JP2023028821A - Method for producing alkali-soluble resin, and photosensitive resin composition - Google Patents

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

Compositions containing alkali-soluble resins are used, for example, in color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, organic insulating films, organic protective films, etc. used in liquid crystal display devices and solid-state imaging devices. Application to various applications such as various optical members and electric/electronic devices has been studied, and resins and resin compositions having excellent properties required for each application have been developed. 2. Description of the Related Art In recent years, optical members, electric and electronic devices, etc. have been becoming smaller, thinner, and energy-saving. In order to meet such demands, research is being conducted on alkali-soluble resins that are used as materials for various members.
In order to improve the curability of alkali-soluble resins, it is known to introduce polymerizable double bonds into the side chains of alkali-soluble resins (polymers) as a technique for improving the crosslinkability and crosslink density of resins. . Such a polymer having a polymerizable double bond in its side chain is obtained by, for example, polymerizing a monomer component containing a monomer having an acid group to obtain a base polymer, A method of introducing a polymerizable double bond into a polymer by subjecting a compound having an epoxy group and a polymerizable double bond to an addition reaction, or a monomer component containing a compound having an epoxy group and a polymerizable double bond It can be obtained by a method of obtaining a base polymer by polymerization, reacting the polymer with a compound having an acid group and a polymerizable double bond, and introducing a polymerizable double bond into the polymer. can. When producing such a polymer having a polymerizable double bond in the side chain, as one of the compounds having an epoxy group and a polymerizable double bond, glycidyl (meth)acrylate (glycidyl acrylate and/or or glycidyl methacrylate) is used.
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 to obtain the radically polymerizable copolymer. As a method, 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 added to an epoxy group-containing ethylenic unsaturated compound. A method for reacting saturated compounds is described.

JP 2012-32772 A

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 a large amount of hydroxyl groups, a dehydration esterification reaction with acid groups and a transesterification reaction with ester groups occur, and in some cases, gelation occurs due to intermolecular cross-linking and the molecular weight distribution widens. When such an alkali-soluble resin is used as a binder in a photosensitive resin composition, there are problems such as hindering uniform development, resulting in peeling development, and generation of foreign matter in the coating film.
SUMMARY OF THE INVENTION 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 of the present invention 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 exposure sensitivity, and to provide a method for producing a cured product thereof.

Specifically, a production method that stably obtains a specific side chain double bond-containing alkali-soluble resin obtained by esterifying an acid group and an epoxy group, and has good exposure sensitivity and solvent resistance even under low temperature curing conditions. An object of the present invention is to provide a photosensitive resin composition that can be a good cured product of.

Means for Solving the Problems As a result of intensive studies, the present inventors have found a method for producing a highly stable specific alkali-soluble resin, a highly reactive photosensitive resin composition, and a method for producing a cured product. That is, the object of the present invention is achieved by the following <1> to <6>.
<1> 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, comprising the step of esterifying an acid group and an epoxy group, A method for producing an alkali-soluble resin having the step of (I) or (II).
(I) a step of polymerizing a monomer component containing an unsaturated carboxylic acid monomer to obtain a base polymer; After the conversion reaches 40% by mass with respect to 100% by mass of glycidyl (meth)acrylate, the reaction is continued at 100° C. or higher until the conversion exceeds 85% by mass (II) (meth)acrylic In the step of polymerizing a monomer component containing a glycidyl acid to obtain a base polymer, and in the addition reaction of an unsaturated carboxylic acid monomer to the base polymer, the reaction is carried out at a temperature of less than 100°C to obtain a total unsaturated carboxylic acid. After the conversion rate reaches 40% by mass with respect to 100% by mass of the acid monomer, the reaction is performed at 100 ° C. or higher, and the esterification reaction is performed until the conversion rate exceeds 85% by mass. (preferably carboxylic anhydride) addition reaction step <2>
The method for producing an alkali-soluble resin according to <1>, wherein the esterification reaction is performed 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>
Photosensitivity containing an alkali-soluble resin having a (meth)acrylate skeleton in the main chain and an ethylenically unsaturated double bond in the side chain and a double bond equivalent weight of 350 g/mol or less, a polyfunctional monomer, and a photopolymerization initiator Resin composition.
<5>
The photosensitive resin composition according to <4>, wherein the photopolymerization initiator contains an oxime initiator (preferably an oxime ester compound).
<6>
A method for producing a cured product, comprising the step of curing the photosensitive resin composition according to <4> or <5> above at a temperature of 150° C. or less.

By using the method for producing an alkali-soluble resin of the present invention, an alkali-soluble resin having a large amount of side chain ethylenically unsaturated double bonds can be stably obtained by widening the molecular weight distribution and suppressing gelation due to intermolecular ester cross-linking. be able to. Moreover, by using a photosensitive resin composition containing a specific highly reactive alkali-soluble resin, it is possible to obtain a cured product that leaves little residue during development and has good solvent resistance. In particular, it is useful as a resist for color filters, solder resists, protective films, interlayer insulating films, etc. Color filters, display devices, substrates, etc. having cured products (cured films) formed from these resists are widely used in the optical field. It will be very useful in the electrical and electronic fields.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the molecular-weight GPC chart about alkali-soluble resin obtained in Example 1 and Comparative Example 1 (Example 1: solid line, Comparative Example 1: broken line).

The present invention will be described in detail below.
In addition, the form which combined two or more of each preferable form of this invention described below is also a preferable form of this invention.
Moreover, in this specification, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and "(meth)acrylate" means "acrylate and/or methacrylate".
Further, in this specification, the numerical range "Min to Max" means the minimum value Min or more and the maximum value Max or less. Furthermore, when describing preferred numerical values in stages for the upper and lower limits, a numerical range obtained by appropriately combining the upper and lower limits that are separately described is also a preferred numerical range.
<Raw materials and production reaction used for production of alkali-soluble resin>
The descriptions of all monomer components and their masses below represent the total mass of the solid content including modifier compounds 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 a double bond equivalent weight of 350 g/mol or less, wherein an acid group and an epoxy group are A method for producing an alkali-soluble resin having a step of esterifying and having the following step (I) or (II).
(I) a step of polymerizing a monomer component containing an unsaturated carboxylic acid monomer to obtain a base polymer; After the conversion reaches 40% by mass with respect to 100% by mass of glycidyl (meth)acrylate, the reaction is continued at 100° C. or higher until the conversion exceeds 85% by mass (II) (meth)acrylic In the step of polymerizing a monomer component containing a glycidyl acid to obtain a base polymer, and in the addition reaction of an unsaturated carboxylic acid monomer to the base polymer, the reaction is carried out at a temperature of less than 100°C to obtain a total unsaturated carboxylic acid. After the conversion rate reaches 40% by mass with respect to 100% by mass of the acid monomer, the reaction is performed at 100 ° C. or higher, and the esterification reaction is performed until the conversion rate exceeds 85% by mass. (preferably carboxylic acid anhydride) addition reaction step

The ethylenically unsaturated double bond of the alkali-soluble resin having an ethylenically unsaturated double bond in the side chain of the present invention and having a double bond equivalent of 350 g/mol or less is produced by an esterification reaction between an acid group and an epoxy group. . Specifically, (1) esterification reaction of an acid group-containing resin obtained by polymerizing a monomer mixture containing a monomer having an acid group and 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, and a monomer having an acid group and a double bond are produced by an esterification reaction. be done. Furthermore, the hydroxyl group generated by the reaction between the acid group and the epoxy group may be further reacted with a polybasic acid anhydride (preferably a carboxylic acid anhydride).
The double bond means a polymerizable double bond, ie, a carbon-carbon double bond, and includes, for example, (meth)acryloyl group, vinyl group and the like.
Examples of monomers having an acid group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; Unsaturated polyvalent carboxylic acids such as acids; mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate, etc. Unsaturation in which the chain is extended between the unsaturated group and the carboxyl group monocarboxylic acids; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Among these, it is preferable to use unsaturated carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids) from the viewpoint of versatility, availability, and the like. More preferably, unsaturated monocarboxylic acids are used in terms of reactivity, alkali solubility, etc., and (meth)acrylic acid is even more preferable. Hereinafter, the unsaturated carboxylic acid monomer is also referred to as unsaturated carboxylic acid monomer (b).
The content of the unsaturated carboxylic acid monomer is consumed by reacting with the epoxy group of glycidyl (meth)acrylate. It is preferable to set it to have an acid number appropriate to have. For example, when used for a color filter resist, the content of the unsaturated carboxylic acid monomer is preferably 1% by mass or more, more preferably 2% by mass, based on the total amount of all monomer components of 100% by mass. Above, more preferably 3% by mass or more. 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 unsaturated carboxylic acid monomer unit is modified with glycidyl (meth)acrylate glycidylate is 65% by mass or more with respect to the total amount of 100% by mass of all monomer components. is preferable, and it is more preferable that it is 70% by mass or more. Moreover, it is preferable that it is 95 mass % or less. More preferably, it is 90% by mass or less.
In order to adjust solvent solubility, viscosity, and other properties required for the intended use, it is preferred that the above-mentioned alkali-soluble resin is further copolymerized with other copolymerizable monomers according to the purpose.
Other copolymerizable monomer components according to the present invention further include monomers capable of introducing a cyclic structure into the main chain of the resin (monomers capable of introducing a cyclic structure into the main chain (a) is preferably included.
Examples of monomers capable of introducing a ring structure into the main chain (including monomers having a ring structure in the main chain) include N-substituted maleimide-based monomers, dialkyl-2,2′-(oxydi Methylene) diacrylate-based monomers, α-(unsaturated alkoxyalkyl) acrylate-based monomers (preferably alkyl-(α-allyloxymethyl) acrylate-based monomers), etc. are preferably used. Here, for example, N-substituted maleimide-based monomers and/or dialkyl-2,2′-(oxydimethylene) diacrylate-based monomers and/or alkyl-(α-allyloxymethyl) acrylate-based monomers When using, it becomes an alkali-soluble resin that can give a cured product with improved heat resistance, hardness, coloring material dispersibility, etc. in color filter resist applications. The content of the monomer capable of introducing a ring structure into the main chain is preferably 50% by mass or less, preferably 45% by mass or less, in the total amount of 100% by mass of all monomer components. It is more suitable. In particular, when N-substituted maleimide-based monomers, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers and/or α-(unsaturated alkoxyalkyl) acrylate-based monomers are included, their content 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 viewpoint of heat resistance, hardness, colorant dispersibility, development speed, transparency, etc. % by mass.

Examples of the N-substituted maleimide-based monomers include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like can be mentioned, and one or more of these can be used. Among them, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are preferred, and N-benzylmaleimide and N-phenylmaleimide are particularly preferred in terms of less coloring and excellent dispersibility.
Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide. , o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide and other halogen-substituted benzylmaleimides.
Examples of the N-phenylmaleimide include phenylmaleimide; alkyl-substituted phenylmaleimide such as p-methylphenylmaleimide and p-butylphenylmaleimide; phenolic hydroxyl group-substituted phenylmaleimide such as p-hydroxyphenylmaleimide; o-chlorophenylmaleimide; Halogen-substituted phenylmaleimides such as o-dichlorophenylmaleimide and p-dichlorophenylmaleimide are included.
As the dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer, from the viewpoint of less coloring, dispersibility, and ease of industrial availability, for example, dimethyl-2,2'-[ Oxybis(methylene)]bis-2-propenoate and the like are preferably used.
Examples of the α-(unsaturated alkoxyalkyl) acrylate monomers include α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α-allyloxymethyl n-propyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, α-Allyloxymethyl acrylate n-amyl, α-Allyloxymethyl acrylate s-amyl, α-Allyloxymethyl acrylate t-amyl, α-Allyloxymethyl acrylate neopentyl acrylate, α-Allyloxymethyl acrylate n -hexyl, s-hexyl α-allyloxymethyl acrylate, n-heptyl α-allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, α-allyl t-octyl oxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, capryl α-allyloxymethyl acrylate, nonyl α-allyloxymethyl acrylate, decyl α-allyloxymethyl acrylate, α-allyloxy undecyl methyl 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, ceryl α-allyloxymethyl acrylate, α-allyloxymethyl Chain saturated hydrocarbon group-containing α-(allyloxymethyl) acrylate such as melisyl acrylate is preferred. In addition, 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 α-(unsaturated alkoxyalkyl) acrylate-based monomer can be produced, for example, by the production method disclosed in International Publication No. 2010/114077.

As the monomer component according to the present invention, the (meth)acrylic acid ester-based monomer is preferably a monomer having an alicyclic skeleton in consideration of 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, dicyclo Pentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylol-tricyclodecanedi(meth)acrylate, pentacyclopentadecanedimethanol di(meth)acrylate, cyclohexanedimethanol Di(meth)acrylate, norbornane dimethanol 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. Among these, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanyl (meth)acrylate are preferably used from the viewpoint of versatility, availability, and the like.
The (meth)acrylic acid ester-based monomers also include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, (meth) ) n-butyl acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, n-(meth)acrylate Hexyl, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic stearyl acid, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, monoglycerol (meth)acrylate, 2-(meth)acrylate Methoxyethyl, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, α-hydroxymethyl methyl acrylate , α-hydroxymethyl acrylate, t-butyl α-hydroxymethyl acrylate, t-amyl α-hydroxymethyl acrylate, etc., as well as 1,4-dioxaspiro[4,5]dec-2-yl methacrylic acid , (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- Also included are dioxolane and the like. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, etc., can easily balance heat resistance, coloring material dispersibility, and solvent re-solubility. Alkyl (meth)acrylates of are preferred.
The content of the (meth)acrylic acid ester-based monomer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and still more preferably 100% by mass of the total amount of all monomer components. is 10 to 20% by mass.

Examples of monomer components according to the present invention include aromatic vinyl-based monomers such as styrene, vinyltoluene, α-methylstyrene, and methoxystyrene. Among them, styrene and/or vinyl toluene are preferable from the viewpoint of the heat-resistant coloring and heat-decomposing properties of the resulting resin.
The polymerization initiator used in the polymerization of the above monomer components is not particularly limited, but examples include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, Organic peroxides such as t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate; 2,2'-azobis(isobutyro nitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) and other azo compounds ; and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of the initiator to be used may be appropriately set according to the combination of monomers to be used, the reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited. 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less based on the total amount of all monomer components (100% by mass of all monomers), in that the concentration can be reduced and a polymer with a small molecular weight distribution can be obtained. is preferably 0.5% by mass or more and less than 3% by mass.
Moreover, when polymerizing the above-mentioned monomer components, a chain transfer agent that is usually used may be added, if necessary, for molecular weight adjustment. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecylmercaptan, mercaptopropionic acid, mercaptoacetic acid and methyl mercaptoacetate, α-methylstyrene dimer, etc., but preferably the chain transfer effect is high. , n-dodecyl mercaptan and mercaptopropionic acid are preferred because they can reduce residual monomers and are readily available. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers to be used, the reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but does not cause gelation. 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, based on the total amount of all monomer components (100% by mass of all monomers), in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained. is preferably 0.2% by mass or more and less than 3% by mass.
Methods for polymerizing the monomers used in the present invention include solution polymerization and emulsion polymerization. Among them, solution polymerization is industrially advantageous, and structural adjustment such as molecular weight is easy, and therefore, it is preferable. In addition, as the polymerization mechanism of the monomer, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used. is also advantageous and therefore preferred. The polymerization initiation method in the above polymerization reaction may be performed by supplying energy necessary for polymerization initiation from an active energy source such as heat, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays), and electron beams to the monomer components. Combined use of an initiator is preferable because the energy required for polymerization initiation can be greatly reduced and the reaction can be easily controlled. The molecular weight of the polymer obtained by polymerizing the above monomers 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 solution polymerization, the solvent used for 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 to be used, the polymerization temperature, and the polymerization concentration. is used, 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 a polymerization solvent. In addition, the solvent will be explained in a suitable manufacturing 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 on an industrial production scale. It is preferably 0.2 to 45 m ³ , more preferably 0.3 to 40 m ³ . The material of the inside of the reaction tank is not particularly limited, and for example, stainless steel, preferably SUS such as SUS304, SUS316, SUS316L, etc., is preferable from the viewpoint of corrosion resistance. In addition, it is desirable that the inside of the reaction vessel be glass lined or the like so as to be inert to the reaction raw materials and reaction products.

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 reactor. In the range exceeding 80% by volume, the proportion of the polymerization reaction solution becomes high, which may lead to difficulties in terms of polymerization control and safety, such as coping with a sudden temperature rise. Further, 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, it is preferable to lower the oxygen concentration in the upper gas phase portion of the polymer solution by substitution with an inert gas (preferably nitrogen substitution). Examples thereof include a method of bubbling an inert gas (nitrogen, helium, argon, carbon dioxide, etc.) into the polymerization reaction solution, and a method of blowing an inert gas into the reaction system to reduce oxygen in the gas phase. A specific method for bubbling nitrogen includes a method in which a nitrogen line fitted with a porous filter is inserted into the reaction solution (preferably at the bottom), and nitrogen is flowed while stirring the reaction solution. As a method of blowing the inert gas into the reaction system, a nitrogen inlet is provided at the upper part of the reaction tank to blow the inert gas into the reaction system. In that case, provide an exhaust port. The inert gas is preferably nitrogen, which is the most abundant gas in the atmosphere, is extremely inert at normal temperature and normal pressure, and is less expensive than rare gases such as argon. Regarding the amount of nitrogen introduced, for example, on a laboratory scale (0.5 to 5 liters), it is preferable to blow in at a flow rate of 0.1 (ml/min) to 300 (ml/min), and more preferably 1 (ml/min). ) to 150 (ml/min). On an industrial production scale (0.5 to 5 m ³ ), it is preferable to blow at a flow rate of 0.1 (l/min) to 300 (l/min), more preferably 1 (l/min) to 150 (l/min). ) is preferably blown at a flow rate of As a result, the oxygen concentration in the gas phase can be controlled to 5% by volume or less, preferably 3% by volume or less.

The shape of the reaction tank (reaction vessel) to be used is not particularly limited, and examples thereof include polygonal and cylindrical shapes, but cylindrical shapes are preferred from the viewpoints of stirring effect, handleability, versatility, and the like. Further, the baffle plate may or may not be present, but the uniformity of the polymerization reaction solution can be improved by providing the baffle plate. The stirrer is composed of a power source such as an electric motor, a rotating shaft, a stirrer, etc., but the shape of the stirring blades is not limited. Agitators include desk turbines, fan turbines, curved fan turbines, Yabane turbines, multi-stage fan turbines, Faudler blades, Burmargin blades, angled blades, propeller blades, multi-stage blades, anchor blades, gate blades, and double ribbon blades. , screw blades, Maxblend blades, and the like. The stirring power (industrial production scale) during the polymerization reaction is 0.1 to 4.0 kW/m ³ , preferably 0.1 to 3.0 kW/m ³ , more preferably 0.2 to 2.0 kW/m ³ . be. By controlling within this range, the homogeneity of the polymerization reaction solution is improved, and the polymerization reaction solution scatters on the inner wall surface of the reaction vessel (reaction vessel), causes a reaction on the inner wall surface of the reaction vessel, and forms a gel. can be prevented. In addition, regarding the pressure inside the vessel during the polymerization reaction, there is no need to control the increase or decrease in pressure. Unless a special operation is performed or a special raw material is used, normal pressure may be used. When distilling off the low boiling point solvent, the pressure may be appropriately reduced. The method of adding the monomers during the polymerization reaction is not particularly limited, and a part may be initially charged and the rest may be added dropwise, or the entire amount may be added dropwise. It is preferable to initially charge a portion and drop the rest, or to drop the entire amount. In the present specification, charging the monomers in advance into the reaction vessel (throwing the monomers into the reaction vessel before polymerization) is also referred to as initial charging.

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. However, at a temperature lower than the boiling point of the polymerization solvent by 20 ° C. or more, Preferably. In the case of a mixed solvent, the temperature is preferably 20° C. or more lower than the boiling point of the solvent with the highest boiling point. For example, 50 to 150°C is preferred, and 70 to 120°C is more preferred. In addition, the polymerization time can be set as appropriate, but is preferably 1 to 8 hours, more preferably 2 to 6 hours, for example.
<Method for producing suitable alkali-soluble resin>
As a preferred embodiment of the present invention, the first (I) comprises a monomer component containing a monomer (a) capable of introducing a ring structure into the main chain and an unsaturated carboxylic acid monomer (b). A step (I-1) of polymerizing to obtain a base polymer, and a step of reacting the base polymer with glycidyl (meth)acrylate to obtain an alkali-soluble resin having an ethylenically unsaturated double bond in a side chain. A production method having (I-2), and the second (II) is a monomer component containing a monomer (a) capable of introducing a ring structure into the main chain and glycidyl (meth)acrylate. Step (II-1) of polymerizing to obtain a base polymer, and reacting the base polymer with an unsaturated carboxylic acid monomer (b) to obtain an alkali soluble having an ethylenically unsaturated double bond in the side chain Two forms of the production method having the step (II-2) of obtaining a resin are mentioned.
In the production methods (I) and (II) above, the monomers are used so as to finally obtain 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. Adjust body composition.
The double bond equivalent is preferably in the range of 200-350 g/mol, more preferably in the range of 230-330 g/mol, and particularly preferably in the range of 250-300 g/mol. When the double bond equivalent is within 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. In addition, it is possible to achieve both curability and storage stability.
As used herein, the double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of the double bond of the polymer (alkali-soluble resin). The mass of the solid content of the polymer solution is the mass of each monomer component 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 obtained by dividing the mass (g) of the polymer solid content in the polymer solution by the double bond amount (mol) of the polymer. The amount of double bonds in the above polymer can be obtained by confirming the structures of the unsaturated carboxylic acid monomer and the glycidyl (meth)acrylate group-containing monomer used in the synthesis, and determining their amounts. It can also be measured by titration, elemental analysis, various analyzes such as NMR and IR, 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. The double bond equivalent is a measure of the amount of double bonds contained in a molecule. For compounds with the same molecular weight, the larger the double bond equivalent, the less double bonds are introduced. Become.

The above preferred manufacturing steps (I) and (II) are described in detail below.
Manufacturing process (I):
<Step (I-1)>
The preferred production step (I) above comprises 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 form a base. It has a step (I-1) of obtaining a polymer (also referred to as “base polymer 1”).
The method for obtaining the base polymer 1 by polymerizing the monomer components containing the above monomers (a) and (b) is not particularly limited, and known polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. mentioned. Among them, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy. In addition, as the polymerization mechanism of the monomer component, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used. 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, and the like.
Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy- 2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1′-azobis(cyclohexanecarbonitrile), 2,2′-azobis(2,4- dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), hydrogen peroxide, persulfate, and other peroxides and azo compounds that are usually used as polymerization initiators.
Examples of the chain transfer agent include compounds having a mercapto group, such as mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkylmercaptans, mercaptoalcohols, aromatic mercaptans, and mercaptoisocyanurates. includes alkylmercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, more preferably n-dodecylmercaptan and mercaptopropionic acid.
The solvent used in the polymerization is not particularly limited, and examples include monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; polyhydric alcohols such as ethylene glycol and propylene glycol; tetrahydrofuran and dioxane. Ethers such as 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; Fragrance such as toluene, xylene and ethylbenzene group hydrocarbons; chloroform; dimethyl sulfoxide; dimethyl carbonate and the like.
Among the polymerization solvents described above, alcohol solvents (monoalcohols, polyhydric alcohols), ketone solvents, ester solvents and/or ether solvents are preferably used. Among them, propylene glycol monomethyl ether among alcohol-based solvents is preferred because of the solubility of the resulting polymer, surface smoothness when forming a coating film, little impact on the human body and the environment, and ease of industrial availability. , Ethylene glycol or diethylene glycol is preferred, propylene glycol monomethyl ether acetate is preferred among ester solvents, diethylene glycol dimethyl ether or diethylene glycol ethyl methyl ether is preferred among ether solvents, and ethyl lactate is preferred among ketone solvents. 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, more preferably in the range of 130°C to 220°C. In addition, it is preferable to use a non-alcoholic solvent, and it is particularly preferable to use an ester-based solvent whose molecular weight can be easily controlled. Among ester-based solvents, propylene glycol monomethyl ether acetate is generally used as a solvent for resists, and is therefore preferable because it can reduce the time and effort required for solvent replacement. Note that the alcohol solvent is highly basic and causes pigment aggregation in the resist. In particular, when using an alcoholic solvent, it is preferable to use a solvent having a boiling point of 130° C. or higher from the viewpoint of synthesis.
The amount of the polymerization solvent used is preferably 50 to 500 parts by mass with respect to 100 parts by mass of the total amount of the monomer components. More preferably 100 to 300 parts by mass.
Each of the polymerization initiator, chain transfer agent, and polymerization solvent may be used alone, or two or more of them may be used in combination. In addition, the usage amounts of these can be appropriately set.
The polymerization temperature can be appropriately set according to the type and amount of the monomers to be used and the type and amount of the polymerization initiator. .
The polymerization time can be appropriately set, but is preferably 1 to 12 hours, more preferably 3 to 8 hours.
The mixing of the above monomer components is not particularly limited, and may be carried out as appropriate depending on the alkali-soluble resin to be obtained. The total amount of the above monomers (a) and (b) may be mixed simultaneously. Alternatively, the monomer (b) or (a) may be added little by little to the total amount of the monomer (a) or (b) and mixed.
After obtaining the base polymer 1 by polymerizing the above monomer components, the base polymer 1 may be used after removing the volatile matter from the polymerization reaction solution (polymer solution) to separate the base polymer 1. Alternatively, it may be used in a solution state without separation, but for industrial use, it is preferable to use it in a solution state without separation from the viewpoint of cost and the like.
The monomer components are described below. By polymerizing a monomer component containing each monomer, a copolymer having structural units 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 main chain, for example, an N-substituted maleimide monomer (a-1) represented by the following general formula is particularly preferred.

（式中、Ｒは、置換基を有していてもよい、炭素数１～３０の一価の炭化水素基を表す。）
一般式（ａ―１）中、Ｒは、置換基を有していていもよい、炭素数１～３０の一価の炭化水素基である。上記一価の炭化水素基は、炭素数が１～２０であることが好ましく、６～１２であることがより好ましい。
上記炭化水素基としては、鎖状又は環状の脂肪族炭化水素基、又は芳香族炭化水素基が挙げられる。
上記脂肪族炭化水素基は、飽和脂肪族炭化水素基であってもよいし、不飽和脂肪族炭化水素基であってもよいが、飽和脂肪族炭化水素基であることが好ましい。
鎖状の飽和脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、２－メチルペンチル基、３－メチルペンチル基、２，２－ジメチルブチル基、２，３－ジメチルブチル基、ヘプチル基、２－メチルヘキシル基、３－メチルヘキシル基、２，２－ジメチルペンチル基、２，３－ジメチルペンチル基、２，４－ジメチルペンチル基、３－エチルペンチル基、２，２，３－トリメチルブチル基、オクチル基、メチルヘプチル基、ジメチルヘキシル基、２－エチルヘキシル基、３－エチルヘキシル基、トリメチルペンチル基、３－エチル－２－メチルペンチル基、２－エチル－３－メチルペンチル基、２，２，３，３－テトラメチルブチル基、ノニル基、メチルオクチル基、３，７－ジメチルオクチル基、ジメチルヘプチル基、３－エチルヘプチル基、４－エチルヘプチル基、トリメチルヘキシル基、３，３－ジエチルペンチル基、デシル基、ウンデシル基、ドデシル基等の直鎖状又は分岐鎖状のアルキル基が挙げられる。
なかでも、炭素数１～３０のアルキル基であることが好ましく、炭素数１～２０のアルキル基であることがより好ましく、炭素数１～１２のアルキル基であることが更に好ましい。
環状の脂肪族炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロドデシル基等の単環系脂環式炭化水素基；ジシクロペンタニル基、ノルボルニル基、アダマンチル基等の多環系脂環式炭化水素基；が挙げられる。
なかでも、炭素数３～３０の単環又は多環系脂環式炭化水素基であることが好ましく、炭素数３～１８の単環又は多環系脂環式炭化水素基であることがより好ましく、炭素数６～１２の単環系脂環式炭化水素基であることが更に好ましい。
上記芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、ベンジル基、フェネチル基等を挙げることができる。なかでも、炭素数６～３０の芳香族炭化水素基であることが好ましく、炭素数６～１２の芳香族炭化水素基であることがより好ましい。
上記炭化水素基は、置換基を有していてもよい。上記置換基としては、例えば、アルキル基、アリール基、水酸基、ハロゲン原子、カルボキシル基、アルコキシ基、アリールオキシ基等が挙げられる。
上記Ｎ－置換マレイミド系単量体の具体例としては、例えば、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－プロピルマレイミド、Ｎ－イソプロピルマレイミド、Ｎ－ｔ－ブチルマレイミド、Ｎ－ドデシルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－オクチルマレイミド、Ｎ－２－エチルヘキシルマレイミド、Ｎ－デシルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－テトラデシルマレイミド、Ｎ－ステアリルマレイミド、Ｎ－２－デシルテトラデシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－ベンジルマレイミド、Ｎ－ナフチルマレイミド、Ｎ－クロロフェニルマレイミド、Ｎ－メチルフェニルマレイミド、Ｎ－ヒドロキシルエチルマレイミド、Ｎ－ヒドロキシルフェニルマレイミド、Ｎ－メトキシフェニルマレイミド、Ｎ－カルボキシフェニルマレイミド、Ｎ－ニトロフェニルマレイミド、Ｎ－トリブロモフェニルマレイミド、Ｎ，Ｎ’－オルトフェニレンビスマレイミド、Ｎ，Ｎ’－メタフェニレンビスマレイミド、Ｎ，Ｎ’－パラフェニレンビスマレイミド等が挙げられる。なかでも、上記Ｎ－ビニルアミド系単量体との共重合性や耐熱性の観点から、Ｎ－ベンジルマレイミド、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミドが好ましい。特に、耐熱着色性が強く求められる用途ではＮ－ベンジルマレイミドが好適に用いられ、有機微粒子や無機微粒子との親和性が強く求められる用途ではＮ－フェニルマレイミドが好適に用いられる。
上記Ｎ－ベンジルマレイミドとしては、例えば、ベンジルマレイミド；ｐ－メチルベンジルマレイミド、ｐ－ブチルベンジルマレイミド等のアルキル置換ベンジルマレイミド；ｐ－ヒドロキシベンジルマレイミド等のフェノール性水酸基置換ベンジルマレイミド；ｏ－クロロベンジルマレイミド、ｏ－ジクロロベンジルマレイミド、ｐ－ジクロロベンジルマレイミド等のハロゲン置換ベンジルマレイミド；等が挙げられる。
上記Ｎ－置換マレイミド単量体（ａ―１）は、１種単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
なかでも、上記Ｎ－置換マレイミド単量体（ａ―１）は、Ｎ－ベンジルマレイミド及びＮ－フェニルマレイミドであることが好ましい。これら２種の組み合わせにより、顔料の分散安定性が向上したり、硬化後の膜の表面硬度が高くなる場合がある。
Ｎ－ベンジルマレイミドとＮ－フェニルマレイミドの質量比は、９５／５～５／９５であることが好ましく、１０／９０～９０／１０であることがより好ましい。
また、Ｎ－置換マレイミド単量体（ａ―１）として、Ｎ－フェニルマレイミドを主成分として使用する場合のＮ－ベンジルマレイミドの割合は、Ｎ－フェニルマレイミド１００質量部に対して、１～３０質量部であることが好ましく、１～２０質量部であることがより好ましく、１～１０質量部であることが更に好ましく、１～５質量部であることが最も好ましい。また、上記のように併用する場合、Ｎ－ベンジルマレイミドの使用量は、総単量体成分１００質量％に対して、０．０５～５０質量％とすることが好ましく、より好ましくは１～４０質量％、更に好ましくは２～３０質量％である。
上記範囲とすることで、顔料等の有機微粒子や、量子ドット又はシリカ等の無機微粒子との親和性や分散性が向上しうる。
（不飽和カルボン酸単量体（ｂ））
上記不飽和カルボン酸単量体（ｂ）としては、カルボキシル基及び／又はカルボン酸無水物基と重合性二重結合とを有する化合物が好ましい。
上記重合性二重結合としては、例えば、（メタ）アクリロイル基、ビニル基等が挙げられる。なかでも、（メタ）アクリロイル基が好ましい。
上記不飽和カルボン酸単量体の具体例としては、例えば、（メタ）アクリル酸、クロトン酸、ケイ皮酸、ビニル安息香酸等の不飽和モノカルボン酸類；マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸等の不飽和多価カルボン酸類；コハク酸モノ（２－アクリロイルオキシエチル）、コハク酸モノ（２－メタクリロイルオキシエチル）等の不飽和基とカルボキシル基との間が鎖延長されている不飽和長鎖モノカルボン酸類；等が挙げられる。これらのなかでも、汎用性、入手性等の観点から、不飽和モノカルボン酸類が好ましく、（メタ）アクリル酸がより好ましい。
上記不飽和カルボン酸単量体（ｂ）は、１種単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
（上記単量体（ａ）及び単量体（ｂ）と共重合可能な単量体（ｃ））
ベースポリマー１を製造するための単量体成分は、上記単量体（ａ）及び単量体（ｂ）以外に、上記単量体（ａ）及び単量体（ｂ）と共重合可能な単量体（ｃ）を更に含んでいてもよい。
上記単量体（ｃ）としては、上述した単量体（ａ）及び（ｂ）と共重合可能であれば特に限定されず、例えば、下記の単量体を挙げることができる。これらは、１種単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸２，３－ヒドロキシプロピル等のヒドロキシアルキル（メタ）アクリレート等の水酸基含有単量体；
（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸ｉ－プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｎ－アミル、（メタ）アクリル酸ｓ－アミル、（メタ）アクリル酸ｔ－アミル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、１，４－ジオキサスピロ［４，５］デカ－２－イルメタアクリル酸、（メタ）アクリロイルモルホリン、４－（メタ）アクリロイルオキシメチル－２－メチル－２－エチル－１，３－ジオキソラン、４－（メタ）アクリロイルオキシメチル－２－メチル－２－イソブチル－１，３－ジオキソラン、４－（メタ）アクリロイルオキシメチル－２－メチル－２－シクロヘキシル－１，３－ジオキソラン、４－（メタ）アクリロイルオキシメチル－２，２－ジメチル－１，３－ジオキソラン等の（メタ）アクリル酸エステル；
シクロヘキシル（メタ）アクリレート、シクロヘキシルメチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、１－アダマンチル（メタ）アクリレート、（３，４－エポキシシクロヘキシル）メチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジメチロール－トリシクロデカンジ（メタ）アクリレート、ペンタシクロペンタデカンジメタノールルジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、ノルボルナンジメタノールジ（メタ）アクリレート、ｐ－メンタン－１，８－ジオールジ（メタ）アクリレート、ｐ－メンタン－２，８－ジオールジ（メタ）アクリレート、ｐ－メンタン－３，８－ジオールジ（メタ）アクリレート、ビシクロ［２．２．２］－オクタン－１－メチル－４－イソプロピル－５，６－ジメチロールジ（メタ）アクリレート等の脂環式（メタ）アクリレート；
（メタ）アクリル酸β－メチルグリシジル、（メタ）アクリル酸β－エチルグリシジル、ビニルベンジルグリシジルエーテル、アリルグリシジルエーテル、（メタ）アクリル酸（３，４－エポキシシクロヘキシル）メチル、ビニルシクロヘキセンオキシド等の、（メタ）アクリル酸グリシジル以外のエポキシ基含有単量体；
Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド等の（メタ）アクリルアミド類；ポリスチレン、ポリメチル（メタ）アクリレート、ポリエチレンオキシド、ポリプロピレンオキシド、ポリシロキサン、ポリカプロラクトン、ポリカプロラクタム等の重合体分子鎖の片末端に（メタ）アクリロイル基を有するマクロモノマー類；１，３－ブタジエン、イソプレン、クロロプレン等の共役ジエン類；酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、２－エチルヘキシルビニルエーテル、ｎ－ノニルビニルエーテル、ラウリルビニルエーテル、シクロヘキシルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、メトキシエトキシエチルビニルエーテル、メトキシポリエチレングリコールビニルエーテル、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル等のビニルエーテル類；Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－ビニルイミダゾール、Ｎ－ビニルモルフォリン、Ｎ－ビニルアセトアミド等のＮ－ビニル化合物類；スチレン、ビニルトルエン、α－メチルスチレン、キシレン、メトキシスチレン、エトキシスチレン等の芳香族ビニル類；（メタ）アクリル酸イソシアナトエチル、アリルイソシアネート等の不飽和イソシアネート類；等。
上記単量体（ａ）、（ｂ）及び（ｃ）の各含有量は、得ようとするアルカリ可溶性樹脂の目的、用途に応じて適宜設定することができる。
上記単量体（ａ）は、総単量体成分１００質量％に対して、０．０５～５０質量％とすることが好ましく、より好ましくは１～４０質量％、更に好ましくは２～３０質量％である。
上記単量体（ｂ）は、総単量体成分１００質量％に対して、１質量％以上であることが好ましく、より好ましくは２質量％以上、更に好ましくは３質量％以上である。また、３０質量％以下であることが好ましく、より好ましくは２０質量％以下、更に好ましくは１０質量％以下である。
上記単量体（ｃ）は、総単量体成分１００質量％に対して、１～５０質量％とすることが好ましく、より好ましくは５～３０質量％、更に好ましくは１０～２０質量％である。
上記単量体（ａ）、（ｂ）、（ｃ）の各含有量は、２種以上の単量体を含む場合、その合計量である。

(In the formula, R represents an optionally substituted monovalent hydrocarbon group having 1 to 30 carbon atoms.)
In general formula (a-1), R is an optionally substituted monovalent hydrocarbon group having 1 to 30 carbon atoms. The monovalent hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
Examples of the hydrocarbon group include chain or cyclic aliphatic hydrocarbon groups and aromatic hydrocarbon groups.
The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but is preferably a saturated aliphatic hydrocarbon group.
Chain saturated aliphatic hydrocarbon groups include, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, pentyl group and 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, etc. straight-chain or branched-chain alkyl groups.
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 even more preferable.
Cyclic aliphatic hydrocarbon groups include, for example, monocyclic alicyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl groups. hydrocarbon group; polycyclic alicyclic hydrocarbon group such as dicyclopentanyl group, norbornyl group, and adamantyl group;
Among them, a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 30 carbon atoms is preferable, and a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms is more preferable. A monocyclic alicyclic hydrocarbon group having 6 to 12 carbon atoms is preferred, and more preferred.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, benzyl group, and phenethyl group. 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 hydrocarbon group may have a substituent. Examples of the substituents include alkyl groups, aryl groups, hydroxyl groups, halogen atoms, carboxyl groups, alkoxy groups, and aryloxy groups.
Specific examples of the N-substituted maleimide monomers include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, Nt-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-hydroxylethylmaleimide, N-hydroxylphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenyl maleimide, N-tribromophenylmaleimide, N,N'-orthophenylenebismaleimide, N,N'-metaphenylenebismaleimide, N,N'-paraphenylenebismaleimide and the like. Of these, N-benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide are preferred from the viewpoint of copolymerizability with the N-vinylamide-based monomer and heat resistance. In particular, N-benzylmaleimide is preferably used in applications where heat coloring resistance is strongly required, and N-phenylmaleimide is preferably used in applications where affinity with organic fine particles or inorganic fine particles is strongly required.
Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide. , o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide and other halogen-substituted benzylmaleimides;
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. A combination of these two types may improve the dispersion stability of the pigment or increase the surface hardness of the cured film.
The mass ratio of N-benzylmaleimide and N-phenylmaleimide is preferably 95/5 to 5/95, more preferably 10/90 to 90/10.
Further, when N-phenylmaleimide is used as the main component as the N-substituted maleimide monomer (a-1), the ratio of N-benzylmaleimide is 1 to 30 parts per 100 parts by mass of N-phenylmaleimide. It is preferably 1 to 20 parts by mass, even more preferably 1 to 10 parts by mass, and most preferably 1 to 5 parts by mass. 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, based on 100% by mass of the total monomer components. % by mass, more preferably 2 to 30% by mass.
Within the above range, 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 a (meth)acryloyl group and a vinyl group. Among them, a (meth)acryloyl group is preferred.
Specific examples of the unsaturated carboxylic acid monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, citracone; Unsaturated polycarboxylic acids such as acid and mesaconic acid; mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate and other unsaturated groups and carboxyl groups are chain-extended unsaturated long-chain monocarboxylic acids; Among these, unsaturated monocarboxylic acids are preferable, and (meth)acrylic acid is more preferable from the viewpoint of versatility, availability, and the like.
The 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 component for producing the base polymer 1 is, in addition to the monomer (a) and the monomer (b), copolymerizable with the monomer (a) and the monomer (b). It may further contain a monomer (c).
The monomer (c) is not particularly limited as long as it can be copolymerized with the monomers (a) and (b) described above, and examples thereof include the following monomers. These may be used individually by 1 type, and may be used in combination of 2 or more type.
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, hydroxyl group-containing monomers such as hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate and 2,3-hydroxypropyl (meth)acrylate;
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, t-amyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic Acid 2-methoxyethyl, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 1,4-dioxaspiro [4,5]dec-2-ylmethacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxy methyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2, (meth)acrylic acid esters such as 2-dimethyl-1,3-dioxolane;
Cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, di Cyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, pentacyclopentadecanedimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, norbornane dimethanol 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, cycloaliphatic (meth)acrylates such as bicyclo[2.2.2]-octane-1-methyl-4-isopropyl-5,6-dimethylol di(meth)acrylate;
β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, vinylcyclohexene oxide, etc. Epoxy group-containing monomers other than glycidyl (meth)acrylate;
(Meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam and the like; Macromonomers having a (meth)acryloyl group at one end of the combined molecular chain; Conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Class; 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- Vinyl ethers such as hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine and N-vinylacetamide; styrene, vinyl aromatic vinyls such as toluene, α-methylstyrene, xylene, methoxystyrene and ethoxystyrene; unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate;
Each content of the above monomers (a), (b) and (c) can be appropriately set according to the purpose and application of the alkali-soluble resin to be obtained.
The 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 with respect to 100% by mass of the total monomer component. %.
The content of the 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, relative to 100% by mass of the total 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 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 with respect to 100% by mass of the total monomer component. be.
Each content of the above monomers (a), (b), and (c) is the total amount when two or more types of monomers are included.

<Step (I-2)>
The production step (I) further includes reacting the base polymer 1 obtained in the step (I-1) with glycidyl (meth)acrylate to obtain an alkali having an ethylenically unsaturated double bond in the side chain. It has a step (I-2) of obtaining a soluble resin.
The method for reacting the base polymer 1 with glycidyl (meth)acrylate is not particularly limited. A polymer solution containing the base polymer 1 is mixed with glycidyl (meth)acrylate and reacted by a known method. It is better to let By the above reaction, the acid group (carboxyl group) of the base polymer 1 and the epoxy group of the glycidyl (meth)acrylate are esterified, and the glycidyl (meth)acrylate is added to the base polymer 1 to form a side chain. A polymer having ethylenically unsaturated double bonds is obtained.
As the temperature for the above addition reaction, in order to obtain an alkali-soluble resin having a double bond equivalent of 350 g/mol or less, the temperature at which the addition reaction proceeds stably while suppressing the increase in molecular weight due to intermolecular ester cross-linking. , When the glycidyl (meth)acrylate is added, the reaction is carried out at less than 100 ° C., and after the conversion reaches 40% by mass with respect to 100% by mass of the total glycidyl (meth)acrylate, the conversion is 85% by mass. It is preferred to carry out the reaction at 100° C. or higher until the The temperature range is preferably from 70 to less than 100°C, more preferably from 80 to less than 100°C, until the conversion rate reaches 40% by mass. After the conversion reaches 40% by mass, the temperature is preferably 100 to 150°C, more preferably 100 to 120°C, until the conversion exceeds 85% by mass.
The total reaction time of the above addition reaction is not particularly limited, but is, for example, 50 minutes to 36 hours, preferably 3 to 26 hours, more preferably 6 to 20 hours.
Further, 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, until the conversion rate reaches 40% by mass. After the conversion reaches 40% by mass, the reaction time is preferably 30 minutes to 20 hours, more preferably 2 hours to 16 hours, and 4 hours to 13 hours until the conversion exceeds 85% by mass. Time is more preferred. In addition, 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.
The amount of glycidyl (meth)acrylate used in the step (I-2) is preferably set appropriately so that the resulting alkali-soluble resin has a double bond equivalent of 350 g/mol or less. It is preferably 30 to 180 parts by mass, more preferably 50 to 150 parts by mass, and even more preferably 80 to 150 parts by mass with respect to 100 parts by mass of the total monomer components that give the base polymer 1. .
The 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 and triphenylphosphine; ammonium salts such as tetraethylammonium chloride; A known catalyst such as a phosphonium salt such as tetraphenylphosphonium compound and an amide compound such as dimethylformamide may be used. Among them, amine compounds and phosphines are preferable, and triethylamine and dimethylbenzylamine are more preferable, in terms of less coloring and industrial availability.
The amount of the catalyst used can be appropriately set, but it is preferably 0.05 to 5% by mass, and 0.1 to 1% by mass, based on the total amount of base polymer 1 and glycidyl (meth)acrylate. %, more preferably 0.1 to 0.5% by mass. If the amount of the catalyst used is less than the above range, the reaction time will be prolonged, which may be industrially disadvantageous. If the above range is exceeded, a salt may be formed with the base polymer when the catalyst is added, making the catalyst insoluble, making stirring difficult, and the heat coloration of the obtained polymer may become strong.
The production method (I) may have other steps in addition to the steps (I-1) and (I-2) described above. Examples of the other steps include an aging step, a neutralization step, a deactivation step of 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 performed by a known method.
Manufacturing process (II):
<Step (II-1)>
The production step (II) comprises 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 (“base polymer 2”). (also referred to as
As the monomer (a) capable of introducing a ring structure into the main chain and glycidyl (meth)acrylate, the “monomer capable of introducing a ring structure into the main chain” described in the production method (I) above may be used. Examples thereof include those similar to the monomer (a)” and “glycidyl (meth)acrylate”. The same can be used for other components such as solvents.
The monomer component for producing the base polymer 2 may further contain the monomer (a) and the monomer (d) copolymerizable with the glycidyl (meth)acrylate.
Examples of the monomer (d) include the same monomers as the monomer (c) described in the production method (I). These may be used individually by 1 type, and may be used in combination of 2 or more type.
The polymerization method is not particularly limited, but preferably includes the same polymerization method as described in the production method (I).
Each content of the monomer (a), glycidyl (meth)acrylate, and the monomer (d) is appropriately set according to the double bond content and acid value of the alkali-soluble resin to be obtained. be able to.
The monomer (a) is preferably 1% by mass or more, more preferably 50% by mass or more, and 60% by mass with respect to 100% by mass of the total monomer component that gives the base polymer 2. It is more preferably 95% by mass or less, and more preferably 90% by mass or less.
The glycidyl (meth)acrylate is more preferably 50% by mass or more, still more preferably 60% by mass or more, and 95% by mass with respect to 100% by mass of the total monomer component that gives the base polymer 2. % or less, more preferably 90 mass % or less.
The content of the monomer (d) is preferably 1% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass, based on 100% by mass of the total monomer component that gives the base polymer 2. It is more preferably 60% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.
Each content of the monomer (a), glycidyl (meth)acrylate, and the monomer (d) is the total amount when two or more monomers are included.
<Step (II-2)>
The production method (II) further includes reacting the base polymer 2 obtained in the step (II-1) with an unsaturated carboxylic acid monomer (b) to form an ethylenically unsaturated double polymer on the side chain. It has a step (II-2) of obtaining an alkali-soluble resin having a bond.
The method for reacting the unsaturated carboxylic acid monomer (b) with the base polymer 2 is not particularly limited. , and, if necessary, a polymerization initiator, a chain transfer agent, a catalyst, etc., may be mixed and reacted by a known method.
Through the above reaction, the carboxyl group of the unsaturated carboxylic acid monomer (b) undergoes an esterification reaction with the epoxy group of the base polymer 2, and the unsaturated carboxylic acid monomer (b) is added to form a side chain. An alkali-soluble resin having an ethylenically unsaturated double bond is obtained.
Examples of the unsaturated carboxylic acid monomer (b) include those similar to the unsaturated carboxylic acid monomer (b) described in the production step (I) above.
As the temperature for the above addition reaction, base polymer 2 is used as the temperature for stably proceeding the addition reaction while suppressing the increase in molecular weight due to intermolecular ester cross-linking in order to obtain an alkali-soluble resin having a double bond equivalent of 350 g/mol or less. When the unsaturated carboxylic acid monomer (b) is subjected to the addition reaction, the reaction is performed at less than 100 ° C., and the conversion rate reaches 40% by mass with respect to 100% by mass of the total unsaturated carboxylic acid monomer (b). After that, it is preferable to carry out the reaction at 100° C. or higher until the conversion rate exceeds 85% by mass. The temperature range is preferably from 40 to less than 100°C, more preferably from 70 to less than 100°C, so that the conversion rate is up to 40% by mass. After the conversion reaches 40% by mass, the temperature is preferably 100 to 180°C, more preferably 100 to 150°C, and particularly preferably 100 to 120°C until the conversion exceeds 85% by mass. preferable.
The total reaction time of the above addition reaction is not particularly limited, but is, for example, 50 minutes to 36 hours, preferably 3 to 26 hours, more preferably 6 to 20 hours.
Further, 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, until the conversion rate reaches 40% by mass. After the conversion reaches 40% by mass, the reaction time is preferably 30 minutes to 20 hours, more preferably 2 hours to 16 hours, and 4 hours to 13 hours until the conversion exceeds 85% by mass. Time is more preferred. The esterification reaction is completed when the conversion rate is more preferably 90% by mass or more, and most preferably 95% by mass or more.
The amount of the unsaturated carboxylic acid monomer (b) used in the step (II-2) is preferably set appropriately so that the resulting alkali-soluble resin has a double bond equivalent of 350 g/mol or less. However, for example, it is preferably 10 to 60 parts by mass, more preferably 25 to 50 parts by mass, and 30 to 40 parts by mass with respect to 100 parts by mass of the monomer component that provides the base polymer 2. is more preferred.
The above reaction (esterification reaction) is preferably carried out in the presence of a basic compound. For example, known catalysts such as amine compounds such as triethylamine and dimethylbenzylamine; ammonium salts such as tetraethylammonium chloride; phosphonium salts such as tetraphenylphosphonium bromide; and amide compounds such as dimethylformamide; The amount of the catalyst used can be set as appropriate.
<Step (II-3)>
In the production step (II), after the step (II-2), the alkali-soluble resin having an ethylenically unsaturated double bond in the side chain is further reacted with a polybasic acid or a polybasic acid anhydride. It is preferable to have a step (II-3) of causing the By performing the above step (II-3), the hydroxyl group generated by the reaction of the epoxy group and the carboxyl group in the above step (II-2) is reacted with a polybasic acid or a polybasic anhydride to convert the carboxyl group. The acid value of the alkali-soluble resin can be adjusted to an appropriate range.
Examples of the polybasic acid or polybasic acid anhydride include polybasic acids such as succinic acid, maleic acid, phthalic acid, and tetrahydrophthalic acid; succinic anhydride (also known as succinic anhydride), maleic anhydride, anhydride Dibasic acid anhydrides such as phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and itaconic anhydride product; trimellitic anhydride; and the like. Among them, succinic acid and polybasic acid anhydrides are preferred, and carboxylic acid anhydrides are preferred from the viewpoint of high reactivity and industrial availability, and succinic anhydride, maleic anhydride, and tetrahydrophthalic anhydride are particularly preferred. and hexahydrophthalic anhydride are preferred.
The reaction temperature in the reaction with the polybasic acid or polybasic acid anhydride (preferably carboxylic acid anhydride) is not particularly limited as long as it is a temperature at which the reaction proceeds, and examples thereof include 0 to 200°C. , preferably 20 to 150°C, more preferably 30 to 120°C.
Although the reaction time is not particularly limited, it may be, for example, 1 to 12 hours, preferably 2 to 12 hours, more preferably 2 to 8 hours.
The amount of polybasic acid or polybasic acid anhydride (preferably carboxylic acid anhydride) to be used is not particularly limited, and may be set so that the resulting alkali-soluble resin has an acid value within a desired range.
The production step (II) may have other steps in addition to the steps (II-1), (II-2) and (II-3) described above. Examples of the other steps include an aging step, a neutralization step, a deactivation step of 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 performed by a known method.
Thus, when an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain obtained by the production process (I) or (II) and having a double bond equivalent of 350 g/mol or less is used, adhesion and resistance of the cured film are improved. Solvent resistance is remarkably excellent.
The alkali-soluble resin preferably has the following structure ((A) is optional).
Specifically, 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 preferred. The structural unit (B) is a structure derived from glycidyl (meth)acrylate.

（一般式（Ｂ１）中、Ｒ^１及びＲ^３は、同一又は異なって、水素原子又はメチル基を表す。Ｒ^２は、二価の結合基を表す。ａは、０又は１である。
一般式（Ｂ２）中、Ｒ^４は、水素原子又はメチル基を表す。Ｒ^５は、エチレン性不飽和結合含有基を表す。
一般式（Ｂ３）中、Ｒ^６は、水素原子又はメチル基を表す。Ｒ^７は、エチレン性不飽和結合含有基を表す。Ｘは、二価の炭化水素基を表す。）
上記構造単位（Ｂ）を与える（メタ）アクリル酸グリシジルは、重合により直接構造単位（Ｂ）を与えるものではなく、他の単量体成分由来の官能基と反応等して、上記構造単位（Ｂ）を形成しうる重合体原料である。すなわち、上記構造単位（Ｂ）は、（メタ）アクリル酸グリシジル由来の構造を有する。
上記一般式（Ｂ１）で表される構造単位を有する重合体は、上述した製造方法（Ｉ）の方法により得ることができる。
上記一般式（Ｂ２）で表される構造単位を有する重合体は、上述した製造方法（ＩＩ）の方法により得ることができ、好ましくは工程（ＩＩ－１）～（ＩＩ－２）の方法より得ることができる。
上記一般式（Ｂ３）で表される構造単位を有する重合体は、上述した製造方法（ＩＩ）の方法により得ることができ、好ましくは工程（ＩＩ－１）～（ＩＩ－３）の方法により得ることができる。
このような、上記製造工程（Ｉ）又は（ＩＩ）により得られる重合体（アルカリ可溶性樹脂）を含む組成物も本発明の一つである。
以下に、側鎖にエチレン性不飽和二重結合を有する二重結合当量３５０ｇ／ｍｏｌ以下のアルカリ可溶性樹脂を含む組成物の好ましい態様の一例について説明する。
<感光性樹脂組成物>
本発明の第２の形態である感光性樹脂組成物は、主鎖に（メタ）アクリレート骨格を有し、側鎖にエチレン性不飽和二重結合を有する二重結合当量３５０ｇ／ｍｏｌ以下のアルカリ可溶性樹脂、多官能モノマー、及び光重合開始剤を含むことが好ましい。
上記感光性樹脂組成物は、主鎖に（メタ）アクリレート骨格を有し、側鎖にエチレン性不飽和二重結合を有する二重結合当量３５０ｇ／ｍｏｌ以下のアルカリ可溶性樹脂を含むので、１６０℃以下、例えば９０℃程度の低温硬化条件下でも耐溶剤性に優れた硬化物を与えることができる。また、多官能モノマーを更に含むので、硬化性や、基材への密着性、表面硬度、耐熱性等の各種物性にも優れた硬化物を与えることができる。
なお、本明細書中、「固形分総量」とは、硬化物を形成する成分の総量、すなわち硬化物の形成時に揮発する溶媒等を除く成分（固形分、不揮発分）の総量を意味する。具体的には、アルカリ可溶性樹脂と、多官能モノマーと、更に他の硬化物形成成分（例えば、光重合開始剤、顔料分散体等）を含む場合は当該成分との合計の固形分質量を意味する。
本発明の感光性樹脂組成物において、上記アルカリ可溶性樹脂の含有量は、特に限定されず、用途や他成分の配合等に応じて適宜設定すればよいが、例えば、感光性樹脂組成物の固形分総量１００質量％に対して、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、１５質量％以上であることが更に好ましく、また、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることが更に好ましい。
上記二重結合当量３５０ｇ／ｍｏｌ以下のアルカリ可溶性樹脂を含むことで、活性エネルギー線の照射等により硬化性が大きく向上する。この特定の二重結合含有樹脂は、側鎖および／または末端にエチレン性不飽和二重結合を含んでいることが必須であるが、特に側鎖に二重結合を有することが好ましい。側鎖に二重結合を持たせることにより、熱や光で硬化させることができる。その為、レジスト用硬化性樹脂組成物（感光性樹脂組成物）としたときの光に対する感度が向上し、低い温度や少ない光量で硬化し、かつ硬化後の機械強度も高くなる。二重結合の含有量は、一般に二重結合当量であらわされ、二重結合当量が２００～３５０ｇ／ｍｏｌの範囲が好ましく、２３０～３３０ｇ／ｍｏｌの範囲がより好ましく、２５０～３００ｇ／ｍｏｌの範囲が特に好ましい。上記二重結合当量が上述の範囲であると、アルカリ可溶性樹脂の硬化性（熱、光に対する感度）が良好になり、硬化物の密着性が向上する。また、硬化性と保存安定性の両立が可能となる。
重量平均分子量は、特に制限されないが、レジスト用バインダー用途に好適に使用できる観点からは、５０００～２０００００、より好ましくは１１０００～１０００００、さらに好ましくは１４０００～５００００であるのがよい。特に本発明の樹脂は、重量平均分子量が１４０００以上である場合に、密着性に優れるという特徴が顕著に見られる。５０００未満であるとレジストバインダーとして使用した場合に、基板への密着性などが劣る場合がある。
上記アルカリ可溶性樹脂の分子量分布（Mw/Mn）は、４．０以下であることが好ましく、３．５以下であることより好ましく、３．０以下であることが特に好ましい。分子量分布が上記範囲であれば、高分子量成分が多いことによる現像性の低下や低分子量成分が多いことによる硬度の低下が抑制される。なお、分子量分布とは、（アルカリ可溶性樹脂の重量平均分子量（Ｍｗ））／（アルカリ可溶性樹脂の数平均分子量（Ｍｎ））によって求められるものである。分子量分布が小さいほど分子量分布の幅が狭い、分子量のそろったアルカリ可溶性樹脂となり、その値が１．０のとき最も分子量分布の幅が狭い。
上記アルカリ可溶性樹脂は、レジストバインダーとして使用される場合には酸価を有することが好ましい。その場合の酸価は、特に制限されないが、好ましくは２０～１５０ｍｇＫＯＨ／ｇ、より好ましくは５０～１００ｍｇＫＯＨ／ｇであるのがよい。アルカリ可溶性樹脂の酸価が上記範囲の場合、アルカリ物質による可溶性が充分となり、且つ高粘度となり過ぎず塗膜をより形成しやすくなる。
主鎖に（メタ）アクリレート骨格を有し、側鎖にエチレン性不飽和二重結合を有する二重結合当量３５０ｇ／ｍｏｌ以下のアルカリ可溶性樹脂の製造方法は、上述した製造方法を採用することが好ましく、（メタ）アクリレート系モノマーを必須成分として同様の原料を用いて重合し、側鎖に特定範囲のエチレン性不飽和二重結合を導入すればよい。その導入のための酸基とエポキシ基をエステル化反応させる温度は、特に制限されないが、８０℃～１４０℃が好ましい。この温度範囲に制御することで、反応の進行が早く、且つ発熱が大きすぎることなく反応中のゲル化を低減ないし無くすことができる。更に好ましくは、９０℃～１３０℃であり、最も好ましくは９０℃～１２０℃である。
また、反応温度は、装置のスケールや除熱能力等に応じて適切な反応速度が得られるように、小スケール予備試験等で予め反応速度を測定して決定することが好ましい。また、発熱が激しい反応初期は温度を低めに設定し、発熱が収まったのちに反応温度を上昇させ、反応速度を高くすることも好ましい製造方法である。
反応時間は、設定する反応温度、触媒量、反応速度、反応率等により決定されるが、工業的製造の観点からは、４８時間以内が好ましく、２４時間以内が更に好ましく、１２時間以内が最も好ましい。反応が長時間を要する場合、連続して反応させてもよいが、反応途中で一旦８０℃以下まで冷却して中断し、再度昇温して反応を継続させることも出来る。
さらに、上記酸基とエポキシ基の反応時には、禁止効果のあるガスを反応系中に導入したり、禁止剤を添加したりしてもよい。禁止効果のあるガスを反応系中に導入したり、禁止剤を添加したりすることにより、付加反応時のゲル化を防ぐことができる。禁止効果のあるガスとしては、空気、酸素・窒素混合ガス等があげられるが、爆発範囲を避けて安全に反応させることができる点で、５～１０体積％酸素濃度の酸素・窒素混合ガスをバブリングすることが好ましい。また、重合禁止剤としては、フェノール系重合禁止剤を添加することが好ましい。例えば、ハイドロキノン、メチルハイドロキノン、トリメチルハイドロキノン、ｔ－ブチルハイドロキノン、メトキノン、６－ｔ－ブチル－２，４－キシレノール、２，６－ジ－ｔ－ブチルフェノール、２，６－ジ－ｔ－ブチル－４－メトキシフェノール、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）等のフェノール系禁止剤が好適に使用される。フェノール系重合禁止剤の添加量は、溶媒を除く反応系全体に対して、１０質量ｐｐｍ～１質量％が好ましく、１００～３０００質量ｐｐｍが更に好ましい。更に、エステル化触媒を添加してもよい。エステル化触媒としては、トリエチルアミン、ジメチルベンジルアミン等のアミン類、トリエチルホスフィン、トリフェニルホスフィン等のホスフィン類、およびこれらのアミン類、ホスフィン類の塩、アミド化合物、金属塩化合物等である。

(In general formula (B1), R ¹ and R ³ are the same or different and represent a hydrogen atom or a methyl group. R ² represents a divalent bonding group. a is 0 or 1;
In general formula (B2), ^R4 represents a hydrogen atom or a methyl group. ^R5 represents an ethylenically unsaturated bond-containing group.
In general formula (B3), ^R6 represents a hydrogen atom or a methyl group. ^R7 represents an ethylenically unsaturated bond-containing group. X represents a divalent hydrocarbon group. )
Glycidyl (meth)acrylate that gives the structural unit (B) does not give the structural unit (B) directly by polymerization, but reacts with functional groups derived from other monomer components to form the structural unit ( B) is a polymer raw material capable of forming B). That is, the structural unit (B) has a structure derived from glycidyl (meth)acrylate.
A polymer having a structural unit represented by the general formula (B1) can be obtained by the production method (I) described above.
A polymer having a structural unit represented by the general formula (B2) can be obtained by the production method (II) described above, preferably by the method of steps (II-1) to (II-2). Obtainable.
A polymer having a structural unit represented by the general formula (B3) can be obtained by the production method (II) described above, preferably by the method of steps (II-1) to (II-3). Obtainable.
A composition containing such a polymer (alkali-soluble resin) obtained by the production step (I) or (II) is also one aspect of the present invention.
An example of a preferred embodiment of a composition containing an alkali-soluble resin having an ethylenically unsaturated double bond in the side chain and a double bond equivalent weight of 350 g/mol or less will be described below.
<Photosensitive resin composition>
A photosensitive resin composition according to a second aspect of the present invention is an alkali having a (meth)acrylate skeleton in the main chain and an ethylenically unsaturated double bond in the side chain and a double bond equivalent of 350 g/mol or less. It preferably contains a soluble resin, a polyfunctional monomer, and a photopolymerization initiator.
The photosensitive resin composition contains an alkali-soluble resin having a (meth)acrylate skeleton in the main chain and an ethylenically unsaturated double bond in the side chain and having a double bond equivalent of 350 g/mol or less. In the following, a cured product having excellent solvent resistance can be obtained even under low-temperature curing conditions of, for example, about 90°C. Moreover, since it further contains a polyfunctional monomer, it is possible to give a cured product excellent in various physical properties such as curability, adhesion to substrates, surface hardness and heat resistance.
In the present specification, the "total solid content" means the total amount of components forming the cured product, that is, the total amount of components (solid content, non-volatile content) excluding the solvent that volatilizes during the formation of the cured product. Specifically, when containing an alkali-soluble resin, a polyfunctional monomer, and other cured product-forming components (e.g., photopolymerization initiators, pigment dispersions, etc.), it means the total solid mass of the components. do.
In the photosensitive resin composition of the present invention, the content of the alkali-soluble resin is not particularly limited, and may be appropriately set according to the application and the blending of other components. It is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and 80% by mass or less with respect to the total amount of 100% by mass. is preferred, 75% by mass or less is more preferred, and 70% by mass or less is even more preferred.
By including the alkali-soluble resin having a double bond equivalent of 350 g/mol or less, curability is greatly improved by irradiation with active energy rays or the like. It is essential that this specific double bond-containing resin contains an ethylenically unsaturated double bond in the side chain and/or the end, but it is particularly preferred to have the double bond in the side chain. By giving the side chain a double bond, it can be cured by heat or light. Therefore, the curable resin composition for resist (photosensitive resin composition) has improved sensitivity to light, can be cured at a low temperature or a small amount of light, and has a high mechanical strength after curing. The double bond content is generally represented by the double bond equivalent, and the 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 more preferably in the range of 250 to 300 g/mol. is particularly preferred. When the double bond equivalent is within 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. In addition, it is possible to achieve both curability and storage stability.
Although the weight average molecular weight is not particularly limited, it is preferably 5,000 to 200,000, more preferably 11,000 to 100,000, and still more preferably 14,000 to 50,000 from the viewpoint of being suitable for use as a resist binder. In particular, when the resin of the present invention has a weight-average molecular weight of 14,000 or more, the characteristic of being excellent in adhesion is remarkably observed. If it is less than 5,000, adhesion to a substrate may be poor when used as a resist binder.
The molecular weight distribution (Mw/Mn) of the alkali-soluble resin is preferably 4.0 or less, more preferably 3.5 or less, and particularly preferably 3.0 or less. When the molecular weight distribution is within the above range, deterioration in developability due to a large amount of high molecular weight components and deterioration in hardness due to a large amount of low molecular weight components are suppressed. The molecular weight distribution is determined by (weight average molecular weight (Mw) of alkali-soluble resin)/(number average molecular weight (Mn) of alkali-soluble resin). The narrower the molecular weight distribution, the narrower the molecular weight distribution, the more uniform the molecular weight of the alkali-soluble resin. When the value is 1.0, the narrowest molecular weight distribution.
The alkali-soluble resin preferably has an acid value when used as a resist binder. Although the acid value in that case is not particularly limited, it is preferably 20 to 150 mgKOH/g, more preferably 50 to 100 mgKOH/g. When the acid value of the alkali-soluble resin is within the above range, the solubility with alkaline substances is sufficient, and the viscosity is not excessively high, making it easier to form a coating film.
As a method for producing an alkali-soluble resin having a (meth)acrylate skeleton in the main chain and an ethylenically unsaturated double bond in the side chain and having a double bond equivalent of 350 g/mol or less, the above-described production method can be adopted. Preferably, a (meth)acrylate-based monomer is used as an essential component and the same raw materials are used for polymerization to introduce a specific range of ethylenically unsaturated double bonds into the side chains. The temperature at which the acid group and the epoxy group are esterified for the introduction is not particularly limited, but is preferably 80°C to 140°C. By controlling the temperature within this range, the reaction proceeds quickly, and gelling during the reaction can be reduced or eliminated without excessive heat generation. It is more preferably 90°C to 130°C, most preferably 90°C to 120°C.
Moreover, the reaction temperature is preferably determined by measuring the reaction rate in advance in a small-scale preliminary test or the like so that an appropriate reaction rate can be obtained according to the scale of the apparatus, the heat removal capacity, and the like. In addition, it is also preferable to increase the reaction rate by setting the temperature lower at the initial stage of the reaction when the heat generation is intense, and then increasing the reaction temperature after the heat generation subsides.
The reaction time is determined by the set reaction temperature, amount of catalyst, reaction rate, reaction rate, etc. From the viewpoint of industrial production, it is preferably within 48 hours, more preferably within 24 hours, most preferably within 12 hours. preferable. When the reaction requires a long time, the reaction may be carried out continuously, but it is also possible to suspend the reaction by cooling it to 80° C. or lower once in the middle of the reaction, and then raise the temperature again to continue the reaction.
Furthermore, during the reaction between the acid group and the epoxy group, a gas having an inhibitory effect may be introduced into the reaction system, or an inhibitor may be added. Gelation during the addition reaction can be prevented by introducing a gas having an inhibitory effect into the reaction system or by adding an inhibitor. Gases with a prohibited effect include air, oxygen/nitrogen mixed gas, etc. However, oxygen/nitrogen mixed gas with an oxygen concentration of 5 to 10% by volume is recommended in that it can be reacted safely while avoiding the explosion range. Bubbling is preferred. Moreover, as a polymerization inhibitor, it is preferable to add a phenolic polymerization inhibitor. For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4 -Methoxyphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol) and other phenolic inhibitors are preferably used. The amount of the phenol-based polymerization inhibitor added is preferably 10 mass ppm to 1 mass %, more preferably 100 to 3000 mass ppm, relative to the entire reaction system excluding the solvent. Furthermore, an esterification catalyst may be added. Esterification catalysts include amines such as triethylamine and dimethylbenzylamine, phosphines such as triethylphosphine and triphenylphosphine, salts of these amines, phosphines, amide compounds, and metal salt compounds.

Next, polyfunctional monomers suitably contained in the photosensitive resin composition will be described.
Examples of the polyfunctional monomer include the following compounds.
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 Bifunctional (meth)acrylate compounds such as di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate; 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 ) 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)acrylates, 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 acrylates, 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) ) Trifunctional or higher polyfunctional (meth)acrylate compounds such as acrylate;
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, ditri Methylolpropane 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 Polyfunctional vinyl ethers such as added dipentaerythritol hexavinyl ether; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, (meth)acryl 2-vinyloxypropyl acid, 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-(vinyloxyethoxy)acrylate (meth) Vinyl ether group-containing (meth)acrylic acid esters such as ethoxyethoxy)ethyl;
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, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether; allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; tri(acryloyloxyethyl) isocyanate Polyfunctional (meth)acryloyl group-containing isocyanurates such as nurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; triallyl polyfunctional allyl group-containing isocyanurates such as isocyanurate; polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate; polyfunctional urethane (meth)acrylates obtained by reaction with hydroxyl group-containing (meth)acrylates; polyfunctional aromatic vinyls such as divinylbenzene;

A bifunctional or higher polyfunctional (meth)acrylate compound, which is a particularly preferred polyfunctional monomer, will be described in detail below.
A bifunctional or higher polyfunctional (meth)acrylate compound (hereinafter also simply referred to as a “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 functionality of the polyfunctional (meth)acrylate compound is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more. Moreover, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.
The (meth)acryloyl group means a methacryloyl group and/or an acryloyl group, but an acryloyl group is preferable from the viewpoint of excellent reactivity. That is, the polyfunctional (meth)acrylate compound is particularly preferably a polyfunctional acrylate compound having two or more acryloyl groups.

The content of the polyfunctional monomer may be appropriately set according to the type of the polyfunctional monomer and the alkali-soluble resin used, as well as the purpose and application. It is preferably 2 parts by mass or more and preferably 85 parts by mass or less with respect to 100 parts by mass of the total solid content of the 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, and particularly preferably. is 50 parts by mass or less, most preferably 40 parts by mass or less.
Moreover, 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 having higher adhesion and hardness can be obtained, and the developability is further improved, coupled with the preferable weight average molecular weight of the alkali-soluble resin being 5000 or more. will be More preferably, it is 80 parts by mass or more. Moreover, from the viewpoint of further improving developability, it is more preferably 400 parts by mass or less. More preferably 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 components described above. The photopolymerization initiator is preferably a radically polymerizable photopolymerization initiator. Radically polymerizable photopolymerization initiators are those that generate polymerization initiation radicals by irradiation with active energy rays such as electromagnetic waves and electron beams, and one or more of commonly used ones can be used. . Moreover, you may use together 1 type(s) or 2 or more types of a photosensitizer, a photoradical polymerization accelerator, etc. as needed. Sensitivity and curability are further improved by using a photosensitizer and/or a photoradical polymerization accelerator together with the photopolymerization initiator.

Although the photopolymerization initiator is not particularly limited, 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 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-methylthio Phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-( α-, such as 4-dimethylaminophenyl)-butan-1-one, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morphonyl)phenyl]-1-butanone Aminoketone compounds; 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 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-morpholinopropan-1-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;
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, and other halomethylated triazine compounds 2-trichloromethyl-5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4- Halomethylated oxadiazole compounds such as oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 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, Biimidazole compounds such as 2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]-,1-(O-acetyloxime) and other oxime ester compounds; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole) -1-yl)-phenyl) titanocene compounds such as titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; 1-hydroxycyclohexylphenyl Ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy- α-hydroxyketone compounds such as 2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one;
Among the above photopolymerization initiators, it is particularly preferable to use at least an oxime initiator such as the above oxime ester compound from the viewpoint of improving adhesion and fine pattern processability.
The content ratio of the photopolymerization initiator is not particularly limited, and it is preferable to set it appropriately in consideration of the ratio of other components such as a coloring material. , preferably 0.05 to 40 parts by mass. This further enhances the curability and solvent resistance. More preferably 0.5 to 30 parts by mass, still more preferably 1.5 to 20 parts by mass. Examples of photosensitizers and photoradical polymerization accelerators that may be used in combination with the photopolymerization initiator include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyrromethene dyes; dialkylaminobenzene-based compounds such as ethyl dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole; be done. The content (total amount) of the photosensitizer and the photoradical polymerization accelerator may be appropriately set according to the purpose and application, and is not particularly limited. From the point of view, 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 0.01 to 15 parts by mass, still more preferably 0.05 to 10 parts by mass.
The oxime initiator particularly preferably used in the present invention is described in detail below.
Oxime-based initiators are preferred because they have high sensitivity and high polymerization efficiency, can be cured regardless of the colorant (colorant) concentration, and are easy to design with a high colorant concentration.
Specific examples of the oxime-based initiator include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166. Specific examples of oxime initiators include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyiminopentane. -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.

As an oxime initiator, J.P. 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, compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, and compounds described in JP-A-2006-342166. be done.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also commercially available. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO. LTD), Adeka Arcles NCI-930 (manufactured by ADEKA) can also be used.

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

An oxime-based initiator having a fluorene ring can also be used as the radical photopolymerization initiator. Specific examples of the oxime initiator having a fluorene ring include compounds described in JP-A-2014-137466. The contents of which are incorporated herein.

An oxime-based initiator having a fluorine atom can also be used as the radical photopolymerization initiator. Specific examples of the oxime-based initiator having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. Examples include compound (C-3) described above. The contents of which are incorporated herein.

An oxime initiator having a nitro group can be used as the radical photopolymerization initiator. 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 and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466; Adeka Arcles NCI-831 (manufactured by ADEKA) can be mentioned.
The oxime-based initiator is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in the wavelength range of 360 nm to 480 nm, and particularly preferably a compound having high absorbance at 365 nm and 405 nm. .

The molar extinction coefficient of the oxime initiator at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 300,000, from the viewpoint of sensitivity. 200,000 is particularly preferred. A known method can be used to measure the molar extinction coefficient of a compound. 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 compound concentration of 0.01 g/L.

The oxime initiators may be used in combination of two or more as needed.

The content of the oxime initiator is preferably 0.05 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, and still more preferably 1 part by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. to 25 parts by mass, most preferably 1.5 to 20 parts by mass. Within this range, better sensitivity and fine pattern formability can be obtained.
The photosensitive resin composition of the present invention also preferably contains a coloring material in addition to the components described above. As the coloring material, for example, pigments and dyes are preferably used. These may be used alone or in combination of two or more. Also, a pigment and a dye may be combined. For example, when forming red, blue, and green pixels of a color filter, a method of combining color materials such as blue and purple, green and yellow, and the like to exhibit desired color characteristics is preferably used. Also, when forming a black matrix, it can be formed using a black coloring material.
Among the above pigments and dyes, pigments (e.g., organic pigments or inorganic pigments) are superior in terms of durability, and dyes are superior in terms of improving brightness of panels, etc. These may be selected or used together. Among pigments, organic pigments are more preferable.
Examples of the above pigments include azo pigments, phthalocyanine pigments, polycyclic pigments (e.g., quinacridone-based, perylene-based, perinone-based, isoindolinone-based, isoindoline-based, dioxazine-based, thioindigo-based, anthraquinone-based, and quinophthalone-based pigments). , metal complex-based, diketopyrrolopyrrole-based, etc.), organic pigments such as dye lake-based pigments; Color pigments (e.g. yellow lead, cadmium-based, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine blue, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.) , black pigments (e.g. carbon black, bone black, graphite, iron black, titanium black, etc.), luster pigments (e.g. pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (e.g. zinc sulfide, strontium sulfide, strontium aluminate etc.) and other inorganic pigments. The colors of pigments that can be used include yellow, red, purple, blue, green, brown, black, and white.
The above 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, and wax coating, depending on the purpose and application.
Specific examples of the above-mentioned pigments are shown below by color by color index (C.I.; published by The Society of Dyers and Colourists) number, but the colorant of the present invention is not limited to these. Moreover, these may be used individually and may be used in combination of 2 or more types. The following "C.I." means Color Index, and the numbers mean Color Index Number.
Examples of yellow pigments include C.I. 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 and the like.
Examples of orange pigments include C.I. 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 and the like.
Examples of purple pigments include C.I. 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 and the like.
Examples of red pigments include C.I. 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 and the like.
Examples of blue pigments include C.I. 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 and the like.
Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like.
Examples of brown pigments include C.I. I. Pigment Brown 5, 6, 23, 24, 25, 32, 41, 42 and the like.
Examples of black pigments include aniline black, carbon black, lamp black, bone black, black iron, titanium black, C.I. I. Pigment Black 1, 6, 7, 9, 10, 11, 12, 13, 20, 31, 32, 34 and the like. Examples of white pigments include C.I. I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28 and the like.
Examples of the dye include organic dyes described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599. can. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable. When a dye is used as the colorant, it can be uniformly dissolved in the photosensitive resin composition to obtain, for example, a color filter resist composition. Dyes that can be used are not particularly limited, and conventionally known dyes for color filters can be used.
The content ratio of the coloring material (that is, the total ratio of the pigment and the dye) can be appropriately set according to the purpose and application, but the preferred range of the content ratio of the coloring material is the solid content of the photosensitive resin composition. It is 3 to 70 parts by mass with respect to 100 parts by mass of the total amount. More preferably 5 to 60 parts by mass, still more preferably 10 to 50 parts by mass.
The photosensitive resin composition of the present invention can also contain radically polymerizable oligomers and radically polymerizable monomers in addition to the above-described alkali-soluble resins and polyfunctional monomers. Unsaturated polyesters, epoxy acrylates, urethane acrylates, polyester acrylates and the like can be used as radically polymerizable oligomers.
Radical polymerizable monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; and vinyl ester monomers such as vinyl acetate and vinyl adipate. 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)acrylic monomers such as meth)acrylate and tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; triallyl cyanurate and the like can be used. These are appropriately selected according to the required properties, and one or more of them can be used.
The photosensitive resin composition of the present invention preferably contains a solvent. A solvent is preferably used as a diluent or the like. That is, specifically, it is preferably used for lowering viscosity and improving handleability; forming a coating film by drying; serving as a dispersion medium for coloring materials; is a low-viscosity organic solvent or water capable of dissolving or dispersing each component of . As the solvent, one commonly used can be used, and it may be appropriately selected according to the purpose and application, and is not particularly limited. Examples include methanol, ethanol, isopropanol, n-butanol, s-butanol, and the like. Monoalcohols; 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; ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate , 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethyl sulfoxide; and 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 solvent is preferably 10 to 90 mass % with respect to 100 mass % of the total amount of the photosensitive resin composition. More preferably, it is 20 to 80% by mass.
The total solid content excluding the solvent in 100% by mass of the photosensitive resin composition is more preferably 5 to 70% by mass, still more preferably 10 to 50% by mass.
The photosensitive resin composition of the present invention preferably also contains a dispersant. Although the dispersant is not particularly limited, for example, it has an interaction site for the coloring material and an interaction site for the dispersion medium (alkali-soluble resin, solvent, etc.), and stabilizes the dispersion of the coloring material in the dispersion medium. It is preferable to have the function of In general, dispersants that are classified into resin-type dispersants (polymeric dispersants), surfactants (low-molecular-weight dispersants), and pigment derivatives and that are commonly used may be used.
Examples of the resin-type dispersant include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , long-chain polyaminoamide phosphates, hydrogen group-containing polycarboxylic acid esters, amides and salts thereof formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/polypropylene oxide adducts, etc. mentioned. Among them, from the structural point of view, the main chain is an anchor chain having an interaction site with the coloring material, and the graft chain is a compatible chain having interaction with the dispersion medium. A resin having a block structure with a compatible chain is particularly preferably used.
Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions 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 alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazoline;
The dye derivative is a compound having a structure in which a functional group is introduced into a dye. Examples of functional groups include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, dialkylamino groups, hydroxyl groups, carboxyl groups, amide groups, and phthalimide groups. Azo type, anthraquinone type, quinophthalone type, phthalocyanine type, quinacridone type, benzimidazolone type, isoindoline type, dioxazine type, indanthrene type, perylene type and diketopyrrolopyrrole type.

The content of the dispersant is not particularly limited, and may be appropriately set according to the purpose and application. , 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 coloring material. More preferably 0.1 to 90 parts by mass, still more preferably 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-resistant improvers; leveling agents; coupling agents; development aids; aluminum hydroxide, talc, clay, fillers such as barium sulfate; Dot Particle; Sensitizer; Release Agent; Lubricant; Plasticizer; Antioxidant; Flame Retardant; Polymerization Inhibitor; stabilizers; flame retardant aids; curing aids such as polyfunctional thiol compounds; fluorine-based additives; cationic polymerizable compounds;
The amount of the above-mentioned other components used may be appropriately set according to the purpose and application, but for example, it is preferably 0 to 70 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition. More preferably 0.01 to 70 parts by mass, still more preferably 0.1 to 60 parts by mass, and particularly preferably 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 components described above using various mixers or dispersers. The dispersing step and the mixing step are not particularly limited, and may be carried out by ordinary methods, and may further include other steps that are usually carried out. When the photosensitive resin composition contains a colorant, it is preferably prepared through known steps such as a colorant dispersion treatment step. Specifically, for example, after preparing a coloring material dispersion (millbase) containing a coloring material, a dispersant, a binder resin (such as an alkali-soluble resin) and a solvent, a polyfunctional monomer, a photopolymerization initiator, and a binder are added. It is preferable to prepare by adding a transparent resist solution (also called a clear resist solution) containing a resin (such as an alkali-soluble resin) and a solvent. The resulting photosensitive resin composition is preferably filtered using a filter or the like to remove fine dust.
In preparing the colorant dispersion, it is preferable to disperse the colorant into fine particles using a dispersing machine such as a paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, or blender. More preferably, after kneading and dispersing with a roll mill, kneader, blender, etc., finely dispersing with a media mill such as a bead mill filled with beads of 0.01 to 1 mm.

<Cured product>
A cured product obtained by curing the photosensitive resin composition of the present invention has excellent solvent resistance. A cured product of such a photosensitive resin composition is also one aspect of the present invention.
When the cured product is a cured film, the film thickness is preferably 0.1 μm or more. When the film thickness is 0.1 μm or more, even better solvent resistance can be exhibited. The film thickness is more preferably 0.5 μm or more, and even more preferably 1 μm or more. The upper limit of the film thickness is not particularly limited, and may be appropriately set according to the purpose and application of the cured film. It is even more preferable to have
The method for obtaining the cured product is not particularly limited, and a known method may be used. For example, the photosensitive resin composition is coated on a substrate, or the molded product is dried, heated, or exposed to ultraviolet light. A method of obtaining a cured product by curing by irradiation with an energy beam such as the above, or a combination thereof.
By using the photosensitive resin composition of the present invention, a cured product having excellent solvent resistance can be obtained even under low-temperature curing conditions. Examples of the method for producing such a cured product include, for example, a step of applying the photosensitive resin composition on a substrate to form a coating film, a step of irradiating the formed coating film with light, and light irradiation A preferred method includes a step of heating the coated film at a temperature of 150° C. or less. That is, the present invention is also a method for producing a cured product, which includes the step of curing the photosensitive resin composition at a temperature of 150° C. or lower.
The base material is not particularly limited, and may be appropriately selected according to the purpose and application. Examples thereof include base materials made of various materials such as a glass plate and a plastic plate.
The method of applying the photosensitive resin composition to form a coating film is not particularly limited, and known methods such as spin coating, slit coating, roll coating and cast coating can be used.
In the production method described above, it is preferable to form a coating film by coating the photosensitive resin composition on a substrate and then drying the coating. The drying can be performed by a known method, and specifically, it can be performed by a method similar to the drying method described in the "arrangement step" of "<color filter manufacturing method>" described later.
The manufacturing method includes a step of irradiating the coating film with light after forming the coating film.
The method of irradiating the coating film formed above with light is not particularly limited, and can be carried out by a known method. can be carried out in a manner similar to that described in .
When the coating film is irradiated with light, the light irradiation may be performed through a photomask. As a photomask, a mask in which a light-shielding portion is formed according to an intended pattern is preferably used. When light irradiation is performed through a photomask, it is preferable to perform a development step after that. A desired pattern can be formed on the coating film by performing the development step. The development method is not particularly limited, and can be carried out by a known method. Specifically, it is carried out by the same method as described in "Development step" in "<Color filter manufacturing method>" described later. be able to.
The manufacturing method also includes a step of heating the irradiated coating film at 150° C. or less.
That is, the present invention is also a method for producing a cured product, which includes the step of curing the photosensitive resin composition at a temperature of 150° C. or lower.
Since the above production 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 less.
The heating temperature is preferably 145° C. or lower, more preferably 140° C. or lower. The lower limit of the heating temperature is preferably 70° C. or higher, more preferably 90° C. or higher, from the viewpoint of maintaining curability.
The heating method other than the temperature is not particularly limited, and can be performed by a known method. It can be carried out.

<Application>
The photosensitive resin composition of the present invention undergoes a sufficient curing reaction even under low-temperature curing conditions of 150° C. or lower, for example, about 90° C., and can give a cured product with excellent solvent resistance. Therefore, it can be suitably used in applications that require sufficient curing under low-temperature conditions and applications that require solvent resistance.
Specifically, the photosensitive resin composition of the present invention is, for example, a color filter, a black matrix, a photo Spacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, films, organic protective films, etc. can be used. Among them, it is preferably used for color filter applications.
The photosensitive resin composition of the present invention is suitably used as an optical material, and is also suitably used as a negative type.
<Color filter>
A color filter having a cured product of the above photosensitive resin composition on a substrate is also one of preferred embodiments of the present invention.
In the above-mentioned color filter, the cured product formed from the above-mentioned photosensitive resin composition is particularly suitable as, for example, a black matrix or a segment that requires coloring such as each pixel of red, green, blue, yellow, etc. However, it is also suitable for segments that do not necessarily require coloring, such as photospacers, protective layers, and alignment control ribs.
Examples of the substrate used in the color filter include glass substrates such as white plate glass, soda plate glass, alkali-strengthened glass, silica-coated soda plate glass; Sheets, films or substrates made of thermoplastic resins such as additives; 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 a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member composed of various materials such as a glass substrate having a coloring material layer on its surface (for example, a color filter for LCD); Among them, a glass substrate and a sheet, film or substrate made of a heat-resistant resin are preferable from the viewpoint of heat resistance. Also, the substrate is preferably a transparent substrate.
If necessary, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a silane coupling agent, or the like.
<Manufacturing method of color filter>
In order to obtain the color filter, for example, for each pixel color (that is, for each pixel of one color), a step of disposing the above-described photosensitive resin composition on a substrate (also referred to as an arrangement step), A step of irradiating the arranged photosensitive resin composition with light (also referred to as a light irradiation step), a step of developing with a developer (also referred to as a developing step), and a step of heat treatment (also referred to as a heating step). It is preferable to employ a manufacturing method that employs a technique that includes a single color and then repeats the same technique for each color. Note that the order in which the pixels of each color are formed is not particularly limited.
(1) Placement step (preferably coating step)
The placement step is preferably performed by coating. Examples of the method for applying the photosensitive resin composition on the substrate include spin coating, slit coating, roll coating, casting coating, and the like, and any of these methods can be preferably used.
In the placement 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, or the like. 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 the drying can be performed at a temperature of 50 to 160° C. for 10 to 300 seconds. preferred.
(2) Light irradiation step In the light irradiation step, the light source of actinic rays used includes, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, Lamp light sources such as carbon arcs and fluorescent lamps, laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers are used. As for the system of the exposure machine, there are a proximity system, a mirror projection system, and a stepper system, and the proximity system is preferably used.
In addition, in the step of irradiating the active energy beam, depending on the application, the active energy beam may be irradiated through a predetermined mask pattern. In this case, the exposed portion is cured, and the cured portion becomes insoluble or slightly soluble in the developer.
(3) Development process The development process described above is a process in which, after the light irradiation process described above, development is performed with a developer to remove the unexposed portions to form a pattern. Thereby, a patterned cured film can be obtained. Development can be carried out at a development temperature of generally 10 to 50° C. by methods such as immersion development, spray development, brush development and ultrasonic development.
The developer used in the development step is not particularly limited as long as it dissolves the photosensitive resin composition, but usually an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may also be used. In addition, when using alkaline aqueous solution as a developer, it is preferable to wash with water after development. Examples of the organic solvent and alkaline aqueous solution include those described in JP-A-2015-157909.
(4) Heating step The heating step is a step (also referred to as a "post-curing step") of further hardening the exposed portion (cured portion) by baking after the above-described developing step. Examples include a step of post-exposure with a light amount of 0.5 to 5 J/cm ² using a light source such as a high-pressure mercury lamp, and a step of post-heating at a temperature of 60 to 200° C. for 10 seconds to 120 minutes. be done. By performing such a post-curing step, it is possible to further increase the hardness and adhesion of the patterned cured film.
The heating step is generally carried out at a temperature of about 200 to 260° C., but if the photosensitive resin composition is used, the heating process can be performed under relatively low temperature conditions of 200° C. or less, preferably 160° C. or less. Sufficient curing can be performed. Therefore, it is possible to obtain excellent solvent resistance without impairing the properties held by the substrate or the cured product.
In the heating step, the heating temperature is preferably 160° C. or lower, more preferably 155° C. or lower, and even more preferably 150° C. or lower. Moreover, the heating temperature is preferably 70° C. or higher, more preferably 90° C. or higher, and even more preferably 95° C. or higher.
The heating time in the heating step is not particularly limited, but is preferably 5 to 60 minutes, for example. Moreover, the heating method is not particularly limited, either, but for example, it can be performed using a heating device such as a hot plate, a convection oven, or a high-frequency heater.
The thickness of the cured film obtained by the heating step (that is, the cured coating film obtained by thermally curing the photosensitive resin composition) is preferably 0.1 to 20 μm. The film thickness is more preferably 0.5 to 15 μm, still more preferably 1 to 10 μm.
<Display device>
A display device including the color filter described above is also one of preferred embodiments of the present invention. A member for a display device and a display device having a cured product of the photosensitive resin composition are also included in preferred embodiments of the present invention. The cured product (cured film) formed from the photosensitive resin composition is stable, has excellent adhesion to a substrate, etc., has high hardness, exhibits high smoothness, and has high transmittance. Therefore, 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 display device, for example, a liquid crystal display device, a solid-state imaging device, a touch panel display device, or the like is suitable.
When the cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multilayer member composed of the cured film, or the single-layer or multilayer It may be a member in which another layer is further combined with the member of (1), or a member including the cured film in its configuration.
As described above, the photosensitive resin composition (curable resin composition) of the present invention can give a cured product having excellent solvent resistance even under low-temperature curing conditions. The photosensitive resin composition of the present invention can be used as various optical members and structural members used in liquid crystal, organic EL, quantum dot, micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, etc. can be suitably used for various applications.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples do not limit the present invention, and all modifications and implementations without departing from the spirit of the present invention are included in the technical scope of the present invention. be done.
Hereinafter, the present invention will be specifically described by way of examples, comparative examples, and characteristic evaluations. In the examples and comparative examples, % means % by mass and part means part by mass unless otherwise specified. Moreover, the weight (% by weight) measured in the present invention is the same value as the mass (% by mass).
[Evaluation method]
(1) weight average molecular weight (Mw)
HLC-8220GPC (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent, column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) by GPC (gel permeation chromatography) method Weight average molecular weight (Mw), number Average molecular weight (Mn) was measured.
(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 a 0.1 N KOH aqueous solution as a titrant. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per gram of solid content (mgKOH/g) was determined from the acid value of the solution and the solid content of the solution.
(3) Solid content About 1 g of the polymer solution was weighed into an aluminum cup, and about 3 g of acetone was added to dissolve it, followed by natural drying at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Co., Ltd.), it was dried under vacuum at 140° C. for 1.5 hours, then allowed to cool in a desiccator, and the mass was measured. The solid content (% by mass) of the polymer solution was calculated from the mass reduction amount.
(4) GMA/AA conversion (wt% of monomers consumed)
The amount of unreacted monomer in the reactor was determined by a known method using gas chromatography. The conversion rate was obtained by subtracting the unreacted monomer amount (%) from 100 (%).
(5) Double bond equivalent (g/mol)
It was obtained by dividing the mass (g) of the polymer solid content by the double bond amount (mol) of the polymer.
(6) The solvent-resistant photosensitive resin composition is spin-coated on a 5 cm square glass substrate, dried at 100°C for 3 minutes, and then exposed at 200 mJ using a high-pressure mercury lamp at 90°C or 110°C. A heat treatment (post-curing) was performed for 40 minutes to obtain a cured film having a 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. (manufactured), and the absorbance was measured and evaluated according to the following criteria. The larger the absorbance value, the more coloring material was eluted into the immersion liquid, and the lower the solvent resistance of the photosensitive resin composition was evaluated.
(Evaluation criteria)
◎: Absorbance value is less than 0.2 ○: Absorbance value is 0.2 or more and less than 0.4 ×: Absorbance value is 0.4 or more (7) Residue during development On a glass substrate of 10 cm square, photosensitive The resin composition was applied by a spin coater and dried in an oven at 90°C for 3 minutes. After drying, the entire surface of the coating film was irradiated with ultraviolet rays at an intensity of 100 mJ/cm2 (365 nm illuminance conversion) using a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON) equipped with a 2.0 kW ultra-high pressure mercury lamp. After the ultraviolet irradiation, a 0.05% potassium hydroxide aqueous solution was sprayed on the coating film for 20 seconds using a spin developing machine, and then washed with pure water for 10 seconds.
After that, it was heated in an oven at 230° C. for 30 minutes.
The presence or absence of residues was confirmed using a laser microscope (trade name “VK-9700”, manufactured by Keyence Corporation).
An alkali-soluble resin (polymer solution) was prepared as follows.
[Example 1] Polymer solution (A-1)
183 parts of propylene glycol monomethyl ether acetate (PGMEA) and 84 parts of propylene glycol monomethyl ether (PGME) were charged into a separable flask equipped with a cooling tube as a reactor, and the temperature was raised to 90° C. under a nitrogen atmosphere. On the other hand, 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 the dropping tank 1. bottom. In the dropping tank 2, 6 parts of n-dodecyl mercaptan and 14 parts of PGMEA were mixed. Each was fed continuously over 3 hours. After maintaining the temperature at 90°C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90°C for 30 minutes. After that, 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 glycidyl methacrylate (GMA), 0.3 parts of 6-t-butyl-2,4-xylenol, and 0.6 parts of triethylamine (TEA) were added, and the oxygen concentration was 7%. The temperature was raised to 90° C. while bubbling a nitrogen/air mixed gas adjusted to Thereafter, the temperature was raised to 110° C. and the reaction was carried out for 10 hours to complete the reaction, and the mixture was cooled to room temperature to obtain a polymer solution (A-1). Various physical properties of the obtained polymer solution (A-1) were measured. The heavy 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 equipped with a cooling tube as a reactor, 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 the dropping tank 1 . In the dropping tank 2, 4.5 parts of n-dodecyl mercaptan and 15.5 parts of PGMEA were mixed. Each was fed continuously over 3 hours. After maintaining the temperature at 90°C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90°C for 30 minutes. After that, the temperature was raised to 115° C. and the polymerization was continued for 1.5 hours. After cooling to room temperature, 98.6 parts of GMA, 0.3 parts of 6-t-butyl-2,4-xylenol, and 0.6 parts of TEA are added, and a nitrogen/air mixed gas adjusted to an oxygen concentration of 7% is bubbled. Then, the temperature was raised to 90° C. and the reaction was carried out for 4 hours. After that, the temperature was raised to 110° C. and the reaction was carried out for 16 hours to complete the reaction and cooled to room temperature to obtain a polymer solution (A-2). Various physical properties of the obtained polymer solution (A-2) were measured. The heavy bond equivalent was 290 g/mol.
[Example 3] Polymer solution (A-3)
168 parts of PGMEA and 78 parts of PGME were charged into a separable flask equipped with a cooling tube as a reactor, and the temperature was raised to 90° C. in 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 are mixed in the dropping tank 1. bottom. 7 parts of n-dodecyl mercaptan and 13 parts by mass of PGMEA were mixed in the dropping tank 2 . Each was fed continuously over 3 hours. After maintaining the temperature at 90°C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90°C for 30 minutes. After that, the temperature was raised to 115° C. and the polymerization was continued for 1.5 hours. After cooling to room temperature, 98.6 parts of GMA, 0.3 parts of 6-t-butyl-2,4-xylenol, and 0.6 parts of TEA are added, and a nitrogen/air mixed gas adjusted to an oxygen concentration of 7% is bubbled. Then, the temperature was raised to 90° C. and the reaction was carried out for 4 hours. After that, the temperature was raised to 110° C. and the reaction was carried out for 16 hours to complete the reaction and cooled to room temperature to obtain a polymer solution (A-3). When various physical properties were measured for the obtained polymer solution (A-3), the weight average molecular weight was 11500, Mw/Mn was 2.7, and the acid value per solid content determined by titration was 42 mgKOH/g. The heavy bond equivalent was 290 g/mol.
[Example 4] Polymer solution (A-4)
120 parts of PGMEA and 59 parts of PGME were introduced into a separable flask equipped with a cooling tube as a reactor, and the temperature was raised to 90° C. under a nitrogen atmosphere. On the other hand, 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 the dropping vessel 1. 2 parts of n-dodecyl mercaptan and 18 parts by mass of PGMEA were mixed in the dropping tank 2 . Each was fed continuously over 3 hours. After maintaining the temperature at 90°C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90°C for 30 minutes. After that, the temperature was raised to 115° C. and the polymerization was continued for 1.5 hours. After cooling to room temperature, 78.9 parts of GMA, 0.3 parts of 6-t-butyl-2,4-xylenol, and 0.6 parts of TEA were added, and a nitrogen/air mixed gas adjusted to an oxygen concentration of 7% was bubbled. Then, the temperature was raised to 90° C. and the reaction was carried out for 4 hours. Thereafter, the temperature was raised to 110° C. and the reaction was allowed to proceed for 10 hours to complete the reaction, and the mixture was cooled to room temperature to obtain a polymer solution (A-4). When various physical properties were measured for the obtained polymer solution (A-4), the weight average molecular weight was 19000, Mw/Mn was 3.7, and the acid value per solid content determined by titration was 73 mgKOH/g. The heavy bond equivalent was 330 g/mol.
[Example 5] Polymer solution (A-5)
161 parts of PGMEA and 117 parts of PGME were charged into a separable flask equipped with a cooling tube as a reactor, 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 the dropping tank 1 . 6 parts of n-dodecyl mercaptan and 14 parts by mass of PGMEA were mixed in the dropping tank 2 . Each was fed continuously over 3 hours. After maintaining the temperature at 90°C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90°C for 30 minutes. After that, the temperature was raised to 115° C. and the polymerization was continued for 1.5 hours. After cooling to room temperature, 96.6 parts of GMA, 0.3 parts of 6-t-butyl-2,4-xylenol, and 0.6 parts of TEA are added, and a nitrogen/air mixed gas adjusted to an oxygen concentration of 7% is bubbled. Then, the temperature was raised to 90° C. and the reaction was carried out for 7 hours. Then, 41.4 parts of GMA was added to the reactor, heated to 95° C. and reacted for 7 hours, further heated to 110° C. and reacted for 6 hours to complete the reaction, cooled to room temperature, and polymer solution was obtained. (A-5) was obtained. Various physical properties of the obtained polymer solution (A-5) were measured. The heavy bond equivalent was 250 g/mol.
[Example 6] Polymer solution (A-6)
179 parts of PGMEA was charged into a separable flask equipped with a cooling tube as a reactor, 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 a dropping tank. Feed continuously over 3 hours. After that, the temperature was kept at 90° C. for 1 hour. After that, the temperature was raised to 115° C. and the polymerization was continued for 1.5 hours.
After cooling to room temperature, 33 parts of AA, 0.4 parts of dimethylbenzylamine, and 0.1 parts of a polymerization inhibitor (Antage (registered trademark) W400, manufactured by Kawaguchi Chemical Industry Co., Ltd.) were added to adjust the oxygen concentration to 7%. The temperature was raised to 90° C. while bubbling a mixed gas of nitrogen and air, and the reaction was carried out for 4 hours. After that, the temperature was raised to 110° C. and the reaction was carried out for 10 hours to complete the reaction.
Then, the mixture was cooled to room temperature, 9 parts of succinic anhydride (SAH) was added, reacted at 110° C. for 5 hours, and then cooled to room temperature to obtain a polymer solution (A-6).
Various physical properties of the obtained polymer solution (A-6) were measured. The heavy bond equivalent was 310 g/mol.
[Comparative Example 1] Polymer solution (A-7)
183 parts of PGMEA and 84 parts of PGME were charged into a separable flask equipped with a cooling tube as a reactor, and the temperature was raised to 90° C. under a nitrogen atmosphere. On the other hand, 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 the dropping tank 1 . In the dropping tank 2, 6 parts of n-dodecyl mercaptan and 14 parts of PGMEA were mixed. Each was fed continuously over 3 hours. After maintaining the temperature at 90°C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90°C for 30 minutes. After that, the temperature was raised to 115° C. and the polymerization was continued for 1.5 hours. After cooling to room temperature, 98.6 parts of GMA, 0.3 parts of 6-t-butyl-2,4-xylenol, and 0.6 parts of TEA are added, and a nitrogen/air mixed gas adjusted to an oxygen concentration of 7% is bubbled. The temperature was raised to 110° C. while the temperature was low, and the reaction was allowed to proceed for 9 hours to complete the reaction. After cooling to room temperature, a polymer solution (A-7) was obtained. Various physical properties of the obtained polymer solution (A-7) were measured. The heavy bond equivalent was 300 g/mol.
A transparent solution was obtained with the polymer solution (A-7), but the molecular weight distribution was larger than that of the polymer solution (A-1).
[Comparative Example 2] Polymer solution (A-8)
148 parts of PGMEA and 71 parts of PGME were charged into a separable flask equipped with a cooling tube as a reactor, and the temperature was raised to 90° C. in a nitrogen atmosphere. On the other hand, 65 parts of MMA, 35 parts of AA, and 2 parts of PBO were mixed in the dropping tank 1 . 1 part of n-dodecyl mercaptan and 19 parts by mass of PGMEA were mixed in the dropping tank 2 . Each was fed continuously over 3 hours. After maintaining the temperature at 90°C for 30 minutes, 0.5 part of PBO was added, and the reaction was continued at 90°C for 30 minutes. After that, the temperature was raised to 115° C. and the polymerization was continued for 1.5 hours. After cooling to room temperature, 59 parts of GMA, 0.3 parts of 6-t-butyl-2,4-xylenol, and 0.5 parts of TEA were added, and while bubbling a nitrogen/air mixed gas adjusted to an oxygen concentration of 7%. The temperature was raised to 110° C. and the reaction was allowed to proceed for 7 hours to complete the reaction and cooled to room temperature to obtain a polymer solution polymer solution (A-8). When various physical properties were measured for the polymer solution (A-8) obtained, the weight average molecular weight was 19000, Mw/Mn was 3.8, and the acid value per solid content determined by titration was 93 mgKOH/g. The heavy bond equivalent was 390 g/mol.
Table 1 shows the production conditions and physical property evaluation results (Examples 1 to 6 and Comparative Examples 1 and 2).

（実施例７～１２、比較例３～４）
得られたアルカリ可溶性樹脂溶液（重合体溶液Ａ－１～Ａ－８）を用いて、下記の方法で感光性樹脂組成物を調製し、上述した評価方法にて耐溶剤性及び現像時残渣を評価した。結果を表２に示す。
（顔料分散体１の調製）
ＰＧＭＥＡを１２．９部、分散剤としてディスパロンＤＡ－７３０１を０．４部、色材としてＣ．Ｉ．ピグメントグリーン５８を２．２５部、及び、Ｃ．Ｉ．ピグメントイエロー１３８を１．５部混合し、ペイントシェーカーにて３時間分散することで顔料分散体１（固形分２２質量％）を得た。
（感光性樹脂組成物の調製）
表２に示すように、固形分量で、アルカリ可溶性樹脂溶液を３５．０部、多官能モノマーとしてジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）を３０．０部、光重合開始剤としてイルガキュアＯＸＥ－０２（ＢＡＳＦジャパン社製）を５．０部、上記で得られた顔料分散体１を３０．０部、更に希釈溶媒（ＰＧＭＥＡ）を感光性樹脂組成物の固形分濃度が２０質量％となるように加え、攪拌することで感光性樹脂組成物を得た。

(Examples 7-12, Comparative Examples 3-4)
Using the obtained alkali-soluble resin solutions (polymer solutions A-1 to A-8), photosensitive resin compositions are prepared by the following method, and the solvent resistance and residue during development are evaluated by the evaluation methods described above. evaluated. Table 2 shows the results.
(Preparation of pigment dispersion 1)
12.9 parts of PGMEA, 0.4 parts of Disparlon DA-7301 as a dispersant, and C.I. I. Pigment Green 58 at 2.25 parts and C.I. I. Pigment Yellow 138 was mixed with 1.5 parts and dispersed for 3 hours with a paint shaker to obtain Pigment Dispersion 1 (solid content: 22% by mass).
(Preparation of photosensitive resin composition)
As shown in Table 2, the solid content is 35.0 parts of the alkali-soluble resin solution, 30.0 parts of dipentaerythritol hexaacrylate (DPHA) as a polyfunctional monomer, and Irgacure OXE-02 (BASF) as a photopolymerization initiator. Japan Co., Ltd.), 30.0 parts of the pigment dispersion 1 obtained above, and a dilution solvent (PGMEA) were added so that the solid content concentration of the photosensitive resin composition was 20% by mass. , to obtain a photosensitive resin composition.

イルガキュア（登録商標）ＯＸＥ０２：ＢＡＳＦジャパン社製、エタノン,１－[９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル]－,１－（Ｏ－アセチルオキシム）

表１、表２、及び図１の結果から、本発明のアルカリ可溶性樹脂の製造方法及び感光性樹脂組成物の優位性を確認できた。
具体的には、表１の実施例１と比較例１では使用する原料が同じで製造方法が異なるものを比較すると、本発明の製造方法を採用した実施例１で得られるアルカリ可溶性樹脂のMw/Mn(分散度)は比較例１より小さく均一性が向上していることが分かる。
また、図１の分子量GPCチャートから、実施例１と比較例１で得られるアルカリ可溶性樹脂では、ピークトップまでのピークは同一だが、エステル化反応の初期を高温で反応させた比較例１では高分子量にショルダーが発生していることが分かる。このことから、実施例１のように、エステル化反応の初期を低温で反応させることにより架橋反応による高分子量化を抑制でき、分散度を小さくできていると考えられる。
また、表２から明らかなように、本発明の感光性樹脂組成物１～６（実施例７～実施例１２）を用いれば、耐溶剤性及び現像時残渣の評価結果が良好であることが分かる。特に比較例１のような、分子量分布の大きいアルカリ可溶性樹脂では、現像時の均一性が乏しく残渣が発生した。また比較例２の感光性樹脂組成物８では、二重結合当量が３９０のアルカリ可溶性樹脂を含んでいるが、低温条件で硬化した場合は耐溶剤性が悪いものであった。
その他、実施例７～実施例１１と、実施例１２の結果より、酸基とエポキシ基をエステル化反応させる工程において、（Ｉ）の行程を採用した製造方法で得られるアルカリ可溶性樹脂を含む感光性樹脂組成物の方が、耐溶剤性に優れるものであった。

Irgacure (registered trademark) OXE02: manufactured by BASF Japan, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime)

From the results in Tables 1 and 2 and FIG. 1, the superiority of the method for producing an alkali-soluble resin and the photosensitive resin composition of the present invention was confirmed.
Specifically, when comparing Example 1 and Comparative Example 1 in Table 1 using the same raw materials and different production methods, the Mw of the alkali-soluble resin obtained in Example 1 employing the production method of the present invention /Mn (dispersion degree) is smaller than that of Comparative Example 1, indicating that the uniformity is improved.
Further, from the molecular weight GPC chart in FIG. 1, the alkali-soluble resins obtained in Example 1 and Comparative Example 1 have the same peak to the peak top, but in Comparative Example 1, in which the esterification reaction was started at a high temperature, the peak is high. It can be seen that a shoulder occurs in the molecular weight. From this, it is considered that by carrying out the esterification reaction at a low temperature in the early stage of the esterification reaction as in Example 1, it is possible to suppress the increase in the molecular weight due to the cross-linking reaction, thereby reducing the degree of dispersion.
In addition, as is clear from Table 2, when the photosensitive resin compositions 1 to 6 (Examples 7 to 12) of the present invention are used, the evaluation results of solvent resistance and residue during development are good. I understand. In particular, with an alkali-soluble resin having a large molecular weight distribution, such as Comparative Example 1, the uniformity during development was poor and a residue was generated. The photosensitive resin composition 8 of Comparative Example 2 contained an alkali-soluble resin having a double bond equivalent of 390, but had poor solvent resistance when cured under low temperature conditions.
In addition, from the results of Examples 7 to 11 and Example 12, in the step of esterifying an acid group and an epoxy group, a photosensitive resin containing an alkali-soluble resin obtained by a production method adopting the step (I) The solvent-resistant resin composition was superior in solvent resistance.

The production method of the present invention stably yields a specific side chain double bond-containing alkali-soluble resin obtained by esterifying an acid group and an epoxy group. The photosensitive resin composition containing the present alkali-soluble resin is used as a colored layer, black matrix, photo spacer, black column spacer, ink, printing plate, printed wiring board, semiconductor, etc. for color filters used in liquid crystal display devices, solid-state imaging devices, etc. It can be suitably used for various optical members such as elements and photoresists.

Claims (6)

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, comprising a step of esterifying an acid group and an epoxy group, and comprising the following (I ) or a method for producing an alkali-soluble resin having the process of (II).
(I) a step of polymerizing a monomer component containing an unsaturated carboxylic acid monomer to obtain a base polymer, and addition reaction of glycidyl (meth)acrylate to the base polymer at a temperature below 100°C After the conversion reaches 40% by mass with respect to 100% by mass of all glycidyl (meth)acrylate, the reaction is continued at 100° C. or higher until the conversion exceeds 85% by mass (II) (meth)acrylic In the step of polymerizing a monomer component containing glycidyl acid to obtain a base polymer, and in the addition reaction of an unsaturated carboxylic acid monomer to the base polymer, the reaction is carried out at a temperature of less than 100° C. to obtain a total unsaturated carboxylic acid. After the conversion rate reaches 40% by mass with respect to 100% by mass of the acid monomer, the reaction is performed at 100 ° C. or higher, and the esterification reaction is performed until the conversion rate exceeds 85% by mass. The process of performing the addition reaction of 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, wherein the polymerization solvent for the polymerization contains a non-alcoholic solvent. Photosensitivity containing an alkali-soluble resin having a (meth)acrylate skeleton in the main chain and an ethylenically unsaturated double bond in the side chain and a double bond equivalent weight of 350 g/mol or less, a polyfunctional monomer, and a photopolymerization initiator Resin composition. 5. The photosensitive resin composition according to claim 4, wherein the photopolymerization initiator contains an oxime initiator. A method for producing a cured product, comprising the step of curing the photosensitive resin composition according to claim 4 or 5 at a temperature of 150°C or less.

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