Method for producing an alkali-soluble resin and photosensitive resin composition

Abstract

To provide a production method for stably obtaining a specific side-chain double bond-containing alkali-soluble resin obtained by esterification reaction between an acid group and an epoxy group, and a photosensitive resin composition which can be formed into a cured product having good exposure sensitivity and good solvent resistance under a low temperature curing condition.SOLUTION: There is provided a method for producing an alkali-soluble resin that has an ethylenically unsaturated double bond and has a double bond equivalent of 350 g / mol or less in a side chain, wherein in a step in which esterification reaction is performed between an acid group and an epoxy group, specific temperature control is performed. There is also provided a photosensitive resin composition which includes: an alkali-soluble resin which has a (meth)acrylate skeleton in a main chain and an ethylenically unsaturated double bond in a side chain and has a double bond equivalent of 350 g / mol or less; a polyfunctional monomer and a photopolymerization initiator. A method for producing a cured product is furthermore provided which includes a step of curing the photosensitive resin composition at a temperature of 150°C or lower.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain and a double bond equivalent of 350 g / mol or less. Furthermore, the present invention relates to a photosensitive resin composition containing an alkali-soluble resin having a (meth)acrylate skeleton in the main chain and an ethylenically unsaturated double bond in the side chain, a polyfunctional monomer, and a photopolymerization initiator, with a double bond equivalent of 350 g / mol or less.

Background Art

[0002] Compositions containing an alkali-soluble resin are being variously considered for applications in various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, organic insulating films, and organic protective films, as well as various applications in electrical and electronic devices such as liquid crystal display devices and solid-state imaging devices. Resins and resin compositions with excellent properties required for each application have been developed. In recent years, miniaturization, thinning, and energy saving of optical members and electrical and electronic devices have been progressing, and accordingly, higher-quality performance has been demanded for various members used. To meet such demands, research has been conducted on alkali-soluble resins used as materials for various members. In order to improve the curability of an alkali-soluble resin, as a method for improving the crosslinkability and crosslinking density of the resin, it is known to introduce a polymerizable double bond into the side chain of the alkali-soluble resin (polymer). Such a polymer having a polymerizable double bond in the side chain can be obtained, for example, by polymerizing a monomer component containing a monomer having an acid group to obtain a base polymer, and adding a compound having an epoxy group and a polymerizable double bond to the polymer to introduce a polymerizable double bond into the polymer, or by polymerizing a monomer component containing a compound having an epoxy group and a polymerizable double bond to obtain a base polymer, and reacting a compound having an acid group and a polymerizable double bond with the polymer to introduce a polymerizable double bond into the polymer. When producing such a polymer having a polymerizable double bond in the side chain, glycidyl (meth)acrylate (glycidyl acrylate and / or glycidyl methacrylate) is used as one of the compounds having an epoxy group and a polymerizable double bond. For example, Patent Document 1 describes a photosensitive resin composition for a color filter containing a carboxyl group-containing radically polymerizable copolymer having an ethylenically unsaturated double bond. As a method for obtaining the above-mentioned radically polymerizable copolymer, a method of reacting an epoxy group-containing ethylenically unsaturated compound with a copolymer obtained by using an N-substituted maleimide compound and an unsaturated carboxylic acid compound such as (meth)acrylic acid (acrylic acid and / or methacrylic acid) as monomer components is described.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, in the production of an alkali-soluble resin having a large amount of ethylenically unsaturated double bonds in the side chain (for example, a double bond equivalent of 350 g / mol or less), a large amount of hydroxyl groups are likely to be by-produced due to the cleavage of epoxy groups. Due to the large amount of hydroxyl groups, a dehydration esterification reaction with acid groups or a transesterification reaction with ester groups may occur, resulting in gelation due to intermolecular cross-linking or a broad molecular weight distribution. When such an alkali-soluble resin is used as a binder in a photosensitive resin composition, there are problems such as preventing uniform development and causing peeling development, or generating foreign substances in the coating film. In view of the above situation, an object of the present invention is to provide a production method capable of stably obtaining an alkali-soluble resin having a large amount of ethylenically unsaturated double bonds in the side chain. Another object is to provide a photosensitive resin composition containing such an alkali-soluble resin having a large amount of side chain double bonds and extremely high photosensitivity, and a production method of a cured product thereof.

[0005] Specifically, an object is to provide a production method capable of stably obtaining a specific side chain double bond-containing alkali-soluble resin obtained by subjecting an acid group and an epoxy group to an esterification reaction, and a photosensitive resin composition that can provide a cured product having good photosensitivity and good solvent resistance even under low-temperature curing conditions.

Means for Solving the Problems

[0006] As a result of intensive studies, the present inventors have found a production method of a specific alkali-soluble resin with high stability, a highly reactive photosensitive resin composition, and a production method of a cured product. That is, the object of the present invention is achieved by the following <1> to <6>. <1> A production method of an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain and a double bond equivalent of 350 g / mol or less, the method having a step of subjecting an acid group and an epoxy group to an esterification reaction, and having the following process (I) or (II). (I) A step of polymerizing a monomer component containing an unsaturated carboxylic acid monomer to obtain a base polymer, and when glycidyl (meth)acrylate is added to the base polymer, the reaction is carried out at a temperature below 100 °C. After the conversion rate reaches 40% by mass based on 100% by mass of the total glycidyl (meth)acrylate, the reaction is carried out at 100 °C or higher until the conversion rate exceeds 85% by mass. (II) A step of polymerizing a monomer component containing glycidyl (meth)acrylate to obtain a base polymer, and when an unsaturated carboxylic acid monomer is added to the base polymer, the reaction is carried out at a temperature below 100 °C. After the conversion rate reaches 40% by mass based on 100% by mass of the total unsaturated carboxylic acid monomer, the reaction is carried out at 100 °C or higher, and an esterification reaction is carried out until the conversion rate exceeds 85% by mass. Further, a step of carrying out an addition reaction of a polybasic acid anhydride (preferably a carboxylic acid anhydride) is carried out. <2> The method for producing an alkali-soluble resin according to <1>, wherein the esterification reaction is carried out in the presence of a basic compound. <3> The method for producing an alkali-soluble resin according to <1> or <2>, wherein the polymerization solvent for the polymerization contains a non-alcoholic solvent. <4> A photosensitive resin composition containing an alkali-soluble resin having a (meth)acrylate skeleton in the main chain and an ethylenically unsaturated double bond in the side chain with a double bond equivalent of 350 g / mol or less, a polyfunctional monomer, and a photopolymerization initiator. <5> The photosensitive resin composition according to <4>, wherein the photopolymerization initiator contains an oxime-based initiator (preferably an oxime ester-based compound). <6> A method for producing a cured product having a step of curing the photosensitive resin composition according to <4> or <5> at a temperature of 150 °C or lower.

Advantages of the Invention

[0007] By using the method for producing an alkali-soluble resin of the present invention, it is possible to suppress the broadening of the molecular weight distribution and gelation due to intermolecular ester crosslinking and stably obtain an alkali-soluble resin having a large amount of side-chain ethylenically unsaturated double bonds. Further, by using a photosensitive resin composition containing a specific alkali-soluble resin having high reactivity, it is possible to obtain a cured product with less residue during development and good solvent resistance. In particular, it is useful as a resist such as a resist for a color filter, a solder resist, a protective film, and an interlayer insulating film, and a color filter, a display device, a substrate, etc. having a cured product (cured film) formed by these resists are very useful in the optical field and the electrical and electronic fields.

Brief Description of Drawings

[0008]

Figure 1

Embodiments for Carrying Out the Invention

[0009] The present invention will be described in detail below. In addition, a form in which two or more of the individual preferred forms of the present invention described below are combined is also a preferred form of the present invention. In addition, in this specification, “(meth)acrylic acid” means “acrylic acid and / or methacrylic acid”, and “(meth)acrylate” means “acrylate and / or methacrylate”. In addition, in this specification, the numerical range “Min~Max” means not less than the minimum value Min and not more than the maximum value Max. Further, when suitable numerical values are described stepwise for the upper limit value and the lower limit value, a numerical range in which the upper limit value and the lower limit value described separately are appropriately combined is also a suitable numerical range. <Raw Materials and Production Reactions Used in the Production of Alkali-Soluble Resin> The description regarding all monomer components and their masses below represents the total mass of the solid content including a compound for modification such as glycidyl (meth)acrylate in addition to the monomer components during polymerization. As described above, the first aspect of the present invention is a method for producing an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain and having a double bond equivalent of 350 g / mol or less, which includes a step of subjecting an acid group and an epoxy group to an esterification reaction, and is a method for producing an alkali-soluble resin having the following process (I) or (II). (I) A step of polymerizing a monomer component containing an unsaturated carboxylic acid monomer to obtain a base polymer, and when subjecting the base polymer to an addition reaction with glycidyl (meth)acrylate, the reaction is carried out at a temperature of less than 100°C, and after the conversion rate reaches 40% by mass with respect to 100% by mass of all glycidyl (meth)acrylate, the reaction is carried out at a temperature of 100°C or higher until the conversion rate exceeds 85% by mass (II) A step of polymerizing a monomer component containing glycidyl (meth)acrylate to obtain a base polymer, and when subjecting the base polymer to an addition reaction with an unsaturated carboxylic acid monomer, the reaction is carried out at a temperature of less than 100°C, and after the conversion rate reaches 40% by mass with respect to 100% by mass of all unsaturated carboxylic acid monomers, the reaction is carried out at a temperature of 100°C or higher, and an esterification reaction is carried out until the conversion rate exceeds 85% by mass, and further a step of carrying out an addition reaction of a polybasic acid anhydride (preferably a carboxylic acid anhydride)

[0010] The ethylenically unsaturated double bond of the alkali-soluble resin having an ethylenically unsaturated double bond in the side chain and having a double bond equivalent of 350 g / mol or less according to the present invention is generated by an esterification reaction between an acid group and an epoxy group. Specifically, (1) an acid group-containing resin obtained by polymerizing a monomer mixture containing a monomer having an acid group is subjected to an esterification reaction with a monomer having an epoxy group and a double bond, or (2) an epoxy group-containing resin obtained by polymerizing a monomer mixture containing a monomer having an epoxy group is subjected to an esterification reaction with a monomer having an acid group and a double bond. Further, a polybasic acid anhydride (preferably a carboxylic acid anhydride) may be reacted with the hydroxyl group generated by the reaction between the acid group and the epoxy group. The above double bond means a polymerizable double bond, that is, a carbon-carbon double bond, and examples thereof include an (meth)acryloyl group and a vinyl group. Examples of the monomer having the above acid group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; unsaturated monocarboxylic acids in which the chain is extended between an unsaturated group and a carboxyl group, such as succinic acid mono(2-acryloyloxyethyl) and succinic acid mono(2-methacryloyloxyethyl); unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and the like. Among these, from the viewpoints of versatility, availability, etc., it is preferable to use unsaturated carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids). More preferably, from the viewpoints of reactivity, alkali solubility, etc., it is preferable to use unsaturated monocarboxylic acids, and even more preferably (meth)acrylic acid. Hereinafter, the unsaturated carboxylic acid monomer is also referred to as unsaturated carboxylic acid monomer (b). The content ratio of the above unsaturated carboxylic acid monomer is preferably set to have an appropriate acid value so that the resin has alkali solubility, for example, when used as a binder for a resist, except for being consumed by reacting with the epoxy group of glycidyl (meth)acrylate. For example, when used in a resist for a color filter, the content ratio of the unsaturated carboxylic acid monomer is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, based on 100% by mass of the total amount of all monomer components. Also, it is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The content ratio of the structural unit in which the above unsaturated carboxylic acid monomer unit is modified with glycidyl (meth)acrylate is preferably 65% by mass or more, more preferably 70% by mass or more, based on 100% by mass of the total amount of all monomer components. Also, it is preferably 95% by mass or less. More preferably, it is 90% by mass or less. In order to adjust various properties required depending on solvent solubility, viscosity, and other uses, it is preferable to copolymerize the above alkali-soluble resin with other copolymerizable monomers according to the purpose. As other copolymerizable monomer components according to the present invention, it is preferable to further include a monomer capable of introducing a ring structure into the main chain of the resin (also referred to as monomer (a) capable of introducing a ring structure into the main chain). Examples of the monomer capable of introducing a ring structure into the main chain (including monomers having a ring structure in the main chain) include N-substituted maleimide monomers, dialkyl-2,2'-(oxydimethylene) diacrylate monomers, α-(unsaturated alkoxyalkyl) acrylate monomers (preferably alkyl-(α-allyloxymethyl) acrylate monomers), etc. It is preferable to use these. Here, for example, when using an N-substituted maleimide monomer and / or a dialkyl-2,2'-(oxydimethylene) diacrylate monomer and / or an alkyl-(α-allyloxymethyl) acrylate monomer, it becomes an alkali-soluble resin capable of providing a cured product with improved heat resistance, hardness, colorant dispersibility, etc. in the resist application for color filters. The content ratio of the monomer capable of introducing a ring structure into the main chain is preferably 50% by mass or less, more preferably 45% by mass or less, in 100% by mass of the total amount of all monomer components. In particular, when including an N-substituted maleimide monomer, a dialkyl-2,2'-(oxydimethylene) diacrylate monomer and / or an α-(unsaturated alkoxyalkyl) acrylate monomer, the content ratio is preferably 0.05 to 50% by mass, more preferably 1 to 40% by mass, still more preferably 2 to 30% by mass, from the viewpoints of heat resistance, hardness, colorant dispersibility, development speed, transparency, etc.

[0011] Examples of the N-substituted maleimide monomers include N-cyclohexyl maleimide, N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, N-t-butyl maleimide, N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide, etc., and one or more of these can be used. Among them, N-cyclohexyl maleimide, N-phenyl maleimide, and N-benzyl maleimide are preferable in terms of less coloring and excellent dispersibility, and particularly N-benzyl maleimide and N-phenyl maleimide are suitable. Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimides such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide, and p-dichlorobenzylmaleimide. Examples of the N-phenylmaleimide include phenylmaleimide; alkyl-substituted phenylmaleimides such as p-methylphenylmaleimide and p-butylphenylmaleimide; phenolic hydroxyl group-substituted phenylmaleimides such as p-hydroxyphenylmaleimide; halogen-substituted phenylmaleimides such as o-chlorophenylmaleimide, o-dichlorophenylmaleimide, and p-dichlorophenylmaleimide. From the viewpoints of less coloring, dispersibility, and easy industrial availability, it is preferable to use, for example, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate as the dialkyl-2,2'-(oxydimethylene) diacrylate monomer. Examples of the α-(unsaturated alkoxyalkyl) acrylate monomer include chain saturated hydrocarbon group-containing α-(allyloxymethyl) acrylates such as α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, n-propyl α-allyloxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate, s-hexyl α-allyloxymethyl acrylate, n-heptyl α-allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, capryl α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, decyl α-allyloxymethyl acrylate, undecyl α-allyloxymethyl acrylate, lauryl α-allyloxymethyl acrylate, tridecyl α-allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, cerinyl α-allyloxymethyl acrylate, and melissyl α-allyloxymethyl acrylate. Other monomers such as alkyl-(α-methallyloxymethyl) acrylate monomers are also preferred. Among them, methyl α-allyloxymethyl acrylate (also referred to as α-(allyloxymethyl) methyl acrylate) is particularly preferred. The above α-(unsaturated alkoxyalkyl) acrylate monomer can be produced, for example, by the production method disclosed in International Publication No. 2010 / 114077 pamphlet.

[0012] As the monomer component according to the present invention, (meth)acrylic acid ester monomers are preferably monomers having an alicyclic skeleton, for example, considering the surface hardness of the resulting cured product. Specifically, for example, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, pentacyclopentadecanedimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, norbornanedimethanol di(meth)acrylate, p-menthane-1,8-diol di(meth)acrylate, p-menthane-2,8-diol di(meth)acrylate, p-menthane-3,8-diol di(meth)acrylate, bicyclo[2.2.2]-octane-1-methyl-4-isopropyl-5,6-dimethylol di(meth)acrylate and the like can be mentioned. Among these, from the viewpoints of versatility, availability, etc., it is preferable to use cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate. The above (meth)acrylic acid ester monomer also includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, monoglycerol (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, t-butyl α-hydroxymethylacrylate, t-amyl α-hydroxymethylacrylate, etc. In addition, 1,4-dioxaspiro[4,5]deca-2-yl methacrylate, (meth)acryloylmorpholine, tetrahydrofurfuryl acrylate, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, etc. are also included. Among them, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and benzyl (meth)acrylate are preferable in terms of being easily balanced in heat resistance, colorant dispersibility, and solvent re-dissolubility. The content ratio of the above-mentioned (meth)acrylic acid ester monomer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass in 100% by mass of the total amount of all monomer components.

[0013] As the monomer component according to the present invention, examples of the aromatic vinyl monomer include styrene, vinyltoluene, α-methylstyrene, methoxystyrene and the like. Among them, styrene and / or vinyltoluene are preferable in terms of the heat-resistant coloring property and heat-resistant decomposability of the obtained resin. The polymerization initiator used during the polymerization of the above monomer components is not particularly limited. For example, organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate; azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate); etc. These polymerization initiators may be used alone or in combination of two or more. The amount of the initiator used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited. However, in terms of reducing the concentration of the oligomer (for example, with a molecular weight of 500 or less) and obtaining a polymer with a small molecular weight distribution, it is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and less than 3% by mass, based on all monomer components (100% by mass of the total amount of all monomers). When polymerizing the above monomer components, a commonly used chain transfer agent may be added as necessary for molecular weight adjustment. Examples of the chain transfer agent include mercaptan-based chain transfer agents such as n-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid, methyl mercaptoacetate, and α-methylstyrene dimer. Preferably, n-dodecyl mercaptan and mercaptopropionic acid, which have a high chain transfer effect, can reduce residual monomers, and are easily available, are preferred. When using a chain transfer agent, its usage amount may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited. However, in terms of obtaining a polymer with a weight average molecular weight of several thousand to several tens of thousands without gelation, it is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.2% by mass or more and less than 3% by mass, based on all monomer components (total 100% by mass of all monomers). Examples of the method for polymerizing the monomer used in the present invention include solution polymerization and emulsion polymerization. Among these, solution polymerization is preferable because it is industrially advantageous and it is easy to adjust the structure such as the molecular weight. Further, as the polymerization mechanism of the above monomer, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used, but a polymerization method based on a radical polymerization mechanism is preferable because it is also industrially advantageous. As the polymerization initiation method in the above polymerization reaction, energy necessary for polymerization initiation may be supplied to the monomer component from an active energy source such as heat, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.), or electron beams. Further, if a polymerization initiator is used in combination, the energy necessary for polymerization initiation can be greatly reduced, and the reaction control becomes easy, which is preferable. Further, the molecular weight of the polymer obtained by polymerizing the above monomer can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like. When the above monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction. For example, it may be appropriately set according to the polymerization conditions such as the polymerization mechanism, the type and amount of the monomer used, the polymerization temperature, and the polymerization concentration. However, when a solvent is used as a diluent or the like when forming a photosensitive resin composition later, it is efficient and preferable to use a solvent containing the solvent for the solution polymerization of the monomer component. In the production method of the present invention, it is efficient to use a non-alcoholic solvent as the polymerization solvent. The solvent will be described in a preferred production method described later. The volume of the reaction tank (reaction vessel) used in the production method of the present invention is 0.5 to 10 liters on a laboratory scale and usually 0.1 to 50 m 3 in an industrial production scale. Preferably it is 0.2 to 45 m 3 , more preferably 0.3 to 40 m 3 . The material inside the above reaction tank is not particularly limited. For example, those made of stainless steel, preferably SUS such as SUS304, SUS316, and SUS316L are preferable from the viewpoint of corrosion resistance. Further, it is desirable that the inside of the reaction tank is subjected to glass lining processing or the like to make it inert to the reaction raw material and the reaction product.

[0014] The volume of the finally obtained polymer solution is preferably controlled to 40 to 80% by volume, more preferably 50 to 70% by volume, of the volume of the reaction vessel. In a range exceeding 80% by volume, the proportion of the polymerization reaction solution becomes high, and there may be difficulties in polymerization control and safety aspects, such as coping with a sudden temperature rise. Also, the solid content concentration (polymerization concentration) of the finally obtained polymer solution is preferably 10 to 70% by mass. More preferably, it is 30 to 50% by mass. In addition, the gas phase part above the polymer solution is preferably made to have a low oxygen concentration by substitution with an inert gas (preferably nitrogen substitution). For example, methods include bubbling an inert gas (nitrogen, helium, argon, carbon dioxide, etc.) into the polymerization reaction solution, and blowing an inert gas into the reaction system to reduce the oxygen in the gas phase part. As a specific method of bubbling nitrogen, a method of placing a nitrogen line equipped with a porous filter into the reaction solution (preferably the lower part) and flowing nitrogen while stirring the reaction solution can be mentioned. As a method of blowing an inert gas into the reaction system, providing a nitrogen inlet at the upper part of the reaction vessel and blowing it in can be mentioned. In that case, an exhaust port should be provided. As the inert gas, nitrogen, which is the most abundant gas in the atmosphere and is extremely inert under normal temperature and pressure and is cheaper than noble gases such as argon, is preferable. The introduction amount of the nitrogen is, for example, in a laboratory scale (0.5 to 5 liters), it is preferably blown in at a flow rate of 0.1 (ml / min) to 300 (ml / min), and more preferably at a flow rate of 1 (ml / min) to 150 (ml / min). 3 In an industrial production scale (0.5 to 5 m

[0015] The shape of the reaction vessel (reaction container) to be used is not particularly limited, and examples include polygonal, cylindrical, etc. However, from the viewpoints of stirring effect, handleability, versatility, etc., a cylindrical shape is preferred. Also, baffles may or may not be provided, but by providing baffles, the uniformity of the polymerization reaction solution can be enhanced. The stirrer is composed of a power source such as an electric motor, a rotating shaft, a stirrer, etc., and the shape of its stirring blade is not limited. Examples of the stirrer include a disk turbine, a fan turbine, a curved fan turbine, a pitched blade turbine, a multi-stage fan turbine, a Faudler blade, a Blumargin type, an angled blade, a propeller type, a multi-stage blade, an anchor type, a gate type, a double ribbon blade, a screw blade, a Max Blend blade, etc. The stirring power (industrial production scale) during the polymerization reaction is 0.1~4.0kW / m 3 , preferably 0.1~3.0kW / m 3 , more preferably 0.2~2.0kW / m 3 . By controlling within this range, the uniformity of the polymerization reaction solution is improved, and also, it can be prevented that the polymerization reaction solution scatters on the inner wall surface of the reaction vessel (reaction container) and reacts on the inner wall surface of the reaction vessel to cause gelation. In addition, regarding the pressure inside the container during the polymerization reaction, there is no need to control pressurization or depressurization. Usually, it may be carried out at normal pressure unless special operations are performed or special raw materials are used. When distilling off a low-boiling solvent, appropriate depressurization may be carried out. The monomer charging method during the polymerization reaction is not particularly limited, and a part may be initially charged and the rest may be dropped, or the whole amount may be dropped. However, from the viewpoint of controlling the heat generation amount, it is preferable to initially charge a part and drop the rest, or drop the whole amount. In this specification, charging the monomer into the reaction vessel in advance (introducing the monomer into the reaction vessel before polymerization) is also referred to as initial charging.

[0016] Regarding the above polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomers used, the type and amount of the polymerization initiator, etc., but it is preferably a temperature 20°C or more lower than the boiling point of the polymerization solvent. In the case of a mixed solvent, it is preferably a temperature 20°C or more lower than the boiling point of the solvent with the highest boiling point. For example, 50 to 150°C is preferable, and 70 to 120°C is more preferable. Also, the polymerization time can be similarly set appropriately. For example, 1 to 8 hours is preferable, and 2 to 6 hours is more preferable. <Method for producing a preferable alkali-soluble resin> As a preferable embodiment of the present invention, the first (I) is a step (I-1) of polymerizing a monomer component containing a monomer (a) capable of introducing a ring structure into the main chain and an unsaturated carboxylic acid monomer (b) to obtain a base polymer, and a step (I-2) of reacting the above base polymer with glycidyl (meth)acrylate to obtain an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain. And the second (II) is a step (II-1) of polymerizing a monomer component containing a monomer (a) capable of introducing a ring structure into the main chain and glycidyl (meth)acrylate to obtain a base polymer, and a step (II-2) of reacting the above base polymer with an unsaturated carboxylic acid monomer (b) to obtain an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain. Two forms of the production method are mentioned. In the above production methods (I) and (II), finally, the monomer components are adjusted so that an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain and a double bond equivalent of 350 g / mol or less can be obtained. The above double bond equivalent is preferably in the range of 200 to 350 g / mol, more preferably in the range of 230 to 330 g / mol, and particularly preferably in the range of 250 to 300 g / mol. When the above double bond equivalent is in the above range, the curability (sensitivity to heat and light) of the alkali-soluble resin is improved, and the adhesion of the cured product is improved. Also, it becomes possible to achieve both curability and storage stability. In this specification, the double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of double bonds in the polymer (alkali-soluble resin). The mass of the solid content of the polymer solution is the sum of the masses of the respective monomer components constituting the polymer (for example, the mass of the base polymer component and the mass of the compound capable of imparting a polymerizable double bond group to the side chain). The double bond equivalent can be determined by dividing the mass (g) of the polymer solid content of the polymer solution by the amount (mol) of double bonds in the polymer. The amount of double bonds in the polymer can be determined from the structures of the unsaturated carboxylic acid monomer and the glycidyl (meth)acrylate group-containing monomer used during synthesis and their amounts. It can also be measured using various analyses such as titration, elemental analysis, NMR, IR, etc., and differential scanning calorimetry. For example, it may be calculated by measuring the number of ethylenic double bonds contained per 1 g of the polymer in accordance with the iodine value test method described in JIS K 0070:1992. Further, the double bond equivalent is a measure of the amount of double bonds contained in the molecule, and for compounds with the same molecular weight, the larger the numerical value of the double bond equivalent, the smaller the amount of double bonds introduced.

[0017] The above-mentioned preferred production processes (I) and (II) are described in detail below. Production process (I): <Process (I-1)> The above-mentioned preferred production process (I) has a step (I-1) of polymerizing a monomer component containing a monomer (a) capable of introducing a ring structure into the main chain and an unsaturated carboxylic acid monomer (b) to obtain a base polymer (also referred to as "base polymer 1"). The method for polymerizing the monomer component containing the above-mentioned monomers (a) and (b) to obtain base polymer 1 is not particularly limited, and examples include known polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization. Among them, solution polymerization is preferred in terms of being industrially advantageous and having easy structural adjustment such as molecular weight. Further, for the polymerization mechanism of the above-mentioned monomer component, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used, but in terms of industrial advantages, a polymerization method based on a radical polymerization mechanism is preferred. The molecular weight of the base polymer 1 obtained by polymerizing the above monomer components can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, etc. Examples of the polymerization initiator include peroxides and azo compounds that are usually used as polymerization initiators such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), hydrogen peroxide, persulfates, etc. Examples of the chain transfer agent preferably include compounds having a mercapto group such as mercapto carboxylic acids, mercapto carboxylic acid esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercapto isocyanurates, etc. More preferably, alkyl mercaptans, mercapto carboxylic acids, mercapto carboxylic acid esters are included, and still more preferably, n-dodecyl mercaptan, mercaptopropionic acid are included. The solvent used for the above polymerization is not particularly limited. For example, monoalcohols such as methanol, ethanol, isopropanol, n-butanol, s-butanol; polyhydric alcohols such as ethylene glycol, propylene glycol; ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform; dimethyl sulfoxide; dimethyl carbonate, etc. Among the polymerization solvents described above, it is preferable to use alcohol solvents (monohydric alcohols, polyhydric alcohols), ketone solvents, ester solvents and / or ether solvents. Among them, from the solubility of the resulting polymer, the surface smoothness when forming a coating film, the low impact on the human body and the environment, and the ease of industrial availability, among alcohol solvents, propylene glycol monomethyl ether, ethylene glycol or diethylene glycol is preferable, among ester solvents, propylene glycol monomethyl ether acetate is preferable, among ether solvents, diethylene glycol dimethyl ether or diethylene glycol ethyl methyl ether is preferable, and among ketone solvents, it is preferable to use ethyl lactate. In the production method of the present invention, the boiling point of the polymerization solvent is preferably in the range of 130°C to 250°C, and more preferably in the range of 130°C to 220°C. Further, it is preferable to use a non-alcohol solvent, and it is particularly preferable to use an ester solvent that is easy to control the molecular weight. Since propylene glycol monomethyl ether acetate is widely used as a resist solvent among ester solvents, it is also preferable in terms of reducing the labor of solvent substitution. In addition, since alcohol solvents have high basicity and cause pigment aggregation in the resist, it is preferably 50% by mass or less in the total solvent. In particular, when using an alcohol solvent, it is preferable to use a solvent having a boiling point of 130°C or higher from the synthetic aspect. The amount of the polymerization solvent used is preferably 50 to 500 parts by mass, more preferably 100 to 300 parts by mass, based on 100 parts by mass of the total amount of the monomer components. Only one kind of the polymerization initiator, chain transfer agent, and polymerization solvent may be used, or two or more kinds may be used in combination. Further, the amounts used thereof can be set as appropriate. The polymerization temperature can be appropriately set according to the type and amount of the monomer used, the type and amount of the polymerization initiator, etc. For example, 50 to 200°C is preferable, and 80 to 120°C is more preferable. The polymerization time can be appropriately set. For example, 1 to 12 hours is preferable, and 3 to 8 hours is more preferable. The mixing of the above monomer components is not particularly limited and may be appropriately carried out according to the alkali-soluble resin to be obtained. The total amounts of the above monomers (a) and (b) may be mixed simultaneously, or the above monomer (b) or (a) may be added little by little to the total amount of the above monomer (a) or (b) and mixed. After polymerizing the above monomer components to obtain Base Polymer 1, the volatile components may be removed from the polymerization reaction solution (polymer solution) to separate Base Polymer 1, and then Base Polymer 1 may be used. Alternatively, it may be used in a solution state without separation. However, from the viewpoint of cost and the like, it is preferable to use it in a solution state without separation for industrial use. The monomer components will be described below. By polymerizing the monomer components containing each monomer, a copolymer having a structural unit derived from each monomer can be obtained. (Monomer (a) capable of introducing a ring structure into the main chain) As the monomer (a) capable of introducing a ring structure into the above main chain, for example, an N-substituted maleimide monomer (a-1) represented by the following general formula is particularly preferable.

[0018] [Chemical formula] (In the formula, R represents a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.) In the general formula (a-1), R is a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. The above monovalent hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the above hydrocarbon group include a chain or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group. The above aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but is preferably a saturated aliphatic hydrocarbon group. Examples of the chain-like saturated aliphatic hydrocarbon group include linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, octyl group, methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, nonyl group, methyloctyl group, 3,7-dimethyloctyl group, dimethylheptyl group, 3-ethylheptyl group, 4-ethylheptyl group, trimethylhexyl group, 3,3-diethylpentyl group, decyl group, undecyl group, dodecyl group and the like. Among them, an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, and an alkyl group having 1 to 12 carbon atoms is still more preferable. Examples of the cyclic aliphatic hydrocarbon group include monocyclic alicyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group; polycyclic alicyclic hydrocarbon groups such as dicyclopentanyl group, norbornyl group, adamantyl group; and the like. Among them, a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 30 carbon atoms is preferable, a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms is more preferable, and a monocyclic alicyclic hydrocarbon group having 6 to 12 carbon atoms is still more preferable. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, benzyl group, phenethyl group and the like. Among them, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferable. The above hydrocarbon group may have a substituent. Examples of the above substituent include an alkyl group, an aryl group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an aryloxy group, etc. Specific examples of the above N-substituted maleimide monomer include, for example, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-t-butylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-octylmaleimide, N-2-ethylhexylmaleimide, N-decylmaleimide, N-laurylmaleimide, N-tetradecylmaleimide, N-stearylmaleimide, N-2-decyltetradecylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-hydroxyethylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-tribromophenylmaleimide, N,N'-ortho-phenylenebismaleimide, N,N'-meta-phenylenebismaleimide, N,N'-para-phenylenebismaleimide, etc. Among them, from the viewpoints of copolymerizability with the above N-vinylamide monomer and heat resistance, N-benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide are preferable. In particular, N-benzylmaleimide is preferably used in applications where strong heat-resistant coloring properties are required, and N-phenylmaleimide is preferably used in applications where strong affinity with organic fine particles or inorganic fine particles is required. Examples of the above N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimides such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide, and p-dichlorobenzylmaleimide; etc. The above N-substituted maleimide monomer (a-1) may be used alone or in combination of two or more. Among them, the N-substituted maleimide monomer (a-1) is preferably N-benzylmaleimide and N-phenylmaleimide. By combining these two types, the dispersion stability of the pigment may be improved, or the surface hardness of the film after curing may be increased. The mass ratio of N-benzylmaleimide to N-phenylmaleimide is preferably from 95 / 5 to 5 / 95, more preferably from 10 / 90 to 90 / 10. Also, when using N-phenylmaleimide as the main component as the N-substituted maleimide monomer (a-1), the proportion of N-benzylmaleimide is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 1 to 10 parts by mass, and most preferably 1 to 5 parts by mass with respect to 100 parts by mass of N-phenylmaleimide. Further, when used in combination as described above, the amount of N-benzylmaleimide used is preferably 0.05 to 50% by mass, more preferably 1 to 40% by mass, still more preferably 2 to 30% by mass with respect to 100% by mass of the total monomer component. By setting it within the above range, the affinity and dispersibility with organic fine particles such as pigments and inorganic fine particles such as quantum dots or silica can be improved. (Unsaturated carboxylic acid monomer (b)) As the unsaturated carboxylic acid monomer (b), a compound having a carboxyl group and / or a carboxylic anhydride group and a polymerizable double bond is preferable. Examples of the polymerizable double bond include, for example, a (meth)acryloyl group, a vinyl group, etc. Among them, a (meth)acryloyl group is preferable. Specific examples of the above unsaturated carboxylic acid monomers include, for example, unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; unsaturated long-chain monocarboxylic acids in which the chain is extended between an unsaturated group and a carboxyl group, such as succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl); and the like. Among these, from the viewpoints of versatility, availability, etc., unsaturated monocarboxylic acids are preferred, and (meth)acrylic acid is more preferred. The above unsaturated carboxylic acid monomer (b) may be used alone or in combination of two or more. (Monomer (c) copolymerizable with the above monomer (a) and monomer (b)) The monomer components for producing Base Polymer 1 may further contain, in addition to the above monomer (a) and monomer (b), a monomer (c) copolymerizable with the above monomer (a) and monomer (b). The above monomer (c) is not particularly limited as long as it is copolymerizable with the above-mentioned monomers (a) and (b), and examples thereof include the following monomers. These may be used alone or in combination of two or more. Hydroxyl group-containing monomers such as hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate; (Meth)acrylic acid methyl, (meth)acrylic acid ethyl, (meth)acrylic acid n-propyl, (meth)acrylic acid i-propyl, (meth)acrylic acid n-butyl, (meth)acrylic acid s-butyl, (meth)acrylic acid t-butyl, (meth)acrylic acid n-amyl, (meth)acrylic acid s-amyl, (meth)acrylic acid t-amyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid isodecyl, (meth)acrylic acid tridecyl, (meth)acrylic acid octyl, (meth)acrylic acid isooctyl, (meth)acrylic acid lauryl, (meth)acrylic acid stearyl, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid benzyl, (meth)acrylic acid tetrahydrofurfuryl, (meth)acrylic acid N,N-dimethylaminoethyl, 1,4-dioxaspiro[4,5]deca-2-yl methacrylate, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane and other (meth)acrylic acid esters; Cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, pentacyclopentadecanedimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, norbornanedimethanol di(meth)acrylate, p-menthane-1,8-diol di(meth)acrylate, p-menthane-2,8-diol di(meth)acrylate, p-menthane-3,8-diol di(meth)acrylate, bicyclo[2.2.2]-octane-1-methyl-4-isopropyl-5,6-dimethylol di(meth)acrylate and other alicyclic (meth)acrylates; (Meth)acrylic acid β-methyl glycidyl, (meth)acrylic acid β-ethyl glycidyl, vinyl benzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, vinyl cyclohexene oxide and other epoxy group-containing monomers other than glycidyl (meth)acrylate; (Meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N-methylol(meth)acrylamide; Macromonomers having a (meth)acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; Conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide; Aromatic vinyls such as styrene, vinyltoluene, α-methylstyrene, xylene, methoxystyrene, and ethoxystyrene; Unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; etc. The respective contents of the above monomers (a), (b), and (c) can be appropriately set according to the purpose and use of the alkali-soluble resin to be obtained. The above monomer (a) is preferably 0.05 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 2 to 30% by mass based on 100% by mass of the total monomer component. The above monomer (b) is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more based on 100% by mass of the total monomer component. Also, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. The above monomer (c) is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass based on 100% by mass of the total monomer components. When the above monomer (a), (b), and (c) each contain two or more monomers, their contents are the total amounts.

[0019] <Step (I-2)> The above production step (I) further includes a step (I-2) of reacting the base polymer 1 obtained in the above step (I-1) with glycidyl (meth)acrylate to obtain an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain. The method of reacting the above base polymer 1 with glycidyl (meth)acrylate is not particularly limited. It is preferable to mix glycidyl (meth)acrylate with a polymer solution containing the base polymer 1 and react it by a known method. By the above reaction, the esterification reaction occurs between the acid group (carboxyl group) of the base polymer 1 and the epoxy group of glycidyl (meth)acrylate, and glycidyl (meth)acrylate is added to the base polymer 1 to obtain a polymer having an ethylenically unsaturated double bond in the side chain. As the temperature of the above addition reaction, in order to obtain an alkali-soluble resin with a double bond equivalent of 350 g / mol or less and to stably progress the addition reaction while suppressing the increase in molecular weight due to intermolecular ester crosslinking, when glycidyl (meth)acrylate is added to the base polymer, the reaction is carried out at a temperature below 100 °C. After the conversion rate reaches 40% by mass with respect to 100% by mass of the total glycidyl (meth)acrylate, it is preferable to carry out the reaction at a temperature of 100 °C or higher until the conversion rate exceeds 85% by mass. As the temperature range, until the conversion rate reaches 40% by mass, it is preferably 70 to less than 100 °C, and more preferably 80 to less than 100 °C. After the conversion rate reaches 40% by mass, it is preferably 100 to 150 °C, and more preferably 100 to 120 °C until the conversion rate exceeds 85% by mass. The total reaction time of the above addition reaction is not particularly limited, and examples thereof include 50 minutes to 36 hours, preferably 3 to 26 hours, and more preferably 6 to 20 hours. Also, when the conversion rate is up to 40% by mass, the reaction time is preferably 20 minutes to 10 hours, more preferably 1 hour to 8 hours, and particularly preferably 2 hours to 5 hours. After the conversion rate reaches 40% by mass, until the conversion rate exceeds 85% by mass, the reaction time is preferably 30 minutes to 20 hours, more preferably 2 hours to 16 hours, and still more preferably 4 hours to 13 hours. Note that the completion of the esterification reaction is more preferably when the conversion rate is 90% by mass or more, and most preferably 99% by mass or more. As the amount of glycidyl (meth)acrylate used in the above step (I-2), it is preferably appropriately set so that the double bond equivalent of the resulting alkali-soluble resin is 350 g / mol or less. For example, with respect to 100 parts by mass of the total monomer component that gives the above base polymer 1, it is preferably 30 to 180 parts by mass, more preferably 50 to 150 parts by mass, and still more preferably 80 to 150 parts by mass. The above addition reaction (esterification reaction) is preferably carried out in the presence of a basic compound. For example, amine compounds such as trimethylamine, triethylamine, triisopropylamine, tributylamine, dimethylbenzylamine, methyldibenzylamine, tribenzylamine; phosphines such as triethylphosphine, triphenylphosphine; ammonium salts such as tetraethylammonium chloride; phosphonium salts such as tetraphenylphosphonium bromide, amide compounds such as dimethylformamide; and other known catalysts may be used. Among them, amine compounds and phosphines are preferred in terms of less coloring and easy industrial availability, and triethylamine and dimethylbenzylamine are more preferred. The amount of the above catalyst used can be appropriately set, but it is preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass, and still more preferably 0.1 to 0.5% by mass with respect to the total amount of base polymer 1 and glycidyl (meth)acrylate. If the amount of the above catalyst used is less than the above range, the reaction time may become long, which may be industrially disadvantageous. Also, if it exceeds the above range, there is a risk that a salt will be formed with the base polymer at the time of catalyst addition, causing insolubilization and difficulty in stirring, or the thermal coloring of the obtained polymer will become strong. In addition to the above-described steps (I-1) and (I-2), the above production method (I) may have other steps. Examples of the other steps include an aging step, a neutralization step, a step for deactivating a polymerization initiator and a chain transfer agent, a dilution step, a drying step, a concentration step, a purification step, and the like. These steps can be carried out by known methods. Production step (II): <Step (II-1)> The above production step (II) has a step (II-1) of polymerizing a monomer component containing a monomer (a) capable of introducing a ring structure into the main chain and glycidyl (meth)acrylate to obtain a base polymer (also referred to as "base polymer 2"). As the monomer (a) capable of introducing a ring structure into the main chain and glycidyl (meth)acrylate, the same ones as the "monomer (a) capable of introducing a ring structure into the main chain" and "glycidyl (meth)acrylate" described in the above production method (I) can be respectively cited. The same components such as other solvents can also be used. The monomer component for producing the above base polymer 2 may further contain a monomer (d) copolymerizable with the above monomer (a) and the above glycidyl (meth)acrylate. Examples of the monomer (d) include the same monomers as the above monomer (c) described in the above production method (I). These may be used alone or in combination of two or more. The polymerization method is not particularly limited, but preferably the same method as the polymerization method described in the above production method (I) can be cited. The respective contents of the above monomer (a), glycidyl (meth)acrylate, and the above monomer (d) can be appropriately set according to the double bond amount and acid value of the alkali-soluble resin to be obtained. The above monomer (a) is preferably 1% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less based on 100% by mass of the total monomer component that gives the base polymer 2. The above glycidyl (meth)acrylate is more preferably 50% by mass or more, still more preferably 60% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less based on 100% by mass of the total monomer components that give the base polymer 2. The above monomer (d) is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, preferably 60% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less based on 100% by mass of the total monomer components that give the base polymer 2. When the above monomer (a), glycidyl (meth)acrylate, and the above monomer (d) each contain two or more monomers, their total amounts are used. <Step (II-2)> The above production method (II) further has a step (II-2) of reacting the base polymer 2 obtained in the above step (II-1) with an unsaturated carboxylic acid monomer (b) to obtain an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain. The method of reacting the above base polymer 2 with the above unsaturated carboxylic acid monomer (b) is not particularly limited, and the above unsaturated carboxylic acid monomer (b), and, if necessary, a polymerization initiator, a chain transfer agent, a catalyst, etc. may be mixed with a polymer solution containing the base polymer 2 and reacted by a known method. By the above reaction, the carboxyl group of the unsaturated carboxylic acid monomer (b) is esterified with the epoxy group of the base polymer 2, the unsaturated carboxylic acid monomer (b) is added, and an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain is obtained. Examples of the above unsaturated carboxylic acid monomer (b) include the same ones as the unsaturated carboxylic acid monomer (b) described in the above production step (I). As the temperature of the addition reaction, in order to obtain an alkali-soluble resin having a double bond equivalent of 350 g / mol or less, while suppressing the increase in molecular weight due to intermolecular ester crosslinking and allowing the addition reaction to proceed stably, when the unsaturated carboxylic acid monomer (b) is added to the base polymer 2, the reaction is preferably carried out at a temperature below 100 °C. After the conversion rate reaches 40% by mass with respect to 100% by mass of the total unsaturated carboxylic acid monomer (b), the reaction is preferably carried out at a temperature of 100 °C or higher until the conversion rate exceeds 85% by mass. As the temperature range, until the conversion rate reaches 40% by mass, it is preferably 40 to less than 100 °C, more preferably 70 to less than 100 °C. After the conversion rate reaches 40% by mass, it is preferably 100 to 180 °C, more preferably 100 to 150 °C, and particularly preferably 100 to 120 °C until the conversion rate exceeds 85% by mass. The total reaction time of the addition reaction is not particularly limited, and examples thereof include 50 minutes to 36 hours, preferably 3 to 26 hours, and more preferably 6 to 20 hours. Also, until the conversion rate reaches 40% by mass, the reaction time is preferably 20 minutes to 10 hours, more preferably 1 to 8 hours, and particularly preferably 2 to 5 hours. After the conversion rate reaches 40% by mass, the reaction time is preferably 30 minutes to 20 hours, more preferably 2 to 16 hours, and even more preferably 4 to 13 hours until the conversion rate exceeds 85% by mass. It should be noted that the completion of the esterification reaction is more preferably when the conversion rate is 90% by mass or higher, and most preferably 95% by mass or higher. The amount of the unsaturated carboxylic acid monomer (b) used in the above step (II-2) is preferably set as appropriate so that the double bond equivalent of the resulting alkali-soluble resin is 350 g / mol or less. For example, it is preferably 10 to 60 parts by mass, more preferably 25 to 50 parts by mass, and even more preferably 30 to 40 parts by mass with respect to 100 parts by mass of the monomer component that gives the above base polymer 2. The above reaction (esterification reaction) is preferably carried out in the presence of a basic compound. For example, amine compounds such as triethylamine and dimethylbenzylamine; ammonium salts such as tetraethylammonium chloride; phosphonium salts such as tetraphenylphosphonium bromide, amide compounds such as dimethylformamide; and other known catalysts may be used. The amount of the above catalyst used can be set appropriately. <Step (II-3)> In the above production step (II), after the above step (II-2), it preferably has a step (II-3) of reacting a polybasic acid or a polybasic acid anhydride with the alkali-soluble resin having an ethylenically unsaturated double bond in the side chain. By performing the above step (II-3), a polybasic acid or a polybasic anhydride is reacted with the hydroxyl group generated by the reaction of the epoxy group and the carboxyl group in the above step (II-2), so that a carboxyl group can be generated, and the acid value of the above alkali-soluble resin can be adjusted to an appropriate range. Examples of the above polybasic acid or polybasic acid anhydride include polybasic acids such as succinic acid, maleic acid, phthalic acid, and tetrahydrophthalic acid; dibasic acid anhydrides such as succinic anhydride (also known as succinic anhydride), maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylethylenetetrahydrophthalic anhydride, and itaconic anhydride; trimellitic anhydride; and the like. Among them, succinic acid and polybasic acid anhydrides are preferred, and carboxylic acid anhydrides are more preferred due to their higher reactivity and easier industrial availability. In particular, carboxylic acid anhydrides selected from succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred. The reaction temperature in the reaction with the above polybasic acid or polybasic acid anhydride (preferably a carboxylic acid anhydride) is not particularly limited as long as the reaction proceeds. For example, 0 to 200°C can be mentioned, preferably 20 to 150°C, and more preferably 30 to 120°C. The reaction time is not particularly limited, and examples thereof include 1 to 12 hours, preferably 2 to 12 hours, and more preferably 2 to 8 hours. The amount of the polybasic acid or polybasic acid anhydride (preferably carboxylic acid anhydride) used is not particularly limited, and may be set so that the acid value of the resulting alkali-soluble resin falls within a desired range. In addition to the above-described steps (II-1), (II-2), and (II-3), the above production step (II) may have other steps. Examples of the other steps include an aging step, a neutralization step, a step for deactivating a polymerization initiator and a chain transfer agent, a dilution step, a drying step, a concentration step, a purification step, and the like. These steps can be carried out by known methods. When an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain and having a double bond equivalent of 350 g / mol or less obtained by the production step (I) or (II) is used in this manner, the adhesion and solvent resistance of the cured film are remarkably excellent. The above alkali-soluble resin preferably has the following structure ((A) is optional). Specifically, a polymer having a structural unit (A) derived from a monomer capable of introducing a ring structure into the main chain and a structural unit (B) represented by the following general formula (B1), (B2), or (B3) is particularly preferable. The structural unit (B) is a structure derived from glycidyl (meth)acrylate.

[0020]

Chemical formula

[0021] Next, the polyfunctional monomers suitably contained in the photosensitive resin composition will be described. Examples of the above polyfunctional monomers include the following compounds, etc. Bifunctional (meth)acrylate compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate; trifunctional or higher polyfunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate; Polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether; Vinyl ether group-containing (meth)acrylic acid esters such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate; Polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether; allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional urethane (meth)acrylates obtained by the reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate; polyfunctional aromatic vinyls such as divinylbenzene; etc.

[0022] The polyfunctional (meth)acrylate compounds having two or more functional groups, which are particularly preferred polyfunctional monomers, will be described in detail below. A polyfunctional (meth)acrylate compound having two or more functional groups (hereinafter also simply referred to as "polyfunctional (meth)acrylate compound") is a compound having two or more (meth)acryloyl groups in one molecule. By including such a compound, the photosensitive resin composition becomes excellent in photosensitivity and curability, and it becomes possible to obtain a cured product with extremely high hardness. The number of functional groups of the above polyfunctional (meth)acrylate compound is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, the number of functional groups is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less. In addition, the (meth)acryloyl group means a methacryloyl group and / or an acryloyl group, and an acryloyl group is preferable from the viewpoint of excellent reactivity. That is, it is particularly preferable that the above polyfunctional (meth)acrylate compound is a polyfunctional acrylate compound having two or more acryloyl groups.

[0023] The content ratio of the above polyfunctional monomer may be appropriately set according to the type of the polyfunctional monomer used, the type of the above alkali-soluble resin, and the purpose and application, etc. However, from the viewpoint of excellent developability and curability, it is preferably 2 parts by mass or more, and preferably 85 parts by mass or less, based on 100 parts by mass of the total solid content of the photosensitive resin composition. The lower limit is more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, particularly preferably 15 parts by mass or more, and the upper limit is more preferably 75 parts by mass or less, still more preferably 60 parts by mass or less, particularly preferably 50 parts by mass or less, and most preferably 40 parts by mass or less. Also, the content of the polyfunctional monomer is preferably 50 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. When the content of the polyfunctional monomer is within this range, a cured product with higher adhesion and hardness can be obtained. Moreover, combined with the fact that the preferred weight average molecular weight of the alkali-soluble resin is 5000 or more, the developability will be further improved. More preferably, it is 80 parts by mass or more. Also, from the viewpoint of further improving the developability, it is more preferably 400 parts by mass or less. Even more preferably, it is 300 parts by mass or less, particularly preferably 200 parts by mass or less, and most preferably 150 parts by mass or less. The photosensitive resin composition of the present invention also preferably contains a photopolymerization initiator in addition to the above-described components. Preferably, the photopolymerization initiator is a radical-polymerizable photopolymerization initiator. A radical-polymerizable photopolymerization initiator generates polymerization-initiating radicals upon irradiation with active energy rays such as electromagnetic waves or electron beams, and one or more commonly used ones can be used. Also, if necessary, one or more photosensitizers, photo radical polymerization accelerators, etc. may be used in combination. By using a photosensitizer and / or a photo radical polymerization accelerator together with the photopolymerization initiator, the sensitivity and curability are further improved.

[0024] The photoinitiator is not particularly limited, and examples thereof include the following compounds. 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propan-1-one, 2-dimethylamino-1-(4-ethylphenyl)-2-methylpropan-1-one, 2-dimethylamino-1-(4-isopropylphenyl)-2-methylpropan-1-one, 1-(4-butylphenyl)-2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1-(4-methoxyphenyl)-2-methylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylthiophenyl)propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butan-1-one, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholyl)phenyl]-1-butanone and other α-aminoketone compounds; 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone compounds; Halogenomethylated triazine compounds such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; Halogenomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetoxime); Titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; Benzoic acid ester compounds such as p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid; Acridine compounds such as 9-phenylacridine; α-Hydroxy ketone compounds such as 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one; etc. Among the above photoinitiators, from the viewpoints such as excellent adhesion and fine pattern processability, it is particularly preferable to use at least an oxime-based initiator such as the above oxime ester compound. The content ratio of the above photoinitiator is not particularly limited, and it is also preferable to appropriately set it in consideration of the ratios of other components such as colorants. For example, it is preferably 0.05 to 40 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. Thereby, the curability and solvent resistance are further enhanced. More preferably, it is 0.5 to 30 parts by mass, and still more preferably 1.5 to 20 parts by mass. Further, examples of the photosensitizer and the photo radical polymerization accelerator that may be used in combination with the above photoinitiator include dye-based compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin-based compounds, and pyromethene dyes; dialkylaminobenzene-based compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; and mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. The content (total amount) of the photosensitizer and the photo radical polymerization accelerator may be appropriately set according to the purpose and use, and is not particularly limited. However, from the viewpoints of curability, the influence of decomposition products, and the balance of economy, it is preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 0.01 to 15 parts by mass, and still more preferably 0.05 to 10 parts by mass. The oxime-based initiator particularly preferably used in the present invention will be described in detail below. The oxime-based initiator is preferred because it has high sensitivity, high polymerization efficiency, can be cured regardless of the colorant (coloring agent) concentration, and it is easy to design a high colorant concentration. As specific examples of the oxime-based initiator, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166 can be used. Specific examples of the oxime-based initiator include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

[0025] Examples of the oxime-based initiator include the compounds described in J.C.S. Perkin II (1979) pp. 1653-1660, J.C.S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, the compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-T-2004-534797, and JP-A-2006-342166. As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), and Adeka Arcles NCI-930 (manufactured by ADEKA) can also be used.

[0026] In addition, as oxime-based initiators other than those described above, compounds described in JP-T-2009-519904 in which an oxime is linked to the N-position of carbazole, compounds described in US Patent No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, JP-A-2010-15025 in which a nitro group is introduced into the dye moiety, and those described in US Patent Publication 2009-292039 compounds, and oxime-based initiators described in International Patent Publication No. 2009-131189, compounds described in US Patent No. 7,556,910 containing a triazine skeleton and an oxime skeleton in the same molecule, compounds described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, etc. may also be used. Preferably, for example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, and this content is incorporated into the present specification.

[0027] As the photo radical polymerization initiator, an oxime-based initiator having a fluorene ring can also be used. Specific examples of the oxime-based initiator having a fluorene ring include the compounds described in JP-A-2014-137466. This content shall be incorporated into the present specification.

[0028] As the photo radical polymerization initiator, an oxime-based initiator having a fluorine atom can also be used. Specific examples of the oxime-based initiator having a fluorine atom include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-T-2014-500852, and the compound (C-3) described in JP-A-2013-164471, etc. This content shall be incorporated into the present specification.

[0029] As the photo radical polymerization initiator, an oxime-based initiator having a nitro group can be used. Specific examples of the oxime-based initiator having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012, 0070 to 0079 of JP-A-2014-137466, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation). As the oxime-based initiator, a compound having a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm is preferable, a compound having an absorption wavelength in the wavelength range of 360 nm to 480 nm is more preferable, and a compound having high absorbance at 365 nm and 405 nm is particularly preferable.

[0030] From the viewpoint of sensitivity, the molar extinction coefficient of the oxime-based initiator at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000. For the measurement of the molar extinction coefficient of the compound, known methods can be used. Specifically, for example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L of the compound.

[0031] The oxime-based initiator may be used in combination of two or more kinds as necessary.

[0032] The content of the oxime-based initiator is preferably 0.05 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, still more preferably 1 to 25 parts by mass, and most preferably 1.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. Within this range, better sensitivity and fine pattern formability can be obtained. The photosensitive resin composition of the present invention preferably further contains a colorant in addition to the above-described components. As the colorant, for example, pigments and dyes are preferably used. These may be used alone or in combination of two or more kinds. Also, a combination of a pigment and a dye may be used. For example, when forming red, blue, and green pixels of a color filter, a method of combining colorants such as blue and purple, green and yellow, etc. to exhibit the desired color characteristics is preferably used. Also, when forming a black matrix, it can be formed using a black colorant. Among the above-mentioned pigments and dyes, for example, in terms of durability, pigments (such as organic pigments or inorganic pigments) are excellent, and in terms of improving the brightness of panels or the like, dyes are excellent. Therefore, these may be appropriately selected or used in combination according to the required characteristics. Among the pigments, organic pigments are more preferable. Examples of the above-mentioned pigments include organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments (such as quinacridone-based, perylene-based, perinone-based, isoindolinone-based, isoindoline-based, dioxazine-based, thioindigo-based, anthraquinone-based, quinophthalone-based, metal complex-based, diketopyrrolopyrrole-based, etc.), and dye lake pigments; white and extender pigments (such as titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (such as lead yellow, cadmium-based, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine blue, dark blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), black pigments (such as carbon black, bone black, graphite, iron black, titanium black, etc.), brightening agent pigments (such as pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (such as zinc sulfide, strontium sulfide, strontium aluminate, etc.). Examples of the colors of the pigments that can be used include yellow, red, purple, blue, green, brown, black, white, etc. The above-mentioned pigments may also be subjected to surface treatments such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., according to the purpose and application. Specific examples of the above-mentioned pigments are shown below by color according to the Color Index (C.I.; published by The Society of Dyers and Colourists) number, but the color materials of the present invention are not limited to these. These may be used alone or in combination of two or more kinds. Hereinafter, "C.I." means Color Index, and the numbers mean Color Index numbers. Examples of yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 49, 53, 55, 60, 61, 61:1, 62, 62:1, 63, 65, 71, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 127:1, 128, 129, 130, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 209, 209:1, 212, 213, 214, 215, 219, etc. Examples of orange pigments include, for example, C.I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 31, 34, 36, 38, 39, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, 81, etc. Examples of purple pigments include, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 13, 14, 15, 16, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 39, 42, 44, 47, 49, 50, etc. Examples of red pigments include C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 37, 38, 40, 41, 42, 47, 48, 48:1, 48:2, 48:3, 48:4, 48:5, 49, 49:1, 49:2, 50:1, 52, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 54, 57, 57:1, 57:2, 58, 58:2, 58:4, 60, 60:1, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 89, 90:1, 95, 97, 101, 101:1, 102, 104, 105, 106, 108, 108:1, 109, 112, 113, 114, 122, 123, 136, 144, 146, 147, 149, 150, 151, 164, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 215, 216, 220, 221, 224, 226, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 248, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 279, etc. Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17, 17:1, 19, 24, 24:1, 25, 26, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, etc. Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, etc. Examples of the brown pigment include C.I. Pigment Brown 5, 6, 23, 24, 25, 32, 41, 42, etc. Examples of the black pigment include aniline black, carbon black, lamp black, bone black, black iron, titanium black, C.I. Pigment Black 1, 6, 7, 9, 10, 11, 12, 13, 20, 31, 32, 34, etc. Examples of the white pigment include C.I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28, etc. As the above dyes, for example, the organic dyes described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599 can be used. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, etc. are preferable. When using a dye as the coloring material, it can be uniformly dissolved in the photosensitive resin composition to obtain, for example, a resist composition for a color filter. The dyes that can be used are not particularly limited, and conventionally known dyes for color filters can be used. The content ratio of the above coloring material (that is, the total ratio of the pigment and the dye) can be appropriately set according to the purpose and application. The preferable range of the content ratio of the coloring material is 3 to 70 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. More preferably, it is 5 to 60 parts by mass, and still more preferably, it is 10 to 50 parts by mass. The photosensitive resin composition of the present invention can also contain a radically polymerizable oligomer and a radically polymerizable monomer in addition to the above-mentioned alkali-soluble resin and polyfunctional monomer. As the radically polymerizable oligomer, unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, etc. can be used. Examples of the radically polymerizable monomer include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate; vinyl ester monomers such as vinyl acetate and vinyl adipate; (meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)-methyl (meth)acrylate, (di)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; and triallyl cyanurate. These can be appropriately selected according to the required properties, and one or more of them can be used. It is preferable that the photosensitive resin composition of the present invention contains a solvent. The solvent is preferably used as a diluent or the like. Specifically, it is preferably used for reducing viscosity to improve handleability, forming a coating film by drying, serving as a dispersion medium for coloring materials, etc., and is a low-viscosity organic solvent or water that can dissolve or disperse each component contained in the photosensitive resin composition. As the above solvent, those commonly used can be used, and they can be appropriately selected according to the purpose and application, and are not particularly limited. For example, monoalcohols such as methanol, ethanol, isopropanol, n-butanol, and s-butanol; polyhydric alcohols such as ethylene glycol and propylene glycol; ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. These may be used alone or in combination of two or more. The content of the above solvent is preferably 10 to 90% by mass based on 100% by mass of the total amount of the photosensitive resin composition. More preferably, it is 20 to 80% by mass. In addition, the total solid content excluding the solvent in 100% by mass of the photosensitive resin composition is more preferably 5 to 70% by mass, and even more preferably 10 to 50% by mass. The photosensitive resin composition of the present invention also preferably contains a dispersant. The dispersant is not particularly limited. For example, those having an interaction site with the coloring material and an interaction site with the dispersion medium (alkali-soluble resin, solvent, etc.) and having the function of stabilizing the dispersion of the coloring material in the dispersion medium are preferred. Generally, it is classified into resin-type dispersants (polymer dispersants), surfactants (low-molecular dispersants), and pigment derivatives, and commonly used dispersants can be used. Examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyamino amidine salts, hydrogen group-containing polycarboxylic acid esters, amides formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group and salts thereof, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, polyester-based, modified polyacrylates, ethylene oxide / polypropylene oxide adducts, and the like. Among them, from the viewpoint of structure, resins having a graft structure in which the main chain is an anchor chain having an interaction site with the colorant and the graft chain is a compatible chain having an interaction property with the dispersion medium, and resins in which the anchor chain and the compatible chain have a block structure are particularly preferably used. Examples of the surfactant include anionic surfactants such as polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, monolauryl sulfate monoethanolamine, trilauryl sulfate triethanolamine, ammonium lauryl sulfate, sodium stearate, and sodium lauryl sulfate; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkyl betaines such as alkyl dimethylaminoacetic acid betaine and alkyl imidazolines; and the like. The above-mentioned pigment derivative is a compound having a structure in which a functional group is introduced into a pigment. Examples of the functional group include a sulfonic acid group, a sulfonamide group and its quaternary salt, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, a phthalimide group, etc. Examples of the structure of the parent pigment include azo-based, anthraquinone-based, quinophthalone-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindoline-based, dioxazine-based, indanthrene-based, perylene-based, diketopyrrolopyrrole-based, etc.

[0033] The content ratio of the above-mentioned dispersant is not particularly limited and may be appropriately set according to the purpose and application. For example, considering the balance of dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency, etc., the solid content of the dispersant is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the colorant. More preferably, it is 0.1 to 90 parts by mass, and still more preferably, it is 0.5 to 80 parts by mass. The photosensitive resin composition of the present invention may also contain one or more other components as long as the effects of the present invention are not impaired. For example, binder resins other than alkali-soluble resins; heat resistance improvers; leveling agents; coupling agents; development aids; fillers such as aluminum hydroxide, talc, clay, barium sulfate, etc.; defoaming agents; metal oxide particles; quantum dot particles; sensitizers; release agents; lubricants; plasticizers; antioxidants; flame retardants; polymerization inhibitors; thickeners; thermosetting resins such as epoxy resins, phenol resins, polyvinylphenol, etc.; curing agents; reactive diluents; stabilizers; flame retardant aids; curing aids such as polyfunctional thiol compounds; fluorine-based additives; cationic polymerizable compounds; acid generators; etc. The amount of use of the above-mentioned other components may be appropriately set according to the purpose and application. For example, in 100 parts by mass of the total solid content of the photosensitive resin composition, it is preferably 0 to 70 parts by mass. More preferably, it is 0.01 to 70 parts by mass, still more preferably, it is 0.1 to 60 parts by mass, and particularly preferably, it is 0.3 to 50 parts by mass. <Preparation of Photosensitive Resin Composition> The method for producing the photosensitive resin composition of the present invention is not particularly limited. For example, it can be prepared by mixing and dispersing the above-described components using various mixers and dispersers. The dispersion step and the mixing step are not particularly limited and may be carried out by ordinary methods, or may further include other commonly performed steps. When the photosensitive resin composition contains a coloring material, it is preferably prepared through known steps such as a dispersion treatment step of the coloring material. Specifically, for example, after preparing a coloring material dispersion liquid (mill base) containing a coloring material, a dispersant, a binder resin (such as an alkali-soluble resin), and a solvent, etc., further, a transparent resist liquid (also referred to as a clear resist liquid) containing a polyfunctional monomer, a photopolymerization initiator, a binder resin (such as an alkali-soluble resin), and a solvent, etc., is preferably added for preparation. The obtained photosensitive resin composition is preferably subjected to a filtration treatment using a filter or the like to remove fine dust. When preparing the above coloring material dispersion liquid, for example, it is preferable to finely disperse the coloring material using a disperser such as a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, or a blender. More preferably, after kneading and dispersing with a roll mill, a kneader, a blender, etc., a fine dispersion treatment is performed using a media mill such as a bead mill filled with beads of 0.01 to 1 mm.

[0034] <Cured product> The cured product obtained by curing the photosensitive resin composition of the present invention has excellent solvent resistance. Such a cured product of the photosensitive resin composition is also one of the present inventions. When the above cured product is a cured film, its film thickness is preferably 0.1 μm or more. When the film thickness is 0.1 μm or more, more excellent solvent resistance can be exhibited. The film thickness is more preferably 0.5 μm or more, and still more preferably 1 μm or more. The upper limit value of the film thickness is not particularly limited and may be appropriately set according to the purpose and use of the cured film. For example, it is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less. The method for obtaining the above-mentioned cured product is not particularly limited, and known methods can be used. For example, a method of obtaining a cured product by applying a photosensitive resin composition onto a substrate or a molded product and curing it by drying, heating, irradiating with energy rays such as ultraviolet rays, or a combination thereof can be mentioned. When the photosensitive resin composition of the present invention is used, a cured product excellent in solvent resistance can be obtained even under low-temperature curing conditions. As a method for producing such a cured product, for example, a method including a step of applying the above-mentioned photosensitive resin composition onto a substrate to form a coating film, a step of irradiating the formed coating film with light, and a step of heating the light-irradiated coating film at a temperature of 150°C or lower is preferably mentioned. That is, the present invention is also a method for producing a cured product having a step of curing the photosensitive resin composition at a temperature of 150°C or lower. The above-mentioned substrate is not particularly limited and may be appropriately selected according to the purpose and use. For example, substrates made of various materials such as glass plates and plastic plates can be mentioned. The method for applying the above-mentioned photosensitive resin composition to form a coating film is not particularly limited and can be carried out by known methods such as spin coating, slit coating, roll coating, and casting coating. In the above-mentioned production method, after applying the above-mentioned photosensitive resin composition onto a substrate, it is preferable to dry the coated object to form a coating film. The above-mentioned drying can be carried out by a known method, specifically, in the same manner as the drying method described in the "arrangement step" of the "<method for producing a color filter>" described later. The above-mentioned production method includes a step of irradiating the coating film with light after forming the coating film. The method for irradiating the formed coating film with light is not particularly limited and can be carried out by a known method. Specifically, it can be carried out in the same manner as the method described in the "light irradiation step" of the "<method for producing a color filter>" described later. When irradiating the coating film with light, the light irradiation may be performed through a photomask. As the photomask, it is preferable to use a mask in which a light-shielding portion is formed according to the target pattern. When performing light irradiation through a photomask, it is preferable to perform a development process thereafter. By performing the development process, a target pattern can be formed on the coating film. The development method is not particularly limited and can be performed by a known method. Specifically, it can be performed by the same method as the method described in the "development process" of the "method for manufacturing a color filter" described later. The manufacturing method also includes a step of heating the light-irradiated coating film at 150 °C or lower. That is, the present invention is also a method for manufacturing a cured product having a step of curing the photosensitive resin composition at a temperature of 150 °C or lower. Since the above manufacturing method uses the photosensitive resin composition described above, the heating step (post-curing step) after light irradiation can be performed under relatively low temperature conditions such as 150 °C or lower. The heating temperature is preferably 145 °C or lower, more preferably 140 °C or lower. As the lower limit of the heating temperature, it is preferably 70 °C or higher, more preferably 90 °C or higher, in terms of maintaining curability. The heating method other than temperature is not particularly limited and can be performed by a known method. For example, it can be performed by the same method as the method described in the "heating step" of the "method for manufacturing a color filter" described later.

[0035] <Use> The photosensitive resin composition of the present invention can provide a cured product having excellent solvent resistance with a sufficient curing reaction even under low-temperature curing conditions of 150 °C or lower, for example, about 90 °C. Therefore, it can be suitably used for applications that need to be sufficiently cured under low-temperature conditions and applications that require solvent resistance. The photosensitive resin composition of the present invention can be preferably used for various applications such as components of various optical members and electrical and electronic devices, such as color filters, black matrices, photo spacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, films, organic protective films, etc., which are used in, for example, liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. Among them, it is preferably used for color filter applications. The photosensitive resin composition of the present invention is preferably used as an optical material and also preferably used as a negative type. <Color filter> A color filter having a cured product of the above-mentioned photosensitive resin composition on a substrate is also one of the preferred forms of the present invention. In the above color filter, the cured product formed by the above-mentioned photosensitive resin composition is particularly suitable as a segment that requires coloring, such as a black matrix and each pixel of red, green, blue, yellow, etc., but is also suitable as a segment that does not necessarily require coloring, such as a photo spacer, a protective layer, and an alignment control rib. Examples of the substrate used for the above color filter include glass substrates such as white plate glass, blue plate glass, alkali-strengthened glass, and silica-coated blue plate glass; sheets, films, or substrates made of thermoplastic resins such as polyester, polycarbonate, polyolefin, polysulfone, and ring-opening polymers of cyclic olefins and their hydrogenated products; sheets, films, or substrates made of thermosetting resins such as epoxy resins and unsaturated polyester resins; metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates; ceramic substrates; semiconductor substrates having a photoelectric conversion element; members composed of various materials such as glass substrates provided with a coloring material layer on the surface (for example, color filters for LCDs), etc. Among them, from the viewpoint of heat resistance, glass substrates and sheets, films, or substrates made of heat-resistant resins are preferred. Also, the above substrate is preferably a transparent substrate. Further, the above substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc., if necessary. <Method for Manufacturing Color Filter> To obtain the color filter, for example, for each pixel of a single color (i.e., for each pixel of a single color), a step of disposing the above-described photosensitive resin composition on a substrate (also referred to as the disposing step), a step of irradiating light on the photosensitive resin composition disposed on the substrate (also referred to as the light irradiation step), a step of performing development processing with a developer (also referred to as the development step), and a step of performing heat treatment (also referred to as the heating step) are adopted, and it is preferable to adopt a manufacturing method that repeats the same method for each color. Note that the formation order of the pixels of each color is not particularly limited. (1) Disposing Step (Preferably Coating Step) The above disposing step is preferably performed by coating. Examples of methods for coating the photosensitive resin composition on the substrate include spin coating, slit coating, roll coating, casting coating, etc., and any of these methods can be preferably used. In the above disposing step, it is also preferable to dry the coating film after coating the photosensitive resin composition on the substrate. Drying of the coating film can be performed using, for example, a hot plate, an IR oven, a convection oven, etc. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the dryer, etc., but usually, it is preferably performed at a temperature of 50 to 160°C for 10 seconds to 300 seconds. (2) Light Irradiation Step In the above light irradiation step, as the light source of the actinic rays used, for example, lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, etc., and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, semiconductor lasers, etc. are used. Also, examples of the exposure machine method include the proximity method, the mirror projection method, and the stepper method, and the proximity method is preferably used. In the step of irradiating the active energy ray, depending on the application, it may be possible to irradiate the active energy ray through a predetermined mask pattern. In this case, the exposed portion is cured, and the cured portion becomes insoluble or hardly soluble in the developer. (3) Development step The above-described development step is a step of performing development processing with a developer after the above-described light irradiation step to remove the unexposed portion and form a pattern. Thereby, a patterned cured film can be obtained. The development processing can usually be performed by methods such as dipping development, spray development, brush development, and ultrasonic development at a development temperature of 10 to 50°C. The developer used in the above-described development step is not particularly limited as long as it can dissolve the above-described photosensitive resin composition. Usually, an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may also be used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. Examples of the organic solvent and the alkaline aqueous solution include those similar to those described in JP-A-2015-157909. (4) Heating step The above-described heating step is a step (also referred to as a "post-curing step") of further curing the exposed portion (cured portion) by baking after the above-described development step. For example, using a light source such as a high-pressure mercury lamp, post-exposure is performed with a light amount of 0.5 to 5 J / cm 2 Examples include a step of post-heating at a temperature of 60 to 200°C for 10 seconds to 120 minutes. By performing such a post-curing step, it is possible to further strengthen the hardness and adhesion of the patterned cured film. The above-described heating step is generally performed at a temperature of about 200 to 260°C. However, if the above-described photosensitive resin composition is used, sufficient curing can be performed under relatively low temperature conditions of 200°C or lower, preferably 160°C or lower. Therefore, it is possible to obtain a product with excellent solvent resistance without impairing the characteristics held by the substrate or the cured product. In the above-described heating step, the heating temperature is preferably 160°C or lower, more preferably 155°C or lower, and still more preferably 150°C or lower. Also, the heating temperature is preferably 70°C or higher, more preferably 90°C or higher, and still more preferably 95°C or higher. The heating time in the above heating process is not particularly limited, but for example, it is preferably 5 to 60 minutes. Also, the heating method is not particularly limited, and for example, it can be carried out using heating equipment such as a hot plate, a convection oven, a high-frequency heating machine, etc. The film thickness of the cured film obtained by the above heating process (that is, the cured coating film obtained by thermosetting the above photosensitive resin composition) is preferably 0.1 to 20 μm. The above film thickness is more preferably 0.5 to 15 μm, and even more preferably 1 to 10 μm. <Display device> A display device including the above-described color filter is also one of the preferred forms in the present invention. A member for a display device and a display device having a cured product of the above photosensitive resin composition are also included in the preferred embodiments of the present invention. Since the cured product (cured film) formed by the above photosensitive resin composition is stably excellent in adhesion to a substrate or the like, has high hardness, exhibits high smoothness, and has a high transmittance, it is particularly suitable as a transparent member and is also useful as a protective film or an insulating film in various display devices. As the above display device, for example, a liquid crystal display device, a solid-state imaging device, a touch panel type display device, etc. are suitable. In addition, when the above cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multi-layer member composed of the above cured film, or a member in which another layer is further combined with the above single-layer or multi-layer member, or a member including the above cured film during its formation. As described above, the photosensitive resin composition (curable resin composition) of the present invention can provide a cured product excellent in solvent resistance even under low-temperature curing conditions. The photosensitive resin composition of the present invention can be suitably used for various optical members and constituent members used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel type display devices, etc., for various applications such as electrical and electronic devices.

Examples

[0036] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples do not limit the present invention, and any modifications made without departing from the spirit of the present invention are all included in the technical scope of the present invention. Hereinafter, the present invention will be specifically described with reference to examples, comparative examples, and property evaluations. In the examples and comparative examples, unless otherwise specified, % means mass %, and part means part by mass. Also, the weight (weight %) measured in the present invention is the same value as the mass (mass %). [Evaluation Method] (1) Weight-average molecular weight (Mw) Using polystyrene as a standard substance and tetrahydrofuran as an eluent, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation). (2) Acid value (AV) 3 g of the polymer solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using 0.1 N aqueous KOH solution as a titrant. The titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of solid content (mgKOH / g) was determined from the acid value of the solution and the solid content of the solution. (3) Solid content Approximately 1 g of the polymer solution was weighed into an aluminum cup, about 3 g of acetone was added and dissolved, and then it was naturally dried at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by Espec Corporation), it was dried at 140 °C under vacuum for 1.5 hours, cooled in a desiccator, and the mass was measured. The solid content (mass %) of the polymer solution was calculated from the mass reduction amount. (4) GMA / AA conversion rate (mass % of consumed monomer) The amount of unreacted monomer in the reaction tank was determined by a known method using gas chromatography. The conversion rate was obtained by subtracting the amount of unreacted monomer (%) from 100 (%). (5) Double bond equivalent (g / mol) It was determined by dividing the mass (g) of the polymer solid content by the amount of double bonds (mol) of the polymer. (6) Solvent resistance The photosensitive resin composition was spin-coated on a 5 cm square glass substrate, dried at 100 °C for 3 minutes, then exposed using a high-pressure mercury lamp at 200 mJ, and heat-treated (post-cured) at 90 °C or 110 °C for 40 minutes respectively to obtain a cured film with a film thickness of 2 μm. Then, the cured film was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 40 °C for 10 minutes and then taken out. For the immersion liquid (NMP) after taking out the cured film, the absorbance was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) and evaluated according to the following criteria. The larger the value of the absorbance, the more colorant eluted into the immersion liquid, and it is evaluated that the solvent resistance of the photosensitive resin composition is low. (Evaluation Criteria) ◎: The value of the absorbance is less than 0.2 〇: The value of the absorbance is 0.2 or more and less than 0.4 ×: The value of the absorbance is 0.4 or more (7) Residue during development The photosensitive resin composition was applied on a 10 cm square glass substrate by a spin coater and dried in an oven at 90 °C for 3 minutes. After drying, ultraviolet rays were irradiated on the entire surface of the coating film with a UV aligner (trade name "TME-150RNS", manufactured by TOPCON Corporation) equipped with a 2.0 kW ultra-high pressure mercury lamp at an intensity of 100 mJ / cm2 (converted to 365 nm illuminance). After ultraviolet irradiation, a 0.05% aqueous potassium hydroxide solution was sprayed on the coating film for 20 seconds with a spin developer and then washed with pure water for 10 seconds. Thereafter, it was heated in an oven at 230 °C for 30 minutes. The presence or absence of residue was confirmed using a laser microscope (trade name "VK-9700", manufactured by Keyence Corporation). An alkali-soluble resin (polymer solution) was produced as follows. [Example 1] Polymer solution (A-1) Into a separable flask with a cooling tube as a reaction vessel, 183 parts of propylene glycol monomethyl ether acetate (PGMEA) and 84 parts of propylene glycol monomethyl ether (PGME) were charged and heated to 90 °C under a nitrogen atmosphere. On the other hand, in dropping flask 1, 29 parts of cyclohexyl methacrylate (CHMA), 5 parts of N-benzylmaleimide (BzMI), 66 parts of acrylic acid (AA), 2 parts of perbutyl O (PBO), 17 parts of PGMEA, and 7 parts of PGME were mixed. In dropping flask 2, 6 parts of n-dodecyl mercaptan and 14 parts of PGMEA were mixed. They were continuously supplied over 3 hours each. Then, after holding at 90 °C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90 °C for another 30 minutes. Then, the temperature was raised to 115 °C and polymerization was continued for 1.5 hours. Once cooled to room temperature, 98.6 parts of glycidyl methacrylate (GMA), 0.3 part of 6-t-butyl-2,4-xylenol, and 0.6 part of triethylamine (TEA) were added, and the temperature was raised to 90 °C while bubbling a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, and the reaction was carried out for 4 hours. Then, the temperature was raised to 110 °C and the reaction was carried out for 10 hours to complete the reaction, cooled to room temperature, and a polymer solution (A-1) was obtained. When various physical properties of the obtained polymer solution (A-1) were measured, the weight average molecular weight was 17,600, Mw / Mn was 3.8, the acid value per solid content determined by titration was 73 mgKOH / g, and the double bond equivalent was 300 g / mol. [Example 2] Polymer solution (A-2) 197 parts of PGMEA and 91 parts of PGME were charged into a separable flask with a cooling pipe as a reaction vessel, and the temperature was raised to 90 °C under a nitrogen atmosphere. On the other hand, 37.5 parts of CHMA, 6 parts of methyl methacrylate (MMA), 56.5 parts of AA, and 2 parts of PBO were mixed in dropping tank 1. 4.5 parts of n-dodecyl mercaptan and 15.5 parts of PGMEA were mixed in dropping tank 2. They were continuously supplied over 3 hours each. Then, after holding at 90 °C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90 °C for another 30 minutes. Then, the temperature was raised to 115 °C, and the polymerization was continued for 1.5 hours. After cooling to room temperature once, 98.6 parts of GMA, 0.3 part of 6-t-butyl-2,4-xylenol, and 0.6 part of TEA were added, and the temperature was raised to 90 °C while bubbling a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, and the reaction was carried out for 4 hours. Then, the temperature was raised to 110 °C and the reaction was carried out for 16 hours to complete the reaction, cooled to room temperature, and a polymer solution (A-2) was obtained. When various physical properties of the obtained polymer solution (A-2) were measured, the weight average molecular weight was 16,100, Mw / Mn was 3.3, the acid value per solid content determined by titration was 36 mg KOH / g, and the double bond equivalent was 290 g / mol. [Example 3] Polymer solution (A-3) Into a separable flask with a cooling pipe as a reaction vessel, 168 parts of PGMEA and 78 parts of PGME were charged, and the temperature was raised to 90 °C under a nitrogen atmosphere. On the other hand, 10 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate (MD), 33.5 parts of CHMA, 56.5 parts of AA, 34 parts of PGMEA, 15 parts of PGME, and 2 parts of PBO were mixed in dropping tank 1. In dropping tank 2, 7 parts of n-dodecyl mercaptan and 13 parts by mass of PGMEA were mixed. They were continuously supplied over 3 hours each. Then, after holding at 90 °C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90 °C for another 30 minutes. Then, the temperature was raised to 115 °C, and the polymerization was continued for 1.5 hours. After once cooling to room temperature, 98.6 parts of GMA, 0.3 part of 6-t-butyl-2,4-xylenol, and 0.6 part of TEA were added, and the temperature was raised to 90 °C while bubbling a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, and the reaction was carried out for 4 hours. Then, the temperature was raised to 110 °C and the reaction was carried out for 16 hours to complete the reaction, cooled to room temperature, and a polymer solution (A-3) was obtained. When various physical properties of the obtained polymer solution (A-3) were measured, the weight average molecular weight was 11,500, Mw / Mn was 2.7, the acid value per solid content determined by titration was 42 mg KOH / g, and the double bond equivalent was 290 g / mol. [Example 4] Polymer solution (A-4) Into a separable flask with a cooling pipe as a reaction vessel, 120 parts of PGMEA and 59 parts of PGME were charged, and the temperature was raised to 90 °C under a nitrogen atmosphere. On the other hand, in dropping flask 1, 15 parts of methyl (α-allyloxymethyl) acrylate (AMA), 28.5 parts of CHMA, 56.5 parts of AA, 51 parts of PGMEA, 22 parts of PGME, and 2 parts of PBO were mixed. In dropping flask 2, 2 parts of n-dodecyl mercaptan and 18 parts by mass of PGMEA were mixed. They were continuously supplied over 3 hours each. Then, after maintaining 90 °C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90 °C for another 30 minutes. Then, the temperature was raised to 115 °C, and the polymerization was continued for 1.5 hours. After once cooling to room temperature, 78.9 parts of GMA, 0.3 part of 6-t-butyl-2,4-xylenol, and 0.6 part of TEA were added, and the temperature was raised to 90 °C while bubbling a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, and the reaction was carried out for 4 hours. Then, the temperature was raised to 110 °C and the reaction was carried out for 10 hours to complete the reaction, and it was cooled to room temperature to obtain a polymer solution (A-4). When various physical properties of the obtained polymer solution (A-4) were measured, the weight average molecular weight was 19000, Mw / Mn was 3.7, the acid value per solid content determined by titration was 73 mgKOH / g, and the double bond equivalent was 330 g / mol. [Example 5] Polymer solution (A-5) Into a separable flask with a cooling tube as a reaction vessel, 161 parts of PGMEA and 117 parts of PGME were charged, and the temperature was raised to 90 °C under a nitrogen atmosphere. On the other hand, 15 parts of BzMI, 7.5 parts of MMA, 77.5 parts of AA, 44 parts of PGMEA, 29 parts of PGME, and 2 parts of PBO were mixed in dropping flask 1. In dropping flask 2, 6 parts of n-dodecyl mercaptan and 14 parts by mass of PGMEA were mixed. They were continuously supplied over 3 hours each. Then, after holding at 90 °C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90 °C for another 30 minutes. Then, the temperature was raised to 115 °C, and the polymerization was continued for 1.5 hours. After once cooling to room temperature, 96.6 parts of GMA, 0.3 part of 6-t-butyl-2,4-xylenol, and 0.6 part of TEA were added, and while bubbling a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, the temperature was raised to 90 °C, and the reaction was carried out for 7 hours. Then, 41.4 parts of GMA were added to the reaction vessel, the temperature was raised to 95 °C and reacted for 7 hours, and further the temperature was raised to 110 °C and reacted for 6 hours to complete the reaction, and then cooled to room temperature to obtain a polymer solution (A-5). When various physical properties of the obtained polymer solution (A-5) were measured, the weight average molecular weight was 16,500, Mw / Mn was 4.0, the acid value per solid content determined by titration was 41 mgKOH / g, and the double bond equivalent was 250 g / mol. [Example 6] Polymer solution (A-6) Into a separable flask with a cooling tube as a reaction vessel, 179 parts of PGMEA were charged, and the temperature was raised to 90 °C under a nitrogen atmosphere. On the other hand, 35 parts of MMA, 65 parts of GMA, and 2 parts of PBO were mixed in the dropping flask. They were continuously supplied over 3 hours. Then, it was held at 90 °C for 1 hour. Then, the temperature was raised to 115 °C, and the polymerization was continued for 1.5 hours. After once cooling to room temperature, 33 parts of AA, 0.4 part of dimethylbenzylamine, and 0.1 part of a polymerization inhibitor (Antage (registered trademark) W400, manufactured by Kawaguchi Chemical Industry Co., Ltd.) were added, and while bubbling a nitrogen / air mixed gas adjusted to an oxygen concentration of 7%, the temperature was raised to 90 °C, and the reaction was carried out for 4 hours. Then, the temperature was raised to 110 °C and reacted for 10 hours to complete the reaction. Then, it was cooled to room temperature, 9 parts of succinic anhydride (SAH) were added, reacted at 110 °C for 5 hours, and then cooled to room temperature to obtain a polymer solution (A-6). When various physical properties of the obtained polymer solution (A-6) were measured, the weight average molecular weight was 15,000, Mw / Mn was 4.0, the acid value per solid content determined by titration was 50 mgKOH / g, and the double bond equivalent was 310 g / mol. [Comparative Example 1] Polymer solution (A-7) Into a separable flask with a cooling tube as a reaction vessel, 183 parts of PGMEA and 84 parts of PGME were charged, and the temperature was raised to 90 °C under a nitrogen atmosphere. On the other hand, in dropping flask 1, 29 parts of CHMA, 5 parts of BzMI, 66 parts of AA, 2 parts of PBO, 17 parts of PGMEA, and 7 parts of PGME were mixed. In dropping flask 2, 6 parts of n-dodecyl mercaptan and 14 parts of PGMEA were mixed. They were continuously supplied over 3 hours each. Then, after holding at 90 °C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90 °C for another 30 minutes. Then, the temperature was raised to 115 °C, and the polymerization was continued for 1.5 hours. After once cooling to room temperature, 98.6 parts of GMA, 0.3 part of 6-t-butyl-2,4-xylenol, and 0.6 part of TEA were added, and the temperature was raised to 110 °C while bubbling a nitrogen-air mixed gas adjusted to an oxygen concentration of 7%, and reacted for 9 hours to complete the reaction, cooled to room temperature, and a polymer solution (A-7) was obtained. When various physical properties of the obtained polymer solution (A-7) were measured, the weight average molecular weight was 18,300, Mw / Mn was 4.1, the acid value per solid content determined by titration was 73 mgKOH / g, and the double bond equivalent was 300 g / mol. A transparent solution was obtained with the polymer solution (A-7), but the molecular weight distribution became larger compared to the polymer solution (A-1). [Comparative Example 2] Polymer solution (A-8) Into a separable flask with a cooling tube as a reaction vessel, 148 parts of PGMEA and 71 parts of PGME were charged, and the temperature was raised to 90 °C under a nitrogen atmosphere. On the other hand, 65 parts of MMA, 35 parts of AA, and 2 parts of PBO were mixed in dropping flask 1. In dropping flask 2, 1 part of n-dodecyl mercaptan and 19 parts by mass of PGMEA were mixed. They were continuously supplied over 3 hours each. Then, after maintaining 90 °C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90 °C for another 30 minutes. Then, the temperature was raised to 115 °C, and the polymerization was continued for 1.5 hours. After cooling to room temperature once, 59 parts of GMA, 0.3 part of 6-t-butyl-2,4-xylenol, and 0.5 part of TEA were added, and the temperature was raised to 110 °C while bubbling a nitrogen-air mixed gas adjusted to an oxygen concentration of 7% and reacted for 7 hours to complete the reaction. After cooling to room temperature, a polymer solution (polymer solution (A-8)) was obtained. When various physical properties of the obtained polymer solution (A-8) were measured, the weight average molecular weight was 19,000, Mw / Mn was 3.8, the acid value per solid content determined by titration was 93 mg KOH / g, and the double bond equivalent was 390 g / mol. Table 1 shows the manufacturing conditions and physical property evaluation results (Examples 1 to 6 and Comparative Examples 1 to 2).

[0037]

Table 1

[0038]

Table 2

Industrial Applicability

[0039] The production method of the present invention can stably obtain a specific side-chain double bond-containing alkali-soluble resin obtained by subjecting an acid group and an epoxy group to an esterification reaction. The photosensitive resin composition containing this alkali-soluble resin can be suitably used for various optical member applications such as colored layers, black matrices, photo spacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. of color filters used in liquid crystal display devices, solid-state imaging devices, etc.

Claims

1. A method for producing an alkali-soluble resin having an ethylenically unsaturated double bond in a side chain and a double bond equivalent of 350 g / mol or less, comprising the following step (I) or (II) including an esterification reaction between an acid group and an epoxy group, wherein the molecular weight distribution (Mw / Mn) of the obtained alkali-soluble resin is 4.0 or less. (I) A step of polymerizing a monomer component containing an unsaturated carboxylic acid monomer to obtain a base polymer, and a step of performing an addition reaction of glycidyl (meth)acrylate to the base polymer at 70 to 90 °C. After the conversion rate reaches 40% by mass with respect to 100% by mass of the total glycidyl (meth)acrylate, the reaction is carried out at 100 to 150 °C until the conversion rate exceeds 85% by mass. (II) A step of polymerizing a monomer component containing glycidyl (meth)acrylate to obtain a base polymer, and a step of performing an addition reaction of an unsaturated carboxylic acid monomer to the base polymer at 70 to 90 °C. After the conversion rate reaches 40% by mass with respect to 100% by mass of the total unsaturated carboxylic acid monomer, the reaction is carried out at 100 to 150 °C, and an esterification reaction is carried out until the conversion rate exceeds 85% by mass, and a step of performing an addition reaction of a polybasic acid anhydride.

2. The method for producing an alkali-soluble resin according to claim 1, wherein the esterification reaction is carried out in the presence of a basic compound.

3. The method for producing an alkali-soluble resin according to claim 1 or 2, wherein the total reaction time of the esterification reaction is 6 to 20 hours.

4. The method for producing an alkali-soluble resin according to any one of claims 1 to 3, wherein the reaction time until the conversion rate reaches 40% by mass is 1 to 8 hours.

5. The method for producing an alkali-soluble resin according to any one of claims 1 to 4, wherein the polymerization solvent for the polymerization contains an ester-based solvent.

6. The method for producing an alkali-soluble resin according to any one of claims 1 to 5, wherein the weight average molecular weight of the alkali-soluble resin is 11,000 to 100,000.

7. The method for producing an alkali-soluble resin according to any one of claims 1 to 6, wherein the acid value of the alkali-soluble resin is 50 to 100 mgKOH / g. The method for producing an alkali-soluble resin according to any one of claims 1 to 7, wherein the step of obtaining the base polymer further comprises polymerizing a monomer component containing an N-substituted maleimide monomer.

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