Photosensitive resin composition, resin curing film and image display device

Abstract

This invention provides a photosensitive resin composition comprising an alkali-soluble resin, an alkoxysilyl-containing resin, a reactive diluent, a photoradical polymerization initiator, and a solvent. The alkali-soluble resin contains a constituent unit (a-1) from a compound having an aromatic group and containing an vinyl unsaturated group, and contains an acid group and a (meth)acrylic acid group. The vinyl unsaturated group equivalent is 400 g / mol or more and 2500 g / mol or less. The alkali-soluble resin contains 15 mol% to 60 mol% of the constituent unit (a-1) in all repeating constituent units. The alkoxysilyl-containing resin comprises constituent units from a compound having an alkoxysilyl-containing vinyl unsaturated group.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a resin-cured film thereof, and an image display device having the resin-cured film. This invention is based on a patent application filed in Japan on June 21, 2021. Document No. 2021-102284 asserts priority and its contents are adopted herein. Prior Technology

[0002] In recent years, touch panels have become increasingly popular as input devices for mobile phones, tablets, vending machines, and bank ATMs (automated teller machines). Touch panels can be categorized into resistive, optical, ultrasonic, and capacitive types. Capacitive touch panels detect input position by sensing changes in capacitance between electrodes created by pressure.

[0003] Patent document 1 describes a touch panel that uses a detection electrode section with a wide-spacing grid pattern that has a small parasitic capacity and high detection sensitivity, and also uses a conductive component that improves visibility and can suppress interference when the touch panel and the display device are combined. Patent Document 2 discloses a touch panel made of a glass substrate using a coating film forming composition. Patent Document 2 describes a coating film forming composition containing a polysiloxane compound, a polythiol compound that does not contain silicon, a polymerization initiator, and an organic solvent.

[0004] Patent Document 3 describes a protective film and an insulating film for a touch panel, which are formed by curing a photosensitive resin composition. Patent Document 3 also describes a photosensitive resin composition containing: a hydrophilic resin (A) having free radical polymerizable groups, a polyfunctional (meth)acrylate (B) without phosphate groups, a (meth)acrylate (C) having phosphate groups, a silicone compound (D) having amine groups, and a photopolymerization initiator (E). [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] International Publication No. 2018 / 163603 [Patent Document 2] Japanese Patent Application Publication No. 2020-75992 [Patent Document 3] Japanese Patent Application Publication No. 2018-116271 Summary of the Invention

[0006] [The problem this invention aims to solve]

[0007] In image display devices such as touch panels, the materials used for resin-cured films as insulating and / or protective films require photosensitive resin compositions with good storage stability, suitable for use in lithography, and capable of forming resin-cured films with high-precision patterns and shapes, exhibiting excellent imaging properties. Furthermore, the photosensitive resin compositions used in the above applications require that the resin-cured films formed by curing the photosensitive resin compositions have high hardness, good adhesion to the substrate and / or base material, good water resistance, high temperature and humidity resistance, and good transparency. However, conventional photosensitive resin compositions cannot meet all the aforementioned performance requirements of the resin curing film materials used in image display devices.

[0008] In view of the above facts, the present invention aims to provide a photosensitive resin composition that has good storage stability and, when used by photolithography, has good imaging properties that can form a resin curing film with high-precision pattern shape. By curing it, a resin curing film with high hardness and good adhesion to the substrate and / or base material, water resistance, high temperature and high humidity resistance, and transparency can be obtained. Furthermore, the object of the present invention is to provide a resin-cured film formed by curing the photosensitive resin composition of the present invention, which has high hardness, good adhesion to the substrate and / or base material, water resistance, high temperature and high humidity resistance, and good transparency, and an image display device having the above. [Methods for solving problems]

[0009] The present invention provides the following first type of composition. [1] A photosensitive resin composition, characterized in that it contains (A) Alkali-soluble resin, and (B) Resins containing alkoxysilyl groups, and (C) Reactive diluent, with (D) Photoradical polymerization initiator, and (E) Solvent, The aforementioned (A) alkali-soluble resin contains a (a-1) constituent unit derived from a compound (ma-1) having an aromatic group and an vinyl unsaturated group, containing an acid group and a (meth)acrylic acid group, and the vinyl unsaturated group equivalent is 400 g / mol or more and 2500 g / mol or less. The aforementioned (A) alkali-soluble resin contains, in its fully repeating constituent units, at a concentration of 15 mol% and 60 mol% or less of the aforementioned constituent unit (a-1). The aforementioned (B) alkoxysilyl-containing resin comprises (b-1) a constituent unit derived from a compound (mb-1) having an alkoxysilyl-containing vinyl unsaturated group.

[0010] The first embodiment of the present invention preferably has the following features. A combination of two or more of the following features is also preferred. [2] The photosensitive resin composition as in [1], wherein the mass ratio of the aforementioned (A) alkali-soluble resin to the aforementioned (B) alkoxysilyl-containing resin is 40:60 to 99:1. [3] The photosensitive resin composition such as [1] or [2], wherein the content of the aforementioned constituent unit (b-1) in the fully repeating constituent unit of the aforementioned (B) alkoxysilyl resin is 45 mol% or more.

[0011] [4] The photosensitive resin composition of any of [1] to [3], wherein the aforementioned (A) alkali-soluble resin is a resin in which a portion of the carboxyl group of a copolymer of the aforementioned constituent unit (a-1), a constituent unit (a-2) from an unsaturated monocarboxylic acid (ma-2), and a constituent unit (a-3) from a compound (ma-3) having an alicyclic hydrocarbon group containing an ethylene unsaturated group is modified by a constituent unit (a-5) from an epoxy-containing (meth)acrylate (ma-5).

[0012] [5] The photosensitive resin composition of any of [1] to [4], wherein the acid value of the aforementioned (A) alkali-soluble resin is above 20KOH mg / g and below 200KOH mg / g. [6] The photosensitive resin composition of any of [1] to [5], wherein the weight average molecular weight (Mw) of the aforementioned (A) alkali-soluble resin is more than 1,000 and less than 50,000. [7] Photosensitive resin composition of any of [1] to [6], wherein the aforementioned (B) alkoxysilyl-containing resin contains a constituent unit (b-2) derived from an unsaturated monobasic acid (mb-2). The acid value is below 150 KOH mg / g. [8] The photosensitive resin composition of any of [1] to [7], wherein the weight average molecular weight (Mw) of the aforementioned (B) alkoxysilyl resin is more than 1,000 and less than 20,000.

[0013] [9] A photosensitive resin composition as described in any of [1] to [8], wherein, relative to the total of 100 parts by mass of the aforementioned (A) alkali-soluble resin, the aforementioned (B) alkoxysilyl-containing resin, and the aforementioned (C) reactive diluent, Contains 5-75 parts by weight of the aforementioned reactive diluent (C). It contains 0.1 to 20 parts by mass of the aforementioned (D) photoradical polymerization initiator.

[10] A photosensitive resin composition as described in any of [1] to [9], wherein the solvent (E) mentioned above contains one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms. Furthermore, the total content of the aforementioned alcohols in the total solvent is 15-100% by mass.

[0014]

[11] A photosensitive resin composition of any of [1] to

[10] , wherein it further comprises (F) a siloxane coupling agent.

[12] The photosensitive resin composition as in

[11] , wherein the aforementioned (F)siloxane coupling agent has one or more functional groups selected from (meth)acrylyl, vinyl, and styrene.

[13] The photosensitive resin composition as in

[11] or

[12] , wherein, relative to the total of 100 parts by mass of the aforementioned (A) alkali-soluble resin, the aforementioned (B) alkoxysilyl-containing resin, and the aforementioned (C) reactive diluent, It contains 0.1 to 20 parts by weight of the aforementioned (F) siloxane coupling agent.

[0015] The present invention provides a resin-cured film of the second type.

[14] A resin curing film, which is a curing material containing a photosensitive resin composition of any one of [1] to

[13] . The present invention provides a third type of image display device as described below.

[15] An image display device having a resin curing film as described in

[14] . The device of the third embodiment of the present invention preferably has the following features. A combination of two or more of the following features is also preferred.

[16] The image display device as described in

[15] has a protective film made of the aforementioned resin hardened film.

[17] The image display device as described in

[15] has an insulating film made of the aforementioned resin-cured film. [Invention Effects]

[0016] The photosensitive resin composition of this invention contains a specific (A) alkali-soluble resin, a specific (B) alkoxysilyl-containing resin, a reactive diluent, a photoradical polymerization initiator, and a solvent. Therefore, the photosensitive resin composition of this invention exhibits good storage stability. Furthermore, due to its excellent image development properties, the photosensitive resin composition of this invention can be used to form a resin-cured film with a highly precise pattern shape using photolithography. Moreover, by curing, the photosensitive resin composition of this invention can yield a resin-cured film with high hardness and good adhesion to the substrate and / or base material, water resistance, high temperature and humidity resistance, and transparency. Therefore, the photosensitive resin composition of this invention is suitable as a material for resin-cured films used as insulating and / or protective films in image display devices such as touch panels.

[0017] The resin-cured film of the present invention has high hardness due to the presence of the photosensitive resin composition of the present invention as a cured product, and exhibits good adhesion to the substrate and / or base material, water resistance, high temperature and high humidity resistance, and transparency. The image display device of the present invention has excellent reliability and durability due to the resin curing film of the present invention. Implementation

[0018] The following provides a detailed description of preferred embodiments of the photosensitive resin composition, resin curing film, and image display device of the present invention. Furthermore, the present invention is not limited to the embodiments shown below. For example, as long as the scope of the present invention is not exceeded, values, types, quantities, materials, types, times, temperatures, sequences, etc., can be omitted, added, substituted, or otherwise modified. In this specification, "(meth)acrylic acid" means selected from at least one of methacrylic acid and acrylic acid. The same applies to "(meth)acrylate", "(meth)acrylic acid oxy", etc.

[0019] [Photosensitive resin composition] The photosensitive resin composition of this embodiment contains (A) an alkali-soluble resin, (B) an alkoxysilyl-containing resin, (C) a reactive diluent, (D) a photoradical polymerization initiator, and (E) a solvent. If necessary, the photosensitive resin composition of this embodiment may also further contain (F) a siloxane coupling agent. Upon exposure to light, the photosensitive resin composition of this embodiment undergoes polymerization and hardening of (A) the alkali-soluble resin, (B) the alkoxysilyl-containing resin, and (C) the reactive diluent, forming a hardened resin film.

[0020] [(A) Alkali-soluble resin] (A) Alkali-soluble resins contain a constituent unit (a-1) derived from a compound (ma-1) having an aromatic group and an vinyl unsaturated group (hereinafter simply referred to as "constituent unit (a-1)"), and have an acid group and a (meth)acrylic oxy group. However, resins having an alkoxysilyl group are not equivalent to (A) alkali-soluble resins. The photosensitive resin composition of this embodiment contains (A) an alkali-soluble resin, which provides good storage stability. Furthermore, because it contains (A) an alkali-soluble resin, it can become a photosensitive resin composition capable of forming a resin-cured film with good image development, water resistance, and high temperature and humidity resistance.

[0021] Examples of acid groups in (A) alkali-soluble resins include carboxyl groups, phosphate groups (-OP(=O)(OH) 2), and tannic acid groups (-S(=O) 2OH). From the viewpoint of the alkali solubility of photosensitive resin components, the presence of carboxyl groups is preferable. Methods for introducing acid groups into (A) alkali-soluble resins include, for example, introducing them by polymerizing a monomer containing a monomer with an acid group, and introducing them by adding an anhydride to a (A) alkali-soluble resin precursor with an epoxy group.

[0022] As a method for introducing (meth)acrylic acid oxy groups into (A) alkali-soluble resins, a method as shown below can be used. A functionalized resin precursor can be prepared by polymerizing a raw material monomer containing a monomer having a functional group. Then, a compound having a group and a (meth)acrylic acid oxy group that are reactive with the functional group contained in the functionalized resin precursor is reacted with the functionalized resin precursor. Thereby, an (A) alkali-soluble resin having a (meth)acrylic acid oxy group is obtained.

[0023] Examples of combinations of functional groups and reactive groups in functionalized resin precursors include combinations of carboxyl groups and epoxy groups, isocyanate groups and hydroxyl groups. Specifically, combinations of carboxyl groups and epoxy groups include unsaturated monocarboxylic acids such as (meth)acrylic acid and epoxy-containing (meth)acrylates such as glycidyl (meth)acrylate. Specifically, combinations of isocyanate groups and hydroxyl groups include monomers containing isocyanate groups such as 2-(meth)acryloyloxyethyl isocyanate and hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate.

[0024] (A) In the alkali-soluble resin, in addition to the aforementioned constituent unit (a-1), it is preferable to introduce the acid group by having a constituent unit (a-2) derived from an unsaturated monocarboxylic acid (ma-2) (hereinafter simply referred to as "constituent unit (a-2)"). (A) In the alkali-soluble resin, in addition to the aforementioned constituent units (a-1) and (a-2), it is even more preferable to include a constituent unit (a-3) derived from a compound (ma-3) containing an ethylene unsaturated group having an alicyclic hydrocarbon group (hereinafter simply referred to as "constituent unit (a-3)"). (A) In the alkali-soluble resin, in addition to the aforementioned constituent units (a-1) to (a-3), it is also preferable to have a constituent unit (a-4) derived from other compounds (ma-4) containing ethylene unsaturated groups (hereinafter simply referred to as "constituent unit (a-4)").

[0025] In (A) of the alkali-soluble resins, when the acid group of (A) the alkali-soluble resin is a carboxyl group, it is preferable that a portion of the aforementioned carboxyl group has been modified by a constituent unit (a-5) derived from an epoxy-containing (meth)acrylate (ma-5) (hereinafter simply referred to as "constituent unit (a-5)"). That is, it is preferable that (A) the alkali-soluble resin has a (meth)acrylic acid group introduced into its side chain.

[0026] (A) In the alkali-soluble resin, the equivalent amount of vinyl unsaturated groups is 400 g / mol or more, preferably 500 g / mol or more, even more preferably 550 g / mol or more, and even more preferably 590 g / mol or more. If the equivalent amount of vinyl unsaturated groups is 400 g / mol or more, it can react sufficiently with the reactive diluent (C) to become a photosensitive resin composition with good imaging properties, and also a photosensitive resin composition that yields a resin-cured film with high hardness. Furthermore, if the equivalent amount of vinyl unsaturated groups is 400 g / mol or more, it can suppress curing shrinkage in the resin-cured film formed by curing the photosensitive resin composition. Therefore, a resin-cured film with good adhesion to the substrate and / or base material can be obtained.

[0027] (A) In the alkali-soluble resin, the equivalent of vinyl unsaturated groups is 2500 g / mol or less, preferably 2000 g / mol or less, even more preferably 1500 g / mol or less, and even more preferably 1400 g / mol or less. If the equivalent of vinyl unsaturated groups is 2500 g / mol or less, sufficient alkali solubility and sufficient imaging properties can be ensured. By curing it, it becomes a photosensitive resin composition that can obtain a resin-cured film with sufficient resistance to high temperature and high humidity. (A) The equivalent of vinyl unsaturated groups in alkali-soluble resins can be adjusted according to, for example, the proportion of units (a-2) from unsaturated monocarboxylic acids (ma-2) and / or the proportion of units (a-5) from epoxy-containing (meth)acrylates (ma-5) in alkali-soluble resins.

[0028] In this specification, "ethylene unsaturated bond equivalent" refers to the mass of 1 mol of polymer per unsaturated bond. The ethylene unsaturated bond equivalent of (A) alkali-soluble resin can be calculated (g / mol) by dividing the mass of (A) alkali-soluble resin by the number of moles of unsaturated bonds contained in (A) alkali-soluble resin. In this specification, the theoretical value calculated from the amount of monomers (ma-1) to (ma-5) added when manufacturing (A) alkali-soluble resin can be used as the "ethylene unsaturated bond equivalent".

[0029] <Constituting Unit (a-1)> (A) The alkali-soluble resin contains a constituent unit (a-1) of a compound (ma-1) that does not have an acid group or an epoxy group and is derived from an aromatic group containing an vinyl unsaturated group. In this embodiment, (A) the alkali-soluble resin, because it contains the constituent unit (a-1), becomes a photosensitive resin composition capable of forming a resin-cured film with good image development, water resistance, and high temperature and humidity resistance. The constituent unit (a-1) may be a compound (ma-1) derived from only one type of aromatic group containing an ethylene unsaturated group, or it may be a compound (ma-1) derived from two or more types of aromatic group containing an ethylene unsaturated group.

[0030] Examples of compounds (ma-1) containing aromatic groups and vinyl unsaturated groups that serve as raw materials for the constituent unit (a-1) include styrene compounds such as styrene, methoxystyrene, tert-butoxystyrene, methylstyrene, chlorostyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylammonostyrene; styrene compounds containing aromatic rings such as benzyl (meth)acrylate, rosin (meth)acrylate, triphenylmethyl (meth)acrylate, benzyl (meth)acrylate, isopropylphenyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, biphenoxyethyl (meth)acrylate, naphthyl (meth)acrylate, and anthracene (meth)acrylate; vinyl unsaturated monomers containing phenolic hydroxyl groups such as 4-hydroxybenzylmethyl acrylate and N-hydroxybenzylmaleimide; and ethylene toluene.

[0031] Among these compounds (ma-1) containing aromatic groups and vinyl unsaturated groups, from the viewpoint of availability of raw materials and ease of reaction, styrene compounds and (meth)acrylates with aromatic rings are preferred. Furthermore, from the viewpoint of controlling the base reaction, vinyl unsaturated monomers with phenolic hydroxyl groups are preferred. The compound (ma-1) containing vinyl unsaturated groups is preferably selected from one or more of benzyl (meth)acrylates, styrene, and 4-hydroxybenzyl methacrylates, with benzyl (meth)acrylates and / or styrene being even more preferred.

[0032] <Constituting Unit (a-2)> (A) In alkali-soluble resins, acid groups can also be introduced by containing a constituent unit (a-2) from an unsaturated monobasic acid (ma-2). (A) In alkali-soluble resins, by containing a constituent unit (a-2), a photosensitive resin composition with better alkali solubility is formed.

[0033] The constituent unit (a-2) can be derived from only one type of unsaturated monocarboxylic acid (ma-2), or from two or more types of unsaturated monocarboxylic acids (ma-2). Examples of unsaturated monocarboxylic acids (ma-2) that serve as the raw materials for the constituent unit (a-2) include (meth)acrylic acid, itaconic acid, crotonic acid, ethylene benzoic acid, and α-haloalkyl, alkoxy, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid. Among these unsaturated monocarboxylic acids (ma-2), (meth)acrylic acid is preferred for forming a photosensitive resin with good imaging properties.

[0034] <Compositional Units (a-3)> (A) Alkali-soluble resins may also contain constituent units (a-3) of compounds (ma-3) that do not have aromatic groups, acid groups, or epoxy groups and are derived from alicyclic hydrocarbon groups containing vinyl unsaturated groups. (A) By having constituent units (a-3), alkali-soluble resins can produce resin-cured films with higher hardness, good resistance to high temperature and humidity, excellent resistance to heat yellowing, and good transparency.

[0035] The constituent unit (a-3) can be a compound (ma-3) derived from only one type of alicyclic hydrocarbon group containing an ethylene-unsaturated group, or it can be a compound (ma-3) derived from two or more types of alicyclic hydrocarbon groups containing an ethylene-unsaturated group. Examples of constituent units (a-3) include monomer units derived from alicyclic alcohols and ester compounds of methacrylic acid. As an alicyclic alcohol, it is preferred to have 6 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms. Alicyclic alcohols can also be monocyclic or polycyclic, with polycyclic alicyclic alcohols being more preferred.

[0036] Examples of compounds (ma-3) containing ethylene-containing unsaturated groups with alicyclic hydrocarbon groups that serve as raw materials for the constituent unit (a-3) include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, tricyclodecyl (meth)acrylate (dicyclopentyl (meth)acrylate), tricyclodecyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isocamphenyl (meth)acrylate, adamantyl (meth)acrylate, rosin (meth)acrylate, norcamphenyl (meth)acrylate, 5-methylnorcamphenyl (meth)acrylate, and 5-ethylnorcamphenyl (meth)acrylate.

[0037] Among these compounds (ma-3) containing ethylene-containing unsaturated groups with alicyclic hydrocarbon groups, in order to obtain a photosensitive resin composition that produces a resin-curing film with high hardness, good resistance to high temperature and humidity, excellent resistance to heat yellowing, and good transparency, it is preferable to use (meth)acrylates with alicyclic hydrocarbon groups having 6 to 20 carbon atoms, and even more preferable to use (meth)acrylates with polycyclic alicyclic hydrocarbon groups, and even more preferable to use tricyclic decyl (meth)acrylates.

[0038] From the viewpoint of the physical properties and raw material availability of the resin-cured film formed by curing the photosensitive resin composition, the preferred combination of constituent units in (A) alkali-soluble resin is that the constituent unit (a-1) is selected from one or more of benzyl (meth)acrylate, styrene, and hydroxyphenyl (meth)acrylate from a compound (ma-1) containing an aromatic group and an vinyl unsaturated group; the constituent unit (a-2) is selected from (meth)acrylic acid from an unsaturated monocarboxylic acid (ma-2); and the constituent unit (a-3) is selected from tricyclodecyl (meth)acrylate from a compound (ma-3) containing an alicyclic hydrocarbon group and an vinyl unsaturated group.

[0039] <Compositional Units (a-4)> (A) In alkali-soluble resins, as necessary, in addition to the constituent units (a-1) to (a-3), the resin may also contain constituent units (a-4) from other compounds containing vinyl unsaturated groups (ma-4). The constituent unit (a-4) may be derived from only one other compound containing vinyl unsaturated groups (ma-4), or it may be derived from two or more other compounds containing vinyl unsaturated groups (ma-4).

[0040] Other compounds containing vinyl unsaturated groups (ma-4) that serve as raw materials for the constituent unit (a-4) are acceptable as long as they do not have aromatic groups, acid groups, or alicyclic hydrocarbon groups, and possess vinyl unsaturated groups. There are no particular limitations. Examples include dienes such as butadiene, isoprene, and chloroprene; methacrylates, ethyl methacrylates, n-propyl methacrylates, isopropyl methacrylates, n-butyl methacrylates, tert-butyl methacrylates, pentyl methacrylates, neopentyl methacrylates, isopentyl methacrylates, hexyl methacrylates, 2-ethylhexyl methacrylates, lauryl methacrylates, dodecyl methacrylates, tetrahydrofuran methacrylates, 1,1,1-trifluoroethyl methacrylates, and perfluoroethyl methacrylates. Acrylates, perfluoro-n-propyl (meth)acrylates, perfluoro-isopropyl (meth)acrylates, 3-(N,N-dimethylamino)propyl (meth)acrylates, etc., are (meth)acrylates without aromatic rings; methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dipropylacrylamide, N,N-diisopropylacrylamide, etc. (Meth)acrylic acid amide; (meth)acrylic acid aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, ethylene toluene, etc.; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl butenedioic acid, diethyl itaconic acid, etc.; monomaleimides such as N-benzenemaleimide, N-laurylmaleimide, etc.; etc.

[0041] Among the other vinyl unsaturated group-containing compounds (ma-4) that are the raw materials for these constituent units (a-4), in order to become a photosensitive resin composition that has good adhesion to the substrate and / or base, it is preferable to be a (meth)acrylate without an aromatic ring, and even more preferably to be a tetrahydrofuran methyl (meth)acrylate.

[0042] <Epoxy-containing (meth)acrylates (ma-5)> (A) When the acid group of the alkali-soluble resin is a carboxyl group, (A) in the alkali-soluble resin, by modifying a portion of the aforementioned carboxyl group through the constituent unit (a-5) from the epoxy-containing (meth)acrylate (ma-5), a (meth)acrylic acid group can also be introduced. (A) In the alkali-soluble resin, it is preferable that a portion of the carboxyl group from the aforementioned unsaturated monocarboxylic acid (ma-2) is modified through the aforementioned constituent unit (m-5).

[0043] In the (A) alkali-soluble resin, a portion is modified by the constituent unit (m-5). During the manufacturing process of the (A) alkali-soluble resin, the resin is reacted with an epoxy-containing (meth)acrylate (ma-5) to modify a portion of the resin into the constituent unit (m-5). Therefore, it is easier to obtain an (A) alkali-soluble resin with an ethylene unsaturated group equivalent within a favorable range. Thus, when a portion of the (A) alkali-soluble resin is modified by the constituent unit (m-5), it is easier to obtain a photosensitive resin composition with good image development and the ability to form a resin-cured film with good resistance to high temperatures and humidity.

[0044] There are no particular limitations on (meth)acrylates containing epoxy groups (ma-5) as long as they do not have aromatic or acid groups and have epoxy groups. The constituent unit (a-5) may be derived from only one type of epoxy-containing (meth)acrylate (ma-5), or from two or more types of epoxy-containing (meth)acrylate (ma-5).

[0045] Examples of epoxy-containing (meth)acrylates (ma-5) that serve as raw materials for constituting unit (a-5) include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl meth (meth)acrylate, (meth)acrylates having alicyclic epoxy groups and their lactone adducts, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, epoxy compounds of dicyclopentenyl (meth)acrylate, and epoxy compounds of dicyclopentenyloxyethyl (meth)acrylate. Among these epoxy-containing (meth)acrylates (ma-5), glycidyl (meth)acrylate and 3,4-epoxycyclohexyl meth (meth)acrylate are preferred in terms of the ease of obtaining raw materials.

[0046] (A) The alkali-soluble resin contains: a-1 (a-1) of a compound (ma-1) having an aromatic group and containing an ethylene unsaturated group, a-2 (a-2) of an unsaturated monocarboxylic acid (ma-2), and a-3 (a-3) of a compound (ma-3) having an alicyclic hydrocarbon group. If necessary, it is preferable that a portion of the carboxyl group of a resin precursor composed of a copolymer containing a-4 (a-4) of another compound (ma-4) containing an ethylene unsaturated group is modified with a functional group (a-5) of an epoxy-containing (meth)acrylate (ma-5). That is, (A) the alkali-soluble resin contains the resin precursor's constituent units (a-1) to (a-3), and if necessary, it is preferable that the side chain of a copolymer containing unit (a-4) is modified with unit (a-5).

[0047] <(A) Proportion of each constituent unit in alkali-soluble resin> In this specification, "(A) alkali-soluble resin's fully repeatable constituent units" means the constituent units that make up the main chain of (A) alkali-soluble resin, excluding constituent units that have been modified and introduced into the side chains.

[0048] (A) The content of constituent unit (a-1) in the fully repeating constituent units of the alkali-soluble resin is 15 mol% or more, preferably 20 mol% or more, even more preferably 30 mol% or more, and even more preferably 35 mol% or more. If the content of constituent unit (a-1) is 15 mol% or more, it will become a photosensitive resin composition with sufficient image development and capable of forming a resin curing film with sufficient water resistance and high temperature and humidity resistance.

[0049] Furthermore, the content of constituent unit (a-1) is 60 mol% or less, preferably 50 mol% or less, and even more preferably 45 mol% or less. When the content of constituent unit (a-1) is 60 mol% or less, a resin-cured film with sufficient transparency can be obtained. Furthermore, when the content of constituent unit (a-1) is 60 mol% or less, the functions provided by other components including constituent unit (a-1) can be fully obtained. Therefore, if the content of constituent unit (a-1) is excessive, it can prevent the formation of a photosensitive resin composition that easily results in a resin-cured film with deteriorated adhesion to the substrate and / or base material.

[0050] When the alkali-soluble resin contains constituent unit (a-2), the content of constituent unit (a-2) in the fully repeating constituent unit of the alkali-soluble resin is preferably 15 mol% to 60 mol%, preferably 20 mol% to 55 mol%, and preferably 25 mol% to 50 mol% from the perspective of the solubility of the photosensitive resin composition in the alkali developing solution.

[0051] When the alkali-soluble resin contains constituent unit (a-3), the content of constituent unit (a-3) in the fully repeating constituent units of (A) alkali-soluble resin is preferably 2 mol% to 50 mol%, more preferably 5 mol% to 40 mol%, and even more preferably 9 mol% to 30 mol%. If the content of constituent unit (a-3) is 2 mol% or more, it will result in a photosensitive resin composition that produces a resin-cured film with higher hardness, good resistance to high temperature and humidity, excellent resistance to heat yellowing, and good transparency. If the content of constituent unit (a-3) is 50 mol% or less, it will ensure sufficient content of other constituent units of constituent unit (a-3) and result in a photosensitive resin composition or resin-cured film that achieves a better balance of various properties.

[0052] (A) The acid group of the alkali-soluble resin is a carboxyl group, and a portion of the aforementioned carboxyl group is modified by an epoxy-containing (meth)acrylate (ma-5) to transform it into a constituent unit (a-5). The modified mass of the carboxyl group transformed into a constituent unit (a-5) is preferably 15 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, and even more preferably 30 mol% to 70 mol%. The modified mass of the carboxyl group transformed into a constituent unit (a-5) refers to the ratio of the number of constituent units (a-5) to the total number of carboxyl groups in (A) alkali-soluble resin.

[0053] If the mass of the carboxyl group converted into the constituent unit (a-5) is 15 mol% or more, then a sufficient amount of (meth)acrylic acid oxygen will be introduced into (A) alkali-soluble resin, which can react fully with (C) reactive diluent, and a resin-cured film with good imaging properties, sufficient hardness, and adhesion to the substrate and / or base material will be obtained. If the carboxyl group modification mass is less than 90 mol%, then (A) a sufficient amount of carboxyl groups will remain in the alkali-soluble resin. Therefore, it can ensure sufficient alkali solubility, has good imaging properties, and become a photosensitive resin composition that can produce a resin-cured film with sufficient resistance to high temperature and high humidity. If the modified carboxyl group has a mass of 15 mol% to 90 mol%, it is easy to become a photosensitive resin composition of (A) alkali-soluble resin with an equivalent of 400 g / mol to 2500 g / mol of vinyl unsaturated group.

[0054] <(A) Acid value of alkali-soluble resin> (A) The acid value of the alkali-soluble resin is preferably 20KOH mg / g~200KOH mg / g, even better is 25KOH mg / g~180KOH mg / g, and preferably 30KOH mg / g. A value of 150 mg / g KOH is preferred. An acid value of 20 mg / g or higher results in a photosensitive resin composition with excellent solubility in alkaline developing solutions and good developing properties. An acid value of 200 mg / g or lower inhibits (A) the decomposition of (B) alkoxysilyl-containing resins caused by excessively high acid values ​​in alkali-soluble resins, and results in a photosensitive resin composition with good storage stability. The aforementioned acid value can be arbitrarily selected within the above range, and can be, for example, 40 mg / g to 130 mg / g, or 60 mg / g to 100 mg / g. KOH mg / g, etc.

[0055] The acid value of (A) alkali-soluble resin can be adjusted, for example, by adjusting the amount of unsaturated monocarboxylic acid (ma-2) used as a raw material for constituent unit (a-2), thereby adjusting the content of constituent unit (a-2). When a portion of the (A) alkali-soluble resin is modified by constituent unit (m-5), during the manufacturing process of the (A) alkali-soluble resin, a portion of the carboxyl group from the unsaturated monocarboxylic acid (ma-2) is modified by constituent unit (m-5) from an epoxy-containing (meth)acrylate (ma-5). Sometimes, the acid value of the (A) alkali-soluble resin may be insufficient. In this case, a portion of the (A) alkali-soluble resin modified by constituent unit (m-5) can also introduce carboxyl groups to compensate for the insufficient acid value. Specifically, this can be achieved by using the aforementioned epoxy group ring-opening method contained in a portion of the (A) alkali-soluble resin modified by constituent unit (m-5) to add anhydrides to the resulting hydroxyl groups.

[0056] In this embodiment, the acid value of (A) alkali-soluble resin is determined according to JIS K6901 5.3 using a mixture of bromophenyl phenol blue and phenol red as indicators. The acid value of (A) alkali-soluble resin refers to the number of mg of potassium hydroxylate required to neutralize the acidic components contained in 1 g of a sample containing (A) alkali-soluble resin.

[0057] <(A) Weight average molecular weight (Mw) of alkali-soluble resins> (A) The weight-average molecular weight (Mw) of the alkali-soluble resin, converted from polystyrene, is preferably 1,000 to 50,000, more preferably 5,000 to 45,000, and even more preferably 8,000 to 42,000. (A) If the weight-average molecular weight (Mw) of the alkali-soluble resin is above 1,000, the curing shrinkage of the resin-cured film formed by the curing of the photosensitive resin composition will be sufficiently reduced, and the adhesion to the substrate and / or base material will be better. (A) If the weight-average molecular weight (Mw) of the alkali-soluble resin is below 50,000, it will become a photosensitive resin composition with good imaging properties.

[0058] In this embodiment, the weight-average molecular weight (Mw) of the alkali-soluble resin (A) was determined using gel permeation chromatography (GPC) under the following conditions and calculated using polystyrene. Tube string: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40℃ Sample: A tetrahydrofuran solution containing (A) alkali-soluble resin at a content of 0.2% by mass. Solvent: Tetrahydrofuran Detector: Differential refractometer (trade name: Showdex RI-71S, manufactured by Showa Denko Co., Ltd.) Flow rate: 1 mL / min

[0059] <(A) Manufacturing Method of Alkali-Soluble Resin> As a method for manufacturing (A) alkali-soluble resin, conventionally known methods can be used. For example, (A) alkali-soluble resin comprises: a constituent unit (a-1) from a compound (ma-1) having an aromatic group and containing an ethylene unsaturated group, a constituent unit (a-2) from an unsaturated monocarboxylic acid (ma-2), and a constituent unit (a-3) from a compound (ma-3) having an alicyclic hydrocarbon group, and, if necessary, further comprises a resin precursor from a copolymer containing a constituent unit (a-4) of another ethylene unsaturated group (ma-4) that has been modified with a constituent unit (a-5) from an epoxy-containing (meth)acrylate (ma-5), it can be manufactured by the method shown below.

[0060] A monomeric material consisting of a compound containing an aromatic, vinyl unsaturated group (ma-1), an unsaturated monocarboxylic acid (ma-2), a compound containing an alicyclic hydrocarbon group (ma-3), and other compounds containing vinyl unsaturated groups as necessary (a-4) is added to a solvent along with a polymerization initiator, and copolymerized at 50–130°C for 1–20 hours. This produces a reaction solution containing a resin precursor composed of copolymers comprising constituent units (a-1) to (a-3) and, as necessary, constituent units (a-4).

[0061] As polymerization initiators, t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, azobisisovalerate, 2,2'-azobis(methyl isobutyrate), benzoyl peroxide, etc., can be used. These polymerization initiators can be used alone or in combination of two or more. The amount of polymerization initiator used relative to the total amount of raw material monomers added is 100 parts by weight, generally 0.5 to 20 parts by weight, preferably 1.0 to 10 parts by weight.

[0062] As a solvent, it is acceptable as long as it is inert in the polymerization reaction of the raw monomers; there are no particular limitations. Examples of solvents include alkanols such as propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, and dodecyl alcohol; benzyl alcohol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, 3-methoxy-1-butanol, etc. (poly)alkylene glycol monoalkyl ethers; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and other (poly)alkylene glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. 2-Hydroxypropionate, 2-Hydroxypropionate, 2-Hydroxy-2-methylpropionate, 2-Hydroxy-2-methylpropionate, 3-Methoxypropionate, 3-Methoxypropionate, 3-Ethoxypropionate, 3-Ethoxypropionate, Ethyl ethoxylate, Ethyl hydroxyacetate, 2-Hydroxy-3-methylbutyrate, 3-Methyl-3-methoxybutylacetic acid, 3-Methyl-3-methoxybutyl... Esters including ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentane acetate, i-pentane acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-side-oxyethyl butyrate, etc. Aromatic hydrocarbons such as toluene and xylene; Carboxylic acid amines such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0063] Among these solvents, glycol ether solvents are preferred, especially (poly)alkyl glycol monoalkyl ethers such as propylene glycol monomethyl ether and (poly)alkyl glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate. These solvents can be used alone or in mixtures of two or more.

[0064] Subsequently, an epoxy-containing (meth)acrylate (ma-5) is added to the reaction solution, along with a catalyst and / or polymerization inhibitor as needed, to allow it to react. Thereby, a portion of the carboxyl group in the constituent unit (a-2) of the resin precursor undergoes a ring-opening addition reaction with the epoxy group in the epoxy-containing (meth)acrylate (ma-5). As a result, an alkali-soluble resin (A) is obtained, in which a portion of the side chain of the copolymer of the resin precursor is modified from the constituent unit (m-5) of the epoxy-containing (meth)acrylate (ma-5). In this embodiment, the epoxy-containing (meth)acrylate (ma-5) used in the reaction reacts entirely with the carboxyl group in the constituent unit (a-2) contained in the resin precursor, which can be regarded as being modified by the constituent unit (a-5).

[0065] As a catalyst, substances such as triphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, and p-styrene-diphenylphosphine can be used. As polymerization inhibitors, substances such as hydroquinone, butylated hydroxytoluene, hydroquinone, methoxyphenol, and methylhydroquinone can be used.

[0066] [(B) Resins containing alkoxysilyl groups] (B) The alkoxysilyl resin contains a constituent unit (b-1) derived from a compound (mb-1) having an alkoxysilyl vinyl unsaturated group (hereinafter simply referred to as "constituent unit (b-1)"). (B) The resin containing alkoxysilyl groups may, as necessary, also contain constituent units (b-2) (hereinafter simply referred to as "constituent units (b-2)") from unsaturated monocarboxylic acids (mb-2) and / or constituent units (b-3) (hereinafter simply referred to as "constituent units (b-3)") from other compounds containing vinyl unsaturated groups (mb-3). The photosensitive resin composition of this embodiment contains (B) an alkoxysilyl resin, which results in a photosensitive resin composition with high hardness and the ability to form a resin curing film with good resistance to high temperature and high humidity.

[0067] <Construction Unit (b-1)> The constituent unit (b-1) may be a compound derived from only one type of alkoxysilyl group containing an ethylene-containing unsaturated group (mb-1), or it may be a compound derived from two or more types of alkoxysilyl groups containing an ethylene-containing unsaturated group (mb-1).

[0068] The compound (mb-1) containing an alkoxysilyl group and an vinyl unsaturated group, which serves as the raw material for the constituent unit (b-1), can be any monomer containing both an alkoxysilyl group and an vinyl unsaturated group, without particular limitation. It is preferable that the alkoxysilyl group has 1 to 6 carbon atoms, more preferably 1 to 4, and even more preferably 1 to 2. The alkoxysilyl group can also have one or more alkoxy groups. If the alkoxysilyl group is a trialkoxysilyl group with three alkoxy groups, it will become a resin containing an alkoxysilyl group (B) with more crosslinking points in the constituent unit (b-1), thus becoming a photosensitive resin composition with better curability, which is preferable.

[0069] The compound (mb-1) containing an alkoxysilyl group with an ethylene-containing unsaturated group is preferred because it has better reactivity and is easier to obtain when synthesizing (B) alkoxysilyl-containing resins. The constituent unit (b-1) is preferably represented by the constituent unit of the following formula (1).

[0070] [In formula (1), R1 represents a hydrogen atom or a methyl group. R2 to R4 each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. At least one of R2 to R4 is an alkoxy group with 1 to 6 carbon atoms. n is an integer from 1 to 10].

[0071] In formula (1), R1 represents a hydrogen atom or a methyl group, with methyl being preferred. In formula (1), R2 to R4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. At least one of R2 to R4 is an alkoxy group having 1 to 6 carbon atoms. When R2 to R4 are alkyl groups having 1 to 6 carbon atoms, 1 to 4 carbon atoms are preferred, and 1 to 2 carbon atoms are even more preferred. When R2 to R4 are alkoxy groups having 1 to 6 carbon atoms, 1 to 4 carbon atoms are preferred, and 1 to 2 carbon atoms are even more preferred.

[0072] In formula (1), it is preferable that R2 to R4 are each independently an alkyl group with 1 to 6 carbon atoms or an alkoxy group with 1 to 6 carbon atoms. It is even more preferable that two or three of R2 to R4 are alkoxy groups with 1 to 6 carbon atoms, since it will become a resin containing alkoxysilyl groups with more crosslinking points in the (B) constitutive unit (b-1) and become a photosensitive resin composition with better curability. Therefore, it is even more preferable that all three of R2 to R4 are alkoxy groups with 1 to 6 carbon atoms. As a specific example, in formula (1), it is preferable that R2 to R4 are each independently methyl, ethyl, methoxy or ethoxy, and it is even more preferable that at least one of R2 to R4 is methoxy or ethoxy. In equation (1), n ​​is an integer from 1 to 10, with 1 to 4 being preferred.

[0073] As a specific example of the constituent unit represented by the above formula (1), there are examples from 3-(meth)propenyloxypropylmethyldimethoxysiloxane (in formula (1), R1: hydrogen atom (or methyl); R2: methyl; R3, R4: methoxy; n: 3), 3-(methyl)propenyloxypropylethyl dimethoxysiloxane (in formula (1), R1: hydrogen atom (or methyl); R2: ethyl; R3, R4: methoxy; n: 3), 3-(methyl)propenyloxypropylmethyldiethoxysiloxane (in formula (1), R1: hydrogen atom (or methyl); R2: methyl; R3, R4: ethoxy; n: 3), 3-(methyl)propenyloxypropylethyl diethoxysiloxane (in formula (1), R1: hydrogen atom (or methyl); R2: ethyl; R3, R4: ethoxy; n: 3), 3-(methyl)propenyloxypropyltrimethoxysiloxane (in formula (1), R1: hydrogen atom (or methyl); R2~R4: methoxy; n: 3), 3-(methyl)propenyloxypropyltriethoxysiloxane (in formula (1), R1: hydrogen atom (or methyl); R2~R4: ethoxy; n: 3) The constituent units of compounds such as .

[0074] Among the constituent units represented by formula (1), since the reaction is more readily available and easier to obtain when synthesizing (B) resins containing alkoxysilyl groups, it is preferable to use constituent units derived from 3-(meth)propenyloxypropylmethyldiethoxysiloxane and / or derived from 3-(meth)propenyloxypropyltriethoxysiloxane.

[0075] As a compound containing an alkoxysilyl group with an vinyl unsaturated group (mb-1), commercially available products can also be used. For example, the following compounds (the names in parentheses are trade names) manufactured by Shin-Etsu Chemical Industry Co., Ltd. are also available: 3-methylpropenyloxypropylmethyldiethoxysiloxane (KBE-502), 3-methylpropenyloxypropyltriethoxysiloxane (KBE-503), 3-methylpropenyloxypropylmethyldimethoxysiloxane (KBM-502), 3-methylpropenyloxypropyltrimethoxysiloxane (KBM-503), methylpropenyloxyoctyltrimethoxysiloxane (KBM-5803), 3-propenyloxypropyltrimethoxysiloxane (KBM-5103), etc.

[0076] <Constituting Unit (b-2)> The constituent unit (b-2) can be derived from only one type of unsaturated monocarboxylic acid (mb-2), or from two or more types of unsaturated monocarboxylic acids (mb-2). It is preferable that the unsaturated monocarboxylic acid (mb-2) from which the constituent unit (b-2) is derived be a compound possessing an acid group and an ethylene unsaturated group and not containing silicon. There are no particular limitations on the acid group possessed by the unsaturated monocarboxylic acid (mb-2), but it must be a carboxyl group or a phosphate group. (-OP(=O)(OH) 2) and tannic acid group (-S(=O) 2OH) are preferred. Among these acid groups, carboxyl groups are preferred in order to form a photosensitive resin composition with good imaging properties.

[0077] Examples of unsaturated monocarboxylic acids (mb-2) that serve as raw materials for the constituent unit (b-2) include (meth)acrylic acid, crotonic acid, cinnamic acid, vinyl tannic acid, 2-(meth)acrylic acid oxyethyl succinic acid, 2-(meth)acrylic acid oxyethyl phthalic acid, 2-(meth)acrylic acid oxyethyl hexahydrophthalic acid, and 2-(meth)acrylic acid oxyethyl phosphate. Among these unsaturated monocarboxylic acids (mb-2), (meth)acrylic acid is preferred because it exhibits better reactivity and is readily available when synthesizing resins containing alkoxysilyl groups (B).

[0078] <Constituent Unit (b-3)> The constituent unit (b-3) is not a compound containing an alkoxysilyl group (mb-1), nor an unsaturated monocarboxylic acid (mb-2). It may be a compound derived from only one other group containing an alkoxysilyl group (mb-3), or it may be a compound derived from two or more groups containing an alkoxysilyl group (mb-3).

[0079] Other compounds containing ethylene unsaturated groups (mb-3) that serve as raw materials for the constituent unit (b-3) can be compounds containing ethylene unsaturated groups that do not have acid groups or alkoxysilyl groups, such as dienes like butadiene, (meth)acrylates, (meth)acrylate amines, ethylene compounds, styrene compounds, unsaturated dicarboxylic acid diesters, and unsaturated polybasic anhydrides.

[0080] Specific examples of (meth)acrylates include meth(meth)acrylates, ethyl(meth)acrylates, n-propyl(meth)acrylates, isopropyl(meth)acrylates, n-butyl(meth)acrylates, sec-butyl(meth)acrylates, isobutyl(meth)acrylates, tert-butyl(meth)acrylates, pentyl(meth)acrylates, neopentyl(meth)acrylates, benzyl(meth)acrylates, isopentyl(meth)acrylates, hexyl(meth)acrylates, 2-ethylhexyl(meth)acrylates, benzyl(meth)acrylates, lauryl(meth)acrylates, dodecyl(meth)acrylates, and cyclopentyl(meth)acrylates. Acrylates, Cyclohexyl (meth)acrylates, Methylcyclohexyl (meth)acrylates, Ethylcyclohexyl (meth)acrylates, 1,4-Cyclohexanediethanol mono (meth)acrylates, Rosin (meth)acrylates, Norbornel (meth)acrylates, 5-Methylnorbornel (meth)acrylates, 5-Ethylnorbornel (meth)acrylates, Allyl (meth)acrylates, Tetrahydrofuran methyl (meth)acrylates, 1,1,1-Trifluoroethyl (meth)acrylates, Perfluoroethyl (meth)acrylates, Perfluoro-n-propyl (meth)acrylates, Perfluoro-isopropyl (meth)acrylates, Triphenylmethyl (meth)acrylates, Isopropylphenyl (meth)acrylates, 3 -(N,N-dimethylamino)propyl (meth)acrylate, glycerol mono(meth)acrylate, butylene glycerol mono(meth)acrylate, pentylene glycerol mono(meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, isocamphenyl (meth)acrylate, adamantyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl meth (meth)acrylate, (3-ethylepoxypropane-3-yl)meth (meth)acrylate, 2-isocyanoethyl (meth)acrylate, 2 - Isocyanopropyl (meth)acrylate, 3-isocyanopropyl (meth)acrylate, 2-isocyano-1-methylethyl (meth)acrylate, 2-isocyano-1,1-dimethylethyl (meth)acrylate, 4-isocyanocyclohexyl (meth)acrylate, compounds with block isocyanate groups formed by using a blocking agent to block the isocyanate groups of the aforementioned vinyl unsaturated compounds with isocyanate groups, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, tetramethylpiperidinyl (meth)acrylate, hexamethylpiperidinyl (meth)acrylate, etc.

[0081] Specific examples of (meth)acrylic acid amides include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylacrylic acid amide, (meth)acrylic acid N,N-diethylacrylic acid amide, (meth)acrylic acid N,N-dipropylacrylic acid amide, (meth)acrylic acid N,N-di-isopropylacrylic acid amide, (meth)acrylic acid anthracene amide, N-isopropyl(meth)acrylic acid amide, (meth)acrylic acid morphofroline, diacetone(meth)acrylic acid amide, etc.

[0082] Specific examples of ethylene compounds include protobornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5.1 7,10]dodecyl-3-ene, 8-methyltetracyclo[4.4.0.1 2,5.1 7,10]dodecyl-3-ene, and 8-ethyltetracyclo[4.4.0.1 2,5.1 7,10]dodecyl-3-ene. [4.4.0.1 2,5.1 7,10]dodecyl-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 2,6]dec-8-ene, tricyclo[5.2.1.0 2,6]dec-3-ene, tricyclo[4.4.0.1 2,5]undecyl-3-ene, tricyclo[6.2.1.0 1,8]undecyl-9-ene, tricyclo[6.2.1.0 1,8]undecyl-4-ene, tetracyclo[4.4.0.1 2,5.1 7,10.0 1,6]dodecyl-3-ene, 8-methyltetracyclo[4.4.0.1 2,5.1 7,10.0 1,6]dodecyl-3-ene, 8-ethylidene tetracyclo [4.4.0.1 2,5.1 7,12]dodecyl-3-ene, 8-ethylidene tetracyclo [4.4.0.1 2,5.1 7,10.0 1,6]dodecyl-3-ene, pentacyclic [6.5.1.1 3,6.0 2,7.0 9,13]pentadecano-4-ene, pentacyclic [7.4.0.1 2,5.1 9,12.0 8,13]pentadecano-3-ene, 5-probornene-2,3-dicarboxylic anhydride, (meth)acrylic acid aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, ethylene toluene, probornene, etc.

[0083] Specific examples of styrene include styrene, and styrene derivatives such as α-, O-, M-, P-alkyl, nitro, cyano, and acetamine derivatives. Specific examples of unsaturated dicarboxylic acid diesters include diethyl citrate, diethyl maleate, diethyl butenedioate, and diethyl itaconic acid. Specific examples of unsaturated polybasic anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride.

[0084] Among these other compounds containing ethylene unsaturated groups (mb-3), methacrylate, 2-ethylhexylmethacrylate, benzylmethacrylate, dicyclopentylmethacrylate, glycidylmethacrylate, (3-ethylepoxypropane-3-yl)methacrylate, N,N-diethylaminoethylmethacrylate, N,N-dimethylamino(meth)acrylate, (meth)acrylic acid morphofuroline, styrene, ethylene toluene, and protobornene are preferred, with methacrylate, benzylmethacrylate, dicyclopentylmethacrylate, glycidylmethacrylate, (3-ethylepoxypropane-3-yl)methacrylate, styrene, and ethylene toluene being even more preferred.

[0085] Furthermore, as other compounds containing ethylene unsaturated groups (mb-3), it can become a photosensitive resin component that can produce a resin-cured film with excellent heat decomposition resistance, heat yellowing resistance, and good high temperature and high humidity resistance. Therefore, alkyl (meth)acrylates are preferred, and meth (meth)acrylates, benzyl (meth)acrylates, and dicyclopentyl (meth)acrylates are preferred.

[0086] Furthermore, from the viewpoint that other compounds containing ethylene unsaturated groups (mb-3) can be used to obtain photosensitive resin compositions that produce resin-cured films with good solvent resistance, polymerizable compounds with functional groups that react with acid groups are preferred. Examples of functional groups that react with acid groups include glycidyl, glycidyl, isocyanate, or block isocyanate groups. Specifically, when synthesizing (B) resins containing alkoxysilyl groups, the reaction is more readily available and the compounds are easier to obtain; therefore, glycidyl (meth)acrylate and (3-ethylepoxypropane-3-yl)methyl (meth)acrylate are preferred.

[0087] As for other compounds containing ethylene unsaturated groups (mb-3), examples of block agents used when the isocyanate group of an ethylene unsaturated compound containing an isocyanate group is block-modified using a block agent include, for example, endoamines such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl ceroxysulfonyl, butyl ceroxysulfonyl, methyl carbitol, benzyl alcohol, benzoylsulfonyl, furanol, and cyclohexanol; phenols such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrylphenol, oxybenzoate, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; and dimalonate. Reactive methylene compounds such as methyl ester, diethyl malonate, methyl acetoacetate, ethyl acetoacetone, and acetoacetone; thiol compounds such as butyl thiol, thiophenol, and tert-dodecyl thiol; amine compounds such as diphenylamine, benzenenaphthylamine, aniline, and triphenylamine; acid-acetylamine compounds such as acetoaniline, aceto-p-methoxyaniline, acetate, and benzoylamine; acid-acetylimine compounds such as succinate and maleate; imidium... Imidazole series such as azole, 2-methylimidazole, 2-ethylimidazole, etc.; urea series such as urea, thiourea, ethylene urea, etc.; carbamate series such as N-anilinecarbamate benzene, 2-oxazolidinone, etc.; imine series such as ethyleneimine, polyethyleneimine, etc.; oxime series such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, etc.; bisulfite series such as sodium bisulfite, potassium bisulfite, etc.

[0088] <(B) Proportion of each constituent unit in resins containing alkoxysilyl groups> (B) The content of constituent unit (b-1) in the fully repeating constituent units of the alkoxysilyl resin is preferably 45 mol% or more, more preferably 50 mol% or more, and even more preferably 55 mol% or more. If the content of constituent unit (b-1) is 45 mol% or more, it will result in a photosensitive resin composition that produces a resin-cured film with higher hardness and better resistance to high temperature and humidity. There is no particular upper limit to the content of constituent unit (b-1), but it can be 99 mol% or less, 90 mol% or less, or 85 mol% or less. The content of the aforementioned constituent unit (b-1) can be arbitrarily selected within the above range, and can be, for example, 50 mol% or more and 100 mol% or less, or 60 mol% or more and 95 mol% or less, or 65 mol% or more and 80 mol% or less, or 70 mol% or more and 75 mol% or less, etc.

[0089] (B) When the resin containing alkoxysilyl groups includes constituent unit (b-2), its content in the completely repeating constituent unit of the resin containing alkoxysilyl groups in (B) is preferably 1 mol% to 40 mol% from the viewpoint of the solubility and storage stability of the photosensitive resin composition in alkaline developing solution, 10 mol% to 30 mol% is even better, and 15 mol% to 25 mol% is even better.

[0090] (B) When the resin containing alkoxysilyl groups includes the constituent unit (b-3), its content is preferably 1 mol% to 40 mol% of the completely repeating constituent unit of the resin containing alkoxysilyl groups in (B), preferably 5 mol% to 30 mol%, and even more preferably 10 mol% to 25 mol%.

[0091] <(B) Acid Value of Resins Containing Alkoxysilyl Groups> (B) The acid value of the alkoxysilyl-containing resin is preferably below 150 KOH mg / g, even more preferably below 100 KOH mg / g, and even more preferably below 70 KOH mg / g. An acid value below 150 KOH mg / g results in a photosensitive resin composition with excellent storage stability, excellent solubility in alkaline developing solutions, and good developing properties. (B) There is no particular limitation on the lower limit of the acid value of the alkoxysilyl-containing resin, but it can be, for example, above 1 KOH mg / g, above 5 KOH mg / g, or above 10 KOH mg / g. (B) An acid value of 1 KOH mg / g or higher can impart alkaline developing properties to the (B) alkoxysilyl-containing resin. (B) The acid value of resins containing alkoxysilyl groups can be adjusted by adjusting the amount of unsaturated monocarboxylic acid (mb-2) used as a raw material for the constituent unit (b-2), thereby adjusting the content of the constituent unit (b-2). (B) The acid value of resins containing alkoxysilyl groups can be determined in the same way as the acid value of alkali-soluble resins in (A).

[0092] <(B) Weight average molecular weight (Mw) of resins containing alkoxysilyl groups> (B) The weight-average molecular weight (Mw) of the alkoxysilyl-containing resin, converted from polystyrene, is preferably 1,000 to 20,000, more preferably 1,500 to 10,000, and even more preferably 3,000 to 6,000. (B) If the weight-average molecular weight (Mw) of the alkoxysilyl-containing resin is 1,000 or higher, it will become a photosensitive resin composition with good imaging properties. (B) If the weight-average molecular weight (Mw) of the alkoxysilyl-containing resin is 20,000 or lower, it will become a photosensitive resin composition with an appropriate imaging time. (B) The weight average molecular weight (Mw) of resins containing alkoxysilyl groups is calculated in the same way as that of alkali-soluble resins in (A).

[0093] <(B) Silicone equivalent of resins containing alkoxysilyl groups> (B) The silane equivalent of the alkoxysilyl-containing resin is not particularly limited, but it is preferably 100 g / mol to 700 g / mol, more preferably 150 g / mol to 500 g / mol, and most preferably 290 g / mol to 450 g / mol. (B) If the silane equivalent of the alkoxysilyl-containing resin is 100 g / mol or more, it will become a photosensitive resin composition with higher hardness and better image development. On the other hand, if the silane equivalent of the alkoxysilyl-containing resin is 700 g / mol or less, it will become a photosensitive resin composition that can obtain a resin-cured film with sufficient hardness and good adhesion to the substrate and / or base material.

[0094] (B) The silane equivalent of the alkoxysilyl-containing resin is the value obtained by dividing the molecular weight of the alkoxysilyl-containing resin of (B) by the average number of silane groups per molecule of the alkoxysilyl-containing resin of (B). The average number of silane groups per molecule of the alkoxysilyl-containing resin of (B) is a calculated value based on the amount of compound (mb-1) containing an alkoxysilyl-containing vinyl unsaturated group that forms the raw material of the constituent unit (b-1) of the alkoxysilyl-containing resin of (B).

[0095] <Content of (A) alkali-soluble resin and (B) resin containing alkoxysilyl groups> The mass ratio of (A) alkali-soluble resin to (B) alkoxysilyl-containing resin in the photosensitive resin composition of this embodiment ((A) alkali-soluble resin : (B) alkoxysilyl-containing resin) is preferably 40:60~99:1, more preferably 50:50~99:1, even more preferably 60:40~90:10, and particularly preferably 60:40~80:20. The aforementioned ratio can be selected as needed within the above range, for example, it can also be 55:45~85:15 or 65:35~75:25. If the mass ratio of (A) alkali-soluble resin to (B) alkoxysilyl-containing resin is within the above range, then since the properties obtained by including (B) alkoxysilyl-containing resin can be fully obtained, it will become a photosensitive resin composition capable of forming a resin-cured film with higher hardness and good resistance to high temperature and humidity. Furthermore, if the mass ratio of (A) alkali-soluble resin to (B) alkoxysilyl resin is within the above range, the properties obtained by including (A) alkali-soluble resin can be fully obtained, thus becoming a photosensitive resin composition that can form a resin hardened film with better storage stability, superior imaging properties, and better water resistance and high temperature and humidity resistance.

[0096] <(B) Manufacturing method of resins containing alkoxysilyl groups> As a method for manufacturing (B) alkoxysilyl-containing resin, conventionally known methods can be used. Specifically, for example, a reaction solution containing a copolymer of (B) alkoxysilyl-containing resin (mb-1), an alkoxysilyl-containing vinyl unsaturated group (mb-1), other unsaturated monocarboxylic acid (mb-2) added as necessary, and an alkoxysilyl-containing compound (mb-3) added together with a polymerization initiator is generated by copolymerizing the copolymer.

[0097] As polymerization initiators, 2,2'-azobis(isobutyric acid) dimethyl ester, t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, azobisisovalerate, benzoyl peroxide, etc. can be used. As a solvent, the same solvents that can be used in the manufacturing method of the aforementioned (A) alkali-soluble resin can be used. Among these, from the viewpoint of ease of acquisition and storage stability as a photosensitive resin component, either a primary alcohol or a secondary alcohol is preferred, with 3-methoxy-1-butanol and propylene glycol monomethyl ether being even more preferred.

[0098] [(C) Reactive diluent] As a (C) reactive diluent, low molecular weight compounds having vinyl unsaturated groups such as vinyl, allyl, and (meth)acrylic acid oxy groups can be used. A single (C) reactive diluent can be used alone, or two or more can be used in combination. Examples of (C) reactive diluents include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; (meth)acrylates; polyfunctional (meth)acrylates; and triallyl cyanurate. Among these (C) reactive diluents, polyfunctional (meth)acrylates are particularly preferred because they form photosensitive resin compositions that produce resin-cured films with good development and sufficient hardness.

[0099] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, ethylene-toluene, divinylbenzene, diallyl phthalate, and diallyl phenyl phosphate. Specific examples of (meth)acrylates include meth(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, β-hydroxyethyl(meth)acrylate, and hydroxypropyl(meth)acrylate.

[0100] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(hydroxyethyl)isocyanurate tri(meth)acrylate.

[0101] <(C) Content of reactive diluent> The content of the reactive diluent (C) in the photosensitive resin composition of this embodiment is preferably 5 to 75 parts by mass, more preferably 15 to 65 parts by mass, and most preferably 20 to 55 parts by mass, relative to the total of (A) alkali-soluble resin, (B) alkoxysilyl-containing resin, and (C) reactive diluent in the photosensitive resin composition, for a total of 100 parts by mass. If the content of the reactive diluent (C) is within the above range, the viscosity and photocurability of the photosensitive resin composition will be more suitable.

[0102] (D) Photoradical polymerization initiator As an initiator for (D) photoradical polymerization, any compound that generates free radicals due to light irradiation is acceptable, and there are no particular limitations. A single (D) photoradical polymerization initiator can be used alone, or two or more can be used in combination.

[0103] Examples of photoradical polymerization initiators include benzoin and its alkyl ethers, such as benzoin methyl ether and benzoin ethyl ether; acetophenones, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; alkyl acetophenones, such as 1-hydroxycyclohexylacetophenone and 2-hydroxy-2-methyl-1-phenylpropane-1-one; anthraquinones, such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones, such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals, such as acetophenone dimethyl ketal and benzyl dimethyl ketal; and benzophenone and 4-(1-t-butyldioxy-1-methylethyl)diphenylacetophenone. Benzophenones such as 3,3',4,4'-tetra(t-butyldioxycarbonyl)benzophenone; 1,2-octanedione, 2-(benzoyloxyimino)-1-[4-(phenylthio)benzene]-1-octanone, 1-[4-(phenylthio)-2-(o-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-triphenylamine-3- Oxime esters such as 1-(o-acetylgoxymeta); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; acetylgphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; flavonoids, etc.

[0104] <(D) Content of photoradical polymerization initiator> The content of the photoradical polymerization initiator (D) in the photosensitive resin composition of this embodiment is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and most preferably 3 to 10 parts by mass, relative to the total of (A) alkali-soluble resin, (B) alkoxysilyl-containing resin, and (C) reactive diluent in the photosensitive resin composition. If the content of the photoradical polymerization initiator (D) is 0.1 parts by mass or more, it will become a photosensitive resin composition with sufficient photocurability. If the content of the photoradical polymerization initiator (D) is 20 parts by mass or less, the photoradical polymerization initiator (D) will not adversely affect the storage stability of the photosensitive resin composition or the performance of the resin film cured from it.

[0105] [(E) solvent] (E) The solvent is not particularly limited as long as it is inert to each component contained in the photosensitive resin composition of this embodiment and can dissolve each component. (E) A single solvent may be used alone, or two or more solvents may be used in combination.

[0106] (E) The solvent may include the same solvent used in the preparation of (A) the alkali-soluble resin and / or (B) the alkoxysilyl-containing resin, or it may be a different solvent. For example, it is not necessary to separate or remove the solvent used in the preparation of (A) the alkali-soluble resin and (B) the alkoxysilyl-containing resin; they can be used directly as part or all of the solvent in (E) of the photosensitive resin composition. Furthermore, when mixing the components of the photosensitive resin composition, a new solvent may be added that is the same as the solvent used in the preparation of (A) the alkali-soluble resin and / or (B) the alkoxysilyl-containing resin. Remove part or all of the solvent used in the preparation of (A) alkali-soluble resin and / or (B) alkoxysilyl-containing resin. When mixing the components of the photosensitive resin composition, a solvent that is the same as or different from the solvent used in the preparation of (A) alkali-soluble resin and / or (B) alkoxysilyl-containing resin may also be added.

[0107] (E) Solvent: To ensure the photosensitive resin composition has good storage stability, it is preferable to contain one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms. Examples of primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms include alkanols, benzyl alcohols, and (poly)alkyl glycol monoalkyl ethers. For ease of acquisition and to ensure good storage stability, (poly)alkyl glycol monoalkyl ethers are preferred.

[0108] As solvent (E), other solvents not selected from one or more primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms may be used with the alcohols mentioned above, or may replace the alcohols mentioned above. Only one other solvent may be used, or two or more other solvents may be used.

[0109] In the examples of solvents used in the formulation of (A) alkali-soluble resins and / or (B) alkoxysilyl-containing resins mentioned above, (poly)alkylene glycol monoalkyl ether acetate solvents, such as propylene glycol monomethyl ether acetate, are preferred because they provide good solubility for the components contained in the photosensitive resin composition. Furthermore, (poly)alkylene glycol monoalkyl ether acetate solvents are preferred because they exhibit good compatibility when mixed with one or more alcohols selected from primary alcohols and secondary alcohols having 3 to 10 carbon atoms.

[0110] (E) The total content of one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms in the solvent is preferably 15 to 100% by mass in the total solvent. For better storage stability of the photosensitive component, the content of the above-mentioned alcohols is preferably 25% by mass or more, and even more preferably 35% by mass or more. There is no particular upper limit to the content of the above-mentioned alcohols, but it can also be 90% by mass or 80% by mass.

[0111] <(E) Solvent Content> The content of solvent (E) in the photosensitive resin composition of this embodiment is preferably 30 to 1000 parts by mass relative to 100 parts by mass of the total components in the photosensitive resin composition excluding solvent (E), more preferably 50 to 800 parts by mass, and most preferably 100 to 500 parts by mass. If the content of solvent (E) is within the above range, the viscosity of the photosensitive resin composition can be adjusted to an appropriate range.

[0112] The viscosity of the photosensitive resin composition in this embodiment can be appropriately adjusted according to the thickness of the desired resin curing film. For example, when the thickness of the resin curing film is adjusted to 1μm~4μm, a viscosity of 4mP·s~25mP·s is preferred, 6mP·s~20mP·s is even more preferred, and 8mP·s~15mP·s is still preferred.

[0113] In this manual, the viscosity of the photosensitive resin composition refers to the value measured using an E-type viscometer (RE-80, manufactured by Toki Sangyo, shaft type: standard cone 1°34'×R24, shaft belt: 1) at 25°C.

[0114] [(F)Siloxane Coupling Agent] The photosensitive resin composition of this embodiment can contain (F) a siloxane coupling agent as necessary. The (F) siloxane coupling agent can improve the compatibility of (A) alkali-soluble resin, (B) alkoxysilyl-containing resin, and (C) reactive diluent contained in the photosensitive resin composition. As a (F)siloxane coupling agent, it is preferable to use a low molecular weight compound having one or more functional groups selected from (meth)acrylic, vinyl, and styrene groups. A single (F)siloxane coupling agent may be used alone, or a combination of two or more may be used.

[0115] As a (F) siloxane coupling agent, commercially available products can also be used. For example, siloxane coupling agents manufactured by Shin-Etsu Chemical Industry Co., Ltd., as shown below (the names in parentheses are trade names), can be used. Examples include ethylene trimethoxysiloxane (KBM-1003), ethylene triethoxysiloxane (KBE-1003), octenyl trimethoxysiloxane (KBM-1083), p-styrene trimethoxysiloxane (KBM-1403), 3-methacryloxypropylmethyldimethoxysiloxane (KBM-502), 3-methacryloxypropyltrimethoxysiloxane (KBM-503), 3-methacryloxypropylmethyldiethoxysiloxane (KBE-502), 3-methacryloxypropyltriethoxysiloxane (KBE-503), methacryloxyoctyltrimethoxysiloxane (KBM-5803), and 3-acryloxypropyltrimethoxysiloxane (KBM-5103).

[0116] <(F) Content of siloxane coupling agent> When the photosensitive resin composition of this embodiment includes (F) a siloxane coupling agent, the content of (F) a siloxane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and most preferably 3 to 10 parts by mass relative to the total of (A) alkali-soluble resin, (B) alkoxysilyl-containing resin, and (C) reactive diluent contained in the photosensitive resin composition, for a total of 100 parts by mass. If the content of (F) a siloxane coupling agent is within the above range, it will become a photosensitive resin composition with more suitable compatibility and photocurability between (A) alkali-soluble resin, (B) alkoxysilyl-containing resin, and (C) reactive diluent.

[0117] [Other ingredients] In this embodiment of the photosensitive resin composition, as necessary, in order to impart specific properties, other components may be included that are different from (A) alkali-soluble resin, (B) alkoxysilyl-containing resin, (C) reactive diluent, (D) photoradical polymerization initiator, (E) solvent, and (F) siloxane coupling agent. Other components include known additives such as leveling agents and thermal polymerization inhibitors. The content of other components in the photosensitive resin composition is not particularly limited, as long as it does not impair the effects of the present invention.

[0118] [Manufacturing method of photosensitive resin composition] The photosensitive resin composition of this embodiment can be manufactured by, for example, mixing (A) an alkali-soluble resin, (B) an alkoxysilyl-containing resin, (C) a reactive diluent, (D) a photoradical polymerization initiator, (E) a solvent, and (F) a siloxane coupling agent and / or other components as necessary, using a known mixing apparatus.

[0119] In the method for manufacturing the photosensitive resin composition of this embodiment, the order in which (A) an alkali-soluble resin, (B) an alkoxysilyl-containing resin, (C) a reactive diluent, (D) a photoradical polymerization initiator, (E) a solvent, and (F) a siloxane coupling agent and / or other components, as necessary, are mixed is not particularly limited. Alternatively, it can be manufactured by, for example, preparing a resin composition comprising (A) an alkali-soluble resin, (B) an alkoxysilyl-containing resin, and (E) a solvent, and then mixing (C) a reactive diluent, (D) a photoradical polymerization initiator, and (F) a siloxane coupling agent and / or other components into the resulting resin composition.

[0120] The photosensitive resin composition of this embodiment contains (A) an alkali-soluble resin, (B) an alkoxysilyl-containing resin, (C) a reactive diluent, (D) a photoradical polymerization initiator, and (E) a solvent. Therefore, through the addition effects of (1) to (3) as shown below, it maintains better stability and image development, and by curing it, it can obtain a resin-cured film with high hardness and good adhesion to the substrate and / or base material, water resistance, high temperature and humidity resistance, and transparency. Therefore, the photosensitive resin composition of this embodiment is more suitable as a material for resin-cured films used as insulating and / or protective films in image display devices such as touch panels.

[0121] (1) The alkali-soluble resin contained in the photosensitive resin composition contains acid groups and (meth)acrylic acid groups, and the equivalent of vinyl unsaturated groups is more than 400 g / mol and less than 2500 g / mol. Therefore, it is possible to obtain a resin-cured film with sufficiently small curing shrinkage and good adhesion to the substrate and / or base. It is also possible to obtain a resin-cured film with good storage stability and image development, and good resistance to high temperature and high humidity.

[0122] (2)(A) The alkali-soluble resin contains a constituent unit (a-1) from a compound (ma-1) with an aromatic group and an ethylene-containing unsaturated group, and the total repeating constituent unit of (A) contains more than 15 mol% and less than 60 mol% of the aforementioned constituent unit (a-1), thus it becomes a photosensitive resin composition capable of forming a resin hardening film with good image development, water resistance, high temperature and humidity resistance, and good transparency. (3) In the photosensitive resin composition, (B) the alkoxysilyl resin contains a constituent unit (b-1) from a compound (mb-1) containing an alkoxysilyl vinyl unsaturated group, thus a resin hardening film with high hardness and good resistance to high temperature and humidity can be obtained.

[0123] [Resin-cured film] The resin curing film of this embodiment contains a cured form of the photosensitive resin composition of this embodiment. The resin curing film of this embodiment can be suitable for use as a protective film and / or insulating film in image display devices such as touch panels. The resin-cured film of this embodiment can be formed on a substrate or base. Examples of substrates or bases include components used in image display devices such as touch panels. Specifically, substrates or bases can be made from materials such as glass substrates, electrode materials such as ITO, molybdenum, and metal mesh, or organic films.

[0124] The resin curing film of this embodiment can be manufactured using known methods. For example, it can be manufactured by coating the photosensitive resin composition of this embodiment onto a substrate or base using a known method to form a coating film, and then irradiating the resulting coating film with light using a known method to cure the photosensitive resin composition. Furthermore, when the resin-cured film of this embodiment has a specific pattern shape, photolithography can be used. Specifically, it is preferable to perform the coating step, pre-baking (pre-heat treatment) step, exposure step, development step, and post-baking step in this order.

[0125] (Coating Steps) In the coating step, the photosensitive resin composition of this embodiment is coated onto a substrate or base to form a coating film. As a method for coating a photosensitive resin composition onto a substrate or base, known methods can be used. Specifically, examples of coating methods for photosensitive resin compositions include screen printing, roll coating, curtain coating, spray coating, spin coating, and slot coating.

[0126] (Pre-baking (pre-heating treatment) steps) In the pre-baking step, by heating the substrate or base on which the coating film is to be formed, the content of (E) solvent contained in the coating film can be reduced. In the pre-baking step, the method of heating the substrate or base to which the coating film is formed can be a known method such as using a hot plate.

[0127] The heating temperature in the pre-baking step can be appropriately determined according to the composition of the photosensitive resin. For example, a heating temperature of 70~120℃ or 90~110℃ is preferred. The heating time in the pre-baking step can be appropriately determined according to the composition of the photosensitive resin and the thickness of the coating. For example, the heating time can be set to 10~600 seconds, and 120~180 seconds is preferred.

[0128] (Exposure Steps) During the exposure step, a portion of the coating film after the previous baking step is irradiated with light through a photomask with a pattern shape corresponding to the manufactured resin curing film, so that it is photocured. In the exposure step, the light source used for illumination can be any known type. Specifically, examples of light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, and metal halide lamps. The amount of light irradiated during the exposure step (exposure) is not particularly limited and can be appropriately set according to the shape of the photomask, the composition of the photosensitive resin, the thickness of the coating, etc.

[0129] (Developing steps) In the developing step, the unexposed parts of the coating after the exposure step are dissolved and removed using a developing solution. As a developing solution, known alkaline developing solutions used for developing photosensitive components can be used. Specifically, for example, aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxylide, potassium hydroxylide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine, etc.; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxylate; aqueous solutions of p-phenylenediamine compounds such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonylamine ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates, etc., are preferred among these alkaline developing solutions.

[0130] In alkaline developing solutions, one or more additives such as defoamers and surfactants may be added as needed. The developing conditions, such as developing temperature and developing time, in the developing process can be appropriately determined according to the composition of the photosensitive resin, the composition of the developing solution, and the thickness of the coating. In the developing step, it is better to use the above-mentioned alkaline developing solution to dissolve and develop the unexposed parts of the coating, and then wash it with water to dry it.

[0131] (Post-baking step) The coating after the heating and developing step in the post-baking process. In the post-baking step, as a method for coating after the heating and developing step, known methods such as using a hot plate can be employed.

[0132] The heating temperature in the post-baking step can be appropriately determined according to the composition of the photosensitive resin, the material of the substrate or base to which the coating film is formed, etc. For example, the heating temperature can be set to 130°C to 250°C. The heating time in the post-baking step can be appropriately determined according to the composition of the photosensitive resin and the thickness of the coating. The heating time can be set from 10 minutes to 60 minutes. Through the above steps, a resin-cured film with a specific pattern shape can be obtained.

[0133] The resin-cured film of this embodiment contains a cured material formed by curing the photosensitive resin composition of this embodiment. Therefore, it has higher hardness and better adhesion to the substrate and / or base material, water resistance, high temperature and humidity resistance, and transparency. Furthermore, when the resin-cured film of this embodiment has a specific pattern shape formed by photolithography, it achieves high precision because it is formed using the photosensitive resin composition of this embodiment with good image development properties. Therefore, the resin-cured film of this embodiment is more suitable as an insulating film and / or protective film in image display devices such as touch panels.

[0134] [Image display device] The image display device of this embodiment includes the resin curing film of this embodiment. The image display device of this embodiment is particularly preferably a touch panel. The resin curing film in the image display device of this embodiment is preferably selected from the group consisting of protective films and insulating films, and is especially preferably a protective film or insulating film for the touch panel. The image display device of this embodiment can be manufactured using conventionally known methods.

[0135] The image display device of this embodiment has a resin-cured film with high hardness, good adhesion to the substrate and / or base material, good water resistance, high temperature and humidity resistance, and good transparency, thus exhibiting excellent reliability and durability. [Example]

[0136] The present invention will now be described in detail with reference to embodiments and comparative examples. Furthermore, the embodiments shown below are provided to facilitate a better understanding of the invention. The invention is not limited to these embodiments. [(A) Synthesis of alkali-soluble resins] The alkali-soluble resins of Synthetic Examples 1 to 8, Comparative Synthetic Example 1 and Comparative Synthetic Example 2 were manufactured by the method shown below.

[0137] [Synthesis Example 1 (Sample No. A1)] In a flask equipped with a stirring device, dropping funnel, condenser, thermometer and gas inlet tube, the solid content of the sample containing (A) alkali-soluble resin is made to be 30% by mass. 700.0 g of propylene glycol monomethyl ether acetate, the solvent shown in Table 1, is added. Nitrogen substitution is carried out while stirring, and the temperature is raised to 120°C.

[0138] Next, 142.6 g (0.45 mol) of benzyl methacrylate containing monomers (ma-1) to (ma-3) as shown in Table 1, 69.7 g (0.45 mol) of methacrylic acid, and 39.6 g (0.1 mol) of dicyclopentyl methacrylate were mixed to form a monomer mixture.

[0139] 4.5 g (1.8 parts by mass) of t-butylperoxy-2-ethylhexanoate, a polymerization initiator, was added to the monomer mixture and added dropwise over 1 hour in a stirred solvent at 120°C in the flask described above. The resulting reaction solution was then stirred at 120°C for 2 hours to allow for copolymerization, producing a reaction solution containing a resin precursor of the copolymer.

[0140] Next, the flask containing the resin precursor was replaced with 6% oxygen. 38.3 g (0.15 mol) of glycidyl methacrylate (ma-5) as shown in Table 1, 0.871 g of triphenylphosphine as a catalyst, and 0.871 g of hydroquinone as a polymerization inhibitor were added to the reaction solution containing the resin precursor in the flask. An addition reaction was carried out at 120°C for 6 hours to obtain a sample (sample number A1) of the alkali-soluble resin of Synthetic Example 1 (A), containing modified side chains of the resin precursor.

[0141] [Synthetic Examples 2-8, Comparative Synthetic Example 1 and Comparative Synthetic Example 2 (sample numbers A2-A10)] In Synthesis Example 1, except that the monomers (ma-1) to (ma-4) shown in Table 1 were used to replace the monomers used in the monomer mixture in proportions shown in Table 1, and the amount of polymerization initiator added was the same as in Synthesis Example 1, a reaction solution containing the resin precursors of Synthesis Examples 2 to 8, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 was generated.

[0142] Subsequently, in the reaction solution containing the resin precursor in the flask, except that the monomer (ma-5) shown in Table 1 was added in the proportion shown in Table 1, the same as in Synthesis Example 1 was used to obtain the alkali-soluble resin samples (sample numbers A2 to A10) of Synthesis Example 2 to Synthesis Example 8, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 (A) containing the modified side chain of the resin precursor.

[0143]

[0144] The compounds used in Table 1 are shown below. BZMA: Benzyl methacrylate Styrene PQMA: 4-Hydroxyphenylmethyl acrylate MAA: Methacrylic acid TCDMA: Dicyclopentyl methacrylate THFMA: Tetrahydrofuran Methyl Methacrylate GMA: Epichlorohydrin methacrylate TBO: t-Butylperoxy-2-ethylhexanoate (trade name; PERBUTYL O (Japan Oil Company Limited) PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0145] The values ​​of monomers (ma-1) to (ma-4) in Table 1 represent the proportion (mol%) of each monomer relative to the total amount of monomers (ma-1) to (ma-4) used in the resin precursor. The value of monomer (ma-5) in Table 1 represents the amount added (parts by mass) relative to the total of 100 parts by mass of monomers (ma-1) to (ma-4) used in the resin precursor. The solvent values ​​in Table 1 represent the content (mass %) of (A) alkali-soluble resin in the sample. The values ​​of polymerization initiators shown in Table 1 represent the amount added (parts by mass) relative to a total of 100 parts by mass of monomers (ma-1) to (ma-4) used in the resin precursor.

[0146] Regarding the alkali-soluble resins (A) of Synthetic Examples 1 to 8, Comparative Synthetic Example 1, and Comparative Synthetic Example 2 obtained in this way, the weight-average molecular weight (Mw) and acid value were determined by the above method, and the equivalent of the vinyl unsaturated group was calculated by the method shown below. The results are shown in Table 1.

[0147] (Ethylene unsaturated base equivalent) The mass of (A) alkali-soluble resin in each 1 mol of unsaturated bond is calculated from the amount of monomers (ma-1) to (ma-5) added during the manufacture of (A) alkali-soluble resin, and is taken as the equivalent of the vinyl unsaturated group of (A) alkali-soluble resin (g / mol).

[0148] [(B) Synthesis of resins containing alkoxysilyl groups] The alkoxysilyl-containing resins of Synthetic Examples 9 to 13 (B) were manufactured by the method shown below.

[0149] [Synthesis Example 9 (Sample No. B1)] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 600 g of 3-methoxy-1-butanol, the solvent shown in Table 2, was added to make the solid content of the sample containing (B) alkoxysilyl resin reach 40% by mass. Nitrogen substitution was carried out while stirring, and the temperature was raised to 105°C.

[0150] Next, 327.0 g (0.8 mol) of 3-methacryloxypropylmethyldiethoxysiloxane, one of the monomers (mb-1) and (mb-2) shown in Table 2, and 27.0 g (0.2 mol) of methacrylic acid were mixed to form a monomer mixture. 46.0 g (13 parts by mass) of 2,2'-azobis(isobutyric acid)dimethyl, a polymerization initiator, was added dropwise to the monomer mixture in a stirred solvent at 105°C in the flask described above, as the reaction solution. The resulting reaction solution was further stirred at 105°C for 2 hours to allow for copolymerization, yielding a sample (sample number B1) of the alkoxysilyl-containing resin of Synthesis Example 9 (B) containing the copolymer.

[0151] [Synthesis Examples 10-13 (Sample Numbers B2-B5)] Except that the monomers (mb-1) to (mb-3) shown in Table 2 were used to replace the monomers used in the monomer mixture in Synthesis Example 9 in proportions shown in Table 2, and the amount of polymerization initiator added was the same as in Synthesis Example 9, samples (sample numbers B2 to B5) of the alkoxysilyl-containing resins (B) of Synthesis Examples 10 to 13 were obtained.

[0152]

[0153] The compounds used in Table 2 are shown below. KBE-502: 3-Methylpropenyloxypropylmethyldiethoxysiloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) KBE-503: 3-Methylpropenyloxypropyltriethoxysiloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) MAA: Methacrylic acid AA: Acrylic acid Styrene GMA: Epichlorohydrin methacrylate AIBME: 2,2'-Azobis(isobutyric acid)dimethyl MB: 3-Methoxy-1-butanol

[0154] The values ​​of monomers (mb-1) to (mb-3) in Table 2 represent the proportion (mol%) of each monomer relative to the total amount of monomers (mb-1) to (mb-3) used in (B) alkoxysilyl resins. The solvent values ​​in Table 2 represent the content (mass %) of the resin containing (B) alkoxysilyl groups in the sample. The values ​​for polymerization initiators shown in Table 2 represent the amount (parts by mass) added relative to a total of 100 parts by mass of monomers (mb-1) to (mb-3) used in (B) alkoxysilyl-containing resins.

[0155] Regarding the alkoxysilyl-containing resins of Synthetic Examples 9 to 13 (B) obtained in this way, the weight-average molecular weight (Mw), acid value, and silyl equivalent were determined by the above method. The results are shown in Table 2.

[0156] (Maintain stability) Next, regarding the (B) alkoxysilyl-containing resins (sample numbers B1-B5) from Synthetic Examples 9 to 13, the storage stability of the (B) alkoxysilyl-containing resins (test samples) was evaluated using the method shown below. The results are shown in Table 2.

[0157] For each test substance, the weight-average molecular weight (Mw) was determined using GPC (GPC-101, manufactured by Shodex). Furthermore, the viscosity of each test substance at 25°C was determined using the method described above. Weigh 10g of each test sample into each 20ml glass container, seal it, let it stand, and store it in a thermostat maintained at 40℃ for 1 month to conduct the storage test. For each test sample after the preservation test, the weight average molecular weight (Mw) and viscosity at 25°C were determined again using the above method.

[0158] Using the weight-average molecular weight (Mw) before and after the storage test, and the viscosity at 25°C before and after the storage test, the increase rate of weight-average molecular weight and the increase rate of viscosity at 25°C were calculated using the following formula (I), and evaluated based on the following criteria. The results are shown in Tables 2 to 7. Increase rate (%) = ((before storage test - after storage test) / before storage test) × 100 (I) Evaluation Criteria ○ (Acceptable): Both the increase in molecular weight and the increase in viscosity are less than 10%. × (Not allowed): The rate of increase in molecular weight or the rate of increase in viscosity, or both, is 10% or more.

[0159] As shown in Table 2, the alkoxysilyl-containing resins (sample numbers B1 to B5) of Synthetic Examples 9 to 13 (B) were all confirmed to have excellent storage stability, with an evaluation of ○ (okay).

[0160] <Examples 1-16, Comparative Examples 1-5> [Preparation of photosensitive resin composition] The alkali-soluble resins (sample numbers A1-A10) of Synthetic Examples 1-8, Comparative Synthetic Examples 1 and 2, the alkoxysilyl-containing resins (sample numbers B1-B5) of Synthetic Examples 9-13, the reactive diluents (C) shown in Tables 3-7, the photoradical polymerization initiators (D), the solvents (E), and the siloxane coupling agents (F) were mixed in the proportions shown in Tables 3-7 to prepare the photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-5.

[0161]

[0162]

[0163]

[0164]

[0165]

[0166] The compounds used in Tables 3 to 7 are shown below. DPHA: Dipentaerythritol hexaacrylate (manufactured by Dong-A Synthetic Co., Ltd.) OXE-01: 2-(benzoyloxyimino)-1-[4-(phenylthio)benzene]-1-octanone (manufactured by BASF Japan) PGMEA: Propylene Glycol Monomethyl Ether Acetate MB: 3-Methoxy-1-butanol KBE-503: 3-Methylpropenyloxypropyltriethoxysiloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

[0167] The values ​​for (A) alkali-soluble resin shown in Tables 3 to 7 only include components other than the solvent in the samples containing (A) alkali-soluble resin synthesized in Synthetic Examples 1 to 8, Comparative Synthetic Example 1, and Comparative Synthetic Example 2, and do not include the solvent. The values ​​for (B) alkoxysilyl-containing resins shown in Tables 3 to 7 only include components other than the solvent in the samples of (B) alkoxysilyl-containing resins synthesized in Synthetic Examples 9 to 13, and do not include the solvent.

[0168] The blending amounts of (A) alkali-soluble resin, (B) alkoxysilyl-containing resin, (C) reactive diluent, (D) photoradical polymerization initiator, and (F) siloxane coupling agent in Tables 3-7 represent the individual content (parts by mass) of each component (A)-(D)(F) relative to a total of 100 parts by mass of (A)-(C). (E) The amount of solvent mixed is expressed as the content (parts by mass) relative to the total of 100 parts by mass of (A) to (D) and (F) above.

[0169] (Maintain stability) The storage stability of the formulations of Examples 1 to 16 and Comparative Examples 1 to 5 shown in Tables 3 to 7 was evaluated in the same manner as the storage stability tests of Synthetic Examples 9 to 13, without the addition of (C) reactive diluent, (D) photoradical polymerization initiator, and (E) siloxane coupling agent. The results are shown in Tables 3 to 7.

[0170] As shown in Tables 3 to 7, the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 5 all had a storage stability rating of ○ (okay), indicating excellent storage stability.

[0171] Next, regarding the resin-cured films formed by curing the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 5, the following methods were used to evaluate each of the following items: (1) hardness (pencil hardness), (2) transmittance (transparency), (3) adhesion, (4) water resistance, (5) high temperature and high humidity resistance, (6) image development, and (7) overall determination.

[0172] (1) Hardness (pencil hardness) A photosensitive resin composition was coated onto a 5cm long and 5cm wide glass substrate (alkali-free glass substrate) using a spin coater to form a coating film. The coated glass substrate was then heated on a hot plate at 100°C for 3 minutes to reduce the content of the (E) solvent in the coating film, thus forming the coating film on the glass substrate. Next, the coating film was photocured by irradiating it with light of 365nm at an exposure dose of 200mJ / cm². Finally, the glass substrate with the photocured coating film was heated at 230°C for 30 minutes in a dryer to obtain a resin-cured film with a thickness of 2.0μm.

[0173] The pencil hardness of the resin-cured film thus produced was determined using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Co., Ltd.), and according to... The determination was performed using JIS K5600-5-4. The results are shown in Tables 4-6.

[0174] (2) Transmittance (transparency) Regarding the glass substrate with the resin-cured film manufactured in the same manner as when evaluating the hardness mentioned above (1), the spectral transmittance from 400 to 800 nm was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). Furthermore, the transmittance at a wavelength of 400 nm was evaluated according to the criteria shown below. The results are shown in Tables 3 to 7. Evaluation Criteria ○(Acceptable): 98% or higher × (Not allowed): Less than 98%

[0175] (3) Adhesion (to glass, ITO, metal mesh (Cu, Ag), Mo) A glass substrate with a resin-cured film made in the same manner as when evaluating the hardness of (1) above was prepared as the test material. Furthermore, except for substrates used to form indium tin oxide (ITO) films on glass substrates, substrates to form metal meshes (Cu, Ag), and substrates to form molybdenum (Mo) films on glass substrates to replace glass substrates, resin-cured films were prepared in the same manner as when evaluating the hardness of (1) above, and used as test subjects.

[0176] For test specimens with resin-cured films prepared in this manner, the adhesion of the resin-cured films was evaluated using the cross-adhesion method of JIS K5600-5-6. Specifically, the number of peels out of 100 squares was counted, and the evaluation was based on the following criteria. The results are shown in Tables 3 to 7. "Judgment Criteria" ○(Available): 0 peels × (Not allowed): More than 1 item can be peeled.

[0177] (4) Water resistance As with the evaluation of hardness in (1) above, a glass substrate with a resin-cured film was prepared and immersed in water at 100°C for 1 hour. For glass substrates with resin-cured films produced in this manner, the adhesion of the resin-cured film was evaluated using the cross-hatching method of JIS K5600-5-6. Specifically, the number of peelings out of 100 squares was counted, and the evaluation was based on the following criteria. The results are shown in Tables 3 to 7. "Judgment Criteria" ○(Available): 0 peels × (Not allowed): More than 1 item can be peeled.

[0178] (5) Resistance to high temperature and high humidity A photosensitive resin composition is coated onto a molybdenum (Mo) substrate measuring 5 cm in length and 5 cm in width using a spin coater to form a coating film (coating step). The molybdenum substrate with the coating film is then heated on a hot plate at 100°C for 3 minutes (pre-baking step) to reduce the content of the (E) solvent in the coating film, thus forming the coating film on the molybdenum substrate. Next, a photomask with a row spacing of 3-100 μm is arranged between the photomask and the surface of the coating film at 100 μm intervals. Then, the coating film is irradiated with light from an ultra-high pressure mercury lamp at an exposure dose of 200 mJ / cm² through the photomask to photocur it (exposure step).

[0179] Next, the unexposed areas on the exposed coating are dissolved and removed using a developing solution (developing step). The developing solution used is Semi-clean DL-A10 (trade name: Yokohama Yushi Kogyo Co., Ltd.), diluted 75 times with an aqueous solution containing 4.0-5.0% potassium hydroxyl and 1.0-15.0% nonionic surfactant. Development is performed by spraying the developed solution onto the exposed coating at a temperature of 23°C and a pressure of 0.1 MPa for 30-60 seconds. Next, the glass substrate with the light-cured coating is heated at 230°C for 30 minutes in a dryer (post-baking step). Through the above steps, a resin-cured film with a thickness of 2.0 μm and a row spacing pattern of 3~100 μm is fabricated on a molybdenum substrate.

[0180] The molybdenum substrate with the resin-cured film thus prepared was placed in a constant temperature and humidity bath at 85°C and 85%RH for 1000 hours. Afterward, the molybdenum substrate with the resin-cured film was removed, and the presence or absence of discoloration of the resin-cured film was evaluated visually according to the criteria shown below. The results are shown in Tables 3 to 7. "Judgment Criteria" ○ (OK): No color change at all ×(Not allowed): Slightly turns blue

[0181] (6) Imaging Except for replacing the molybdenum substrate with a glass substrate (alkali-free glass substrate) that is 5cm long and 5cm wide, the rest is the same as when evaluating the high temperature and high humidity resistance mentioned above (5), a resin-cured film with a line spacing pattern of 2.0μm thick and 3~100μm wide is made.

[0182] Regarding the glass substrate with the resin-cured film thus fabricated, the resin-cured film was observed at 500x magnification using a microscope (trade name: RH-2000, manufactured by HIROX Corporation), and the minimum linewidth (minimum developing size) of the image was measured. The results are shown in Tables 3 to 7. Furthermore, the resin-cured film was observed using the above method and a microscope, and the presence or absence of residue in the unexposed areas between the resolvable patterns was evaluated according to the criteria shown below. The results are shown in Tables 3 to 7. "Judgment Criteria" ○ (Acceptable): No residue in the unexposed areas between the graphics. × (Not allowed): There are imperfections in the unexposed areas of the image.

[0183] (7) Overall Judgment The evaluation was conducted according to the criteria shown below. The results are presented in Tables 3 through 7. Evaluation Criteria ○(Yes): Satisfies all of the following items. (1) The hardness of pencils is 4H or higher. (2) Transmission rate is over 98%. (3) The number of peels in the adhesion is 0. (4) The number of peels in the water resistance test is 0. (5) No discoloration was observed during the evaluation of high temperature and high humidity resistance. (6) The minimum developing size in the image is less than 20 μm, and there is no residue in the unexposed areas between the patterns. × (Not allowed): Not meeting any one or more of the items shown in ○ (Yes) above.

[0184] As shown in Tables 3 to 6, the resin hardened films of Examples 1 to 16 have the following evaluations: (1) Pencil hardness is 4H or 5H, (2) Transmittance (transparency), (3) Adhesion, (4) Water resistance, (5) High temperature and high humidity resistance, and (6) Imaging properties (residue) are all rated as ○ (acceptable), (6) Minimum imaging size is 20μm or less, and (7) Overall rating is ○ (acceptable).

[0185] In contrast, as shown in Table 7, the total determination of (7) for the resin hardened films of Comparative Examples 1 to 5 is × (not acceptable). More specifically, the hardness of the resin-cured films of Comparative Examples 1 and 2, which do not contain (B) alkoxysilyl groups, is H in pencil hardness (1), which is insufficient. Furthermore, the high temperature and humidity resistance (5) of the resin-cured films of Comparative Examples 1 and 2 is × (not acceptable), indicating insufficient resistance to high temperature and humidity.

[0186] The smallest image size in the (6) imaging properties of the resin-cured film of Comparative Example 3, which does not contain (A) alkali-soluble resin, is 50 μm, which is worse than the resin-cured films of Examples 1 to 16.

[0187] (A) The resin-cured film of Comparative Example 4, which has a lower content of the constituent unit (a-1) of the compound (ma-1) containing an aromatic group and an ethylene-containing unsaturated group in the fully repeating composition of the alkali-soluble resin, was evaluated as × (not acceptable) for (4) water resistance and (5) high temperature and humidity resistance, and its water resistance and high temperature and humidity resistance were less than adequate. Furthermore, the minimum image size in (6) imaging properties of the resin-cured film of Comparative Example 4 was 30 μm, which was worse than that of the resin-cured films of Examples 1 to 16.

[0188] (A) The resin-cured film of Comparative Example 5, whose alkali-soluble resin has an ethylene unsaturated group equivalent of 2500 g / mol or more, was rated as × (not acceptable) in terms of high temperature and high humidity resistance, and its high temperature and high humidity resistance was not sufficient. Furthermore, the smallest image size of the resin-cured film of Comparative Example 5 was 30 μm, which was worse than that of the resin-cured films of Examples 1 to 16. [Industry Availability]

[0189] This invention provides a photosensitive resin composition that exhibits good storage stability and, when used in photolithography, demonstrates excellent imaging properties, enabling the formation of resin-cured films with high-precision patterns. Furthermore, by curing the resin, a resin-cured film with high hardness, good adhesion to the substrate and / or base material, good water resistance, high temperature and humidity resistance, and good transparency can be obtained. This photosensitive resin composition is preferably used as a material for protective films and insulating films of touch panels.

Claims

1. A photosensitive resin composition, characterized by comprising: (A) an alkali-soluble resin, (B) an alkoxysilyl-containing resin, (C) a reactive diluent, (D) a photoradical polymerization initiator, (E) a solvent, and (F) a siloxane coupling agent, wherein the aforementioned (A) alkali-soluble resin comprises a constituent unit (a-1) of a compound (ma-1) having an aromatic group and containing an vinyl unsaturated group, containing an acid group and a (meth)acrylic acid group, and the vinyl unsaturated group equivalent is 400 g / mol or more and 2500 g / mol or less, wherein the aforementioned (A) alkali-soluble resin comprises a constituent unit (b-1) of the aforementioned constituent unit (a-1) in all repeating constituent units, and the aforementioned (B) alkoxysilyl-containing resin comprises a constituent unit (b-1) of a compound (mb-1) having an alkoxysilyl-containing group.

2. The photosensitive resin composition as claimed in claim 1, wherein, The mass ratio of the aforementioned (A) alkali-soluble resin to the aforementioned (B) alkoxysilyl-containing resin is 40:60~99:

1.

3. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, In the aforementioned (B) resin containing alkoxysilyl groups, the content of the aforementioned constituent unit (b-1) is 45 mol% or more.

4. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, The aforementioned (A) alkali-soluble resin is a resin in which a portion of the carboxyl group in a copolymer of the aforementioned constituent unit (a-1), a constituent unit (a-2) from an unsaturated monocarboxylic acid (ma-2), and a constituent unit (a-3) from a compound containing an ethylene-containing unsaturated group with an alicyclic hydrocarbon group (ma-3) is modified by a constituent unit (a-5) from an epoxy-containing (meth)acrylate (ma-5).

5. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, The acid value of the aforementioned (A) alkali-soluble resin is 20KOH mg / g ~ 200KOH mg / g.

6. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, The weight average molecular weight (Mw) of the aforementioned (A) alkali-soluble resin is 1000~50000.

7. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, The aforementioned (B) alkoxysilyl-containing resin contains a constituent unit (b-2) derived from an unsaturated monobasic acid (mb-2), and has an acid value of less than 150 KOH mg / g.

8. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, The weight average molecular weight (Mw) of the aforementioned (B) alkoxysilyl-containing resin is 1000~20000.

9. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, Compared to the total of 100 parts by mass of the aforementioned (A) alkali-soluble resin, the aforementioned (B) alkoxysilyl-containing resin, and the aforementioned (C) reactive diluent, the product contains 5 to 75 parts by mass of the aforementioned (C) reactive diluent and 0.1 to 20 parts by mass of the aforementioned (D) photoradical polymerization initiator.

10. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, The aforementioned solvent (E) contains one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms, and the total content of the aforementioned alcohols in the total solvent is 15 to 100% by mass.

11. The photosensitive resin composition as claimed in claim 1, wherein, The aforementioned (F) siloxane coupling agent has one or more functional groups selected from (meth)acrylyl, vinyl, and styryl.

12. The photosensitive resin composition as claimed in claim 1, wherein, Relative to 100 parts by mass of the aforementioned (A) alkali-soluble resin, the aforementioned (B) alkoxysilyl-containing resin, and the aforementioned (C) reactive diluent, the aforementioned (F) siloxane coupling agent is contained in 0.1 to 20 parts by mass.

13. A resin-cured film, which is a cured product containing a photosensitive resin composition as claimed in claim 1.

14. An image display device comprising a resin-cured film as claimed in claim 13.

15. The image display device as claimed in claim 14, wherein, It has a protective film made of the aforementioned resin-cured film.

16. The image display device as claimed in claim 14, wherein, It has an insulating film made of the aforementioned resin-cured film.

17. The photosensitive resin composition of claim 1 is composed solely of the aforementioned (A) alkali-soluble resin, the aforementioned (B) alkoxysilyl-containing resin, the aforementioned (C) reactive diluent, the aforementioned (D) photoradical polymerization initiator, the aforementioned (E) solvent, and the aforementioned (F) siloxane coupling agent.

18. The photosensitive resin composition as claimed in claim 1 or claim 2, wherein, The weight average molecular weight (Mw) of the aforementioned (B) alkoxysilyl-containing resin is 3,000 to 6,000.