboxylic acid or an acid anhydride thereof lacks a double bond, resulting in shorter wavelength absorption and improved lightfastness at higher temperatures. Furthermore, since the alicyclic structure has a hydrocarbon group directly bonded thereto, the hydrophobicity is further increased, and durability under high temperature and high humidity conditions is likely to be improved.

[0059] From the viewpoint of ease of synthesis, the compound used to form M is preferably an acid anhydride of the above dicarboxylic acid or tricarboxylic acid.

[0060] The weight-average molecular weight (Mw) of the alkali-soluble silicone compound according to this embodiment is preferably 500 to 10,000, and more preferably 1,000 to 8,000. When the Mw is 500 or more, the volatility of the compound when hydrolyzed during storage as a cured resin film under high temperature and humidity conditions can be reduced, thereby reducing the film loss rate. When the Mw is 10,000 or less, compatibility in the cured resin film can be improved, making it easier to reduce haze. The weight-average molecular weight of the alkali-soluble silicone compound is measured using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and is calculated as a value converted into a standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0061] The acid value of the alkali-soluble silicone compound according to this embodiment is preferably 20 mgKOH / g to 300 mgKOH / g, more preferably 40 mgKOH / g to 250 mgKOH / g, and even more preferably 60 mgKOH / g to 200 mgKOH / g. By setting the acid value to 20 mgKOH / g or more, when used for pattern formation, the development rate during alkaline development can be shortened and residues can be reduced. By setting the acid value to 300 mgKOH / g or less, when used for pattern formation, penetration of the alkaline developer can be appropriately adjusted, and peeling development due to rapid penetration of the alkaline developer can be suppressed. The acid value can be determined by titration with a 1 / 10 N aqueous KOH solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0062] The linear or cyclic silicone compound used in the alkali-soluble silicone compound according to this embodiment is preferably an alkali-soluble silicone compound represented by the following general formula (1) (hereinafter also referred to as the "first embodiment") or an alkali-soluble silicone compound represented by the following general formula (2) (hereinafter also referred to as the "second embodiment") The first embodiment and the second embodiment will each be described in detail below.

[0063] From the viewpoint of easily improving durability under high temperature and high humidity, the alkali-soluble silicone compound of the second embodiment is preferred. Generally, in silicones, the bond length and bond angle of the silicon-oxygen bond in the main chain are larger than those of the carbon-carbon bond, making the main chain more likely to rotate. By using a cyclic silicone compound as in the second embodiment, the main chain skeleton is constrained and less likely to rotate freely, and when a cured resin film is formed, the mobility of the three-dimensional crosslinked structure is more likely to be suppressed. This makes it easier to suppress water absorption, and even if water is absorbed, the water and the like cannot move freely, so attack on the carbonyl carbon is suppressed. As a result, hydrolysis is more likely to be suppressed, making it easier to improve durability under high temperature and high humidity.

[0064] On the other hand, from the viewpoint of easily improving light resistance at high temperatures, the alkali-soluble silicone compound of the first embodiment is preferred. In the first embodiment, the compound has a linear silicone main chain, which results in a linear structure with little strain, and the bond energy is easily increased, which makes it easy to improve light resistance at high temperatures.

[0065] 1-1. First embodiment of alkali-soluble silicone compound A first aspect of the alkali-soluble silicone compound according to this embodiment is an alkali-soluble silicone compound having an isocyanuric ring skeleton, a carboxy group, and a polymerizable unsaturated group in one molecule, represented by the following general formula (1):

[0066] [ka]

[0067] In general formula (1), R1 independently represents a hydrocarbon group having 1 to 10 carbon atoms. R2 independently represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. X independently represents a divalent substituent which may contain a heteroatom therein. Y independently represents a hydrogen atom or a substituent represented by general formula (3). Z independently represents a hydrogen atom or a substituent represented by general formula (3) above. General formula (1) contains at least one substituent represented by general formula (3) above. m and n each independently represent a number from 0 to 50, and p is a number from 0 to 200.

[0068] R1 independently represents a hydrocarbon group having 1 to 10 carbon atoms. Examples of such hydrocarbon groups include linear hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, isooctyl, and decyl groups, aliphatic cyclic hydrocarbon groups such as cyclohexyl, and aromatic hydrocarbon groups such as phenyl, but are not limited thereto, and may be the same or different. Methyl groups are preferred.

[0069] R2 independently represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Examples of such hydrocarbon groups include, but are not limited to, methylene, ethylene, propylene, butylene, hexylene, decylene, dodecylene, and divalent substituents represented by the following general formula (7), and may be the same or different. A propylene group is preferred.

[0070] [ka]

[0071] In general formula (7), R9 is a hydrocarbon group having 1 to 17 carbon atoms or a single bond, * indicates the bonding site to the silicon atom, and ** indicates the bonding site to Z.

[0072] In general formula (1), X represents a divalent substituent that may contain a heteroatom. Examples of such substituents include aliphatic hydrocarbon groups such as ethylene, propylene, butylene, hexylene, decylene, and dodecylene; divalent substituents represented by the following general formula (5); and divalent substituents represented by the following general formula (8). X is preferably an ethylene group, a divalent substituent represented by the following general formula (5), or a divalent substituent represented by the following general formula (8), and more preferably a divalent substituent represented by the following general formula (5). By using a divalent substituent represented by the following general formula (5), a polymerizable unsaturated group and a carboxyl group can be introduced into the side chain, facilitating crosslinking. This improves heat resistance while maintaining patternability and compatibility with other components.

[0073] The term "substituent that may contain a heteroatom" refers to a functional group that may contain a heteroatom or a functional group that contains a heteroatom. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms. Examples of functional groups that contain heteroatoms include hydroxy groups, carboxy groups, carbonyl groups, ester groups, cyano groups, amino groups, imino groups, nitro groups, amide groups, thiol groups, urethane groups, and sulfo groups. Among these, preferred heteroatoms and functional groups that may be contained in the substituent that may contain a heteroatom are oxygen atoms, nitrogen atoms, ester groups, carboxy groups, carbonyl groups, and the like.

[0074] [ka]

[0075] In general formula (5), R5 independently represents a hydrogen atom or a methyl group. R6 independently represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a heteroatom. R7 independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. L represents a hydrogen atom or a substituent represented by general formula (4). * represents a bonding site to R2 or the silicon atom.

[0076] [ka]

[0077] In the general formula (8), * indicates a bonding site.

[0078] In the above general formula (5), R5, R6, and R7 have the same meanings as R5, R6, and R7 in general formula (3), and the preferred ranges are also the same. In addition, the substituent represented by general formula (4) in general formula (5) has the same meaning as the substituent represented by general formula (4) in general formula (3), and the preferred ranges are also the same.

[0079] Furthermore, general formula (1) contains at least one substituent represented by general formula (3), and at least one of Y may be a substituent represented by general formula (3), or at least one of Z may be a substituent represented by general formula (3). Of these, it is preferable that at least one of Z is a substituent represented by general formula (3).

[0080] In general formula (1), Y is a hydrogen atom or a substituent represented by general formula (3). The introduction rate of the substituent represented by general formula (3), relative to the total number of moles of Y (100 mol%), is preferably 50 mol% to 100 mol%, more preferably 75 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%, even more preferably 95 mol% to 100 mol%, and even more preferably 99 mol% to 100 mol%, and most preferably Y consists solely of the substituent represented by general formula (3). The higher the introduction rate of the substituent represented by general formula (3), the higher the introduction rate of the carboxy group, isocyanuric ring, and polymerizable unsaturated group, which tends to improve alkali solubility, improve patterning properties, and also tends to increase the degree of crosslinking, thereby improving light resistance and durability.

[0081] In general formula (1), Z is a hydrogen atom or a substituent represented by general formula (3). The introduction rate of the substituent represented by general formula (3) is preferably 50 mol% to 100 mol%, more preferably 75 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%, even more preferably 95 mol% to 100 mol%, and even more preferably 99 mol% to 100 mol%, relative to the total number of moles of Z (100 mol%). Z most preferably consists solely of the substituent represented by general formula (3). The higher the introduction rate of the substituent represented by general formula (3), the higher the introduction rate of the carboxy group, isocyanuric ring, and polymerizable unsaturated group. This increases the alkali solubility, improves patterning properties, and also increases the degree of crosslinking, thereby improving light resistance and durability.

[0082] m is a number from 0 to 50, and preferably a number from 0 to 30. When m is a number of 30 or less, the proportion of terminal groups in the alkali-soluble silicone compound is relatively increased, which tends to improve durability at high temperatures and high humidity.

[0083] n is a number from 0 to 50, and preferably a number from 1 to 20. When n is a number of 1 or more, the introduction rate of carboxy groups, isocyanuric rings, and polymerizable unsaturated groups increases, which tends to increase alkali solubility, improve patterning properties, and also tends to increase the degree of crosslinking, thereby improving light resistance and durability. When n is a number of 20 or less, the proportion of silicon-oxygen bond sites in the alkali-soluble silicone compound relatively increases, which is favorable in terms of light resistance.

[0084] p is a number from 0 to 200, preferably a number from 1 to 150. When the compound represented by general formula (1) is a mixture of different p's, it is preferable that all p's are numbers between 0 and 150, and it is more preferable that p is 1 or greater. When p is 1 or greater, the introduction rates of carboxy groups, isocyanuric rings, and polymerizable unsaturated groups increase, which tends to increase alkali solubility, improve patterning properties, and increase light resistance (blue LED resistance). When p is 150 or less, compatibility with other components is favorable.

[0085] In general formula (1), m and n are values ​​measured by mass spectrometry such as gas chromatography-mass spectrometry (GC / MS). Furthermore, p in general formula (1) is a value calculated based on the molecular weight distribution measured by gel permeation chromatography (GPC). Measurement of molecular weight distribution by GPC is performed under the following conditions. Measurement is performed using an "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, speed: 0.6 ml / min), and the molecular weight distribution is determined as a value converted into a standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit). p is calculated based on the m and n determined by mass spectrometry.

[0086] 1-1-1. Method for producing alkali-soluble silicone compounds represented by general formula (1) The method for producing the alkali-soluble silicone compound represented by general formula (1) will now be described in detail.

[0087] The alkali-soluble silicone compound represented by the general formula (1) is a) A step of obtaining an epoxy silicone compound by hydrosilylation of a silicone compound having a Si-H group in part with a compound containing a polymerizable unsaturated group, an epoxy group, and an isocyanuric ring, and other polymerizable unsaturated group-containing compounds having 1 to 20 carbon atoms and optionally containing heteroatoms. b) A step of reacting the epoxysilicone compound obtained in the above step with a carboxylic acid compound in which a (meth)acryloyl group and a carboxyl group are linked by a hydrocarbon chain having 4 to 20 carbon atoms and which may contain a heteroatom, to obtain a hydroxysilicone compound containing a polymerizable unsaturated group. c) a step of reacting the hydroxysilicone compound obtained in the above step with a divalent or trivalent carboxylic acid or an anhydride thereof to obtain an alkali-soluble silicone compound; It can be synthesized by

[0088] Such alkali-soluble silicone compounds have a polymerizable unsaturated group and a carboxy group, and therefore when made into an alkali-developable photosensitive resin composition, they impart excellent photocurability, developability, and patterning properties.

[0089] 1-1-1-1. a) Step for obtaining an epoxysilicone compound The epoxy compound represented by the general formula (1) is, for example, a)-1: A hydrosilylation reaction between a compound represented by the following general formula (9) and an epoxy compound (Ea) containing one double bond, an epoxy group, and an isocyanuric ring in one molecule: A)-2: A hydrosilylation reaction of a compound represented by the following general formula (9), the above epoxy compound (Ea), and a compound (Eb) containing two double bonds in one molecule: The silicone compound can be synthesized through at least one of the steps (a)-1 and (b)-2. In this case, an alkali-soluble silicone compound in which p=0 is finally obtained from the above step (a)-1. An alkali-soluble silicone compound in which p≧1 is finally obtained from step (a)-2.

[0090] [ka]

[0091] In addition to at least one of the steps A)-1 and A)-2, A)-3: A hydrosilylation reaction may be carried out between a compound represented by the general formula (9) above and a polymerizable unsaturated group-containing compound (Ec) having 1 to 20 carbon atoms and optionally containing a heteroatom (provided that the compound (Ec) is a compound not included in the epoxy compounds (Ea) and (Eb)). This reaction may be carried out simultaneously with the reactions A)-1 and A)-2, or may be carried out as a separate step. When carried out as a separate step, the raw material used in the reactions A)-1, A)-2, and A)-3 is not the compound represented by the general formula (9) above, but may be a compound represented by the general formula (9) above in which an arbitrary substituent having 1 to 20 carbon atoms and optionally containing a heteroatom has been introduced into a part of the Si—H group.

[0092] R1, n, and m in general formula (9) have the same meanings as R1, n, and m in general formula (1), and the preferred ranges are also the same. Note that n and m indicate the number of repeating units introduced into general formula (9), and do not necessarily indicate that they are introduced in a block manner, but may be introduced randomly. Furthermore, n and m in general formula (9) are values ​​measured by a mass spectrometry method such as gas chromatography mass spectrometry (GC / MS). Since n and m do not usually change in the hydrosilylation reaction described below, the number of repeating units (n, m) of an epoxy compound of general formula (1) obtained from a compound represented by general formula (9) having a certain number of repeating units (n, m) usually has the same value as n and m in general formula (9).

[0093] The epoxy compound (Ea) provides Z and / or R2, and examples of the epoxy compound (Ea) include, but are not limited to, epoxy compounds such as N-allyl-N',N''-diglycidyl isocyanurate and N-allyl-N',N''-diepoxycyclohexyl isocyanurate. From the viewpoint of easy availability, the epoxy compound (Ea) is preferably N-allyl-N',N''-diglycidyl isocyanurate.

[0094] The compound (Eb) containing two double bonds in one molecule is not particularly limited as long as it can undergo an addition reaction with an Si-H group to give the above X and / or R2, and various compounds can be used. Examples of the compound (Eb) include N-N'-diallyl-N"-monoglycidyl isocyanurate and N-N'-diallyl-N"-monoepoxycyclohexyl isocyanurate. From the viewpoint of easy availability, N-N'-diallyl-N"-monoglycidyl isocyanurate is a preferred example of the compound (Eb).

[0095] The compound (Ec) is not particularly limited. From the viewpoint of easily improving light resistance by adjusting the amount of polymerizable unsaturated bonds introduced into the compound represented by general formula (1) while maintaining durability, the compound (Ec) is preferably a hydrocarbon having 6 to 20 carbon atoms which may contain a heteroatom, more preferably a branched aliphatic hydrocarbon having 6 to 20 carbon atoms which may contain a heteroatom or an alicyclic hydrocarbon having 6 to 20 carbon atoms which may contain a heteroatom, and examples of such functional groups include 5,5-trimethyl-1-hexene and vinylcyclohexane.

[0096] The boiling point of the compound (Ec) is preferably 115°C or higher. By setting the temperature at this level, volatilization during each reaction when obtaining the epoxy compound represented by general formula (1) is suppressed, and it is possible to easily achieve the desired introduction rate of functional groups derived from the compound (Ec). The upper limit of the boiling point of the compound (Ec) can be set to, for example, 300°C or lower.

[0097] The catalyst used in the above-mentioned addition reaction (hydrosilyl addition reaction) can be any of various known noble metal catalysts or complex compounds thereof. Examples of noble metal catalysts include, but are not limited to, platinum, rhodium, palladium, ruthenium, and iridium, and two or more types may be used as needed. Furthermore, these metals may be immobilized on a fine particle support material, such as carbon, activated carbon, aluminum oxide, or silica.

[0098] Complex compounds of precious metals include platinum halide compounds (PtCl4, H2PtCl6·6H2O, Na2PtCl6·4H2O, etc.), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-carbonyl complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, bis(γ-picoline)-platinum dichloride, trimethylenedipyridine-platinum dichloride, etc. Examples of the platinum complex include platinum chloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, bis(alkynyl)bis(triphenylphosphine)platinum complex, bis(alkynyl)(cyclooctadiene)platinum complex, rhodium chloride, tris(triphenylphosphine)rhodium chloride, and tetrakisammonium-rhodium chloride complex, but are not particularly limited thereto, and two or more of them may be used as necessary.

[0099] The noble metal catalyst may be used alone or may be dissolved in a suitable solvent beforehand and then added to the reaction system. The proportion of the noble metal catalyst used is not particularly limited, but is usually 1.0 × 10 based on the total mass of the epoxy compound (Ea) and the compound (Eb) used in the reaction. -5 Mass%~1.0×10 2 It is preferably 1.0×10 -4 It is more preferable that the content is 1.0 mass % to 1.0 mass %.

[0100] The hydrosilyl addition reaction can be carried out without a solvent, but the reaction system may be diluted with an organic solvent as needed. The organic solvent is not particularly limited as long as it does not adversely affect the reaction. Examples of the organic solvent include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; aromatics such as benzene, toluene, ortho-xylene, meta-xylene, para-xylene, chlorobenzene, and dichlorobenzene; and ethers such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether. Two or more of these organic solvents may be selected and used as a mixed solvent.

[0101] The temperature conditions for the hydrosilyl addition reaction are not particularly limited, but are usually 0°C to 200°C, preferably 30°C to 180°C. By setting the temperature at 0°C or higher, the reaction time can be shortened. By carrying out the reaction at 200°C or lower, the addition reaction between the epoxy group and the hydrosilyl moiety can be easily suppressed, making it easier to control the amount of remaining epoxy groups.

[0102] When an alkali-soluble silicone compound having p≧1 is synthesized using epoxy compound (Ea) and compound (Eb) as reaction raw materials, the molar amount of double bonds in compound (Eb) is preferably less than 100 mol%, more preferably 80 mol% or less, relative to the molar amount of Si—H groups in the silicone compound of general formula (9). This configuration facilitates the residual Si—H groups at the terminals, facilitating the introduction of epoxy compound (Ea). For example, the reaction may be carried out by simultaneously adding three compounds: the silicone compound of general formula (9), compound (Eb), and epoxy compound (Ea). Alternatively, a two-step reaction may be carried out in which the silicone compound of general formula (9) and compound (Eb) are reacted in advance, followed by the addition of epoxy compound (Ea) to cap the remaining Si—H groups. When multiple Xs are introduced into general formula (1), i.e., when p≧2, the latter two-step reaction is preferred from the standpoint of reaction control.

[0103] Similarly, when epoxy compound (Ea), compound (Eb), and compound (Ec) are used together as reaction raw materials to synthesize an alkali-soluble silicone compound where p≧1, the preferred range of the molar amount of double bonds in compound (Eb) is the same as above. In this case, the reaction method may be, for example, to simultaneously add four types of compounds, i.e., the silicone compound of general formula (9), compound (Eb), epoxy compound (Ea), and compound (Ec), and then carry out the reaction. Alternatively, a two-step reaction may be carried out in which the silicone compound of general formula (9) and compound (Eb) are reacted in advance, and then epoxy compound (Ea) and compound (Ec) are added to cap the remaining Si—H groups. When multiple Xs are introduced into general formula (1), i.e., when p≧2, the latter two-step reaction is preferred from the standpoint of reaction control.

[0104] 1-1-1-2. b) Step for obtaining hydroxysilicone compound The above-mentioned step (i) of obtaining an epoxy silicone compound yields an epoxy silicone compound represented by the following general formula (10): In this step, the epoxy silicone compound represented by the following general formula (10) is reacted with a carboxylic acid compound in which a (meth)acryloyl group and a carboxy group are linked by a hydrocarbon chain having 4 to 20 carbon atoms and which may contain a heteroatom, to obtain a hydroxy silicone compound containing a polymerizable unsaturated group.

[0105] [ka]

[0106] R1, R2, m, n, and p in general formula (10) have the same meanings as R1, R2, m, n, and p in general formula (1), and the preferred ranges and the like are also the same. X' independently represents a divalent substituent which may contain a heteroatom. A independently represents a hydrogen atom or a substituent containing an isocyanuric ring and an epoxy group. B independently represents a hydrogen atom or a substituent containing an isocyanuric ring and an epoxy group, and at least one of the Bs is the substituent containing an isocyanuric ring and an epoxy group.

[0107] The substituent containing an isocyanuric ring and an epoxy group in A and B is *-R 11 -R 12 -(R 13 -E) l (11) and it is preferably a substituent represented by general formula (12).

[0108] In general formula (11), R 12 is a group consisting of an isocyanuric ring skeleton, and R 11 is a single bond or a hydrocarbon group which may contain a heteroatom. 13 has the same meaning as R7 in general formula (3), and the preferred range is also the same. E is an epoxy group, and l is 1 to 2, preferably 2. * indicates a bonding site.

[0109] [ka]

[0110] In general formula (12), * indicates a bonding site.

[0111] In general formula (10), X' independently represents a divalent substituent which may contain a heteroatom. Examples of such a substituent include aliphatic hydrocarbon groups such as ethylene, propylene, butylene, hexylene, decylene, and dodecylene, divalent substituents represented by the following general formula (13), and divalent substituents represented by the following general formula (8), but are not limited thereto. X' is preferably an ethylene group, a divalent substituent represented by the following general formula (13), or a divalent substituent represented by the following general formula (8), and more preferably a divalent substituent represented by the following general formula (13).

[0112] [ka]

[0113] [ka]

[0114] The epoxysilicone compound represented by the above general formula (10) is reacted with a carboxylic acid compound in which a (meth)acryloyl group and a carboxy group are linked by a hydrocarbon chain having 4 to 20 carbon atoms, which may contain a heteroatom. Examples of carboxylic acid compounds in which a (meth)acryloyl group and a carboxy group are linked by a hydrocarbon chain having 4 to 20 carbon atoms, which may contain a heteroatom, include those represented by the following general formula (14).

[0115] [ka]

[0116] R8 and N in general formula (14) have the same meaning as R8 and N in general formula (6), and the preferred ranges and the like are also the same. R5 in general formula (14) has the same meaning as R5 in general formula (3), and the preferred ranges and the like are also the same.

[0117] The epoxysilicone compound represented by the general formula (10) can be reacted with the carboxylic acid compound to obtain a hydroxysilicone compound by a known method. For example, the method described in JP-A-4-355450 can be used to react an epoxy compound with a carboxylic acid.

[0118] 1-1-1-3. c) Step for obtaining an alkali-soluble silicone compound In this step, a hydroxysilicone compound is reacted with a divalent or trivalent carboxylic acid or an anhydride thereof to obtain an alkali-soluble silicone compound.

[0119] The divalent or trivalent carboxylic acid or anhydride thereof used is the same as the divalent or trivalent carboxylic acid or anhydride thereof used to form M in general formula (4), and the preferred ranges are also the same.

[0120] There are no particular limitations on the conditions such as solvent and catalyst used in the above reaction.

[0121] The solvent used as the reaction solvent is preferably one that does not have a hydroxyl group and has a boiling point higher than the reaction temperature, such as cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate, and ketone solvents such as cyclohexanone and diisobutyl ketone.

[0122] As the catalyst, known catalysts can be used, such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine, which are described in detail in JP-A-9-325494.

[0123] The reaction temperature is preferably in the range of 20°C to 140°C, more preferably 40°C to 130°C.

[0124] When synthesizing the alkali-soluble silicone compound represented by general formula (1), the amount of divalent or trivalent carboxylic acid or anhydride thereof added is preferably 10 mol % to 100 mol % relative to the molar amount of hydroxyl groups in the hydroxysilicone compound. The molar ratio of the acid monoanhydride can be changed as desired within the above range in order to adjust the acid value of the alkali-soluble resin represented by general formula (1).

[0125] 1-2. Second aspect of alkali-soluble silicone compound A second aspect of the alkali-soluble silicone compound according to this embodiment is an alkali-soluble silicone compound having an isocyanuric ring skeleton, a carboxy group, and a polymerizable unsaturated group in one molecule, represented by the following general formula (2):

[0126] [ka]

[0127] In general formula (2), R3 independently represents a hydrocarbon group having 1 to 10 carbon atoms. R4 independently represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. G independently represents a hydrogen atom or a substituent represented by general formula (3) above, and at least one of G is a substituent represented by general formula (3) above. q represents a number from 3 to 6.

[0128] In the general formula (2), examples and preferred ranges of R3 are the same as examples and preferred ranges of R1 in the general formula (1).

[0129] R4 independently represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a heteroatom. Among these, R4 may or may not have a hydrocarbon group having 6 to 20 carbon atoms and optionally containing a heteroatom. When R4 has a hydrocarbon group having 6 to 20 carbon atoms and optionally containing a heteroatom, the amount of polymerizable unsaturated group introduced can be adjusted while increasing hydrophobicity and maintaining durability, making it easier to improve transmittance and light resistance (blue LED resistance). The hydrocarbon group having 6 to 20 carbon atoms and optionally containing a heteroatom is preferably a branched aliphatic hydrocarbon group having 6 to 20 carbon atoms and optionally containing a heteroatom, or an alicyclic hydrocarbon group having 6 to 20 carbon atoms and optionally containing a heteroatom, from the viewpoint of being bulky and making it easier to prevent the intrusion of radicals generated by water or light into the vicinity of the main chain, thereby making it easier to improve durability and blue LED resistance. Examples of such functional groups include a 3,5,5-trimethylhexyl group and a cyclohexylmethyl group.

[0130] G is a hydrogen atom or a substituent represented by general formula (3), and when R4 does not have a hydrocarbon group having 6 to 20 carbon atoms which may contain a heteroatom, the introduction rate of the substituent represented by general formula (3) is preferably 90 mol % to 100 mol %, and more preferably 95 mol % to 100 mol %, relative to 100 mol % of the total number of moles of G. The higher the introduction rate of the substituent represented by general formula (3), the higher the introduction rate of the carboxy group, isocyanuric ring, and polymerizable unsaturated group, which tends to increase alkali solubility, improve patterning properties, and also tends to increase the degree of crosslinking, thereby improving light resistance and durability.

[0131] On the other hand, when a portion of R4 is a hydrocarbon group having 6 to 20 carbon atoms and optionally containing a heteroatom, the introduction rate of the substituent represented by general formula (3) is preferably 20 mol % to 100 mol %, more preferably 40 mol % to 100 mol %, and even more preferably 40 mol % to 80 mol %, relative to the total number of moles of G (100 mol %). The introduction rate of the hydrocarbon group having 6 to 20 carbon atoms and optionally containing a heteroatom is preferably 0 mol % to 80 mol %, more preferably 0 mol % to 60 mol %, and even more preferably 20 mol % to 60 mol %, relative to the total number of moles of G (100 mol %). By adopting such an embodiment, the amount of polymerizable unsaturated groups introduced can be adjusted while increasing hydrophobicity and maintaining durability, making it easier to improve transmittance and light resistance (blue LED resistance).

[0132] The content ratio of the substituent in which R4 is a single bond and a hydrogen atom is bonded to the single bond as G is preferably 0 mol % to 10 mol %, and more preferably 0 mol % to 5 mol %, relative to 100 mol % of the total number of moles of G. By setting the introduction rate of the substituent in which R4 is a single bond and a hydrogen atom is bonded to the single bond as G to 10 mol % or less, the amount of unreacted Si—H is reduced, making it less likely that hydrogen will be generated during storage.

[0133] q is 3 to 6. By making q 3 or more, volatility is reduced, so that the compound is more likely to remain in the film even after a heating process, and the effects of the compound represented by general formula (2) (patterning ability due to the alkali-soluble group, curing ability due to the epoxy group, etc.) are more likely to be exhibited. From the same viewpoint, q is preferably 4 or more. Furthermore, by making q 6 or less, compatibility with unsaturated group-containing polymerizable compounds, epoxy compounds, photopolymerization initiators, etc. is improved, so that transparency is more likely to be improved when the compound is made into a cured resin film. From the same viewpoint, q is preferably 5 or less.

[0134] 1-2-1. Method for producing an alkali-soluble silicone compound represented by general formula (2) The method for producing the alkali-soluble silicone compound represented by general formula (2) will now be described.

[0135] The alkali-soluble silicone compound represented by general formula (2) is synthesized in the same manner as in the production method for the alkali-soluble silicone compound represented by general formula (1).

[0136] Specifically, the alkali-soluble silicone compound represented by general formula (2) can be synthesized in the same manner as above, except that the silicone compound having a Si-H group in part, used as a raw material in step (i) above, is changed from the compound represented by general formula (9) above to, for example, a compound represented by general formula (15) below.

[0137] [ka]

[0138] R3 and q in the general formula (15) have the same meanings as R3 and q in the general formula (2), and the preferred ranges are also the same.

[0139] 2. Photosensitive resin composition The photosensitive resin composition according to this embodiment comprises: (A) an alkali-soluble silicone compound represented by general formula (1) or general formula (2) (hereinafter also referred to simply as "component (A)"), (B) an unsaturated group-containing polymerizable compound (hereinafter also referred to simply as "component (B)"), (C) an epoxy compound (hereinafter also referred to simply as "component (C)"), (D) a photopolymerization initiator (hereinafter also referred to simply as "component (D)"); It is preferred that the compound contains:

[0140] By adopting such an embodiment, not only is light resistance in a high temperature environment and durability in a high temperature and high humidity environment excellent, but alkaline developability is also improved, resulting in good patterning properties.

[0141] Preferred embodiments of the component (A) are the same as the preferred embodiments of the alkali-soluble silicone compound represented by general formula (1) and the alkali-soluble silicone compound represented by general formula (2) described above.

[0142] The content of (A) is preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass, based on the total mass of the solid content of the photosensitive resin composition. When it is 10% by mass or more, alkaline developability is enhanced, which is favorable in terms of patterning properties. When it is 90% by mass or less, carboxy groups and epoxy compounds form crosslinks upon thermal curing, which is favorable in terms of heat resistance and durability.

[0143] Hereinafter, each component other than the aforementioned component (A) that may be contained in the composition will be described.

[0144] 2-1.(B) Polymerizable compound containing unsaturated group Component (B) is a compound that has a polymerizable unsaturated group and undergoes a polymerization reaction in response to stimuli such as heat and light, and is not included in component (A). Component (B) enhances the adhesive strength to the adherend and solvent resistance when formed into a cured resin film.

[0145] The unsaturated group-containing polymerizable compound (B) is preferably an unsaturated group-containing polymerizable compound having no carboxy group. By using such a compound, the alkaline development rate can be easily adjusted by adjusting the content ratio with component (A).

[0146] The polymerizable unsaturated group is preferably the same functional group as the polymerizable unsaturated group contained in component (A). Specifically, the polymerizable unsaturated group is preferably a (meth)acryloyl group. Component (B) may be a monomer, oligomer, or polymer.

[0147] Examples of component (B) include: (Meth)acrylic acid esters of 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, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate; urethane acrylate monomers such as pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene isocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer; Epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol fluorene type epoxy (meth)acrylate, diphenyl fluorene type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, and phenol aralkyl type epoxy (meth)acrylate; and Examples of compounds having an ethylenic double bond include dendritic polymers having a (meth)acrylic group.

[0148] Component (B) preferably has two or more (meth)acryloyl groups, and more preferably three or more (meth)acryloyl groups. When component (B) has two or more (meth)acryloyl groups, the crosslinking density is improved, alkali resistance during exposure tends to be enhanced, patterning properties are improved, and the light resistance and durability of the cured resin film are increased.

[0149] Furthermore, from the viewpoint of suppressing visible light absorption by the cured resin film and facilitating increased light resistance (blue LED resistance), the component (B) preferably has a structure that does not contain an aromatic ring.

[0150] From the viewpoint of further improving the adhesion of the adhesive layer to the adherend, it is preferable that the (B) component be an alkylene oxide-modified or lactone-modified compound. These modified compounds are thought to increase the fluidity of the curable composition at the interface with the adherend, filling minute gaps between the adherend and the curable composition to increase the contact area (adhesion area), thereby further improving the adhesion of the adhesive layer to the adherend. In particular, when the (B) component is a high molecular weight compound, the modified (B) component compensates for the decrease in fluidity of the curable composition caused by the (B) component, thereby significantly improving the adhesion.

[0151] The alkylene oxide modified product is preferably a compound having an alkylene oxide group having 2 to 6 carbon atoms, more preferably a compound having an alkylene oxide group having 2 to 4 carbon atoms, and even more preferably a compound having an alkylene oxide group having 2 to 3 carbon atoms.

[0152] The lactone-modified product has a structure in which lactone having 2 to 6 carbon atoms is ring-opened (-C(=O)-(CH2) k -O-, where k is one less than the number of carbon atoms in the lactone), more preferably a compound having a ring-opened structure of a lactone having 4 to 6 carbon atoms, and even more preferably a compound having a ring-opened structure of a lactone having 6 carbon atoms.

[0153] The above alkylene oxide group and lactone ring-opened structure may exist alone in the molecule, or 2 to 6 of the above alkylene oxide groups or lactones may be consecutive, but it is preferable that the alkylene oxide group or lactone is present alone or two of the above alkylene oxide groups or lactones are consecutive.

[0154] The modified product can be, for example, a compound represented by the following general formula (B-1).

[0155] [ka]

[0156] In formula (B-1), V is independently an alkylene oxide group or a group having a structure in which a lactone ring is opened. f to j are independently integers of 0 to 6, provided that at least one of f to j is an integer of 1 to 6. f to j are preferably 1 or 2. R 41 ~R 45 are independently a (meth)acryloyl group or a hydroxy group, provided that R 41 ~R 45 At least two of R are (meth)acryloyl groups. 41 ~R 45 are preferably all (meth)acryloyl groups. T is a group selected from the group consisting of substituted or unsubstituted monovalent to tetravalent hydrocarbon groups, -O- and -S-, and is preferably a substituted or unsubstituted divalent hydrocarbon group, -O- or -S-, with -O- being more preferred. s is independently 0 or 1, and is preferably 0. t is an integer of 1 to 4, the same as the valence of T, and is preferably 2.

[0157] Examples of the modified product represented by general formula (B-1) include ethylene oxide-modified dipentaerythritol hexaacrylate, dipentaerythritol dicaprolactone hexaacrylate, dipentaerythritol tricaprolactone hexaacrylate, dipentaerythritol hexacaprolactone hexaacrylate, dipentaerythritol polycaprolactone hexaacrylate (all manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane propylene oxide-modified triacrylate, and trimethylolpropane ethylene oxide-modified triacrylate (all manufactured by Toagosei Co., Ltd.).

[0158] Examples of the modified products other than the compound represented by general formula (B-1) include bisphenol F ethylene oxide-modified diacrylate, bisphenol A ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified di- and triacrylate, diglycerin ethylene oxide-modified acrylate (all manufactured by Toagosei Co., Ltd.), and alkylene oxide-modified hexa(meth)acrylate of phosphazene.

[0159] The content of component (B) is preferably 5% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and even more preferably 5% by mass to 40% by mass, based on the total mass of the solids in the photosensitive resin composition. When the content of component (B) is 5% by mass or more, sufficient crosslinking is formed, improving pattern formation by development and facilitating improved light resistance and durability of the cured resin film. When the content of component (B) is 60% by mass or less, excessive crosslinking reaction during exposure can be suppressed, improving patterning properties.

[0160] 2-2.(C) Epoxy compounds The curable resin composition according to this embodiment preferably contains the component (C), which tends to improve the chemical resistance, light resistance, and durability of the cured resin film.

[0161] The epoxy compound (C) is a compound not included in the component (A) and is preferably an epoxy compound without a carboxy group. By using such a compound, the alkaline development rate can be easily adjusted by adjusting the content ratio with the component (A).

[0162] Examples of component (C) include bisphenol A type epoxy compounds (e.g., jER828; manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds (e.g., EPPN-501H; manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L; manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000; manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds, tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having a (meth)acrylic group containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having an epoxycyclohexyl group, such as HiREM-1 manufactured by Shikoku Chemicals Corporation, multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-hydroxymethyl)-2,2-bis(hydroxymethyl)-1-butanol, cyclohexane adducts (e.g., EHPE3150, manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB·JP-100, manufactured by Nippon Soda Co., Ltd.), epoxy compounds having a hydrogenated bisphenol A skeleton (e.g., Epolite 4000, manufactured by Kyoeisha Chemical Co., Ltd.), epoxy compounds having a triazine skeleton (e.g., TEPIC-VL, TEPIC-FL, manufactured by Nissan Chemical Co., Ltd.), 4-oxiranyl-1,2-epoxycyclohexane (e.g., TTA-20, manufactured by Tetra), (3,4,3',4'-dicycloxyl)bicyclohexane (e.g., TTA-800: Tetra), and alicyclic epoxy group-containing cyclic siloxane (e.g., KR-470: Shin-Etsu Chemical Co., Ltd.).

[0163] From the viewpoint of suppressing visible light absorption by the cured resin film and facilitating increased light resistance (blue LED resistance), the component (C) preferably has a structure that does not contain an aromatic ring.

[0164] The epoxy equivalent of component (C) is preferably 80 g / eq to 500 g / eq, and more preferably 100 g / eq to 300 g / eq. At 80 g / eq or more, the toughness of the cured resin film is improved, and the adhesion of the cured resin film to metal films and organic resins is improved. Setting it to 500 g / eq or less facilitates an increase in the degree of crosslinking, which in turn facilitates improvements in light resistance and durability.

[0165] The weight-average molecular weight (Mw) of component (C) is preferably 500 to 50,000, and more preferably 3,000 to 40,000. If it is 500 or more, even if a cured film of component (C) is hydrolyzed under high temperature and high humidity, the decomposition products are less likely to volatilize, and the film thickness loss after storage at high temperature and high humidity is more likely to be suppressed. If it is 50,000 or less, compatibility with component (A) is more likely to be improved, and transparency is more likely to be improved. The weight-average molecular weight of component (C) was measured using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0166] The content of component (C) is preferably 5% by mass to 75% by mass, and more preferably 10% by mass to 50% by mass, based on the total mass of the solid content of the photosensitive resin composition. By making it 5% by mass or more, hardness tends to increase. By making it 75% by mass or less, other components such as component (A) can be added sufficiently, which tends to increase heat resistance.

[0167] 2-3.(D) Photopolymerization initiator The component (D) is not particularly limited as long as it is a compound that has a polymerizable unsaturated bond and can initiate polymerization of an addition-polymerizable compound. Examples of the component (D) include photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and oxime ester compounds. In this specification, the term "photopolymerization initiator" is used to include sensitizers.

[0168] Examples of the acetophenone compound include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one. Examples of commercially available acetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad379EG, the Omnirad series is a product of IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0169] Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-propyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and the like.

[0170] Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, and the like.

[0171] Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzophenone, and the like.

[0172] Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxane, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

[0173] Examples of the imidazole compound include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,4,5-triarylimidazole dimer.

[0174] Examples of oxime ester compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-acetate, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one Oxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-adamantane carboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione 2-o-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-o-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethanone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyloxime), ethanone, 1-(9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanediene, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -, 1-(O-acetyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime, 5-(4-isopropylphenylthio)-1,2-indandione, 2-(O-acetyloxime), and the like. The above photopolymerization initiators may be used alone or in combination of two or more.

[0175] Commercially available oxime ester initiators include, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF, and trade name: Lunar 6, DKSH Japan Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Powerful Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Powerful Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino) (hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), TR-PBG-345 (manufactured by Changzhou New Power Electronic Materials Co., Ltd.), TR-PBG-B (manufactured by Changzhou New Power Electronic Materials Co., Ltd.), Nikkacure YJ-04(T) (Nippon Chemical Industry Co., Ltd.), Nikkacure IW-15 (Nippon Chemical Industry Co., Ltd.), ADEKA ARCLES NCI-831E (manufactured by ADEKA Corporation), Omnirad 1312 (manufactured by IGM Resins BV), and DFI-020 (manufactured by Daito Chemix Co., Ltd.).

[0176] Of these, component (D) is preferably an oxime ester-based (including ketoxime) photopolymerization initiator. Because oxime ester-based photopolymerization initiators have high sensitivity, they can sufficiently increase the photosensitivity of the curable resin composition and sufficiently increase the developability (resolution) of the adhesive layer.

[0177] Examples of the oxime ester photopolymerization initiator include O-oxime ester photopolymerization initiators represented by general formula (D-1) or general formula (D-2).

[0178] [ka]

[0179] In formula (D-1), R 51 , R 52 each independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms; R 53 represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be a straight-chain, branched, or cyclic alkyl group.

[0180] [ka]

[0181] In formula (D-2), R 54 and R 55are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 56 are each independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl or alkenyl group may be substituted with -O- groups. 54 ~R 56 Some of the hydrogen atoms in the group may be substituted with halogen atoms.

[0182] Furthermore, it is preferable that the molar absorption coefficient of component (D) at 365 nm is 10,000 L / (mol cm) or more. Such photopolymerization initiators have high sensitivity, which can further enhance the photosensitivity of the curable composition and sufficiently improve the developability (resolution) of the curable resin composition. Examples of such photopolymerization initiators include Omnirad 1312 (manufactured by IGM Resins BV, "Omnirad" is a registered trademark of the company) and Adeka Arcles NCI-831E (manufactured by ADEKA Corporation, "Adeka Arcles" is a registered trademark of the company).

[0183] The molar absorption coefficient of the photopolymerization initiator is a value obtained by measuring the absorbance of a 0.001 wt % acetonitrile solution in a quartz cell with an optical path length of 1 cm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0184] As the component (D), an active radical generator or an acid generator may be used.

[0185] Examples of active radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like.

[0186] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin tosylates.

[0187] The content of component (D) is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass, based on the total mass of solids. When the content of the photopolymerization initiator is 0.01% by mass or more, photopolymerization can be promoted, increasing the photopolymerization rate and improving patterning properties when patterning by pattern exposure. Furthermore, when the content of the photopolymerization initiator is 20% by mass or less, excessive increases in sensitivity can be suppressed, making it less likely that scorching, peeling residue, etc. will occur when ablation is performed by irradiating light.

[0188] The curable composition may also contain a photosensitizer in addition to the component (D).

[0189] Examples of the photosensitizer include acetophenones such as triethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, n-butoxy 4-dimethylaminobenzoate, and n-butyl 4-dimethylaminobenzoate. Benzophenones such as methyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenones such as 4,4'-bisdiethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

[0190] The content of the photosensitizer is preferably 0.5 to 400 parts by mass, and more preferably 1 to 300 parts by mass, when the total mass of component (D) is 100 parts by mass. When the content of the photosensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be improved, and the photopolymerization rate can be increased. Furthermore, when the content of the photosensitizer is 400 parts by mass or less, excessive increases in sensitivity can be suppressed, making it less likely that scorching, peeling residue, etc. will occur when ablation is performed by irradiating light.

[0191] 2-4.Other ingredients The curable resin composition according to the present embodiment may contain additives such as solvents, antioxidants, leveling agents, curing agents, curing accelerators, plasticizers, fillers, antifoaming agents, coupling agents, etc., as needed. The composition may also contain ultraviolet absorbers and pigments for increasing the absorbency of irradiated light.

[0192] 2-4-1.Solvent The photosensitive resin composition according to this embodiment may contain a solvent. The solvent adjusts the viscosity of the photosensitive resin composition and improves the coatability.

[0193] The solvent is preferably an organic solvent, and examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, cyclopentanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, and propylene glycol monomethyl ether. Examples of suitable solvents include glycol ethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing these solvents, a uniform solution-like composition can be obtained. Among these, it is preferable that the solvent contains an ester, and more preferably, it contains diethylene glycol ethyl methyl ether, dimethylene glycol dimethyl ether, or propylene glycol monomethyl acetate.

[0194] The amount of solvent varies depending on the target viscosity, but is preferably 20% by mass to 90% by mass of the total mass of the photosensitive resin composition, as this facilitates imparting suitable coating suitability.

[0195] 2-4-2. Antioxidants The photosensitive resin composition according to this embodiment may contain an antioxidant. The antioxidant can suppress oxidative degradation when the cured resin film is heated, making it less likely to be discolored. There are no limitations on the type of compound that can be used as long as it satisfies this requirement.

[0196] Examples of antioxidants include: Monophenols such as 2,6-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-tert-butyl-p-ethylphenol, and stearyl-β-(3,5-di-tert-butyl-4-4-hydroxyphenyl)propionate; bisphenols such as 2,2-methylenebis(4-methyl-6-tert-butylphenol), 2,2-methylenebis(4-ethyl-6-tert-butylphenol), and 4,4'-thiobis(3-methyl-6-tert-butylphenol); Polyhydric phenols such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and tert-butylcatechol, High molecular weight phenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane; oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; ester skeleton-containing thioether compounds such as dilauryl 3,3'-dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-dilauryl 3,3'-thiodipropionate, distearyl 3,3'-dilauryl 3,3'-thiodipropionate, and pentaerythrityl tetrakis(3-laurylthiopropionate); These antioxidants may be used in combination of two or more kinds, if necessary.

[0197] Examples of commercially available antioxidants include Irganox 1010 (manufactured by BASF Japan Ltd.).

[0198] When an antioxidant is contained, the content of the antioxidant is preferably 0.01% by mass to 5.0% by mass, more preferably 0.05% by mass to 2.5% by mass, and even more preferably 0.1% by mass to 1.0% by mass, based on the total solid content of the photosensitive resin composition. By setting the content within such a range, coloration of the cured resin film can be suppressed while generation of gas derived from the antioxidant can be suppressed.

[0199] 2-4-3.Leveling agent The photosensitive resin composition according to this embodiment may contain a leveling agent. The leveling agent segregates on the coating film surface and controls the viscosity, surface tension, etc. of the coating film surface, thereby making it easier to improve the surface smoothness of the cured resin film.

[0200] Examples of leveling agents include silicone-containing compounds not included in component (A), (meth)acrylic polymers, fluorine-based compounds, etc. The leveling agent is preferably a silicone-containing compound or a fluorine-based compound from the viewpoint of easily improving smoothness. Furthermore, when a coating layer is further provided on the cured resin film, the leveling agent is preferably a (meth)acrylic polymer from the viewpoint of easily suppressing cissing of the coating layer.

[0201] When a leveling agent is contained, the content of the leveling agent is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, even more preferably 0.01% by mass to 5.0% by mass, and most preferably 0.1% by mass to 1.0% by mass, based on the total solid content. Here, by setting the content of the leveling agent to 0.01% by mass or more, smoothness is likely to be improved, and by setting it to 10.0% by mass or less, when a coating layer is formed on the cured resin film, cissing of the coating layer can be easily suppressed.

[0202] 2-4-4.Other The photosensitive resin composition according to this embodiment may contain additives such as a curing agent, a curing accelerator, a plasticizer, a filler, an antifoaming agent, a coupling agent, etc., as needed. In addition, the composition may contain an ultraviolet absorber or a pigment to enhance the absorbency of irradiated light.

[0203] Examples of curing agents include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc., which contribute to the curing of epoxy compounds. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to the curing of epoxy compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, silica, mica, alumina, etc. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

[0204] 3.Resin cured film The cured resin film according to this embodiment is formed from the photosensitive resin composition.

[0205] The method for producing a cured resin film preferably includes a step of applying the photosensitive resin composition to a support, a solvent drying step (pre-baking), and a heat treatment step (post-baking). The solvent drying step and the heat treatment step may be performed separately or may be performed together. When patterning the cured resin film, an exposure and development step may be performed after pre-baking and before post-baking.

[0206] 3-1. Application process The application step is a step of applying the photosensitive resin composition to the surface of a substrate to form a coating film containing the photosensitive resin composition.

[0207] Examples of the method for applying the photosensitive resin composition include known methods such as solution immersion, spin coating, ink jetting, spraying, and methods using a roller coater, land coater, slit coater, or spinner.

[0208] The thickness of the resin film can be selected as desired, and the thickness of the resin film according to this embodiment is preferably 1 μm to 50 μm, and more preferably 3 μm to 30 μm.

[0209] Examples of substrates include semiconductor wafers, semiconductor chips, light-emitting devices, optical glass wafers, metal foils, polishing pads, resin coatings, and wiring layers. The substrate may be a single layer or may have a multilayer structure of two or more layers, and some of the layers may be patterned. The cured resin film obtained from the photosensitive resin composition has good adhesion to metals because some of the silicon-oxygen bonds in component (A) form hydrogen bonds with hydroxyl groups in an oxide film formed on the metal surface. Therefore, it is particularly suitable for application to substrates containing metal foils, metal wiring layers, etc. on their surfaces, and is particularly useful as a light-emitting diode (LED) encapsulant applied to substrates having metal wiring, etc., that drives light-emitting diodes (LEDs).

[0210] 3-2. Solvent drying process (pre-bake) After applying the photosensitive resin composition to the substrate, the solvent is dried (prebaked) to form a coating film. Prebaking is performed by heating using an oven, a hot plate, or the like. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, but the heating temperature is preferably 60°C to 110°C, and the heating time is preferably 1 minute to 10 minutes.

[0211] 3-3. Exposure and development process Examples of light used in the exposure step include visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc. Among the above-mentioned lights, ultraviolet light (wavelength 250 to 400 nm) is preferred.

[0212] In the development step, a developer suitable for alkaline development is used. Examples of the developer include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developers can be selected appropriately depending on the properties of the resin layer, and a surfactant may be added if necessary. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using a commercially available developing machine or ultrasonic cleaner. After alkaline development, the film is usually washed with water. As the development method, shower development, spray development, dip (immersion) development, puddle (liquid puddle) development, etc. can be used.

[0213] 3-4. Heat treatment process (post-bake) In the heat treatment step, the reaction between the remaining polymerizable unsaturated groups and the reaction between the carboxyl group and the epoxy group etc. progresses due to the heat treatment, and a strong crosslinked structure is formed.

[0214] The heat treatment temperature for promoting the crosslinking reaction is preferably 150°C to 250°C, more preferably 180°C to 230°C. The heat treatment time is preferably 10 to 120 minutes, more preferably 30 to 90 minutes. By setting the treatment temperature at 150°C or higher and the treatment time at 10 minutes or longer, the crosslinking reaction proceeds smoothly, resulting in a cured resin film with the desired properties. By setting the treatment temperature at 250°C or lower and the treatment time at 120 minutes or shorter, unintended side reactions do not occur, and coloration of the cured film and a decrease in adhesion strength can be easily suppressed. This can also help prevent thermal degradation of peripheral components, save energy, and improve throughput. In particular, since thermal degradation of LED peripheral components such as LED elements can be easily suppressed, these heat treatment conditions are suitable for use as light-emitting diode (LED) encapsulants.

[0215] 4.Semiconductor Package The semiconductor package according to this embodiment includes the above-described cured resin film.

[0216] The cured resin film according to this embodiment can be used as an insulating film for printed wiring boards and semiconductor packages, for example, resist layers such as solder resist layers, plating resist layers, and etching resist layers, interlayer insulating layers for multilayer printed wiring boards, and protective films for sealing and protecting elements used in semiconductor devices, image display devices, etc. In this specification, the term "semiconductor package" refers to a package that includes a semiconductor chip and is configured to be mounted on a printed circuit board, such as a flip chip package, wafer level package, and the like, for example, a flip chip package stacked on an interposer.

[0217] The alkali-soluble silicone compound according to this embodiment, which uses a compound having an isocyanuric ring, tends to have increased polarity, and is therefore more likely to form interactions such as hydrogen bonds with highly polar compounds such as (meth)acrylate groups. This tends to improve adhesion between a color resist layer formed by the reaction of (meth)acrylate groups and a cured resin film formed from the alkali-soluble silicone compound according to this embodiment. This improves adhesion to the color resist material formed by the reaction of (meth)acrylate groups, making the compound suitable for use as a cured resin film to which a black resist or the like is applied. It is particularly useful as a light-emitting diode (LED) encapsulant, in which a black resist is further applied to the surface of the cured resin film to prevent color mixing between the LED elements.

[0218] 5.Display device The display device according to this embodiment includes the above-described cured resin film as an insulating film or a protective film.

[0219] The display device according to the present embodiment includes the cured resin film as an insulating film in various display devices such as a liquid crystal display, an organic EL display, a μLED display, and a display device using quantum dots, or as a protective film (sealant) for a lens and a semiconductor light-emitting element such as a light-emitting diode (LED). The display device according to the present embodiment may also have a semiconductor package including the cured resin film as an insulating film or protective film.

[0220] The cured resin film according to this embodiment is also suitable as an insulating film or protective film used in an in-vehicle display device, or as a light-emitting diode (LED) encapsulant. Components used in in-vehicle display devices are often exposed to high temperatures and high-temperature, high-humidity environments compared to components used in mobile applications such as mobile phones and display devices such as televisions. The cured resin film according to this embodiment has excellent light resistance at high temperatures and excellent durability at high temperatures and high humidity, and is therefore useful as an insulating film or protective film used in an in-vehicle display device, or as a light-emitting diode (LED) encapsulant.

[0221] 6.Other uses The cured resin film according to this embodiment can be used as a gas barrier film, a top coat for paints or inks, a hard coat for plastics, an anti-corrosion film for metals, and the like. [Example]

[0222] Hereinafter, the present invention will be described in detail based on examples and comparative examples of the alkali-soluble resin represented by general formula (1), but the present invention is not limited thereto. Furthermore, evaluations in the following examples were performed as follows unless otherwise specified.

[0223] When the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place onwards. In the examples, all glass substrates used to prepare the cured film-coated substrates for measurement are subjected to the same treatment. When the first decimal place of the content of each component is 0, the decimal point may be omitted.

[0224] [Solid content concentration] The mass was calculated from the mass [W1(g)] after impregnating 1 g of the resin solution obtained in the Examples and Comparative Examples into a glass filter [mass: W0(g)] and weighing it, and the mass [W2(g)] after heating at 160°C for 2 hours, using the following formula: Solid content concentration (mass%) = 100 × (W2-W0) / (W1-W0)

[0225] [Epoxy equivalent] After dissolving the resin solution in dioxane, a solution of tetraethylammonium bromide in acetic acid was added, and the content was determined by titration with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0226] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0227] [Molecular weight] Measurements were performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, flow rate: 0.6 ml / min), and the molecular weight distribution and weight-average molecular weight (Mw) were calculated as values ​​converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0228] [Number of repeating units of epoxy silicone resin] The values ​​were measured using a gas chromatography mass spectrometer (GC / MS) (7890B GC / 7200B GC / Q-TOF (Agilent)), column: HP-5MS, carrier gas and ionization method: CI method using methylamine).

[0229] The abbreviations used in the synthesis examples are as follows. HOA-MS: 2-acryloyloxyethyl succinate HOA-HH: 2-acryloyloxyethyl hexahydrophthalic acid EOA-HH: 2-(2-acryloyloxyethoxy)ethylhexahydrophthalic acid TPP: Triphenylphosphine THPA: Cyclohex-4-ene-1,2-dicarboxylic anhydride MCA: 4-methylcyclohexane-1,2-dicarboxylic anhydride BPFE: Bisphenol fluorene type epoxy resin (general formula (X1) is Ar x is a benzene ring and u is 0. Epoxy resin (epoxy equivalent: 256 g / eq) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride PGMEA: Propylene glycol monomethyl ether acetate

[0230] [ka]

[0231] [Synthesis Example 1] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 100 parts by mass (0.36 mol) of N-allyl-N'N''-diglycidyl isocyanurate, 285 parts by mass of toluene, and 0.34 parts by mass of a platinum catalyst supported on carbon powder (platinum concentration 3%). The internal temperature was raised to 100°C, and then 104 parts by mass (0.18 mol) of polydimethylsiloxane (Si-H equivalent 294 g / eq) terminated with Si-H groups and 85 parts by mass of toluene were added dropwise over 1 hour. After the addition was completed, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution. After confirming that hydrogen gas generation had ceased, the remaining platinum catalyst was filtered off using Celite. The solvent was removed from the filtrate using an evaporator, yielding 190 parts by mass of epoxy silicone resin (ES1). GC / MS analysis of the polydimethylsiloxane used as the raw material revealed that the resulting epoxy silicone resin (ES1) was a mixture of general formula (1) where n = 0 and m = 0 to 23. Furthermore, p = 0 in general formula (1), and the compound had an internal linear siloxane bond and an isocyanuric ring skeleton with epoxy groups at both ends. The epoxy equivalent of the resulting epoxy silicone resin was 277 g / eq, and Mw by GPC analysis was 1170.

[0232] Next, 100 parts by mass (0.09 mol) of the epoxy silicone resin (ES1), 80 parts by mass (0.36 mol) of HOA-MS, 30 parts by mass of PGMEA, and 0.93 g of TPP were charged into a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and the mixture was stirred and reacted for 10 hours at 100-105°C. Furthermore, 148 parts by mass of PGMEA and 41 parts by mass (0.27 mol) of THPA were charged into a flask and stirred and heated at 120-125°C for 2 hours to obtain alkali-soluble resin (A-1). The solids content of the obtained alkali-soluble resin was 50.3% by mass, the acid value (solids equivalent) was 91.3 mg KOH / g, and the Mw by GPC analysis was 3290. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak of 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0233] [Synthesis Example 2] An epoxy silicone resin (ES1) was obtained in the same manner as in Synthesis Example 1. Next, a reactor equipped with a temperature controller, a stirrer, and a reflux condenser was charged with 100 parts by mass (0.09 mol) of the epoxy silicone resin (ES1), 100 parts by mass (0.36 mol) of HOA-HH, 40 parts by mass of PGMEA, and 0.93 g of TPP, and the mixture was stirred and reacted for 10 hours at 100 to 105°C. Furthermore, a flask was charged with 164 parts by mass of PGMEA and 41 parts by mass (0.27 mol) of THPA, and the mixture was stirred and heated at 120 to 125°C for 2 hours to obtain an alkali-soluble resin (A-2). The solids content of the obtained alkali-soluble resin was 51.2% by mass, the acid value (solids equivalent) was 84.1 mg KOH / g, and the Mw by GPC analysis was 5570. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0234] [Synthesis Example 3] An epoxy silicone resin (ES1) was obtained in the same manner as in Synthesis Example 1. Next, a reactor equipped with a temperature controller, stirrer, and reflux condenser was charged with 100 parts by mass (0.09 mol) of the epoxy silicone resin (ES1), 77 parts by mass (0.36 mol) of HOA-MS, 40 parts by mass of PGMEA, and 0.93 g of TPP, and the mixture was stirred and reacted for 10 hours at 100 to 105°C. Furthermore, a flask was charged with 164 parts by mass of PGMEA and 45 parts by mass (0.27 mol) of MCA, and the mixture was stirred and heated at 120 to 125°C for 2 hours to obtain an alkali-soluble resin (A-3). The solids content of the resulting alkali-soluble resin was 49.6% by mass, the acid value (solids equivalent) was 85.3 mg KOH / g, and the Mw by GPC analysis was 5920. Furthermore, IR measurement of the resulting alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0235] [Synthesis Example 4] An epoxy silicone resin (ES1) was obtained in the same manner as in Synthesis Example 1. Next, a reactor equipped with a temperature controller, a stirrer, and a reflux condenser was charged with 100 parts by mass (0.09 mol) of the epoxy silicone resin (ES1), 122 parts by mass (0.36 mol) of EOA-HH, 40 parts by mass of PGMEA, and 0.93 g of TPP, and the mixture was stirred and reacted for 10 hours at 100 to 105°C. Furthermore, a flask was charged with 183 parts by mass of PGMEA and 41 parts by mass (0.27 mol) of THPA, and the mixture was stirred and heated at 120 to 125°C for 2 hours to obtain an alkali-soluble resin (A-4). The solids content of the obtained alkali-soluble resin was 54.6% by mass, the acid value (solids equivalent) was 73.0 mg KOH / g, and the Mw by GPC analysis was 6130. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0236] [Synthesis Example 5] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 182 parts by mass (0.30 mol) of polydimethylsiloxane (Si-H equivalent: 303 g / eq) terminated in Si-H groups, 290 parts by mass of toluene, and 0.34 parts by mass of a platinum catalyst supported on carbon powder (platinum concentration: 3%). The internal temperature was raised to 100°C, and then 40 parts by mass (0.15 mol) of N-N'-diallyl-N''-monoglycidyl isocyanurate and 40 parts by mass of toluene were added dropwise over 1 hour. After completion of the dropwise addition, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas generation had ceased. After the internal temperature was lowered to 100°C, 85 parts by mass (0.30 mol) of N-allyl-N'N''-diglycidyl isocyanurate and 85 parts by mass of toluene were added dropwise over 1 hour. After the completion of the dropwise addition, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction liquid was added dropwise to a 0.1 N potassium hydroxide / methanol solution. After confirming that hydrogen gas generation had ceased, the remaining platinum catalyst was filtered off using Celite. The solvent was removed from the filtrate using an evaporator, yielding 293 parts by mass of epoxy silicone resin (ES2). GC / MS analysis of the polydimethylsiloxane used as the raw material revealed that the obtained epoxy silicone resin (ES2) was a mixture of general formula (1) where n = 0 and m = 0 to 23. Furthermore, from the molecular weight distribution by GPC analysis and the values ​​of n and m, it was calculated that the resin was a mixture in which p was 0 to 105. The compound had an internal linear siloxane bond and an isocyanuric ring skeleton with epoxy groups at both ends of the molecule, where X in general formula (1) is a divalent substituent represented by general formula (5). The epoxy equivalent of the resulting epoxy silicone resin was 383 g / eq, and the Mw measured by GPC analysis was 2610.

[0237] Next, 100 parts by mass (0.05 mol) of the epoxy silicone resin (ES2), 58 parts by mass (0.26 mol) of HOA-MS, 30 parts by mass of PGMEA, and 0.66 g of TPP were charged into a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and the mixture was stirred and reacted for 10 hours at 100-105°C. Furthermore, 130 parts by mass of PGMEA and 30 parts by mass (0.20 mol) of THPA were charged into a flask and stirred and heated at 120-125°C for 2 hours to obtain alkali-soluble resin (A-5). The solids content of the obtained alkali-soluble resin was 49.7% by mass, the acid value (solids equivalent) was 67.0 mg KOH / g, and the Mw by GPC analysis was 6140. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0238] [Synthesis Example 6] An epoxy silicone resin (ES2) was obtained in the same manner as in Synthesis Example 5. Next, a reactor equipped with a temperature controller, a stirrer, and a reflux condenser was charged with 100 parts by mass (0.05 mol) of the epoxy silicone resin (ES2), 72 parts by mass (0.26 mol) of HOA-HH, 168 parts by mass of PGMEA, and 0.66 g of TPP, and the mixture was stirred and reacted for 10 hours at 100 to 105°C. Furthermore, 30 parts by mass (0.20 mol) of THPA was charged into a flask and stirred and heated at 120 to 125°C for 2 hours to obtain an alkali-soluble resin (A-6). The solids content of the obtained alkali-soluble resin was 53.5% by mass, the acid value (solids equivalent) was 60.0 mg KOH / g, and the Mw by GPC analysis was 7350. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0239] [Synthesis Example 7] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 84 parts by mass (0.30 mol) of N-allyl-N'N''-diglycidyl isocyanurate, 114 parts by mass of toluene, and 0.20 parts by mass of a platinum catalyst supported on carbon powder (platinum concentration 3%). After the internal temperature was raised to 100°C, 50 parts by mass (0.028 mol) of 25-35% methylhydrosiloxane-dimethylsiloxane-Si-H terminated siloxane (Si-H equivalent 169 g / eq) and 50 parts by mass of toluene were added dropwise over 1 hour. After completion of the dropwise addition, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution. After confirming that hydrogen gas generation had ceased, the remaining platinum catalyst was filtered off using Celite. The solvent was removed from the filtrate using an evaporator, yielding 129 parts by mass of epoxy silicone resin (ES3). GC / MS analysis of the polydimethylsiloxane used as the raw material revealed that the resulting epoxy silicone resin (ES3) was a mixture of general formula (1) where m = 0-35 and n = 1-10. Furthermore, p = 0, and the compound had an isocyanuric ring skeleton with epoxy groups on the side chain and both ends. The epoxy equivalent of the resulting epoxy silicone resin was 224 g / eq, and Mw by GPC analysis was 4810.

[0240] Next, 50 parts by mass (0.01 mol) of the epoxy silicone resin (ES3), 60 parts by mass (0.22 mol) of HOA-HH, 110 parts by mass of PGMEA, and 0.59 g of TPP were charged into a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and the mixture was stirred and reacted for 10 hours at 100-105°C. Furthermore, 28 parts by mass (0.17 mol) of THPA was charged into the flask, and the mixture was stirred and heated at 120-125°C for 2 hours to obtain alkali-soluble resin (A-7). The solids content of the obtained alkali-soluble resin was 55.1% by mass, the acid value (solids equivalent) was 74.4 mg KOH / g, and the Mw by GPC analysis was 8490. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1(vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0241] [Synthesis Example 8] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 235 parts by mass (0.84 mol) of N-allyl-N'N''-diglycidyl isocyanurate, 353 parts by mass of toluene, and 0.48 parts by mass of a platinum catalyst supported on carbon powder (platinum concentration 3%). The internal temperature was raised to 100°C, and then 50 parts by mass (0.21 mol) of the cyclic siloxane 1,3,5,7-tetramethylcyclotetrasiloxane (Si-H equivalent 60 g / eq) and 41 parts by mass of toluene were added dropwise over 1 hour. After completion of the dropwise addition, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution. After confirming that hydrogen gas generation had ceased, the remaining platinum catalyst was filtered off using Celite. The solvent was removed from the filtrate using an evaporator to obtain 283 parts by mass of epoxy silicone resin (ES4). The epoxy equivalent of the obtained epoxy silicone resin was 171 g / eq, Mw by GPC analysis was 890, and q = 4 in general formula (2).

[0242] Next, 50 parts by mass (0.04 mol) of the epoxy silicone resin (ES4), 63 parts by mass (0.20 mol) of HOA-MS, 49 parts by mass of PGMEA, and 0.77 g of TPP were charged into a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and the mixture was stirred and reacted for 10 hours at 100-105°C. Furthermore, 102 parts by mass of PGMEA and 49 parts by mass (0.20 mol) of THPA were charged into a flask and stirred and heated at 120-125°C for 2 hours to obtain alkali-soluble resin (A-8). The solids content of the obtained alkali-soluble resin was 49.5% by mass, the acid value (solids equivalent) was 133.0 mg KOH / g, and the Mw by GPC analysis was 4230. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak of 1732 cm -1 (ester bond), 1409 cm -1(vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0243] [Synthesis Example 9] An epoxy silicone resin (ES4) was obtained in the same manner as in Synthesis Example 8. Next, 50 parts by mass (0.04 mol) of the epoxy silicone resin (ES4), 79 parts by mass (0.29 mol) of HOA-HH, 129 parts by mass of PGMEA, and 0.77 g of TPP were charged into a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and the mixture was stirred and reacted for 10 hours at 80 to 85°C. Furthermore, 48 parts by mass of PGMEA and 49 parts by mass (0.29 mol) of THPA were charged into a flask and stirred and heated at 120 to 125°C for 2 hours to obtain an alkali-soluble resin (A-9). The solids content of the resulting alkali-soluble resin was 52.1% by mass, the acid value (solids equivalent) was 167 mg KOH / g, and the Mw by GPC analysis was 5300. Furthermore, IR measurement of the resulting alkali-soluble resin revealed a peak of 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0244] [Synthesis Example 10] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 128 parts by mass (0.45 mol) of N-allyl-N'N''-diglycidyl isocyanurate, 50 parts by mass (0.45 mol) of vinylcyclohexane, 267 parts by mass of toluene, and 0.39 parts by mass of a platinum catalyst supported on carbon powder (platinum concentration 3%). After the internal temperature was raised to 100°C, 55 parts by mass (0.23 mol) of the cyclic siloxane 1,3,5,7-tetramethylcyclotetrasiloxane (Si-H equivalent 60 g / eq) and 45 parts by mass of toluene were added dropwise over 1 hour. After completion of the dropwise addition, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution. After confirming that hydrogen gas generation had ceased, the remaining platinum catalyst was filtered off using Celite. The solvent was removed from the filtrate using an evaporator to obtain 229 parts by mass of an epoxy silicone resin (ES5). The epoxy equivalent of the obtained epoxy silicone resin was 249 g / eq, Mw by GPC analysis was 820, and q = 4 in general formula (2).

[0245] Next, 50 parts by mass (0.05 mol) of the epoxy silicone resin (ES5), 56 parts by mass (0.20 mol) of HOA-HH, 46 parts by mass of PGMEA, and 0.53 g of TPP were charged into a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and the mixture was stirred and reacted for 10 hours at 80-85°C. Furthermore, 61 parts by mass of PGMEA and 31 parts by mass (0.20 mol) of THPA were charged into a flask and stirred and heated at 120-125°C for 2 hours to obtain alkali-soluble resin (A-10). The solids content of the obtained alkali-soluble resin was 56.3% by mass, the acid value (solids equivalent) was 47 mg KOH / g, and the Mw by GPC analysis was 3580. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0246] [Synthesis Example 11] A reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube was charged with 112 parts by mass (0.40 mol) of N-allyl-N'N''-diglycidyl isocyanurate, 50 parts by mass (0.40 mol) of 3,5,5-trimethyl-1-hexene, 243 parts by mass of toluene, and 0.35 parts by mass of a platinum catalyst supported on carbon powder (platinum concentration 3%). After the internal temperature was raised to 100°C, 49 parts by mass (0.20 mol) of the cyclic siloxane 1,3,5,7-tetramethylcyclotetrasiloxane (Si-H equivalent 60 g / eq) and 40 parts by mass of toluene were added dropwise over 1 hour. After completion of the dropwise addition, the internal temperature was raised to 114°C, and the reaction was carried out while refluxing the toluene. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution. After confirming that hydrogen gas generation had ceased, the remaining platinum catalyst was filtered off using Celite. The solvent was removed from the filtrate using an evaporator to obtain 229 parts by mass of epoxy silicone resin (ES6). The epoxy equivalent of the obtained epoxy silicone resin was 249 g / eq, Mw by GPC analysis was 830, and q = 4 in general formula (2).

[0247] Next, 50 parts by mass (0.05 mol) of the epoxy silicone resin (ES6), 57 parts by mass (0.20 mol) of HOA-HH, 46 parts by mass of PGMEA, and 0.53 g of TPP were charged into a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and the mixture was stirred and reacted for 10 hours at 80-85°C. Furthermore, 61 parts by mass of PGMEA and 31 parts by mass (0.20 mol) of THPA were charged into a flask and stirred and heated at 120-125°C for 2 hours to obtain alkali-soluble resin (A-11). The solids content of the obtained alkali-soluble resin was 56.6% by mass, the acid value (solids equivalent) was 48 mg KOH / g, and the Mw by GPC analysis was 3680. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0248] [Synthesis Example 12] An epoxy silicone resin (ES1) was obtained in the same manner as in Synthesis Example 1. Next, a reactor equipped with a temperature controller, a stirrer, and a reflux condenser was charged with 100 parts by mass (0.09 mol) of the epoxy silicone resin (ES1), 26 parts by mass (0.35 mol), 20 parts by mass of PGMEA, and 0.90 g of TPP, and the mixture was stirred and reacted for 10 hours at 100 to 105°C. Furthermore, a flask was charged with 104 parts by mass of PGMEA and 40 parts by mass (0.27 mol) of THPA, and the mixture was stirred and heated at 120 to 125°C for 2 hours to obtain an alkali-soluble resin (F-1). The solids content of the obtained alkali-soluble resin was 57.0% by mass, the acid value (solids equivalent) was 80.4 mg KOH / g, and the Mw by GPC analysis was 1970. Furthermore, IR measurement of the obtained alkali-soluble resin revealed a peak at 1732 cm -1 (ester bond), 1409 cm -1 (vinyl group), 1186cm -1 A peak was observed at the carboxyl group. This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[0249] [Synthesis Example 13] A reaction product was obtained by adding 100 parts by mass (0.20 mol) of BPFE, 109 parts by mass (0.40 mol) of HOA-HH, 0.50 parts by mass of TPP, and 33 parts by mass of PGMEA to a reactor equipped with a temperature controller, a stirrer, and a reflux condenser, and stirring for 12 hours at 100 to 105°C. Thereafter, 15 parts by mass of PGMEA was added and the solid content was adjusted to 50% by mass.

[0250] Next, 29 parts by mass (0.10 mol) of BPDA and 15 parts by mass (0.1 mol) of THPA were added to the resulting reaction product and stirred at 115 to 120°C for 6 hours to obtain unsaturated group-containing curable resin (F-2). The solids concentration of the resulting resin solution was 55.0% by mass, the acid value (solids equivalent) was 41 mgKOH / g, and the Mw by GPC analysis was 4720.

[0251] Photosensitive resin compositions were prepared in the amounts (unit: parts by mass) shown in Table 1. The ingredients used in Table 1 are as follows.

[0252] (Component (A)) A-1: Resin solution obtained in Synthesis Example 1 (solid content concentration: 50.3% by mass) A-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 51.2% by mass) A-3: Resin solution obtained in Synthesis Example 3 (solid content concentration: 49.6% by mass) A-4: Resin solution obtained in Synthesis Example 4 (solid content concentration: 54.6% by mass) A-5: Resin solution obtained in Synthesis Example 5 (solid content concentration: 49.7% by mass) A-6: Resin solution obtained in Synthesis Example 6 (solid content concentration 53.5% by mass) A-7: Resin solution obtained in Synthesis Example 7 (solid content concentration 55.1% by mass) A-8: Resin solution obtained in Synthesis Example 8 (solid content concentration: 49.5% by mass) A-9: Resin solution obtained in Synthesis Example 9 (solid content concentration 52.1% by mass) A-10: Resin solution obtained in Synthesis Example 10 (solid content concentration 56.3% by mass) A-11: Resin solution obtained in Synthesis Example 11 (solid content concentration 56.6% by mass)

[0253] ((B) component) B-1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

[0254] ((C) component) C-1: Bisphenol A epoxy compound (jER-828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 189 g / eq) C-2: 2,2-bis(hydroxymethyl)-1-butanol to 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct (EHPE-3150, Daicel Corporation, epoxy equivalent: 180 g / eq) C-3: Alicyclic epoxy group-containing cyclic siloxane (KR-470, manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 200 g / eq)

[0255] ((D) component) D-1: Oxime ester photoinitiator (Irgacure OXE-01, manufactured by BASF Japan Ltd.)

[0256] (solvent) E-1: Propylene glycol monomethyl ether acetate E-2: Diethylene glycol ethyl methyl ether (EDM)

[0257] (Comparative synthetic resin) F-1: Resin solution obtained in Synthesis Example 12 (solid content concentration: 57.0% by mass) F-2: Resin solution obtained in Synthesis Example 13 (solid content concentration: 55.0% by mass)

[0258] [Table 1]

[0259] [evaluation] The following evaluations were carried out using the cured resin film obtained by curing the above photosensitive resin composition.

[0260] [Blue LED resistance test] Each photosensitive resin composition was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing would be 10.0 μm, and the film was prebaked on a hot plate at 100°C for 5 minutes to produce a dried film. Next, an i-line irradiance of 30 mW / cm was applied to the dried film. 2 100mJ / cm 2 After that, the resin was post-baked at 230° C. for 30 minutes using a hot air dryer to obtain a substrate with a cured resin film.

[0261] The obtained substrate with the cured resin film was placed in a blue LED irradiation device (temperature: 40 to 50°C) with a wavelength of 450 nm, and a test was carried out for 500 hours. Evaluation was carried out as follows.

[0262] (Evaluation method) [Transmittance] After the blue LED light resistance test, the substrate with the cured resin film was measured for transmittance at a wavelength of 350 nm using a spectrophotometer "UH4150" (manufactured by Hitachi High-Technologies Corporation). A rating of △ or higher was considered to be acceptable.

[0263] (Evaluation criteria) ◎: Transmittance is 95% or more ○: Transmittance is 90% or more and less than 95% △: Transmittance is 80% or more but less than 90% ×: Transmittance is less than 80%

[0264] [Moisture resistance test] Each photosensitive resin composition was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing would be 5.0 μm, and then prebaked on a hot plate at 100°C for 3 minutes to produce a dried film. Next, an i-line irradiance of 30 mW / cm was applied to the dried film. 2 100mJ / cm 2 After that, the resin was post-baked at 230° C. for 30 minutes using a hot air dryer to obtain a substrate with a cured resin film.

[0265] The obtained substrate with the cured resin film was placed in a thermo-hygrostat "SH-242-5" (manufactured by Espec Corporation) and subjected to a test for 500 hours under conditions of 85°C and 85% humidity. Evaluation was performed as follows.

[0266] (Evaluation method) [Remaining film rate] Measurements were made using a stylus-type step shape measuring device "P-10" (manufactured by KLA Tencor Corporation). The remaining film rate in the humidity resistance test was calculated using the formula below, with the film thickness before the test being L1 and the film thickness after the test being L2. Note that the higher the remaining film rate, the higher the durability in high-temperature, high-humidity environments, and a rating of △ or better was considered a pass. Remaining film rate (%)=L2 / L1×100

[0267] (Evaluation criteria) ◎: Remaining film rate is 95% or more ○: Remaining film rate is 90% or more but less than 95% △: Remaining film rate is 80% or more but less than 90% ×: Residual film rate is less than 80%

[0268] [Residual dimethylsiloxane rate] Measurements were made using an FT-IR measurement device "FT / IR-6300" (manufactured by JASCO Corporation). The residual dimethylsiloxane ratio was calculated by the 800 cm -1 The peak height S1 and 1461 cm originating from the isocyanuric ring -1 The peak height I1 at 800 cm originates from dimethylsiloxane after the test. -1 The peak height S2 and 1461 cm originating from the isocyanuric ring -1 The peak height I2 of the residual dimethylsiloxane was calculated using the following formula: The higher the residual dimethylsiloxane ratio, the higher the durability in a high-temperature, high-humidity environment, and a rating of △ or better was considered to be acceptable. Residual dimethylsiloxane rate (%) = (S2 / I2) / (S1 / I1) x 100

[0269] (Evaluation criteria) ◎: Residual dimethylsiloxane rate is 80% or more 〇: Residual dimethylsiloxane ratio is 70% or more and less than 80% △: Residual dimethylsiloxane ratio is 60% or more and less than 70% ×: Residual dimethylsiloxane rate is less than 60%

[0270] [Alkaline developability] Each photosensitive resin composition was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing would be 5.0 μm, and then prebaked on a hot plate at 100°C for 3 minutes to produce a dried film. Next, a negative photomask of 10 to 50 μm (in 5 μm increments) was placed on the dried film, and an i-line illuminance of 30 mW / cm was applied. 2 500mJ / cm 2 The photocuring reaction was carried out by irradiating the resin with ultraviolet light.

[0271] Next, the exposed adhesive layer was subjected to dip development in a 0.8% aqueous solution of tetramethylammonium hydroxide at 25°C. Development was continued for 10 seconds from the development time (break time = BT) at which a pattern began to appear, followed by rinsing with water to remove the unexposed portions of the cured film to form a pattern on the glass substrate. This was followed by main curing (post-baking) for 30 minutes at 230°C using a hot air dryer to obtain a substrate with a cured resin film for development evaluation.

[0272] (Evaluation method) [Development time] The time required for the unexposed areas of the coating to completely dissolve during alkaline development was recorded, and if the coating could not be removed and residue remained even after 90 seconds of development, it was marked as ×.

[0273] Line Shape After development, the 20 μm lines were evaluated using a digital microscope VHX-5000 (manufactured by Keyence Corporation) to evaluate the linearity of the pattern and the presence or absence of fringes and peeling.

[0274] (Evaluation criteria) Good: Good linearity, no fringing or peeling △: Fringes occur and linearity is poor ×: Peeling occurs and no pattern is formed.

[0275] The evaluation results are shown in Table 2.

[0276] [Table 2]

[0277] As shown in Table 2, the cured resin film described above was found to have excellent light resistance at high temperatures (blue LED resistance) and durability under high temperature and high humidity conditions. This is thought to be because the polymerizable unsaturated groups in component (A) are highly sensitive, allowing a strong three-dimensional crosslinked structure to be sufficiently formed, thereby suppressing deterioration and decomposition of the cured resin film when exposed to light at high temperatures or in high-temperature, high-humidity environments. [Industrial Applicability]

[0278] According to the present invention, it is possible to obtain an alkali-soluble silicone compound or a photosensitive resin composition that can form a cured resin film that has good light resistance at high temperatures (blue LED resistance) and durability under high temperature and high humidity conditions, and it is expected that this compound will be applied to LED semiconductor packages and their display devices.

Claims

1. An alkali-soluble silicone compound represented by the following general formula (1) or (2): 【Chemistry 1】 (However, R １ R independently represents a hydrocarbon group having 1 to 10 carbon atoms. ２ independently represent a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. X independently represent a divalent substituent which may contain a heteroatom therein. Y independently represent a hydrogen atom or a substituent represented by the following general formula (3). Z independently represent a hydrogen atom or a substituent represented by the following general formula (3). General formula (1) contains at least one substituent represented by the following general formula (3). m and n each independently represent a number from 0 to 50, and p is a number from 0 to 200. 【Chemistry 2】 (However, R ３ R independently represents a hydrocarbon group having 1 to 10 carbon atoms. ４ each independently represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom; G independently represents a hydrogen atom or a substituent represented by general formula (3), and general formula (2) contains at least one substituent represented by the following general formula (3); and q represents a number from 3 to 6. 【Transformation 3】 (However, R ５ R independently represents a hydrogen atom or a methyl group. ６ R independently represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a heteroatom. ７ are independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. L is a hydrogen atom or a substituent represented by the following general formula (4). General formula (3) contains at least one substituent represented by the following general formula (4). * is R ２ or the bond site to the silicon atom.) 【Chemistry 4】 (wherein M represents a divalent or trivalent carboxylic acid residue, and r is 1 or 2. * represents the bonding site to the oxygen atom.)

2. X in the general formula (1) is a divalent substituent represented by general formula (5). The alkali-soluble silicone compound according to claim 1 . 【Transformation 5】 (However, R ５ R independently represents a hydrogen atom or a methyl group. ６ R independently represents a hydrocarbon group having 4 to 20 carbon atoms which may contain a heteroatom. ７ are independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. L is a hydrogen atom or a substituent represented by general formula (4). * is R ２ or the bond site to the silicon atom.)

3. (A) the alkali-soluble silicone compound according to claim 1 or 2; (B) an unsaturated group-containing polymerizable compound; (C) an epoxy compound; (D) a photopolymerization initiator; A photosensitive resin composition comprising:

4. the epoxy equivalent of the component (C) is 80 g / eq to 500 g / eq, Neither the component (B) nor the component (C) contains an aromatic ring structure. The photosensitive resin composition according to claim 3 .

5. A cured resin film formed from the photosensitive resin composition according to claim 3.

6. A semiconductor package comprising the cured resin film according to claim 5.

7. A display device comprising the cured resin film according to claim 5 .

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