Copolymer, photosensitive resin composition, cured product, and laminate

Abstract

To provide a copolymer which has photocrosslinkability and alkali solubility, and achieves both storage stability and thermal crosslinkability, a photosensitive resin composition containing the copolymer, and a cured product of the photosensitive resin composition.SOLUTION: A copolymer contains a constitutional unit derived from a monomer (F) containing a fluorine atom, a constitutional unit derived from a monomer (O) containing an oxetanyl group, and a constitutional unit derived from a monomer (Z) containing an acid group, as constituent monomers, and further contains one or more of a constitutional unit derived from a monomer (X) having a functional group radical generatable by irradiation with active energy rays and a constitutional unit (E) containing an ethylenic unsaturated group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a copolymer, a photosensitive resin composition containing the copolymer, and a photosensitive resin composition containing the copolymer. The present invention relates to a cured product and a laminate having a layer made of the cured product. [Background technology]

[0002] In recent years, luminescent nanocrystals such as quantum dots have become increasingly popular in order to reduce the power consumption and widen the color gamut of displays. Color filters that use particles to form pixels are being investigated. a red pixel containing nanocrystalline particles of luminescence from a light source; a green pixel containing nanocrystalline particles of luminescence from a light source; A liquid crystal display having blue pixels that transmit blue light is known. There are two methods for manufacturing color filters: photolithography and inkjet printing. It is known that the latter method can reduce the loss of ink material. When a color filter containing luminescent nanocrystalline particles is manufactured by an inkjet method, Ink is ejected into the area (pixel portion) surrounded by the cured material thus prepared to form pixels. Therefore, it is necessary to prevent the inks from mixing with each other between adjacent pixels in the area surrounded by the cured material. Therefore, a copolymer with liquid repellency is required as an additive.

[0003] Copolymers that have traditionally been used in cured color filters contain fluoroalkyl groups. It uses a liquid-repellent material. Such a liquid repellent material is, for example, as described in Patent Document 1, capable of resisting light when exposed to actinic energy rays. It contains an ethylenically unsaturated group that allows it to photocrosslink with the distbinder, and furthermore, it has a property that it remains in the unexposed area. The copolymer contains acid groups so that it can be removed during the development process. In addition, Patent Document 2 states that "active energy that generates radicals by irradiation with active energy rays A monomer having a functional group capable of generating radicals upon irradiation with UV rays and a perfluoroalkyl group A copolymer containing a monomer having a hydroxyl group has been proposed, and the radicals are generated by ultraviolet irradiation. By containing the resulting monomer, good exposure sensitivity is ensured. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-140043 [Patent Document 2] Japanese Patent Publication No. 2022-116491 Summary of the Invention [Problem to be solved by the invention]

[0005] As a result of extensive research by the present inventors, it was found that the copolymer in Patent Document 1 is Because it contains olefinic unsaturated groups, photopolymerization occurs when irradiated with active energy rays, resulting in repellent properties. Although it forms a liquid crosslinked film, it does not contain a thermal crosslinking functional group, so it does not undergo crosslinking in the thermal process. It was found that the liquid repellency tends to be insufficient especially under low irradiation conditions. did. On the other hand, the copolymer and photosensitive composition of Patent Document 2 can be irradiated with active energy rays. For example, when used in resist applications, It is thought that a photocrosslinking reaction occurs between the ethylenically unsaturated groups of the soluble resin. Irradiation generates many radicals on the coating surface, which counteracts oxygen inhibition, resulting in high exposure sensitivity. However, the copolymer of Patent Document 2 does not contain an acid group such as a carboxyl group. It is designed to ensure alkali solubility by not substantially copolymerizing monomers having the same properties. Since it does not have a thermal crosslinking group, there is a concern that the pattern may be contaminated by development residue. Therefore, it is thought to be difficult to ensure high liquid repellency. Therefore, the present invention provides a composition having good exposure sensitivity and capable of thermal crosslinking before and after heat treatment of the cured product. The present invention aims to provide a copolymer suitable for use as a color resist for displays.

[0006] As a result of extensive research by the present inventors, it was found that a monomer containing a fluorine atom and a monomer containing an oxetanyl group The monomers are soluble in an organic solvent and contain a monomer having an acid group and a monomer having an acid group as constituent monomers, and the monomer is soluble in an organic solvent and further contains an active energy ray. Monomers having functional groups capable of generating radicals upon irradiation or containing ethylenically unsaturated groups Copolymers containing one or more of the structural units have photocrosslinkability and alkali solubility. Furthermore, they found that both storage stability and thermal crosslinkability were achieved, and thus the present invention was completed. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] A structural unit derived from a monomer (F) containing a fluorine atom and a structural unit derived from a monomer (F) containing an oxetanyl group and a structural unit derived from a monomer (O) containing an acid group (Z), derived from a monomer (X) having a functional group capable of generating radicals upon irradiation with active energy rays or a structural unit (E) containing an ethylenically unsaturated group. A copolymer that [2] The content of the fluorine atoms is 10.0 to 35.0% by mass based on the total solid content of the copolymer. The copolymer according to [1]. [3] The copolymer according to [1] or [2], wherein the monomer (X) has a structure represented by the following formula (Ia): Polymer.

[0008] [ka]

[0009] [In the formula, R 2 represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R 3 , R 4 may or may not be bonded to each other to form a ring. is R 3 and R 4 each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms. When a ring is formed, R 3 and R 4 represent a cyclic structure having 2 to 10 carbon atoms in total. Also, * indicates a connecting move.] [4] Any of [1] to [3], wherein the structural unit (E) has a structure represented by the following formula (Ib): The copolymer according to claim 1.

[0010] [ka]

[0011] [In the formula, R 1 is hydrogen or a methyl group, R 2 is a linear or branched alkyl group having 1 to 5 carbon atoms. represents a phenyl group, and * represents a bond.] [5] The copolymer contains acid groups of 5 to 140 mg KOH / g and is alkali-soluble. The copolymer according to any one of [1] to [4], wherein [6] The copolymer according to any one of [1] to [5], which is used for display purposes. . [7] A photosensitive resin composition containing the copolymer according to any one of [1] to [6]. [8] A photosensitive resin composition containing the copolymer according to any one of [1] to [6] is cured. The hardened product. [Effects of the Invention]

[0012] The fluorine atom-containing monomer (F) of the present invention is irradiated with active energy rays to form a radical. The constituent monomers are a monomer (X) having a functional group capable of forming a copolymer and a monomer (Z) having an acid group. and a copolymer (S) (hereinafter simply referred to as copolymer ( The cured product has high sensitivity to exposure to light, and the liquid repellency of the resulting cured product changes little before and after heat treatment. It has low thermal stability. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail. In the present invention, "(meth)acrylate" refers to the total of acrylates or methacrylates. "(Meth)acrylic" is a general term for acrylic and methacrylic. "Acryloyl" is a general term for acryloyl and methacryloyl. The "~" symbol indicates a range of values, and includes the values ​​before and after it as the lower and upper limits. The numerical ranges disclosed in this specification can be obtained by arbitrarily combining the lower and upper limits. The new numerical range can be created by combining the above.

[0014] <Copolymer (S)> A monomer containing a fluorine atom (F), a monomer containing an oxetanyl group (O), and an acid group The monomer (Z) is contained as a constituent monomer, and when irradiated with active energy rays, Monomer (X) having a radical-generating functional group or a structure containing an ethylenically unsaturated group The present invention relates to a copolymer (S) containing one or more units (E).

[0015] [Fluorine atom-containing monomer (F)] The monomer (F) may be a compound containing a fluorine atom and an ethylenically unsaturated group. do. The fluorine atoms are derived from perfluoroalkyl groups or perfluoropolyether groups. This is suitable for achieving antifouling and liquid repellency (water repellency and oil repellency). Since it is incorporated into a copolymer (S) rather than a single molecule, it effectively reduces the surface energy of the coating film. Furthermore, as mentioned above, the active energy By irradiating the molecule with functional groups capable of generating radicals, even if activated, Even when the amount of energy ray irradiation is small, sufficient crosslink density of the coating film can be ensured. This can significantly improve the liquid repellency.

[0016] As the perfluoroalkyl group, conventionally known compounds can be used. From the viewpoint of compatibility with the monomer, the perfluoroalkyl group usually has 2 to 13 carbon atoms. Among these, perfluoroalkyl groups with 3 to 10 carbon atoms are preferred from the viewpoint of availability. A perfluoroalkyl group having 4 to 8 carbon atoms is more preferable, and when the perfluoroalkyl group has 4 to 8 carbon atoms, the liquid repellency is further improved. Highly cured products can be formed.

[0017] In addition, the fact that the perfluoroalkyl group is a terminal structure, not an internal structure, is important from the viewpoint of liquid repellency. It is preferable to have a terminal structure rather than an internal structure because it is difficult to obtain a surface roughness when the material is cured. The liquid repellency can be improved by unevenly distributing the liquid.

[0018] The main chain and terminal carbon of the perfluoroalkyl group contained in the monomer (F) are usually fluorine atoms. Although the perfluoroalkyl group is substituted with hydrogen atoms, some of the atoms may be hydrogen atoms. When hydrogen atoms are contained, the ratio of the number of hydrogen atoms to 10 fluorine atoms is preferably 8 or less. The ratio is preferably 5 or less, more preferably 4 or less. Because fluorine atoms are introduced at a high rate, copolymer (S) tends to be unevenly distributed on the surface of the cured product. In addition, compatibility with other materials may decrease, resulting in excellent stain resistance and liquid repellency. .

[0019] The perfluoroalkyl group may be linear, for example, a perfluoroisopropyl group. From the viewpoint of excellent stain resistance and liquid repellency, a straight chain is preferred.

[0020] That is, the optimum structure of the perfluoroalkyl group is a perfluoroalkyl group having 2 to 8 carbon atoms. Examples of the perfluoroalkyl group include a perfluorobutyl group and a perfluorohexyl group. In addition, these perfluoroalkyl groups may be used alone or in combination of two or more. The above may be used in combination.

[0021] As the monomer (F), for example, a (meth)acrylic acid ester having a perfluoroalkyl group can be used. In the case of esters, 2,2,3,3-tetrafluoropropyl acrylate (Osaka Organic Chemical Industry Co., Ltd., Viscoat 4F, (carbon number 3, fluorine atoms 4, hydrogen atoms 3), 1H, 1H,5H-Octafluoropentyl acrylate (Osaka Organic Chemical Industry Co., Ltd., Bis Coat 8F, (carbon number 5, fluorine atoms 8, hydrogen atoms 3)), 1H,1H,5H-octafluoro Dipentyl methacrylate (Osaka Organic Chemical Industry Co., Ltd., Viscoat 8FM, (carbon number 5, Fluorine atom 8, hydrogen atom 3), 1H,1H,2H,2H-tridecafluorooctyl alcohol Relate (Osaka Organic Chemical Industry Co., Ltd., Viscoat 13F, (8 carbon atoms, 13 fluorine atoms, Hydrogen atom 4), 1H,1H,2H,2H-nonafluorohexyl acrylate (unima Tech Co., Ltd., CHEMINOX FAAC-4, (6 carbon atoms, 9 fluorine atoms, 4 hydrogen atoms) )), 1H,1H,2H,2H-nonafluorohexyl methacrylate (Unimatec Co., Ltd., CHEMINOX FAMAC-4, (6 carbon atoms, 9 fluorine atoms, 4 hydrogen atoms) , 1H,1H,2H,2H-tridecafluorooctyl methacrylate (Unimatec Co., Ltd., CHEMINOX FAMAC-6, (8 carbon atoms, 13 fluorine atoms, 4 hydrogen atoms) ), 1H,1H,2H,2H-tridecafluorooctyl methacrylate (Daikin Industries C6SFMA (carbon number 8, fluorine atoms 13, hydrogen atoms 4) manufactured by FUJI CO., LTD. is commercially available. These (meth)acrylic acid esters having a fluoroalkyl group are available. The species may be used alone or in combination of two or more.

[0022] Monomer (F) is a perfluoropolyether group (hereinafter sometimes abbreviated as PFPE) When containing, -((CF2)xO)m- (x and m are integers other than 0) is used as the base. The unit is a unit, and multiple units are connected together. When m is 2 or more, each ((CF2)xO) may be the same as or different from each other. That is, PFPE may have a structure consisting of a single unit repeated, or may have a structure consisting of different units repeated. It may also be a structure consisting of a combination of two or more types of units. O) may have a straight or branched carbon chain.

[0023] The unit -((CF2)xO)- includes, for example, CF2O, (CF2)2O, (CF2)3O, (CF2)4O, (CF2)5O, CF(CF3)CF2O, CF(C F3)CF(CF3)CF2O, CF2CF(CF3)CF2CF2O, etc. In particular, the PFPE of the present invention is -((CF2)2O)m -(CF2O)n- (where m and n are integers other than 0) can be preferably used. In this case, the m and n are in the ranges of, for example, about 10≦m≦40 and about 10≦n≦40. However, as long as the molecular weight is within the above range, it is not limited to the above ranges of m and n. It will not be done.

[0024] Commercially available products of the monomer (F) containing a perfluoropolyether group include, for example, Contains perfluoropolyether compounds such as ZMF-402 and FLUOROLINK D-6000, Fomblin D2 (both Solvay Specialty Polymers Co., Ltd.) SUBELYN KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.), Optool DA C-HP (manufactured by Daikin Industries, Ltd.) and the like can be used. The (meth)acrylic acid ester having a triether group may be used alone or in combination of two or more. The above may be used in combination.

[0025] As mentioned above, the monomer (F) is a perfluoroalkyl group or a perfluoropolyether. and monomers having an ether group, but either one or both may be used in combination. From the viewpoint of compatibility with the monomer and solvent, a perfluoroalkyl group is particularly preferred.

[0026] The monomer (F) is a copolymer in which the fluorine atom content in the solid content of the copolymer (S) is 10 to 35 mass %. It is preferable to copolymerize the copolymer so that the content is 12 to 30 mass %. It is preferable to copolymerize the copolymer so that the content is 15 to 25 mass %, and it is preferable to copolymerize the copolymer so that the content is 18 to 23 mass %. It is particularly preferable to copolymerize the copolymer so that the content is within this range. The fluorine atom content of all the monomers constituting the copolymer (S) is It can be calculated from the content ratio of the monomer (F) (described later) or by NMR or gas chromatography. It is also possible to analyze the constituent units from the above and calculate the fluorine atom content.

[0027] [Monomer (O)] The copolymer (S) of the present invention is a copolymer of a monomer (O) containing an oxetanyl group and a monomer (O) containing an acid group. By including the monomer (Z) as a constituent monomer, the oxetanyl group and the acid group undergo an addition reaction upon heating. When used for color resist applications, A thermal crosslinking reaction may also occur with other compounds having acid groups contained in the photosensitive resin composition. In the case of color resists, if the exposure dose is too high, the pattern will be blurred, which is called exposure overprint. On the other hand, a low irradiation dose can cause crosslinking. This results in an insufficient density and insufficient liquid repellency, which is undesirable. To address this issue, we developed a copolymerization method that can increase the crosslink density by heating after pattern formation. The body (S) can achieve high precision in the pattern while also sufficiently enhancing the liquid repellency.

[0028] The monomer (O) containing an oxetanyl group is a monomer having an ethylenically unsaturated bond and an oxetanyl group. A compound having a methyl group can be used. The oxetanyl group has the structure of formula (Ic):

[0029] [ka]

[0030] [In the formula, R 1 is a hydrogen atom, an alkylene group having 1 to 5 carbon atoms, or a secondary or tertiary amino group Nomoto, R 2 is an alkylene group having 1 to 2 carbon atoms or a linear or branched group having 3 to 5 carbon atoms represents an alkylene group of the formula R 3 , R 4 , R 5 , R 6 , R 7 are each independently 1 to 2 carbon atoms or a linear or branched alkyl group having 3 to 5 carbon atoms, * indicates a linking group. show.]

[0031] The ethylenic double bond of the monomer (O) having the above structure may be a vinyl group, an allyl group, Vinyl ether groups, (meth)acryloyl groups, etc. can be used, but from the viewpoint of copolymerizability ( Compounds having a meth)acryloyl group and an oxetanyl group are preferred.

[0032] The compound having a (meth)acryloyl group and an oxetanyl group is represented by the following formula (Id): Examples include those having the structure:

[0033] [ka]

[0034] [In the formula, R 1 represents a hydrogen atom, a methyl group, or an ethyl group, and R 2 is an alkyl group with 1 to 2 carbon atoms. R represents a olefin group or a linear or branched alkylene group having 3 to 5 carbon atoms; 3 , R 4 , R 5, R 6 , R 7 are each independently an alkyl group having 1 to 2 carbon atoms or a It represents a linear or branched alkyl group.

[0035] The compounds having such an ethylenically unsaturated bond and an oxetanyl group are available. Examples of the methyl acrylate include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyl (3-phenyloxetan-3-yl)methyl methacrylate, ) methyl acrylate, (3-phenyloxetan-3-yl) methyl methacrylate, etc. Among these, (3-ethyloxetan-3-yl)methyl acrylate , (3-ethyloxetan-3-yl)methyl methacrylate is compatible with other monomers From the viewpoint of the above, (3-phenyloxetan-3-yl)methyl acrylate is preferable during polymerization. The above-mentioned ethylenically unsaturated bond and oxetanyl group are most preferable in terms of stability. The compounds may be used alone or in combination of two or more.

[0036] Compounds having an ethylenically unsaturated bond and an oxetanyl group can be prepared by converting a hydroxyl group and an oxetanyl group into compounds having a halogen atom such as chlorine or bromine and an oxetanyl group; a compound having a carboxyl group and an oxetanyl group, and a compound having a carboxyl group and an oxetanyl group. The raw materials are functional groups that react with these (for example, isocyanate groups for hydroxyl groups, halo groups for For amines, amino groups, etc., for amino groups, carboxyl groups, isocyanate groups, For carboxyl groups, epoxy groups or amino groups are used. It can also be obtained as a reaction product with a compound. Examples of the compound having a hydroxyl group and an oxetanyl group include 3-oxetanol, 3-methyl -3-oxetanemethanol, 2-hydroxymethyloxetane, 3-ethyl-3-hydroxy 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane, Examples of compounds having a halogen atom and an oxetanyl group include cetane, 3-iodooxetane, 3-(chloromethyl)-3-methyloxetane, 3,3-bis( 3-(chloromethyl)oxetane, 3-(bromomethyl)oxetane, etc. Compounds having an amino group and an oxetanyl group include N-methyloxetan-3-amine, 3-(aminomethyl)oxetane, 3-aminomethyl-3-methyloxetane, 3-aminomethyl 2-oxa-6-azaspiro[3.3]heptane, etc. can be. In addition, compounds such as 3-oxetanecarboxylic acid, which has a carboxyl group and an oxetanyl group, These may be used alone or in combination of two or more.

[0037] The content of the oxetanyl group-containing monomer (O) contained in the copolymer (S) of the present invention is The total solid content of the copolymer (S) is preferably 0.1 to 3.0 mmol / g, more preferably 0.2 to 2.5 It is more preferable that the concentration is 0.3 to 2.0 mmol / g, and it is even more preferable that the concentration is 0.3 to 2.0 mmol / g. It is preferably 0.4 to 1.5 mmol / g, particularly preferably 0.5 to 1.3 mm It is most preferable that the copolymer (S) has a thermal crosslinking property of 100 mol / g. can be made sufficiently high.

[0038] [Monomer (Z) containing an acid group] The copolymer (S) of the present invention contains a monomer (Z) containing an acid group. The polymer (S) has not only thermal crosslinkability with the oxetanyl group but also resistance to an alkaline developer. The solubility (alkali solubility) is improved and the cleaning properties are excellent. It is possible to prevent contamination caused by unincorporated copolymer (S) residue remaining on the surface of the cured product. I discovered that it was possible.

[0039] The acid group is not particularly limited, but may be a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, etc. Among these, carboxyl groups are preferred in consideration of the stability and washability of the copolymer. I wish.

[0040] The copolymer (S) of the present invention is alkali-soluble. The structure other than the acid group is also alkali-soluble. The content of the acid group contained in the copolymer (S) of the present invention is 5 to 140mN. gKOH / g, and next most preferred is 10 to 140 mgKOH / g. It is preferable that the KOH / g is 15 to 120 mgKOH / g, and more preferable that the KOH / g is 20 to 100 mgKOH / g. It is most preferable that the concentration is 30 to 80 mgKOH / g, and particularly preferable that the concentration is 40 to 55 mgKOH / g. Within this range, the thermal crosslinkability and alkali solubility are good, and the copolymer ( S) It is possible to prevent contamination of the cured product by residues. The acid value is the value obtained by neutralizing 1 g of the sample. The mass [mg] of potassium hydroxide required for the reaction is expressed in mgK It is expressed as OH / g.

[0041] The acid group of the copolymer (S) is formed by incorporating a monomer having an acid group into the copolymer through a polymerization reaction. Alternatively, an acid group may be introduced into the copolymer (S) by an addition reaction or the like. From this point of view, the method of incorporating a monomer having an acid group into a copolymer (S) by a polymerization reaction is a reaction This is particularly preferred because it can reduce the number of steps. For convenience, the monomer is a combination of the precursor monomer before addition and the compound for introducing the acid group. Let us consider it as a body (Z).

[0042] As a method for incorporating the monomer into the copolymer (S) by the polymerization reaction of the monomer, The copolymer (S) can be obtained by using only one type of monomer (Z). You can use one of them, or you can use two or more of them in combination.

[0043] As the monomer (Z) containing an acid group, a monomer having a carboxy group is acrylic Acid, methacrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalate, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salts. Examples include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornane 2,3-Trene-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-Tetrahydrophthalic Anhydride, 2-Buten-1-ylsuccinic Acid Among these, those containing a (meth)acryloyl group are particularly popular. This is preferable from the viewpoint of polymer synthesis, and the methacryloyl group is also preferable for liquid repellency and stability. These acid group-containing monomers may be used alone or in combination of two or more. The above may be used in combination.

[0044] Examples of the monomer having a phenolic hydroxyl group include 4-hydroxyphenyl(metha- ) acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxy Styrene and those in which one or more hydrogen atoms of the benzene ring are substituted with a methyl group, an ethyl group, or an n-butyl group. alkyl groups such as butyl groups, alkoxy groups such as methoxy, ethoxy, and n-butoxy groups, halogen atom, haloalkyl group having one or more halogen atoms, nitro group, cyano group, Among these, 4-hydroxybenzoates are the most popular due to their availability. Hydroxyphenyl (meth)acrylate is preferred. The compound having an olefinic unsaturated group may be used alone or in combination of two or more. .

[0045] Examples of monomers having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (methyl sulfonic acid), p) Allylsulfonic acid, 2-hydroxy-3-(meth)allyloxypropanesulfonic acid , (meth)acrylate 2-sulfoethyl, (meth)acrylate 2-sulfopropyl, 2- Hydroxy-3-(meth)acryloyloxypropanesulfonic acid, 2-(meth)acryloyloxypropanesulfonic acid amide-2-methylpropanesulfonic acid and the like.

[0046] In addition, as a method for introducing an acid group into the copolymer (S) by addition reaction, for example, a method of copolymerizing a monomer having an hydroxyl group and then adding an acid anhydride; The method of copolymerizing the copolymer and then adding an acid anhydride, or the method of using an ethylenediamine such as maleic anhydride After copolymerization of acid anhydrides containing carboxylic unsaturated groups, hydroxyl groups, primary or secondary amino groups, A method of adding an active hydrogen-containing compound such as a mercapto group or an epoxy group-containing compound. There are some.

[0047] As will be described later, when the constituent raw materials of the copolymer (S) are known, the acid value is determined by the compound having an acid group. It can be calculated from the molecular weight and the feed ratio. The acid value can be determined by, for example, neutralization titration.

[0048] The copolymer (S) of the present invention has a functional group capable of generating radicals upon irradiation with active energy rays. a monomer (X) having a group or a structural unit (E) containing an ethylenically unsaturated group; By containing one or more of the copolymer (S), the copolymer (S) itself and the copolymer (S) described later can be easily decomposed by irradiation with active energy rays. Photocrosslinking with a compound having an ethylenically unsaturated bond contained in a photosensitive resin composition The monomer (X) and the ethylenediamine compound (E) are combined to form a cured product having liquid repellency. The structural unit (E) containing an ethylenically unsaturated group is said to be photocrosslinkable if it contains one or more of these. Although it is sufficient from the viewpoint of photosensitivity, it must have a structure that can act as a radical source and ensure higher exposure sensitivity. It is preferable that the monomer (X) is contained, and further, a high crosslink density can be ensured by a chain reaction. From the viewpoint of being able to produce a polymerizable compound, the polymerizable compound includes both the monomer (X) and the structural unit (E) containing an ethylenically unsaturated group. It is desirable to include

[0049] a monomer (X) having a functional group capable of generating radicals upon irradiation with active energy rays, or The content of the structural unit (E) containing an ethylenically unsaturated group in the total solid content of the copolymer (S) is The range is preferably 0.1 to 4.0 mmol / g, and more preferably 0.2 to 3.0 mmol / g. It is preferably 0.4 to 2.5 mmol / g, and more preferably 0.7 to 2.0 mmol / g. 1.0 to 1.6 mmol / g is particularly preferred, and 1.0 to 1.6 mmol / g is most preferred. When the content is within this range, the photocrosslinkability of the copolymer (S) can be made sufficiently high. Cut.

[0050] [Monomer (X)] The functional group contained in the monomer (X) can generate radicals when irradiated with active energy rays. The structure that generates radicals when irradiated with active energy rays (having photopolymerization initiation properties) As the structure having photopolymerization initiation property, various known structures can be used. Examples of the hydrogen abstraction type, electron transfer type, and intramolecular cleavage type can be mentioned. Specific examples of functional groups that can generate radicals upon irradiation with active energy rays include benzoyl groups, Phenone group, acetophenone group, benzoin group, α-hydroxyketone group (e.g., 1- [4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone "The group obtained by removing one hydrogen atom from the hydroxyl group in 2-hydroxyethoxy", α-aminoketo amine group, α-diketone group, α-diketone dialkyl acetal group, anthraquinone group, thiol group Examples include xanthone groups and phosphine oxide groups. Benzophenone and acetophenone groups are preferred because they are less susceptible to damage and have good stain resistance and liquid repellency. Acetophenone is preferred in that it can further improve the exposure sensitivity. A non-group and an α-hydroxyketone group are more preferred, and among these, a group having the structure of the following formula (Ia) is particularly preferred. It is more preferable that the compound has a structure represented by the following formula (Ia-2): .

[0051] [ka]

[0052] [In the formula, R 2 represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R 3 , R 4 may or may not be bonded to each other to form a ring. is R 3 and R 4 each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms. When a ring is formed, R 3 and R 4 represent a cyclic structure having 2 to 10 carbon atoms in total. Also, * indicates a connecting move.]

[0053] [ka]

[0054] [In the formula, R 2 represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R 3 , R 4 may or may not be bonded to each other to form a ring. is R 3 and R 4 each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms. When a ring is formed, R 3 and R 4 represent a cyclic structure having 2 to 10 carbon atoms in total. Also, R 5 represents a group having a weight average molecular weight of 500,000 or less, preferably a group having a weight average molecular weight of 100,000 or less, Groups with a molecular weight of 50,000 or less are more preferred.]

[0055] Monomer (X) is active because it contains a radical polymerizable unsaturated bond (e.g., an ethylenically unsaturated group). Incorporating functional groups into copolymer (S) that can generate radicals upon irradiation with energy rays Specific examples of radical polymerizable unsaturated bonds (ethylenically unsaturated groups, etc.) include (meth) ) acryloyl group, (meth)acrylamide group, vinyl group, etc. Examples of the monomer having a functional group capable of generating radicals upon irradiation with active energy rays include: The copolymer (S) is easy to synthesize and can generate radicals by irradiation with active energy rays. From the viewpoint of ease of adjusting the amount of functional groups introduced, radicals are generated by irradiation with active energy rays. (Meth)acrylates having a formable functional group are preferred. Examples of the monomer having a functional group capable of generating radicals upon irradiation with active energy rays include: For example, 4-methacryloyloxybenzophenone, 2-[4-(2-hydroxy-2- methyl-1-oxopropyl)phenoxy]ethyl methacrylate, etc. The functional groups capable of generating radicals upon irradiation with active energy rays are each used alone. Two or more of them may be used in combination.

[0056] The copolymer (S) of the present invention can generate radicals when irradiated with active energy rays. The amount of the functional group is preferably 0.1 to 4.0 mmol / g in the total solid content of the copolymer (S), and more preferably 0.1 to 4.0 mmol / g in the total solid content of the copolymer (S). It is more preferable that the content is 0.2 to 3.0 mmol / g, and more preferably 0.4 to 2.5 mmol / g. It is more preferable that the content is 0.7 to 2.0 mmol / g, and particularly preferable that the content is 1.0 It is most preferable that the copolymer (S) is in this range. The exposure sensitivity is excellent.

[0057] [Structural unit (E) containing an ethylenically unsaturated group] The copolymer (S) of the present invention has a structural unit (E) containing an ethylenically unsaturated group. The copolymer (S) of the present invention has a structure in which the monomer (X) in its backbone is irradiated with active energy rays. Therefore, the structural unit (E) containing a radical-generating functional group or an ethylenically unsaturated group By containing one or more of these, a highly crosslinked structure is formed when irradiated with active energy rays. A cured product having the formula:

[0058] The ethylenically unsaturated group of the present invention is not particularly limited, and may be a vinyl group, an allyl group, a vinyl ... Ether group, propenyl ether group, (meth)acryloyl group, (meth)acrylamide Among these, particularly preferred is (meth)acryloyl. A group, and an acryloyl group is preferred from the viewpoint of high reactivity.

[0059] The structural unit (E) containing an ethylenically unsaturated group may have the following structure (Ib): It is more preferable that the compound has a structure of the following formula (Ib-2).

[0060] [ka]

[0061] [In the formula, R 1 is hydrogen or a methyl group, R 2 is a linear or branched alkyl group having 1 to 5 carbon atoms. represents a phenyl group, and * represents a bond.]

[0062] [ka]

[0063] [In the formula, R 1 is hydrogen or a methyl group, R 2 is a linear or branched alkyl group having 1 to 5 carbon atoms. represents a phenyl group, and R 3 represents a group having a weight average molecular weight of 500,000 or less, and more preferably a group having a weight average molecular weight of 100,000 or less. Preferably, a group having a molecular weight of 50,000 or less is even more preferred.]

[0064] The amount of ethylenically unsaturated groups contained in the copolymer (S) of the present invention is determined based on the total solid content of the copolymer (S). The content in the solids is preferably 0.05 to 4.0 mmol / g, and more preferably 0.1 to 3.0 mmol / g. It is more preferable that the content is 0.2 to 2.0 mmol / g, and further more preferable that the content is 0.3 to 2.0 mmol / g. It is particularly preferable that the concentration is 1.2 mmol / g, and it is preferable that the concentration is 0.4 to 0.8 mmol / g. Within this range, the liquid repellency of the resulting cured product is not impaired even when it is subjected to high temperature treatment. It is possible to obtain a film having excellent thermal stability.

[0065] The ethylenically unsaturated group of the present invention may be introduced into either the main chain or the side chain. When introducing a radically polymerizable ethylenically unsaturated group into the copolymer (S), an allyl group A method of introducing it in a one-step polymerization reaction by copolymerizing a monomer with low radical reactivity, such as However, from the viewpoint of quality and molecular weight control, it is recommended to first obtain the precursor polymer and then apply the polymer. A method of providing an ethylenically unsaturated group by an addition reaction is preferred.

[0066] Here, the copolymer (S) of the present invention is provided as a precursor for introducing the structural unit (E). and the monomer (A) which is the precursor reacts with the functional group of the monomer (A) to form an ethylenically unsaturated The compound (B) for introducing the group will be explained below.

[0067] The monomer (A) may be a copolymer of a monomer having a hydroxyl group. In this case, a compound (B) capable of reacting with the hydroxyl group of the monomer (A) to introduce an ethylenically unsaturated group is Examples of the compound include a compound having an isocyanate group and an ethylenically unsaturated group.

[0068] Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate. acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate 10-hydroxydecyl (meth)acrylate, 12-hydroxydecyl (meth)acrylate Uryl (meth)acrylate, monobutyl hydroxyl fumarate, monobutyl hydroxy (Meth)acrylic acids such as itaconate and N-hydroxymethyl (meth)acrylic acid amide, N-hydroxyethyl (meth)acrylamide and N-(3-hydroxypropyl) (Meth)acrylamides such as (meth)acrylamide can be used. Among these, 2-hydroxyethyl ether is preferred because it is easy to ensure compatibility with other monomers and from the viewpoint of polymerizability. (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-hydroxy Ethyl (meth)acrylamide is preferred, and 2-ethyl (meth)acrylamide is particularly preferred because of its ease of availability as a raw material. Hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, N-hydroxy Ethyl acrylamide is preferred. One of these hydroxyl group-containing monomers may be used alone. Alternatively, two or more of them may be used in combination.

[0069] As a compound having an isocyanate group and an ethylenically unsaturated group, 2-isocyanatoethene is Acryloyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, etc. Among these, 2-isocyanatoethyl (meth)acrylate is the most popular because of its availability. In addition, acrylate is preferable in consideration of reactivity. These compounds having an isocyanate group and an ethylenically unsaturated group should be used alone. Two or more of them may be used in combination.

[0070] Another method for introducing an ethylenically unsaturated group into the side chain of the copolymer (S) is to use the monomer (A) After copolymerizing a monomer having an epoxy group or an oxetanyl group as the copolymerization product, compound (B) A compound having an acid group and an ethylenically unsaturated group is added as a catalyst, and an epoxy group or an oxetanyl group is added as a catalyst. One example is a method in which an ethylenically unsaturated group is introduced into a precursor copolymer by reacting an ethylenically unsaturated group with an acid group. The epoxy group and the oxetanyl group may be used either alone or in combination, but the reactivity From the viewpoint of the height of the bond, it is particularly preferable to use an epoxy group.

[0071] The monomer having an epoxy group or an oxetanyl group is, for example, 3,4-epoxy. C-1-butene, glycidyl (meth)acrylate, allyl glycidyl ether, 3,4 -Epoxycyclohexylmethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Acrylate glycidyl ether is preferred. Glycidyl (meth)acrylate is more preferred. Acrylate, Allyl Glycidyl Ether, 3,4-Epoxycyclohexylmethyl (Meth ) acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether Glycidyl (meth)acrylate is more preferred. The monomer having a xetanyl group may be used alone or in combination of two or more kinds.

[0072] The acid group is not particularly limited, but may be a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, etc. Among these, the compound having high reactivity and capable of easily introducing an ethylenically unsaturated group is preferred. Therefore, carboxylic acids are particularly preferred.

[0073] Examples of the compound having an acid group and an ethylenically unsaturated group include acrylic acid, methacrylic acid, and the like. unsaturated monocarboxylic acids such as maleic acid, maleic anhydride, crotonic acid, etc. Among these, unsaturated dicarboxylic acids such as carboxylic acid, itaconic acid, and citraconic acid can be mentioned. Among them, unsaturated monocarboxylic acids are preferred. More preferred are acrylic acid, methacrylic acid, and chloroisothiazolinone. Protonic acids are preferred, and among these, acrylic acid is particularly preferred.

[0074] Examples of the compound having a phenolic hydroxyl group and an ethylenically unsaturated group include 4- Hydroxyphenyl (meth)acrylate, o-hydroxystyrene, m-hydroxy Styrene, p-hydroxystyrene, and those in which one or more hydrogen atoms of the benzene ring are methyl alkyl groups such as butyl, ethyl, and n-butyl groups, methoxy, ethoxy, and n-butoxy groups Alkoxy groups such as silyl groups, halogen atoms, haloalkyl groups having one or more halogen atoms , nitro group, cyano group, and amide group-substituted compounds. The compound having an acid group and an ethylenically unsaturated group may be used alone or in combination of two or more. That's fine.

[0075] Another method for introducing an ethylenically unsaturated group into the side chain of the copolymer (S) is to After copolymerizing a monomer having an acid group as compound (A), an epoxy group is added as compound (B). Alternatively, a compound having an oxetanyl group and an ethylenically unsaturated group is added and reacted. An example of such a method is to introduce an ethylenically unsaturated group into the side chain of the copolymer (S). Either the oxetanyl group or the oxetanyl group may be used or they may be used in combination. It is particularly preferred to use epoxy groups.

[0076] The monomer having an acid group includes a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, Among these, monomers having high reactivity and containing ethylenically unsaturated groups are preferred. Carboxylic acids are particularly preferred because they can be easily introduced.

[0077] Examples of the monomer having an acid group include acrylic acid, methacrylic acid, and crotonic acid. unsaturated monocarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, and itaconic acid Among these, unsaturated monocarboxylic acids such as carboxylic acid, carboxylic acid, and citraconic acid are preferred. More preferred are acrylic acid, methacrylic acid and crotonic acid. Of these, acrylic acid is particularly preferred. They may be used alone or in combination of two or more.

[0078] Examples of the compound having a phenolic hydroxyl group and an ethylenically unsaturated group include 4- Hydroxyphenyl (meth)acrylate, o-hydroxystyrene, m-hydroxy Styrene, p-hydroxystyrene, and those in which one or more hydrogen atoms of the benzene ring are methyl alkyl groups such as butyl, ethyl, and n-butyl groups, methoxy, ethoxy, and n-butoxy groups Alkoxy groups such as silyl groups, halogen atoms, haloalkyl groups having one or more halogen atoms , nitro group, cyano group, and amide group. The compound having a hydroxyl group and an ethylenically unsaturated group may be used alone or in combination of two or more. may be used in combination.

[0079] [Monomer (R)] The copolymer (S) of the present invention may contain, as required, a fluorine atom-containing monomer (F) and an oxetane monomer. The polymerizable composition includes, as constituent monomers, a monomer (O) containing an aryl group and a monomer (Z) containing an acid group, Furthermore, a monomer (X) having a functional group capable of generating radicals upon irradiation with active energy rays Or, as a component other than the unit (E) containing an ethylenically unsaturated group, any monomer (R) It can include.

[0080] By incorporating the monomer (R) as a spacer into the copolymer (S), it is possible to The reactivity of functional groups capable of generating radicals and ethylenically unsaturated groups is improved by irradiation of light. The compatibility with the polymerizable resin composition can be improved.

[0081] The monomer (R) may be, for example, a monomer having an alkyl group having one or more carbon atoms and a radical polymerizable group. or a compound having a hydroxyl group, a nitrogen-containing monomer such as (meth)acrylonitrile, etc. Styrene-based compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene compounds, vinyl esters such as vinyl propionate and vinyl acetate, phosphorus-containing vinyl monomers, Examples include vinyl halides such as vinyl chloride and vinylidene chloride, and conjugated dienes such as butadiene. do.

[0082] Among the above, a compound having an alkyl group having one or more carbon atoms and a radical polymerizable group, or A monomer having a hydroxyl group is preferred in terms of ease of adjusting the compatibility with the photosensitive resin composition. The ease of compound synthesis and the ease of adjusting the amount of alkyl groups with one or more carbon atoms introduced are particularly noteworthy. From this viewpoint, (meth)acrylic acid alkyl esters having an alkyl group having one or more carbon atoms are preferred. Desirable.

[0083] Among the monomers (R), for example, a monomer having an alkyl group having one or more carbon atoms and a radical polymerizable group The compounds that can be used include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, Hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl Sil (meth)acrylate, Octyl (meth)acrylate, Isooctyl (meth)acrylate acrylate, decyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate decyl (meth)acrylate, isodecyl (meth)acrylate, decyl (meth)acrylate, Decyl (meth)acrylate, Myristyl (meth)acrylate, Cetyl (meth)acrylate acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, trimethylsilyl Decyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, Tricyclodecane (meth)acrylate, dicyclopentanyl (meth)acrylate, isopropyl alcohol Examples thereof include isobornyl (meth)acrylate and adamantyl (meth)acrylate. These compounds having an alkyl group having one or more carbon atoms and a radical polymerizable group can be used alone. You can use two or more of them in combination. In addition, 2-hydroxyethyl (meth)acrylate and 3- Hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl ( meth)acrylate, monobutylhydroxyfumarate, monobutylhydroxyitaconone (Meth)acrylic acids such as N-hydroxymethyl (meth)acrylamide, N- Hydroxyethyl (meth)acrylamide and N-(3-hydroxypropyl) (meth)acrylamide (Meth)acrylamides such as acrylamide can be used. The alkyl (meth)acrylate may be linear or branched. . Among these, the molecular weight of 2 is preferred because it is easy to ensure compatibility with other monomers and from the viewpoint of polymerizability. Monomers of 00 or less are preferred, and methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl butyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred. These hydroxyl group-containing monomers may be used alone or in combination of two or more.

[0084] The ratio of the mass of units based on the monomer (F) to the total mass of all units constituting the copolymer (S) In this case, the content is preferably 1 to 60 mass%, more preferably 10 to 55 mass%, and even more preferably 2 0 to 50% by mass, particularly preferably 30 to 45% by mass, most preferably 33 to 42% by mass When the ratio of units based on the monomer (F) is within the above range, the resulting cured product has liquid repellency. The quality will be good.

[0085] The ratio of the mass of units based on the monomer (O) to the total mass of all units constituting the copolymer (S) In this case, the content is preferably 1 to 40 mass%, more preferably 3 to 35 mass%, and even more preferably 5 to 40 mass%. 20% by mass, particularly preferably 7 to 25% by mass, most preferably 10 to 20% by mass. When the proportion of units based on the monomer (O) is within the above range, the resulting cured product has good liquid repellency. It will be a good thing.

[0086] The ratio of the mass of units based on the monomer (Z) to the total mass of all units constituting the copolymer (S) In this case, the content is preferably 1 to 20 mass%, more preferably 2 to 18 mass%, and even more preferably 4 to 5 mass%. The range of the unit based on the monomer (Z) is preferably from 6 to 17% by mass, and particularly preferably from 6 to 15% by mass. If the ratio is within the above range, good liquid repellency can be achieved during alkaline development.

[0087] The ratio of the monomer (X) or ethylenic unsaturated fatty acid units to the total mass of all units constituting the copolymer (S) The proportion of units based on the structural unit (E) containing a saturated group is preferably 0.1 to 60 mass %, More preferably, it is 1.0 to 55% by mass, even more preferably, it is 5 to 50% by mass, and particularly preferably The content of the monomer (X) is preferably in the range of 10 to 48% by mass, and most preferably in the range of 15 to 45% by mass. When the proportion of the unit is within the above range, the photosensitive resin composition containing the copolymer (S) of the present invention The exposure sensitivity can be improved. The unit containing an ethylenically unsaturated bond group is a unit obtained by combining the monomer (A) and the compound (B). It is an addition.

[0088] The ratio of the units based on the monomer (R) to the total mass of all units constituting the copolymer (S) In this case, the content is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably Preferably, the content is 40% by mass or less, more preferably 30% by mass or less, and most preferably 25% by mass or less. The lower limit is not particularly limited, and may be 0 mass %. Considering this, it is preferable not to include it and to adjust the ratio of other active ingredients. If the ratio of units based on the copolymer ( The compatibility with components other than S) is good, and the appearance of the cured product is good.

[0089] The weight average molecular weight (Mw) of the copolymer (S) is preferably 5,000 to 500,000. , more preferably 10,000 to 300,000, and even more preferably 20,000 to 20 0,000, particularly preferably 30,000 to 140,000, most preferably 40,000 When Mw is in the above range, compatibility with the photosensitive resin composition is good. and the liquid repellency of the cured product is improved.

[0090] The polydispersity (Mw / Mn) of the copolymer (S) is usually 1.02 to 5.00, but is preferably or 1.05 to 4.00, more preferably 1.10 to 3.75, and even more preferably 1. The ratio is preferably 1.30 to 3.30, and more preferably 1.50 to 3.30. This makes it easier to ensure compatibility when the composition is made into a fat composition, and also makes the cured product have good liquid repellency. The Mw of the copolymer (S) was determined by gel permeation chromatography (GPC). The measured value is converted into a standard polystyrene value. Detailed measurement conditions are described in the Examples below. That's right.

[0091] The copolymer (S) is typically obtained by polymerization in the presence of a polymerization initiator. In this case, a chain transfer agent may be used in combination, if necessary. Among these, the method which is easy to operate and has high productivity is preferred. From a high point of view, solution polymerization is preferred.

[0092] Since the solution polymerization of the copolymer (S) is usually carried out in the presence of a solvent, it is also preferable to contain a solvent. The solvent is not particularly limited, but examples thereof include the organic solvents described below. do.

[0093] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propyl Pyrene glycol monomethyl ether, propylene glycol monoethyl ether, Pyrene glycol mono-n-butyl ether, propylene glycol t-butyl ether Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Diethylene glycol mono-n-butyl ether, dipropylene glycol monoethylene ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutyl ethanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether , triethylene glycol monoethyl ether, tripropylene glycol methyl ether glycol monoalkyl ethers such as methyl methyl ether; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene Glycols such as glycol dibutyl ether and dipropylene glycol dimethyl ether alkyl dialkyl ethers; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Terephthalate, Ethylene glycol mono-n-butyl ether acetate, Propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monobutyl ether acetate, 3-methoxy-1-butyl acetate, methoxypentyl ethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Cholesterol monoethyl ether acetate, diethylene glycol mono-n-butyl ether Acetate, Dipropylene Glycol Monomethyl Ether Acetate, Triethylene Glycol Cholesterol monomethyl ether acetate, triethylene glycol monoethyl ether acetate glycol alkyl ethers such as 3-methyl-3-methoxybutyl acetate, Acetates; Ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene Glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanol glycol diacetates such as glycol diacetate; alkyl acetates such as cyclohexanol acetate; Amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di Butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether Ethers such as; Acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, Diisoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone methyl butyl ketone, cyclohexanone, ethyl amyl ketone, methyl hexyl ketone ketones such as pentanone, methyl nonyl ketone, and methoxymethyl pentanone; Methanol, ethanol, propanol, butanol, hexanol, cyclohexanol ethylene glycol, propylene glycol, butanediol, diethylene glycol dipropylene glycol, triethylene glycol, methoxymethyl pentanol, Monohydric or polyhydric alcohols such as glycerin and benzyl alcohol; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, Aliphatic hydrocarbons such as dipentene and dodecane; Cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl Alicyclic hydrocarbons such as; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, acetyl acetate Methyl isobutyrate, ethyl propionate, propyl propionate, butyric acid Butyl, Isobutyl Butyrate, Methyl Isobutyrate, Ethyl Caprylate, Ethyl Benzoate, 3-Ethyl Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, 3-methoxypropionate Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, 3- linear or cyclic esters such as butyl methoxypropionate and gamma-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid ; Halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile; Tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, etc. Examples include tetrahydrofurans.

[0094] Commercially available solvents for these include mineral spirits, Balsol #2, and Apco #18. Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso # 150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol Bitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl Examples include Cellosolve Acetate and Diglyme (both trade names).

[0095] The above solvents are capable of dissolving or dispersing each component of the copolymer (S), The temperature is selected depending on the method of use of the photosensitive resin composition of the present invention, but from the viewpoint of coating properties, the temperature is preferably at atmospheric pressure. It is preferable to select a solvent having a boiling point in the range of 60 to 280°C. It has a boiling point of 70°C or higher and 260°C or lower, for example, propylene glycol monomer. ethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether Acetate, 3-methoxy-1-butyl acetate, methyl isobutyl ketone, butyl acetate Chill is preferred.

[0096] These solvents may be used alone or in combination of two or more. These solvents are added so that the solid content of the copolymer (S) is 10 to 90%. More preferably, it is 20 to 70%, even more preferably, it is 25 to 60%, and particularly preferably, it is 30%. Within this range, it is easy to control the molecular weight and polydispersity of the polymer, and the repellency is improved. A copolymer (S) having excellent liquidity and leveling properties can be obtained.

[0097] [Polymerization inhibitor] When the copolymer (S) is obtained by solution polymerization, it is preferable to add a polymerization inhibitor after the polymerization. Addition of a polymerization inhibitor can improve the storage stability of the copolymer (S). The polymerization inhibitor to be used is not particularly limited, but examples thereof include hydroquinone and hydroquinone monomethyl ester. Ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl Among these, from the viewpoint of polymerization inhibition ability, Hydroquinone or methoxyphenol is preferred, and methylhydroquinone is more preferred. It's nice.

[0098] These polymerization inhibitors may be used alone or in combination of two or more. In addition, the content of these polymerization inhibitors in the solid content of the copolymer (S) is 0.001 to 10%. It is preferably added in an amount of 0.005 to 5%, and more preferably in an amount of 0.01 to 2%. The content is particularly preferably 0.02 to 1%. When the content is within this range, the storage stability of the copolymer (S) is improved. Excellent performance.

[0099] [catalyst] When an ethylenically unsaturated group is introduced into the copolymer (S), a catalyst may be used. The addition of a polymerization inhibitor can increase the efficiency of introducing ethylenically unsaturated groups, and The catalyst is used to improve the reaction rate of the ethylenically unsaturated group. There is no particular limitation as long as it is, and examples thereof include phosphine compounds, chain alkyl tertiary amine compounds, aromatic Examples include tertiary amine compounds, heterocyclic tertiary amine compounds, and organometallic compounds. Examples of the phosphine compound include triphenylphosphine. Examples of the chain alkyl tertiary amine compound include dimethylbenzylamine, trimethylbenzylamine, and methylbenzylamine. Examples include ethylamine, tetramethylethylenediamine, and tri-n-octylamine. do. Examples of the aromatic tertiary amine compound include pyridine, picoline, lutidine, dimethicone, and methyl. ethylaminopyridine and the like. Examples of the heterocyclic tertiary amine compound include N-methylpyrrolidine, N-methylpyrrolidine, Isopiperidine, 1,4-dimethylpiperazine, quinuclidine, 1,4-diazabicyclo{ 2.2.2} Octane (DABCO), N-methylmorpholine, 1,5-diazabicyclo [4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undecane -5-sen (DBU) and others. Organometallic compounds Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dilaurate Ctyl, etc. are used. Among these, dibutyltin diacetate, dibutyltin dilaurate, dilauric acid, Triphenylphosphine is readily available and is therefore preferred.

[0100] These catalysts may be used alone or in combination of two or more. These catalysts are added in an amount of 0.001 to 10% based on the solid content of the copolymer (S). More preferably, it is added in an amount of 0.002 to 5%, even more preferably 0.005% to 2%, and especially preferably 0.005% to 2%. When it is in this range, the ethylenic acid group is easily absorbed into the copolymer (S). Excellent efficiency in introducing unsaturated groups.

[0101] <Photosensitive resin composition> The photosensitive resin composition is a mixture of the above-mentioned copolymer (S), a crosslinking agent, an alkali-soluble resin, a photo-cleaving agent, and a photopolymerizable compound. Examples include those containing an initiator, a pigment, and a solvent. When the photosensitive resin composition is irradiated with active energy rays, the active energy of the copolymer (S) Radicals are generated from functional groups capable of generating radicals by irradiation of radiation, and the generated radicals are The copolymer (S) of the present invention is a photosensitive resin composition having a high curing rate and a high polymerization rate. Radical polymerization by functional groups capable of generating radicals and ethylenically unsaturated groups upon irradiation with γ-rays The simultaneous occurrence of polymerization reactions achieves both good exposure sensitivity and high crosslink density.

[0102] [Copolymer (S)] The content of the copolymer (S) as a solid content in the photosensitive resin composition is The amount is preferably 0.01 to 15 mass % of the total solid content, and more preferably 0.02 to 10 mass %. % by mass, more preferably 0.03 to 5% by mass, particularly preferably 0.05 to 2% by mass, The preferred range is 0.07 to 1% by mass. By using the agent in the above range, the agent has good liquid repellency. This becomes: The nonvolatile content of the photosensitive resin composition is the total mass of components other than the solvent such as the organic solvent. The proportion of nonvolatile matter in the photosensitive resin composition can be measured by a conventionally known method, for example, For example, 1 g of the composition was spread and heated at 100°C for 1 hour to volatilize the organic solvent. It can be calculated from the change in weight.

[0103] [Crosslinking agent] The crosslinking agent contained in the photosensitive resin composition may be any agent having a radical polymerizable group. Various well-known compounds can be used. Among them, polyfunctional compounds having two or more functional groups (metal compounds) are preferred. A suitable material is acrylate.

[0104] The polyfunctional (meth)acrylate is not particularly limited, and examples thereof include bifunctional (meth)acrylates, A mixture of one or more types of trifunctional or higher polyfunctional (meth)acrylates, and a curable resin material or other products that are commercially available in the market, as long as they do not impair the purpose of this embodiment. In addition, other components may be further added to the composition. Among these, trifunctional or higher functional compounds are preferred from the viewpoint of excellent curing properties, stain resistance, and liquid repellency. The polyfunctional (meth)acrylates of the formula are preferred.

[0105] The difunctional polyfunctional (meth)acrylate is not particularly limited, but examples thereof include For example, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedi All di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate Alkanediol di(meth)acrylates, bisphenol A ethylene oxide modified Di(meth)acrylate, bisphenol F, ethylene oxide modified di(meth)acrylate bisphenol-modified di(meth)acrylates, polyethylene glycol di(meth)acrylates, etc. acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate p) acrylates, etc.

[0106] The trifunctional or higher polyfunctional (meth)acrylate is not particularly limited, but may be: For example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetraacetate Pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethicone Cholesterol propane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified diacrylate Pentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol Thuritol tetra(meth)acrylate, ethylene oxide modified pentaerythritol Ethylene oxide modified (meth)acrylates such as tri(meth)acrylate, isocyanate Nuric acid ethylene oxide modified tri(meth)acrylate, ε-caprolactone modified tri Isocyanuric acid-modified tri(meth)acrylates such as tris(acryloxyethyl)isocyanurate Dipentaerythritol penta(meth)acrylate dibasic acid anhydride adduct, Dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate, polyisocyanate ester compound and hydroxyl group-containing (meth)acrylic ester or polyisocyanate compound and poly Urethane obtained by reacting acrylate and hydroxyl group-containing (meth)acrylic acid ester Poly(meth)acrylates; Polyepoxy compounds and hydroxy(meth)acrylates or Epoxy acrylates such as addition products with (meth)acrylic acid; ethylene bis(acrylic acid); acrylamides such as diallyl phthalate; allyl esters such as diallyl phthalate; divinyl phthalate Among these, dipentaerythritol, vinyl group-containing compounds such as thalates, etc. Pentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, Dipentaerythritol tri(meth)acrylate, ethylene oxide modified dipentaerythritol Pentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tetra Tri(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate Acrylate, dipentaerythritol penta(meth)acrylate with dibasic acid anhydride dibasic acid anhydride adducts of pentaerythritol tri(meth)acrylate, etc. These crosslinking agents may be used alone or in combination of two or more.

[0107] In the present invention, the molecular weight of the crosslinking agent is not particularly limited, but from the viewpoint of forming a high film strength, Preferably, it is 100 or more, more preferably 150 or more, and even more preferably 200 or more. , even more preferably 300 or more, particularly preferably 400 or more, and most preferably 500 It is preferably 1,000 or less, more preferably 700 or less. For example, 10 0 to 1,000, preferably 150 to 1,000, more preferably 200 to 1,000, More preferably, it is 300 to 700, even more preferably, it is 400 to 700, and particularly preferably It is 500 to 700.

[0108] The content of the crosslinking agent in the photosensitive resin composition of the present invention is Preferably 1 to 80 mass%, more preferably 5 to 70 mass%, further preferably 10 to 60% by mass, particularly preferably 15 to 50% by mass, most preferably 20 to 40% by mass By using it in the above range, the liquid repellency can be improved and the residue after alkaline development can be reduced. Cut.

[0109] [Alkali-soluble resin] The photosensitive resin composition contains an alkali-soluble resin (P). The alkali-soluble resin (P) in the present invention is a resin that can be developed with an alkali developer, and It does not fall under the copolymer (S) of the present invention. Examples of alkali-soluble resins include various resins having a carboxyl group or a hydroxyl group. However, from the viewpoint of excellent developability, those having a carboxyl group are preferred. In addition, from the viewpoint of improving liquid repellency, an alkali-soluble resin having an ethylenically unsaturated group is preferred. is preferred.

[0110] The alkali-soluble resin (P) of the photosensitive resin composition of the present invention has a side chain containing a hydroxyl group from the viewpoint of liquid repellency. It is preferable that the resin contains an acrylic alkali-soluble resin (PA) having an ethylenically unsaturated group. On the other hand, from the viewpoint of linearity of the cured product pattern, alkali-soluble epoxy resins are preferred. It is preferred that the polymer contains (PE).

[0111] Furthermore, from the viewpoint of achieving both liquid repellency and linearity, alkali-soluble resin (P) is preferably an alkali-soluble resin. Both acrylic alkali-soluble resin (PA) and epoxy alkali-soluble resin (PE) It is preferred that the compound contains: First, we will explain in detail about acrylic alkali-soluble resins (PA).

[0112] [Alkali-soluble acrylic resin (PA)] Alkali-soluble acrylic resin (PA) has an ethylenically unsaturated group in the side chain. By using a compound having an olefinic unsaturated group, photocuring occurs upon exposure to light, forming a stronger film. This makes it difficult for the copolymer (S) to flow out during development, which is thought to facilitate the development of liquid repellency. can be done.

[0113] The acrylic alkali-soluble resin (PA) has a side chain with an ethylenically unsaturated group. The partial structure to be contained is not particularly limited, but from the viewpoint of the ease of radical dissipation due to the flexibility of the film, Therefore, it is preferable that the compound has a partial structure represented by the following general formula (I), for example.

[0114] [ka]

[0115] [In formula (I), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group. * represents a linking hand. vinegar.]

[0116] Furthermore, among the partial structures represented by formula (I), from the viewpoint of sensitivity and alkaline developability, A partial structure represented by the following general formula (I') is preferred.

[0117] [ka]

[0118] [In formula (I'), R 1 and R 2 R each independently represents a hydrogen atom or a methyl group. X is a hydrogen atom represents a dibasic or polybasic acid residue.]

[0119] The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrofuran, Taric acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tet tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, 1 selected from the group consisting of lorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid One or more species may be mentioned. Among these, from the viewpoint of linearity of the cured product pattern, maleic acid and amber are preferable. Acid, Itaconic Acid, Phthalic Acid, Tetrahydrophthalic Acid, Hexahydrophthalic Acid, Pyromellitic Acid tetracarboxylic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferably tetrahydroxybenzoates. These are phthalic acid and biphenyltetracarboxylic acid.

[0120] The acrylic alkali-soluble resin (PA) contains a partial structure represented by the general formula (I). In this case, the content ratio is not particularly limited, but the structure of the acrylic alkali-soluble resin (PA) The amount is preferably 10 mol% or more, more preferably 20 mol% or more, based on the total number of moles of the structural units; More preferably, it is 30 mol % or more, even more preferably 40 mol % or more, and even more preferably 50 mol % or more. or more is particularly preferred, and 99 mol% or less is preferred, and 95 mol% or less is more preferred, More preferably, it is 90 mol % or less, even more preferably 80 mol % or less, and even more preferably 70 mol % or less. For example, 10 to 99 mol %, preferably 20 to 95 mol %, more preferably Preferably 30 to 90 mol%, more preferably 40 to 80 mol%, and even more preferably 50 to 80 mol%. By making the content equal to or greater than the lower limit, the liquid repellency tends to be improved. By adjusting the content to the upper limit or less, a highly precise cured product pattern with a narrow line width tends to be formed. do.

[0121] The acrylic alkali-soluble resin (PA) contains a partial structure represented by the general formula (I'). When the resin is used, the content ratio is not particularly limited, but the content ratio of the acrylic alkali-soluble resin (PA) is It is preferably 10 mol % or more, more preferably 20 mol % or more, based on the total number of moles of the structural units. , more preferably 30 mol% or more, even more preferably 40 mol% or more, and 50 mol% More than 99 mol % is particularly preferred, and 95 mol % or less is more preferred. , more preferably 90 mol % or less, even more preferably 80 mol % or less, and 70 mol % The following is particularly preferred: for example, 10 to 99 mol %, preferably 20 to 95 mol %, more preferably Preferably, it is 30 to 90 mol %, more preferably 40 to 80 mol %, and even more preferably The content is 50 to 70 mol %. By making the content equal to or greater than the lower limit, the liquid repellency tends to be improved. In addition, by setting the content to the upper limit or less, a highly precise cured product pattern with a narrow line width tends to be formed. be.

[0122] (Partial structure represented by general formula (II)) The acrylic alkali-soluble resin (PA) contains a partial structure represented by the general formula (I). In this case, the other partial structures contained are not particularly limited, but from the viewpoint of development adhesion, for example, It is preferable that the compound further has a partial structure represented by the following general formula (II).

[0123] [ka]

[0124] [In formula (II), R 3 represents a hydrogen atom or a methyl group, and R 4 may have a substituent an alkyl group, an aromatic ring group which may have a substituent, or an alkoxy group which may have a substituent; represents a methyl group.]

[0125] (R 4 ) In the formula (II), R 4 is an alkyl group which may have a substituent, and represents an optionally substituted aromatic ring group or an optionally substituted alkenyl group. R 4 The alkyl group in the formula (I) may be a straight-chain, branched-chain or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more. Particularly preferably 8 or more, and more preferably 20 or less, more preferably 18 or less, and most preferably 16 or less. is more preferred, 14 or less is even more preferred, and 12 or less is particularly preferred. For example, 1 to 20 is preferable, 1 to 18 is more preferable, 3 to 16 is even more preferable, and 5 to 14 is It is even more preferable, and particularly preferable is 8 to 12. By making it equal to or more than the lower limit, the film strength is high. The resulting adhesiveness during development tends to improve, and by adjusting the amount to the upper limit or less, the amount of residue is reduced. There is a tendency to decrease.

[0126] Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, and a dicyclopentyl group. Among these, dicyclopentyl group and dodecanyl group are preferred from the viewpoint of developability. A cyclopentanyl group or a dodecanyl group is preferred, and a dicyclopentanyl group is more preferred. The substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, and the like. hydroxyl group, amino group, epoxy group, oligoethylene glycol Examples include acryloyl, phenyl, carboxyl, acryloyl, and methacryloyl groups. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

[0127] R 4 The aromatic ring group in the formula (I) is a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic ring group. The number of carbon atoms is preferably 6 or more, and 24 or less, and more preferably 22 or less. More preferably, 20 or less is furthermore preferable, and 18 or less is particularly preferable. 4, preferably 6 to 22, more preferably 6 to 20, and further preferably 6 to 18. By setting the content to the lower limit or more, the development adhesion tends to be improved, and by setting the content to the upper limit or less, This tends to reduce residue. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pentaerythrene ring, a rylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, Examples include an acenaphthene ring, a fluoranthene ring, and a fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of suitable rings include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, and pyrrolidone rings. azole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazoline ring pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoyl ring isoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring azine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, stilbene ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring quinazoline ring, quinazolinone ring, azulene ring, etc. From this viewpoint, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The substituents that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, and the like. group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group Examples include the carboxylic acid group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

[0128] R 4 The alkenyl group in the formula (I) includes a straight-chain, branched-chain or cyclic alkenyl group. The number of carbon atoms is 2 or more, and preferably 22 or less, more preferably 20 or less. It is more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22, preferably 2 to 20, more preferably 2 to 18, and further preferably 2 to It is preferably 16, and even more preferably 2 to 14. By making it equal to or more than the lower limit, the adhesion during development is improved. By adjusting the content to the upper limit or less, the amount of residue tends to be reduced.

[0129] The substituents that the alkenyl group may have include a methoxy group, an ethoxy group, a chlorine group, a methyl ... C12O group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene Examples include glycol groups, phenyl groups, and carboxyl groups. From the viewpoint of developability, An oxy group and an oligoethylene glycol group are preferred.

[0130] In this way, R 4 represents an alkyl group which may have a substituent, It represents an aromatic ring group or an alkenyl group which may have a substituent. From the viewpoint of the property and film strength, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred. It's nice.

[0131] The acrylic alkali-soluble resin (PA) contains a partial structure represented by the general formula (II). When the resin is used, the content ratio is not particularly limited, but the content ratio of the acrylic alkali-soluble resin (PA) is It is preferably 1 mol% or more, more preferably 2 mol% or more, based on the total number of moles of the structural units. % or more, more preferably 10 mol % or more, particularly preferably 20 mol % or more. It is more preferable that the content is 70 mol % or less, more preferably 60 mol % or less, and more preferably 50 mol % or less. For example, 1 to 70 mol %, more preferably 1 to 70 mol % or less, and particularly preferably 40 mol % or less. Preferably, it is 2 to 70 mol %, more preferably, it is 5 to 60 mol %, and further preferably, it is 10 to 5 0 mol %, particularly preferably 20 to 40 mol %. Furthermore, by making the content equal to or less than the upper limit, the amount of residue tends to be reduced.

[0132] (Partial structure represented by general formula (III)) The acrylic alkali-soluble resin (PA) contains a partial structure represented by the general formula (I). In this case, the partial structure contained therein may be, from the viewpoint of heat resistance and film strength, a structure represented by the following general formula (III): It is preferred that the partial structure shown in the figure is included.

[0133] [ka]

[0134] [In formula (III), R 5 represents a hydrogen atom or a methyl group, and R 6 may have a substituent an alkyl group, an alkenyl group which may have a substituent, an alkyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkyl group, It represents an alkoxy group, a thiol group, or an alkylsulfide group which may have a substituent. t represents an integer from 0 to 5.

[0135] (R 6 ) In the formula (III), R 6 is an alkyl group which may have a substituent, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent. R 6 The alkyl group in the formula (I) may be a straight-chain, branched-chain or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more. , and is preferably 20 or less, more preferably 18 or less, and even more preferably 16 or less. It is more preferably 4 or less, and particularly preferably 12 or less. For example, it is 1 to 20, preferably It is 1 to 18, more preferably 3 to 16, and even more preferably 5 to 14. By setting the value to the upper limit or less, the adhesion of the developing agent tends to be improved. tends to decrease.

[0136] Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, and a dicyclopentyl group. Among these, di- and di-methyl groups are preferred from the viewpoint of developability and film strength. A cyclopentanyl group or a dodecanyl group is preferred, and a dicyclopentanyl group is more preferred. . The substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, and the like. hydroxyl group, amino group, epoxy group, oligoethylene glycol Examples include acryloyl, phenyl, carboxyl, acryloyl, and methacryloyl groups. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

[0137] R 6 The alkenyl group in the formula (I) includes a straight-chain, branched-chain or cyclic alkenyl group. The number of carbon atoms is 2 or more and preferably 22 or less, more preferably 20 or less. Preferably, 18 or less is more preferred, 16 or less is even more preferred, and 14 or less is particularly preferred. For example, it is 2 to 22, preferably 2 to 20, more preferably 2 to 18, and further preferably The range is preferably 2 to 16, and more preferably 2 to 14. Adhesion tends to be improved, and by setting the content to the upper limit or less, residue tends to be reduced. be.

[0138] The substituents that the alkenyl group may have include a methoxy group, an ethoxy group, a chlorine group, a methyl ... C12O group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene Examples include glycol groups, phenyl groups, and carboxyl groups. From the viewpoint of developability, An oxy group and an oligoethylene glycol group are preferred.

[0139] R 6 The alkynyl group in the formula (I) includes a straight-chain, branched-chain or cyclic alkynyl group. The number of carbon atoms is 2 or more and preferably 22 or less, more preferably 20 or less. Preferably, 18 or less is more preferred, 16 or less is even more preferred, and 14 or less is particularly preferred. For example, it is 2 to 22, preferably 2 to 20, more preferably 2 to 18, and further preferably The range is preferably 2 to 16, and more preferably 2 to 14. Adhesion tends to be improved, and by setting the content to the upper limit or less, residue tends to be reduced. be.

[0140] The substituents that the alkynyl group may have include a methoxy group, an ethoxy group, a chlorine group, a methyl ... C12O group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene Examples include glycol groups, phenyl groups, and carboxyl groups. From the viewpoint of developability, An oxy group and an oligoethylene glycol group are preferred.

[0141] R 6 The halogen atoms in the formula include fluorine, chlorine, bromine, and iodine atoms. Among these, fluorine atoms are preferred from the viewpoint of liquid repellency.

[0142] R 6 The alkoxy group in the formula (I) includes a linear, branched or cyclic alkoxy group. The number of carbon atoms is 1 or more and preferably 20 or less, more preferably 18 or less. Preferably, 16 or less is more preferred, 14 or less is even more preferred, and 12 or less is particularly preferred. For example, it is 1 to 20, preferably 1 to 18, more preferably 1 to 16, and further preferably The range is preferably 1 to 14, and more preferably 1 to 12. Adhesion tends to be improved, and by setting the content to the upper limit or less, residue tends to be reduced. be.

[0143] The substituents that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, and the like. hydroxyl group, amino group, epoxy group, oligoethylene glycol Examples include acryloyl, phenyl, carboxyl, acryloyl, and methacryloyl groups. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

[0144] R 6 The alkyl sulfide group in the formula (I) may be a linear, branched or cyclic alkyl sulfide group. The number of carbon atoms is preferably 1 or more and 20 or less. , more preferably 18 or less, even more preferably 16 or less, and even more preferably 14 or less. For example, 1 to 20, preferably 1 to 18, more preferably 1 The lower limit is preferably 1 to 16, more preferably 1 to 14, and even more preferably 1 to 12. By setting the amount to be equal to or greater than the upper limit, the development adhesion tends to be improved. Residue tends to be reduced.

[0145] In addition, examples of the substituent that the alkyl group in the alkyl sulfide group may have include: Methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, Epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl From the viewpoint of developability, hydroxyl groups, oligoethylene groups, etc. are preferred. The glycol group is preferred.

[0146] In this way, R 6 represents an alkyl group which may have a substituent, Alkenyl group, alkynyl group which may have a substituent, hydroxyl group, carboxyl group group, halogen atom, alkoxy group, hydroxyalkyl group, thiol group, or a substituent Among these, from the viewpoint of developability, hydroxyl groups are preferred. An alkoxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0147] In the formula (III), t represents an integer of 0 to 5. From the viewpoint of ease of production, it is preferable that t is 0. It is preferable that:

[0148] The alkali-soluble acrylic resin (PA) has a partial structure represented by the general formula (III) When it is contained, the content ratio is not particularly limited, but acrylic alkali-soluble resin (PA) The amount is preferably 0.5 mol % or more, more preferably 1 mol % or more, based on the total number of moles of the structural units. It is preferably 2 mol % or more, more preferably 4 mol % or more, and more preferably 50 mol % or more. Preferably, the content is 30 mol % or less, more preferably 20 mol % or less, and even more preferably 10 It is more preferably 0.5 to 50 mol % or less, and particularly preferably 6 mol % or less. mol %, preferably 1 to 30 mol %, more preferably 1 to 20 mol %, and even more preferably It is 2 to 10 mol %, and even more preferably 4 to 6 mol %. The uniformity of the film tends to be improved by adjusting the content to the upper limit or less, and the amount of residue is reduced. There is a tendency.

[0149] (Partial structure represented by general formula (IV)) The acrylic alkali-soluble resin (PA) has a partial structure represented by the general formula (I). In this case, the partial structure contained in the compound may be represented by the following general formula (IV) from the viewpoint of developability: It is also preferable that the compound has a partial structure.

[0150] [ka]

[0151] [In formula (IV), R 7 represents a hydrogen atom or a methyl group.

[0152] The alkali-soluble acrylic resin (PA) contains a partial structure represented by the general formula (IV). When the resin is used, the content ratio is not particularly limited, but the content ratio of the acrylic alkali-soluble resin (PA) is It is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total number of moles of the structural units, More preferably, it is 20 mol % or more, and 80 mol % or less is preferable, and 70 mol % or less is preferable. For example, 5 to 80 mol %, preferably It is 10 to 70 mol %, more preferably 20 to 60 mol %. Residue tends to be reduced by setting the content to the upper limit or less, and liquid repellency tends to be improved by setting the content to the upper limit or less. There is.

[0153] On the other hand, the acid value of the acrylic alkali-soluble resin (PA) is not particularly limited, but may be, for example, , 10 to 150 mg KOH / g, preferably 10 to 140 mg KOH / g, more preferably is preferably 15 to 130 mgKOH / g, more preferably 20 to 120 mgKOH / g, and even more preferably It is more preferably 25 to 120 mgKOH / g. Furthermore, by making the content equal to or less than the upper limit, the development adhesion tends to be improved. be.

[0154] The weight average molecular weight (Mw) of the acrylic alkali-soluble resin (PA) is not particularly limited. is usually 1,000 or more, preferably 2,000 or more, more preferably 4,000 or more, More preferably, it is 6,000 or more, even more preferably, it is 7,000 or more, and particularly preferably is 8,000 or more, and is usually 30,000 or less, preferably 20,000 or less, It is more preferably 15,000 or less, and even more preferably 10,000 or less. For example, 1,000 to 30,000, preferably 2,000 to 20,000, more preferably 4, 000 to 20,000, more preferably 6,000 to 15,000, even more preferably It is preferably 7,000 to 15,000, and particularly preferably 8,000 to 10,000. By setting the content to the lower limit or more, the development adhesion tends to be improved, and by setting the content to the upper limit or less, This tends to reduce residue.

[0155] Content of acrylic alkali-soluble resin (PA) in alkali-soluble resin (P) is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, More preferably 0% by mass or more, even more preferably 50% by mass or more, and even more preferably 55% by mass or more is particularly preferred, and 90% by mass or less is preferred, and 80% by mass or less is more preferred. It is more preferably 0% by mass or less, and particularly preferably 65% ​​by mass or less. % by mass, preferably 30 to 80% by mass, more preferably 40 to 80% by mass, and even more preferably is 50 to 70 mass %, and even more preferably 55 to 65 mass %. By setting the value to the upper limit or less, the liquid repellency tends to be improved. It tends to be possible to form a highly precise cured product pattern.

[0156] In addition, alkali-soluble resin (P) is an acrylic alkali-soluble resin (PA) and epoxy If both acrylic alkali-soluble resin (PA) and acrylic alkali-soluble resin (PE) are included, The content ratio of acrylic alkali-soluble resin (PA) and epoxy alkali-soluble resin is 10 to 90 mass%, preferably 30 to 80 mass%, based on the total content of the polyethylene (PE). %, more preferably 40 to 80 mass %, and even more preferably 50 to 70 mass %. By making the content equal to or greater than the lower limit, the liquid repellency tends to be improved. By setting the value to be equal to or less, the perpendicularity of the cross section of the cured product pattern tends to be improved.

[0157] Specific examples of the acrylic alkali-soluble resin (PA) include those disclosed in Japanese Patent Application Laid-Open No. 2002-244994. Examples of the resins include those described in Japanese Patent Application Laid-Open No. 2001-89533 and Japanese Patent Application Laid-Open No. 2001-297366. can be done.

[0158] Next, the alkali-soluble epoxy resin (PE) will be described in detail.

[0159] [Epoxy-based alkali-soluble resin (PE)] Alkali-soluble epoxy resin (PE) is an epoxy resin with an ethylenically unsaturated monocalcium phosphate. After adding a carboxylic acid or an ester compound and optionally reacting with an isocyanate group-containing compound, and further reacted with a polybasic acid or its anhydride. The carboxyl group of an unsaturated monocarboxylic acid is added to the oxy group to form an epoxy group. An ethylenically unsaturated bond is added to the silyl compound via an ester bond (-COO-). The hydroxyl group generated at this stage is then added to one of the carboxyl groups of the polybasic acid anhydride. When adding a polybasic acid anhydride, a polyhydric alcohol can be added at the same time. Some examples include:

[0160] In addition, a compound having a functional group capable of further reacting with the carboxyl group of the resin obtained by the above reaction may be used. Resins obtained by reacting these compounds are also included in the above-mentioned alkali-soluble epoxy resins (PE). do. In this way, epoxy (meth)acrylate resins essentially contain epoxy groups in their chemical structure. and is not limited to "(meth)acrylate", but includes epoxy compounds ( The raw material is epoxy resin, and "(meth)acrylate" is a typical example, so it is commonly used. It is named this way according to

[0161] Here, epoxy resin includes the raw material compounds before they are thermally cured to form the resin. The epoxy resin is selected appropriately from among known epoxy resins. The epoxy resin may be a phenolic compound and an epihalohydrin. The compound obtained by the reaction can be used. or compounds having divalent or higher phenolic hydroxyl groups, whether monomeric or polymeric. good. Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin , Bisphenol S epoxy resin, Phenol novolac epoxy resin, Cresol novolac lac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin Epoxy resin polymerized with phenol and dicyclopentadiene, dihydroxyfur fluorene-type epoxy resin, dihydroxyl alkylene oxyl fluorene-type epoxy resin Diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene , diglycidyl ether of 1,1-bis(4'-hydroxyphenyl)adamantane In this way, those having an aromatic ring in the main chain can be preferably used. .

[0162] Among these, bisphenol A epoxy resin and biphenyl novolac resin are preferred from the viewpoint of high hardened strength. lac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy Resin, phenol and dicyclopentadiene polymerized epoxy resin, 9,9-bis(4' -hydroxyphenyl)fluorene diglycidyl ethers are preferred, Phenol A epoxy resin is particularly preferred. Specific examples of epoxy resins include bisphenol A epoxy resins (e.g., Mitsubishi Chemical Corporation's "jER (registered trademark, hereinafter the same) 828" and "jER1001" "jER1002", "jER1004", "NER-1302" (epoxy) manufactured by Nippon Kayaku Co., Ltd. hydroxyl equivalent 323, softening point 76°C), bisphenol F type resin (e.g., Mitsubishi Chemical "jER807", "jER4004P", "jER4005P", "jER40 07P" and Nippon Kayaku's "NER-7406" (epoxy equivalent: 350, softening point: 66°C) etc.), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g., Mitsubishi Chemical Co., Ltd.'s "jERYX-4000"), phenol novolac epoxy resin (e.g. For example, "EPPN (registered trademark, the same applies hereinafter)-201" manufactured by Nippon Kayaku Co., Ltd., "jER152" and "jER154" manufactured by Dow Chemical Company, and "DEN-438" manufactured by Dow Chemical Company). (o,m,p-)cresol novolac epoxy resin (e.g., "EO CN (registered trademark, the same applies below)-102S", "EOCN-1020", "EOCN-1 04S"), triglycidyl isocyanurate (e.g., "TEPIC ( Trisphenol methane type epoxy resin (for example, "E" manufactured by Nippon Kayaku Co., Ltd.) "PPN-501", "EPPN-502", "EPPN-503"), alicyclic epoxy resin Fat (Daicel Corporation's "Celloxide (registered trademark, the same applies hereinafter) 2021P", "Celloxide" Dicyclopentadiene-phenolic resin (EHPE) is a phenolic resin produced by the reaction of dicyclopentadiene and phenol. Risidylated epoxy resin (e.g., "EXA-7200" manufactured by DIC, "EXA-7200" manufactured by Nippon Kayaku Co., Ltd.) "NC-7300" manufactured by Epoxy Resin Co., Ltd.), epoxy resins represented by the following general formulas (i-11) to (i-14): Specifically, a resin represented by the following general formula (i-11) can be preferably used. The epoxy resin was "XD-1000" manufactured by Nippon Kayaku Co., Ltd., and the epoxy resin was represented by the following general formula (i-12). The epoxy resin used is "NC-3000" manufactured by Nippon Kayaku Co., Ltd., and the epoxy resin represented by the following general formula (i-14) An example of such an epoxy resin is "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

[0163] [ka]

[0164] In the general formula (i-11), n ​​is an average value and represents a number from 0 to 10. 111 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, It represents an alkyl group, a phenyl group, a naphthyl group, or a biphenyl group. Multiple R 111 may be the same or different.]

[0165] [ka]

[0166] In the general formula (i-12), n is an average value and represents a number from 0 to 10. 121 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, It represents an alkyl group, a phenyl group, a naphthyl group, or a biphenyl group. Multiple R 121 may be the same or different.]

[0167] [ka]

[0168] [In the general formula (i-13), X is represented by the following general formula (i-13-1) or (i-13-2): The linking group is represented by the formula: provided that the molecular structure contains one or more adamantane structures. Represents 2 or 3.]

[0169] [ka]

[0170] [In general formulas (i-13-1) and (i-13-2), R 131 ~R 134 and R 135 ~R 1 37 each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, or a phenyl group which may be substituted; * represents a connecting move.]

[0171] [ka]

[0172] [In general formula (i-14), p and q each independently represent an integer of 0 to 4, and R 141 and R 142 R each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom. 143 and R 144 Each of x and y independently represents an alkylene group having 1 to 4 carbon atoms. represent.]

[0173] Among these, epoxy resins represented by any one of general formulas (i-11) to (i-14) It is preferable to use

[0174] Examples of ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid and crotonic acid. , maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., and pentaerythritol Tri(meth)acrylate succinic anhydride adduct, Pentaerythritol tri(meth)acrylate Dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct Dipentaerythritol penta(meth)acrylate anhydride adduct, Dipentaerythritol penta(meth)acrylate anhydride Dipentaerythritol penta(meth)acrylate tetrahydroanhydride Examples include acrylic acid adducts, and reaction products of (meth)acrylic acid and ε-caprolactone. Among these, (meth)acrylic acid is preferred from the viewpoint of sensitivity.

[0175] Examples of polybasic acids (anhydrides) include succinic acid, maleic acid, itaconic acid, and phthalic acid. , tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid phthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydroxybenzoate Hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3 -Ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, Rhomellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and Among them, succinic anhydride, maleic anhydride, etc. are preferred from the viewpoint of outgassing. phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferred. Of these, succinic anhydride or tetrahydrophthalic anhydride is more preferred.

[0176] By using polyhydric alcohol, the molecular weight of the epoxy-based alkali-soluble resin (PE) can be increased. It is possible to increase the size of the polymer and introduce branches into the molecule, achieving a good balance between molecular weight and viscosity. In addition, the introduction rate of acid groups into the molecule can be increased, improving the balance of sensitivity, adhesion, etc. The lance tends to come off easily. Examples of polyhydric alcohols include trimethylolpropane and ditrimethylolpropane. , Pentaerythritol, Dipentaerythritol, Trimethylolethane, 1,2,3 - One or more polyhydric alcohols selected from propanetriol preferable.

[0177] In addition to the above-mentioned epoxy (meth)acrylate resins, there are also those disclosed in Korean Patent Publication No. 10 -2013-0022955 and the like.

[0178] The acid value of the epoxy-based alkali-soluble resin (PE) is not particularly limited, but is preferably 10 mg KOH / g or more is preferable, 30 mgKOH / g or more is more preferable, and 50 mgKOH / g or more is more preferable. is more preferable, and 70 mg KOH / g or more is even more preferable, and 80 mg KOH / g More than 200 mgKOH / g is particularly preferable, and 180 mgKOH / g or less is preferable. g or less, more preferably 150 mgKOH / g or less, even more preferably 120 mgKOH / g or less / g or less is even more preferable, and 110 mgKOH / g or less is particularly preferable. 0 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, more preferably 5 0 to 150 mgKOH / g, more preferably 70 to 120 mgKOH / g, even more preferably The preferred range is 80 to 110 mgKOH / g. By adjusting the value to be equal to or greater than the lower limit, the developability is improved. By adjusting the content to the upper limit or less, the film strength tends to be improved.

[0179] The weight average molecular weight (Mw) of the epoxy alkali-soluble resin (PE) is not particularly limited. is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, More preferably, it is 4,000 or more, and particularly preferably, it is 5,000 or more. 0,000 or less, preferably 20,000 or less, more preferably 15,000 or less, It is preferably 10,000 or less, and particularly preferably 8,000 or less. 00 to 30,000, preferably 2,000 to 20,000, more preferably 3,000 ~15,000, more preferably 4,000 to 10,000, particularly preferably 5,000 By making the molecular weight equal to or greater than the lower limit, the film strength tends to be improved. By adjusting the content to the upper limit or less, the amount of residue tends to be reduced.

[0180] When the alkali-soluble resin (P) contains an epoxy alkali-soluble resin (PE), The content ratio is not particularly limited, but is preferably 10 to 90 mass % in the alkali-soluble resin (P). or 20 to 90% by mass, more preferably 30 to 70% by mass, and further preferably 35 to 70% by mass. It is preferable that the content is 0% by mass, and even more preferably 40 to 60% by mass. By setting the value to be equal to or greater than the upper limit, the linearity tends to improve. It tends to be possible to form a high-definition cured product pattern with a narrow line width.

[0181] The epoxy-based alkali-soluble resin (PE) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and the resulting mixture is heated in the presence of a catalyst and a thermal polymerization inhibitor. the acid or ester compound having an ethylenically unsaturated bond is added to cause an addition reaction, and A method of continuing the reaction by adding a polybasic acid or its anhydride to the reaction mixture can be used. Those listed in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 Examples include the law.

[0182] The organic solvents used in the reaction include methyl ethyl ketone, cyclohexanone, dichloromethane, and methyl methyl ketone. Ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether The catalyst may be one or more organic solvents such as methyl methacrylate, ... is a tertiary amine such as triethylamine, benzyldimethylamine, tribenzylamine, etc. , tetramethylammonium chloride, methyltriethylammonium chloride, Tetraethylammonium chloride, tetrabutylammonium chloride, trimethyl Quaternary ammonium salts such as tribenzyl ammonium chloride, triphenylphosphine One or more of phosphorus compounds such as phenanthrin, stibines such as triphenylstibine, etc. Furthermore, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monomer. Examples of suitable solvents include one or more of methyl ether, methyl hydroquinone, and the like.

[0183] Furthermore, the acid or ester compound having an ethylenically unsaturated bond is, for example, an epoxy resin. Usually, 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1. The amount of the hydroxyl group can be adjusted to 1 chemical equivalent. The temperature during the addition reaction is usually 60 to 180°C. The temperature can be 150°C, preferably 80 to 120°C. The amount of hydroxyl group (hydroxide) used is usually 0. The amount can be 1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents.

[0184] The alkali-soluble resin (P) in the present invention is an acrylic alkali-soluble resin (PA). In addition to epoxy alkali-soluble resin (PE), other alkali-soluble resins are also included. It's okay to be.

[0185] The acid value of the entire alkali-soluble resin (P) is not particularly limited, but is preferably 30 mg KOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more More preferably, it is 200 mg KOH / g or less, and more preferably 150 mg KOH / g or less. It is more preferable that the pH is 100 mgKOH / g or less, and even more preferable that the pH is 100 mgKOH / g or less. For example, mgKOH / g, preferably 50 to 150 mgKOH / g, more preferably 70 to 100 By making the value equal to or greater than the lower limit, the developability tends to be improved. By adjusting the amount of the alkali-soluble toner to be equal to or less than the upper limit of the above range, the adhesion during development tends to be improved. When the resin (P) is a mixture of two or more types, the acid value means the weighted average value according to the content ratio. do.

[0186] The content of the alkali-soluble resin (P) in the photosensitive resin composition of the present invention is not particularly limited. However, it is preferably 5 to 95 mass % based on the total solid content of the photosensitive resin composition, more preferably Preferably, it is 10 to 90% by mass, more preferably 30 to 80% by mass, and particularly preferably 40 to 90% by mass. By making the content of the aluminum alloy equal to or greater than the lower limit, the content of the aluminum alloy is preferably 75% by mass, and most preferably 50 to 70% by mass. Residue after development tends to be reduced, and by keeping the content below the upper limit, the liquid repellency is improved. There is a tendency to rise.

[0187] In addition, the content of the crosslinking agent and the content of the alkali-soluble resin (P) in the total solid content The total amount of the above is not particularly limited, but is preferably 10% by mass or more, and more preferably 30% by mass or more. It is preferable that the content is 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more. % by mass or less is preferable, 92% by mass or less is more preferable, and 90% by mass or less is even more preferable. For example, 10 to 95% by mass, preferably 30 to 95% by mass, more preferably 50 to 92% by mass. By making the content equal to or greater than the lower limit, the cured product The adhesion of the pattern to the substrate tends to be improved, and by setting the value to the upper limit or less, the shielding effect is improved. There is a tendency for light resistance and liquid repellency to improve.

[0188] [Photopolymerization initiator] The photosensitive resin composition of the present invention contains a photopolymerization initiator. For example, the ethylenically unsaturated compound is polymerized by There are no particular limitations on the compound as long as it is a compound that polymerizes ethylenically unsaturated bonds.

[0189] The photosensitive resin composition of the present invention contains, as a photopolymerization initiator, a photopolymerization initiator that is commonly used in this field. A polymerization initiator can be used. Examples of such a photopolymerization initiator include those listed in the Japanese Patent Application Laid-Open No. 2002-20030444. Titanium as described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197 Metallocene compounds including ocene compounds; Hexaarylbiimidazole derivatives; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-phenyl N-aryl-α-amino acids such as glycine, N-aryl-α-amino acid salts, N -Aryl-α-amino acid esters and other radical activators, α-aminoalkylphenones Derivatives; Japanese Patent Publication No. 2000-80068, Japanese Patent Application Publication No. 2006-36750 Examples thereof include oxime ester compounds described in publications and the like.

[0190] Specifically, for example, the metallocene compound is dicyclopentadienyl titanium. Dichloride, Dicyclopentadienyl Titanium Bisphenyl, Dicyclopentadienyl Titanium bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadiene Titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadiene dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl) Titanium di(2,6-difluorophenyl), dicyclopentadienyl titanium di(2 ,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2, 3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium Titanium bis(2,6-difluorophenyl), dicyclopentadienyltitanium 〔2,6 -di-fluoro-3-(pyrrol-1-yl)-phenyl] and the like.

[0191] Biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diimidazole. Phenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methylphenyl)- 2-(2'-fluorophenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-difluoro Phenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole Imidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer etc.

[0192] Halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5- [β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloro 2-(2'-(6''-benzofuryl)vinyl)-1,3,4-oxomethyl-5-[β-(2'-(6''-benzofuryl)vinyl)] ... oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc. Examples include:

[0193] Halomethyl-s-triazine derivatives include 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-ethoxycarbonyl naphthyl)-4,6-bis(trichloromethyl)-s-triazine and the like.

[0194] In addition, α-aminoalkylphenone derivatives include 2-methyl-1[4-(methyl Thio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylamino 4-Dimethylaminoisoamylbenzoate, 4-Diethylaminoisoamylbenzoate Cetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-di Methylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexa Non, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(di ethylamino) chalcone, etc.

[0195] As a photopolymerization initiator, oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties. When using an alkali-soluble resin containing a phenolic hydroxyl group, sensitivity may be poor. Therefore, oxime ester compounds with excellent sensitivity are particularly useful. Oxime ester compounds have a structure that absorbs ultraviolet light and transmits light energy. Because it has both a structure that generates radicals and a structure that generates ions, it has high sensitivity even in small amounts, and It is stable against thermal reactions and a highly sensitive photosensitive resin composition can be obtained with a small amount.

[0196] The oxime ester compound may be, for example, a compound represented by the following general formula (IV): Examples include:

[0197] [ka]

[0198] [In formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or The aromatic ring group may have a substituent. R 21b represents an optional substituent containing an aromatic ring. R 22a represents an alkanoyl group which may have a substituent, or A suitable aryloyl group is shown. n represents an integer of 0 or 1.

[0199] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but it is determined depending on the solubility in the solvent and the sensitivity. From this viewpoint, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less. More preferably, it is 10 or less. For example, it is 1 to 20, preferably 1 to 15, and more preferably is 2 to 10. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a silyl group. Examples include a cyclopentylethyl group. The substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, and a carboxyl group. , halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2 -methylphenyl group or N-acetyl-N-acetoxyamino group, From the viewpoint of ease of use, it is preferably unsubstituted.

[0200] R 21a Examples of the aromatic ring group in the formula (I) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but from the viewpoint of solubility in the photosensitive resin composition, From the viewpoint of developability, it is preferably 30 or less, and more preferably 20 or less. For example, it is 5 to 30, preferably 5 to 20, more preferably 12 or less. Or 5 to 12 or less.

[0201] Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferred, and a phenyl group or a naphthyl group is preferred. A phenyl group is more preferred. The substituents that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, and the like. alkyl groups, amino groups, amide groups, alkyl groups, alkoxy groups, groups in which these substituents are linked, etc. From the viewpoint of developability, alkyl groups, alkoxy groups, and groups formed by linking these groups are preferred. A linked alkoxy group is more preferred. Among these, from the viewpoint of sensitivity, R 21a an alkyl group which may have a substituent, Alternatively, it is preferably an aromatic ring group which may have a substituent.

[0202] Also, R 21bAs the aryl group, a carbazolyl group which may be substituted, a substituted and an optionally substituted diphenyl sulfide group. Among these, from the viewpoint of sensitivity, an optionally substituted carbazolyl group, a substituted An optionally substituted diphenyl sulfide group is preferred, and an optionally substituted carbazo An aryl group is more preferred.

[0203] Also, R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but the solubility in the solvent is From the viewpoint of performance and sensitivity, the number is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably It is 15 or less, more preferably 10 or less, and even more preferably 5 or less. For example, 2 to 20 The number is preferably 2 to 15, more preferably 3 to 10, and even more preferably 3 to 5. Specific examples of the acyl group include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group. groups, etc. The substituents that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, and the like. Examples include alkyl groups, halogen atoms, amino groups, and amide groups. Substitution is preferred.

[0204] Also, R 22a The number of carbon atoms in the aryloyl group is not particularly limited, but the number of carbon atoms in the aryloyl group is determined by the solubility in the solvent. From the viewpoint of performance and sensitivity, the number is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably For example, it is 7 to 20, preferably 7 to 15, more preferably 10 or less. More preferably, it is 8 to 10. Specific examples of the aryloyl group include a benzoyl group, a naphthyl group, and a benzoyl group. Examples of the aryl group include aryl groups. The substituents that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, a hydroxyl group ... Examples include fluorine atoms, amino groups, amide groups, and alkyl groups. Substitution is preferred. Among these, from the viewpoint of sensitivity, R 22a optionally substituted alkanoyl A group is preferred, an unsubstituted alkanoyl group is more preferred, and an acetyl group is even more preferred.

[0205] The photopolymerization initiator may be used alone or in combination of two or more kinds. The photopolymerization initiator may be, if necessary, a compound that responds to the wavelength of the image exposure light source in order to increase sensitivity. The sensitizing dye and polymerization accelerator described in Japanese Patent Application Laid-Open No. 2003-200644 can be blended. Xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Laid-Open No. 4-219756 , as described in Japanese Patent Application Laid-Open No. 3-239703 and Japanese Patent Application Laid-Open No. 5-289335 Coumarin dyes having heterocycles, Japanese Patent Application Laid-Open No. 3-239703, Japanese Patent Application Laid-Open No. 5- 3-ketocoumarin compounds described in Japanese Patent Application Laid-Open No. 289335, Other pyrromethene dyes described in JP-A-47-2528, JP-A-2002-2003, Publication No. 54-155292, Japanese Patent Publication No. 1973-37377, Japanese Patent Publication No. 1973- Publication No. 84183, Japanese Patent Application Publication No. 112681 / 1983, Japanese Patent Application Publication No. 1982-155 Publication No. 03, Japanese Patent Publication No. 60-88005, Japanese Patent Application Publication No. 59-56403 Japanese Patent Publication No. 2-69, Japanese Patent Application Publication No. 168088-1988, Japanese Patent Application Publication No. 1987-168088 Publication No. 5-107761, Japanese Unexamined Patent Publication No. 5-210240, Japanese Unexamined Patent Publication No. 4-2 Examples of the dye include those having a dialkylaminobenzene skeleton described in Patent Publication No. 88818. can.

[0206] Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and A compound having the following in the same molecule is more preferred. '-Dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2- 4-aminobenzophenone, 4,4'-diaminobenzophenone, Benzophenones such as 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone Compounds based on benzoxazole: 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diene 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo [4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7] Benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole Sazol, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethyl 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimida 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p- (p-Diethylaminophenyl)-1,3,4-thiadiazole, (p-Dimethylaminophenyl (p-Diethylaminophenyl)pyridine, (p-Dimethylaminophenyl)pyridine (p-Diethylaminophenyl)quinoline, (p-Dimethylaminophenyl)quinoline, p-Dialkylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. Among these, 4,4'-dialkylaminobenzoates are Zofenone is particularly preferred. The sensitizing dyes may also be used alone or in combination of two or more.

[0207] Examples of the polymerization accelerator include ethyl p-dimethylaminobenzoate, 2-dimethylbenzoate, Aromatic amines such as ethylaminoethyl, n-butylamine, and N-methyldiethanolamine The polymerization accelerator may be used alone or in combination of two or more. The above may be used in combination.

[0208] The content ratio of the photopolymerization initiator in the nonvolatile content (solid content) of the photosensitive resin composition is not particularly limited. However, it is preferably 0.01 to 25% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.01 to 25% by mass. More preferably, it is 0.5 to 10% by mass, particularly preferably 1.0 to 7% by mass, and most preferably The content is 1.5 to 5% by mass. By making the content equal to or greater than the lower limit, the liquid repellency tends to be improved. In addition, by setting the content to the upper limit or less, the amount of residue tends to be reduced.

[0209] It is also preferable to use a chain transfer agent in combination with the photopolymerization initiator. Examples of suitable mercapto group-containing compounds and carbon tetrachloride are compounds that tend to have a high chain transfer effect. Therefore, it is more preferable to use a compound having a mercapto group. The low energy makes bond cleavage more likely, and hydrogen abstraction and chain transfer reactions This is thought to be because it is prone to cause problems. It is effective in improving sensitivity and surface hardening.

[0210] The mercapto group-containing compound includes 2-mercaptobenzothiazole, 2-mercapto Benzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4 -Triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene mercapto group-containing compounds having an aromatic ring such as 1,4-dimethylmercaptobenzene; Hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropio) nate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptomethyl) Butopropionate), ethylene glycol bisthioglycolate, trimethylolpropionate Pantris(3-mercaptopropionate), Trimethylolpropane Tristhioglycol Cholate, Trishydroxyethyl Tristhiopropionate, Pentaerythritol Trachys(3-mercaptopropionate), Pentaerythritol tris(3-mercaptopropionate) butanediol bis(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol Licorbis(3-mercaptobutyrate), Trimethylolpropane Tris(3-mercaptobutyrate) pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), Pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3- Mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-trione and other aliphatic mercapto group-containing compounds, especially those having multiple mercapto groups Examples of compounds include compounds that

[0211] Among these, 2-mercapto group-containing compounds having an aromatic ring are preferred. 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and aliphatic mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred. Among the compounds containing mercapto groups, trimethylolpropane tris(3-mercaptopropione) Pentaerythritol tetrakis(3-mercaptopropionate), Pentaerythritol tetrakis(3-mercaptopropionate), Lithritol tris(3-mercaptopropionate), trimethylolpropane tris( (3-mercaptobutyrate), Pentaerythritol tetrakis(3-mercaptobutyrate) Pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyrate), Tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1 H,3H,5H)-trione is preferred.

[0212] From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred. Methylolpropane tris(3-mercaptopropionate), pentaerythritol Tetrakis(3-mercaptopropionate), Pentaerythritol tris(3-mercaptopropionate) captopropionate), trimethylolpropane tris(3-mercaptobutyrate) , Pentaerythritol tetrakis(3-mercaptobutyrate), Pentaerythritol Lutris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutylo) (1H,3H,5H)-trione Preferred are pentaerythritol tetrakis(3-mercaptopropionate), penta Erythritol tetrakis(3-mercaptobutyrate) is more preferred. These may be used alone or in combination of two or more.

[0213] Among these, from the viewpoint of increasing the taper angle, 2-mercaptobenzothiazole, 2- From the group consisting of mercaptobenzimidazole and 2-mercaptobenzoxazole Use one or more selected compounds in combination with a photopolymerization initiator as a photopolymerization initiator system For example, 2-mercaptobenzothiazole may be used, and 2- Mercaptobenzimidazole may also be used, and 2-mercaptobenzothiazole and 2- Mercaptobenzimidazole may also be used in combination. In addition, from the viewpoint of sensitivity, pentaerythritol tetrakis(3-mercaptopropione) pentaerythritol tetrakis(3-mercaptobutyrate), It is preferable to use one or more selected from the above. 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzothiazole One or more selected from the group consisting of oxazoles and pentaerythritol tetrakis pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate) a photopolymerization initiator and one or more selected from the group consisting of methyl methyl acrylate, methyl butyl acrylate, methyl methyl acrylate, methyl butyl acrylate, methyl methyl butyl acrylate, methyl butyl ... It is preferable to use it as such.

[0214] The content of the chain transfer agent in the nonvolatile content (solid content) of the photosensitive resin composition of the present invention is, in particular, Although not limited thereto, the content is preferably 0.01 to 15 mass %, more preferably 0.1 to 10 mass %. %, more preferably 0.5 to 8 mass%, particularly preferably 0.8 to 6 mass%, and most preferably The content is preferably 1.0 to 4% by mass. By making the content equal to or greater than the lower limit, the liquid repellency tends to be improved. Furthermore, by setting the content to the upper limit or less, a highly precise cured product pattern with a narrow line width can be formed. There is a direction.

[0215] [Coloring agent] The photosensitive resin composition of the present invention contains a colorant. By containing a colorant, it is possible to obtain a suitable light-sensitive resin composition. Absorbency, especially when used to form light-shielding materials such as colored cured products, requires adequate light-shielding properties. can be obtained.

[0216] The colorant in the photosensitive resin composition of the present invention contains a purple pigment, and The content of the purple pigment is 45% by mass or more.

[0217] Purple pigment has an absorption band in the wavelength range of 450nm to 600nm, so Therefore, by including a large amount of purple pigment, the obtained The colored cured material absorbs the green light emitted from the green pixel of the color filter sufficiently. This can absorb light and suppress excitation of the red-light-emitting nanocrystalline particles in the red pixel.

[0218] On the other hand, to obtain a color filter with pixels containing luminescent nanocrystalline particles, a cured A pixel is formed by discharging ink containing dispersed luminescent nanocrystal particles into an area surrounded by an object. To prevent inks from mixing between adjacent pixels, the cured product must have high liquid repellency. A colorant is used to make the cured product a colored cured product. Therefore, the film tends to have low hardness and low liquid repellency.

[0219] In contrast, the photosensitive resin composition of the present invention has a purple pigment content of 45% by mass. By making the content of the colored partition wall 100% by volume or more, it is possible to obtain colored partition walls having good liquid repellency. Purple pigments have an absorption band on the long wavelength side of the visible region, from 450 nm to 600 nm, while It has high transmittance in the short wavelength range of 360nm to 400nm, so it is suitable for colorants containing purple. The high content of color pigments increases the curing property when exposed to ultraviolet light, and the film surface after development is free of any residual color. It is believed that this increases the amount of liquid repellent agent that is absorbed, thereby increasing the liquid repellency of the colored partition walls.

[0220] Furthermore, purple pigments have high transmittance in the wavelength range of 360nm to 400nm, The internal hardening property of the film is high, so even with a thick film, it is possible to form highly precise, vertically aligned colored partition walls. It is believed that this will be possible.

[0221] Purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, and 3. :1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. From the viewpoint of light-blocking properties, CI Pigment Violet 19, 23, 29 is preferable. Preferably CI Pigment Violet 23 and / or CI Pigment Violet On the other hand, from the viewpoint of dispersibility, CI Pigment Violet is It is preferable to use No. 29.

[0222] The content of the purple pigment in the colorant is not particularly limited, but may be determined based on the green light blocking properties and hardening properties. From the viewpoint of chemical properties, the amount of the colorant is 10 to 100% by mass, preferably 20 to 100% by mass, based on the total solid content of the colorant. % by mass, more preferably 25 to 100% by mass, even more preferably 40 to 100% by mass, The content is more preferably 45 to 100% by mass. From the viewpoint of widening the absorption wavelength band, for example, 10 to 99 mass %, preferably Preferably, the content is 20 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 40 to 70% by mass. % by mass, and particularly preferably 45 to 60% by mass.

[0223] Among the above purple pigments, purple pigments are the most popular CI pigments in terms of their ability to block blue light and their curing properties. Preferably, the dye contains Citrine Violet 29. In this case, the content ratio of CI Pigment Violet 29 is not particularly limited. However, it is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 3% by mass or more of the total solid content. More preferably, 4% by mass or more is particularly preferable, and 20% by mass or less is preferable. It is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. For example, 1 to 20% by mass, preferably 2 to 15% by mass, more preferably 3 to 1 0 mass %, more preferably 4 to 5 mass %. The light blocking property tends to be improved, and by making the content equal to or less than the upper limit, the absorption wavelength band can be widened. There is a tendency for The content of CI Pigment Violet 29 in the purple pigment is also limited. However, it is usually, for example, 20 to 99% by mass, preferably 30 to 90% by mass, more preferably It is preferably 40 to 80% by mass, and more preferably 45 to 60% by mass. By setting the value to the upper limit or less, the blue light blocking property and curing property tend to be improved. There is a tendency to be able to widen the absorption wavelength range.

[0224] The colorant does not include colorants other than the purple pigment (hereinafter abbreviated as "other colorants"). Other colorants include pigments and dyes, and pigments are preferred from the viewpoint of heat resistance. In view of color tone, photocurability, and sensitivity, organic pigments are preferred.

[0225] Pigments include yellow pigments, orange pigments, red pigments, blue pigments, green pigments, brown pigments, etc. Organic color pigments are included. Yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, and 9. , 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 3 6, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 6 2, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 1 17, 119, 120, 126, 127, 127:1, 128, 129, 133, 134 , 136, 138, 139, 142, 147, 148, 150, 151, 153, 154 , 155, 157, 158, 159, 160, 161, 162, 163, 164, 165 , 166, 167, 168, 169, 170, 172, 173, 174, 175, 176 , 180, 181, 182, 183, 184, 185, 188, 189, 190, 191 , 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 2 00, 202, 203, 204, 205, 206, 207, and 208 can be mentioned. Among these, CI Pigment Yellow 83, 117, and 118 are the most popular from the viewpoint of dispersibility and reliability. 29, 138, 139, 150, 154, 155, 180, 185 are preferred, and CI Pigment Yellow 138, 139, and 150 are more preferable, and CI Pigment Yellow 139 is particularly preferred.

[0226] Orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 4 6, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73 , 74, 75, 77, 78, 79. Among these, From this viewpoint, it is preferable to use CI Pigment Orange 13, 43, 64, and 72. When the photosensitive resin composition is cured with ultraviolet light, an orange pigment with low ultraviolet absorption rate is used. From this point of view, it is preferable to use CI Pigment Orange 64 and 72. It is more preferable to use CI Pigment Orange 64, and CI Pigment Orange 64 is particularly preferable.

[0227] Red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 4 7, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50 :1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 5 7:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 8 1, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101 :1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123 , 144, 146, 147, 149, 151, 166, 168, 169, 170, 172 , 173, 174, 175, 176, 177, 178, 179, 181, 184, 185 , 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 , 233, 235, 236, 237, 238, 239, 242, 243, 245, 247 , 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, and 276. From the viewpoint of light blocking properties and dispersibility, CI Pigment Red 48:1, 122, 1 49, 168, 177, 179, 194, 202, 206, 207, 209, 224, 2 42, 254, and more preferably CI Pigment Red 177, 209, 224, 2 CI Pigment Red 154 is particularly suitable in terms of dispersibility and light-blocking properties. 77, 254, 272 are preferably used, and the photosensitive resin composition is cured by ultraviolet light. In this case, it is preferable to use a red pigment with low ultraviolet absorption rate. From this point of view, it is more preferable to use CI Pigment Red 254 or 272.

[0228] Blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, and 15:1. , 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 2 9, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 6 7, 68, 71, 72, 73, 74, 75, 76, 78, and 79 can be mentioned. Among these, CI Pigment Blue 15, 15:1, 15 are preferred from the viewpoint of light blocking properties. :2, 15:3, 15:4, 15:6, 16, 60, and more preferably CI pigments Tobre 15:6, 16 can be cited. In terms of dispersibility and light blocking properties, CI Pigment Blue 15:6, 16, and 60 are used. When the photosensitive resin composition is cured by ultraviolet light, it is preferable to use a blue pigment such as It is preferable to use a pigment with low ultraviolet absorption rate. It is more preferable to use Toblue 60.

[0229] Green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, and 1 4, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 Among these, CI pigment groups are preferred from the viewpoint of dispersibility. Examples include Lean 7 and 36.

[0230] Brown pigments include CI Pigment Brown 23, 25, 26, Among these, near-infrared transmittance and blocking properties are From the viewpoint of achieving both high light-transmitting properties and high gloss, CI Pigment Brown 26, 28, and 83 are preferable. , 93 can be cited.

[0231] In addition, a black pigment may be contained as another colorant. Examples include color pigments and inorganic black pigments.

[0232] A specific example of an organic black pigment is Irgaphor® Black k S 0100 CF (manufactured by BASF) is an example. This organic black pigment is preferably dispersed using a dispersant, a solvent, and a method described below. In addition, when dispersing, the compound represented by the general formula (2) or the compound represented by the general formula (2) The presence of sulfonic acid derivatives of geometric isomers of the compounds improves dispersibility and storage stability. There are cases where this happens. In addition, as an organic black pigment, from the viewpoint of optical properties and reliability, The organic black pigments described in Korean Patent Publication No. 18-0052502 and Korean Patent Publication No. 10-2 It is preferable to use the organic black pigments described in JP-A-018-0052864.

[0233] Other organic black pigments include aniline black, cyanine black, and perylene. Black, etc. Carbon black, which is an inorganic black pigment, may also be used.

[0234] Carbon black coated with resin may be used. The use of carbon black has the effect of improving adhesion to the glass substrate and volume resistance. Examples of resin-coated carbon black include those disclosed in Japanese Patent Application Laid-Open No. 09-7173. Carbon black and the like described in Patent Publication No. 3 can be suitably used. In this respect, resin-coated carbon black is preferably used.

[0235] The average primary particle size of the pigment is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably The average primary particle size of the pigment is measured by a transmission electron microscope (TEM), Alternatively, a scanning electron microscope (SEM) can be used to determine the size of primary particles from the electron micrograph. The particle size of each pigment particle is measured by the diameter of a circle with the same area. After determining the particle diameter of each of the pigment particles as the equivalent diameter of the circle with the converted area, Calculate the number average value according to the formula to find the average particle size. Individual pigment particle size: X1,X2,X3,X4,...,Xi,...Xm Average particle diameter=ΣXi / m

[0236] In addition to the above-mentioned pigments, dyes may also be used. Examples of dyes include azo dyes, anthraquinone dyes, and the like. Quinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro Examples of suitable dyes include methyl dyes, carbonyl dyes, and methine dyes. Examples of azo dyes include CI Acid Yellow 11 and CI Acid Orange. CI Acid Red 7, CI Acid Red 37, CI Acid Red 180, CI Acid De Bleu 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green CI Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, C. I. Disperse Blue 165, CI Basic Blue 41, CI Basic Le Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Examples include Dant Black 7.

[0237] Examples of anthraquinone dyes include CI Vat Blue 4 and CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue Examples include CI Disperse Blue 60, CI Blue 56, etc. In addition, phthalocyanine dyes, such as CI Pad Blue 5, are also available. Imine dyes include, for example, CI Basic Blue 3 and CI Basic Blue. 9, etc. are quinoline dyes, for example, CI Solvent Yellow 33, CI A Nitro dyes include CI Disperse Yellow 64 and CI Disperse Yellow 3. CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, etc.

[0238] The content of the colorant in the nonvolatile content (solid content) of the photosensitive resin composition of the present invention is not particularly limited. Although not limited, it is preferably 0.5 to 50 mass %, more preferably 1 to 30 mass %, and further preferably Preferably 2 to 25% by mass, particularly preferably 3 to 20% by mass, most preferably 4 to 10% by mass. By making the content equal to or greater than the lower limit, the light-blocking properties tend to be improved, and by making the content equal to or less than the upper limit, the light-blocking properties tend to be improved. This tends to improve the curability and enable the formation of highly precise partition walls.

[0239] [Dispersant] The photosensitive resin composition of the present invention allows a colorant to be finely dispersed and the dispersed state to be stabilized. In order to achieve this, it is preferable to contain a dispersant. As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, carboxyl group; phosphate group; sulfonic acid group; or their bases; primary, secondary or tertiary alkyl groups Amino group; quaternary ammonium base; nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine Polymer dispersants having functional groups such as primary, secondary or tertiary groups are preferred. Amino groups; quaternary ammonium bases; nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine When polymer dispersants having basic functional groups such as those derived from This is particularly preferred from the viewpoint of dispersibility.

[0240] Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethylene dispersants, and the like. Polyimine-based dispersants, polyallylamine-based dispersants, monomers and macromonomers with amino groups dispersants consisting of mers, polyoxyethylene alkyl ether dispersants, polyoxyethylene Polyester dispersant, polyether phosphate dispersant, polyester phosphate dispersant, Examples of dispersants include aliphatic ester dispersants and aliphatic modified polyester dispersants. Cut.

[0241] A specific example of such a dispersant is EFKA (registered trademark, manufactured by BASF) , DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPERLON (registered trademark, manufactured by Kusumoto) Kasei Co., Ltd.), SOLSPERSE (registered trademark, Lubrizol Corporation), KP (Shin-Etsu Chemical Co., Ltd.) Examples include Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.). It can be done. These polymer dispersants may be used alone or in combination of two or more.

[0242] The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more. and is usually 100,000 or less, preferably 50,000 or less. The weight average molecular weight (Mw) of the molecular dispersant is preferably 700 to 100,000, and more preferably 1,000 ~50,000 is more preferred. Among these, from the viewpoint of pigment dispersibility, the dispersant is a urethane polymer having a functional group. It is preferable that the dispersion contains either one or both of a powder and an acrylic polymer dispersant. It is particularly preferred that the dispersion contains a polymer dispersant. In addition, from the viewpoint of dispersibility and storage stability, it has a basic functional group and is a polyester bond and a polyether bond. Polymeric dispersants having either or both of the carboxyl bonds are preferred.

[0243] Examples of urethane and acrylic polymer dispersants include DISPERBYK-160. ~167, 182 series (both urethane-based), DISPERBYK-2000, 2 001, BYK-LPN21116, etc. (all acrylic) (all BYK-Chemie) (manufactured by the company) Specific examples of preferred chemical structures for urethane-based polymer dispersants include: Polyisocyanate compound and a number average molecular weight of 3 having one or two hydroxyl groups in the same molecule 00-10,000 compounds and compounds having active hydrogen and tertiary amino groups in the same molecule. A dispersion of 1,000 to 200,000 weight average molecular weight obtained by reacting These can be treated with a quaternizing agent such as benzyl chloride to produce tertiary alkyl acrylates. All or part of the amino groups can be converted to quaternary ammonium salt groups.

[0244] The content ratio of the dispersant in the nonvolatile content (solid content) of the colorant of the present invention is not particularly limited. However, it is preferably 1 to 50 mass %, more preferably 2 to 30 mass %, and even more preferably 3 to 50 mass %. 25% by mass, particularly preferably 4 to 20% by mass, and most preferably 5 to 15% by mass. By setting the content to the lower limit or more, there is a tendency that the generation of residue due to aggregates can be suppressed. By adjusting the content to the limit value or less, the liquid repellency and developability tend to be improved.

[0245] When the photosensitive resin composition of the present invention contains a dispersant, the content ratio thereof is not particularly limited. Although not limited, the amount of the photosensitive resin composition is usually 0.1 to 8 mass %, preferably 0.05 to 10 mass %, based on the total solid content of the photosensitive resin composition. 0.1 to 5 mass%, more preferably 0.5 to 3 mass%, and even more preferably 0.5 to 2 mass% By setting the content to the lower limit or more, the generation of residues due to aggregates tends to be suppressed. In addition, by making the content equal to or less than the upper limit, the liquid repellency and developability tend to be improved.

[0246] [solvent] The photosensitive resin composition of the present invention usually contains a solvent, and the above-mentioned components are dissolved or dispersed in the solvent. The solvent is not particularly limited, but for example, the following solvents are used: Examples of suitable organic solvents include:

[0247] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propyl Pyrene glycol monomethyl ether, propylene glycol monoethyl ether, Pyrene glycol mono-n-butyl ether, propylene glycol t-butyl ether Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Diethylene glycol mono-n-butyl ether, dipropylene glycol monoethylene ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutyl ethanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether , triethylene glycol monoethyl ether, tripropylene glycol methyl ether glycol monoalkyl ethers such as methyl methyl ether; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene Glycols such as glycol dibutyl ether and dipropylene glycol dimethyl ether alkyl dialkyl ethers; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Terephthalate, Ethylene glycol mono-n-butyl ether acetate, Propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monobutyl ether acetate, 3-methoxy-1-butyl acetate, methoxypentyl ethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Cholesterol monoethyl ether acetate, diethylene glycol mono-n-butyl ether Acetate, Dipropylene Glycol Monomethyl Ether Acetate, Triethylene Glycol Cholesterol monomethyl ether acetate, triethylene glycol monoethyl ether acetate glycol alkyl ethers such as 3-methyl-3-methoxybutyl acetate, Acetates; Ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene Glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanol glycol diacetates such as glycol diacetate; alkyl acetates such as cyclohexanol acetate; Amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di Butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether Ethers such as; Acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, Diisoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone methyl butyl ketone, cyclohexanone, ethyl amyl ketone, methyl hexyl ketone ketones such as pentanone, methyl nonyl ketone, and methoxymethyl pentanone; Methanol, ethanol, propanol, butanol, hexanol, cyclohexanol ethylene glycol, propylene glycol, butanediol, diethylene glycol dipropylene glycol, triethylene glycol, methoxymethyl pentanol, Monohydric or polyhydric alcohols such as glycerin and benzyl alcohol; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, Aliphatic hydrocarbons such as dipentene and dodecane; Cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl Alicyclic hydrocarbons such as; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, acetyl acetate Methyl isobutyrate, ethyl propionate, propyl propionate, butyric acid Butyl, Isobutyl Butyrate, Methyl Isobutyrate, Ethyl Caprylate, Ethyl Benzoate, 3-Ethyl Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, 3-methoxypropionate Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, 3- linear or cyclic esters such as butyl methoxypropionate and gamma-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid ; Halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile; Tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, etc. Examples include tetrahydrofurans.

[0248] Commercially available solvents for these include mineral spirits, Balsol #2, and Apco #18. Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso # 150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol Bitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl Examples include Cellosolve Acetate and Diglyme (both trade names).

[0249] The solvent is capable of dissolving or dispersing each component in the photosensitive resin composition. The temperature is selected depending on the method of use of the photosensitive resin composition of the present invention. It is preferable to select a solvent having a boiling point under pressure in the range of 60 to 280°C. The boiling point is usually between 70°C and 260°C. For example, propylene glycol monohydrate is methyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether Among these, butyl acetate, 3-methoxy-1-butyl acetate, and 3-methoxy-1-butyl acetate are preferred.

[0250] These solvents may be used alone or in combination of two or more. In addition, these solvents are used so that the content of the total solid content in the photosensitive resin composition solution is usually 10% by mass. % by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably is 25% by mass or more, and is usually 90% by mass or less, preferably 50% by mass or less, more preferably It is preferably used in an amount of 40% by mass or less, more preferably 35% by mass or less. For example, it is preferably 10 to 90% by mass, more preferably 15 to 50% by mass, and even more preferably is 20 to 40% by mass, and more preferably 25 to 35% by mass. By doing so, it is possible to suppress the occurrence of coating unevenness, and by keeping the value below the upper limit, it is possible to prevent the occurrence of foreign matter. , and the occurrence of repelling and the like tends to be suppressed.

[0251] [UV absorber] The photosensitive resin composition of the present invention may contain an ultraviolet absorber. By absorbing the specific wavelength of the light source used in the photo-curing It is added to control the fabric. By adding ultraviolet absorbers, it is possible to achieve high precision with narrow line widths. This has the effect of forming thin partition walls and eliminating residues that remain in unexposed areas after development. As the ultraviolet absorber, from the viewpoint of inhibiting the light absorption of the photopolymerization initiator, for example, a wavelength of 2 Compounds having an absorption maximum between 50 nm and 400 nm can be used. The ultraviolet absorber may be either a benzotriazole-based compound or a triazine-based compound. It is desirable to include either or both of the benzotriazole-based compounds and triazine-based compounds. By including either one or both of the compounds, the light absorption rate of the initiator at the bottom of the film is reduced, and the It is believed that by reducing the line width of the portion, it is possible to form a highly precise barrier rib with a narrow line width.

[0252] Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole. Benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole Triazole, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole Octyl 3-[3-tert-2-yl)-4-hydroxyphenyl]propionate -butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxy phenyl]ethylhexyl propionate, 2-[2-hydroxy-3,5-bis(α,α -dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5 -methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5- Di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy 2-(2H-benzotriazole)-5'-t-octylphenyl)benzotriazole 2-(2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol 2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4 -(1,1,3,3-tetramethylbutyl)phenol, 3-[3-tert-butyl- 5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl] Examples include ester compounds of propionic acid with C7-9 linear and branched alkyl alcohols. do.

[0253] Commercially available benzotriazole compounds include, for example, Sumisorb (registered trademark) Same below.) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb JF350 (Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (Johoku) Chemical Industry Co., Ltd.), TINUVIN (registered trademark, the same applies below) PS, TINUVIN99- 2, TINUVIN109, TINUVIN384-2, TINUVIN326, TIN UVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EV ERSORB70, EVERSORB71, EVERSORB72, EVERSORB7 3, EVERSORB74, EVERSORB75, EVERSORB76, EVERS ORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Eiko Chemical Industry Co., Ltd.), TOMISORB (registered trademark, the same applies below) 1 00, Tomisorb 600 (manufactured by API Corporation), SEESORB (registered trademark Mark, same below.) 701, SEESORB702, SEESORB703, SEESORB B704, SEESORB706, SEESORB707, SEESORB709 (Ship Examples include RUVA-93 (Otsuka Chemical Co., Ltd.) and RUVA-93 (Otsuka Chemical Co., Ltd.).

[0254] Triazine compounds include 2-[4,6-di(2,4-xylyl)-1,3,5- Triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4 -dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyl) 2-(2,4-dihydroxyphenyl)-2-hydroxypropoxy]phenol )-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-ethyl Hexyl glycidyl ether reaction products, 2,4-bis[2-hydroxy-4-butoxy] [2,4-dibutoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine, etc. Among these, from the viewpoint of forming liquid repellency and high-definition partition walls with narrow line widths, hydrophilic Preferred are phenyltriazine compounds. Commercially available triazine compounds include TINUVIN400 and TINU VIN405, TINUVIN460, TINUVIN477, TINUVIN479( (manufactured by BASF)

[0255] Other UV absorbers include benzophenone compounds, benzoate compounds, and cinnamic acid. derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthracene Examples of the organic solvent include thiazolinone compounds and dyes. More specifically, for example, Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB 10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eiko Chemical Industry Co., Ltd.), TOMISORB 80 0 (manufactured by API Corporation), SEESORB100, SEESORB101 , SEESORB101S, SEESORB102, SEESORB103, SEESO RB105, SEESORB106, SEESORB107, SEESORB151 ( Benzophenone compounds such as Sumisorb 400 (Sumitomo Chemical), salicylic acid Benzoate compounds such as phenyl cinnamate; 2-ethylhexyl cinnamate, p-methoxycinnamic acid 2-ethylhexyl, isopropyl methoxycinnamate, isoamyl methoxycinnamate, etc. Cinnamic acid derivatives; α-naphthol, β-naphthol, α-naphthol methyl ether, α- Naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene Phthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene Phthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7 -dihydroxynaphthalene and other naphthalene derivatives; anthracene, 9,10-dihydroxy Anthracene such as cyanthracene and its derivatives; azo dyes, benzophenone dyes, Aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes such as acrylate dyes, triazine dyes, and p-aminobenzoic acid dyes; Among these, cinnamic acid derivatives and naphthalene derivatives can be used from the viewpoint of liquid repellency. It is particularly preferable to use cinnamic acid derivatives. These light absorbing agents may be used alone or in combination of two or more.

[0256] Among these, benzotriazole compounds and hydroxyphenyl compounds are preferred from the viewpoint of tapered shape. Phenyltriazine compounds are preferred, and benzotriazole compounds are particularly preferred.

[0257] The ultraviolet absorber may be used alone or in combination of two or more kinds.

[0258] [Polymerization inhibitor] The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. Since the presence of the polymer inhibits radical polymerization, the taper angle of the resulting partition wall is increased. There is a tendency to be able to Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, and methyl halides. Hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol ( Among these, hydroquinone or BHT is the most effective in inhibiting polymerization. Methoxyphenol is preferred, and methylhydroquinone is more preferred.

[0259] It is preferable to contain one or more polymerization inhibitors. When manufacturing the resin (P), polymerization inhibitors may be included in the resin. Alternatively, in addition to the polymerization inhibitor contained in the resin, the same or a different polymerization inhibitor may be added to the photosensitive material. The additive may be added during the production of the polymeric resin composition.

[0260] [Thermal polymerization initiator] Furthermore, the photosensitive resin composition of the present invention may contain a thermal polymerization initiator. By including a thermal polymerization initiator, the degree of crosslinking of the film tends to be increased. Specific examples of the agent include azo compounds, organic peroxides, and hydrogen peroxide. can be. These may be used alone or in combination of two or more.

[0261] In addition, a thermal polymerization initiator is used in combination with the photopolymerization initiator in the hope of improving the liquid repellency and increasing the crosslink density of the film. When using a photopolymerization initiator, the total content of these components is the content of the photopolymerization initiator in the photosensitive resin composition. It is preferable that the photopolymerization initiator and the thermal polymerization initiator are used in combination in the following ratio: In terms of liquid repellency, the thermal polymerization initiator is mixed in an amount of 5 to 300 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. It is preferable to use parts by mass.

[0262] [1-1-11] Silane coupling agents The photosensitive resin composition of the present invention contains a silane coupling agent in order to improve adhesion to a substrate. Silane coupling agents may be added. The types of silane coupling agents include epoxy and methacrylic. Various types of adhesives such as amine-based and imidazole-based adhesives can be used. Epoxy-based and imidazole-based silane coupling agents are preferred.

[0263] [Inorganic filler] Furthermore, the photosensitive resin composition of the present invention further has the following properties: The inorganic filler may contain, for example, talc, Silica, alumina, barium sulfate, magnesium oxide, titanium oxide, or any combination thereof Examples include those surface-treated with a silane coupling agent.

[0264] [Adhesion improver] The photosensitive resin composition of the present invention contains a phosphate group and an ethylene group for the purpose of imparting adhesion to a substrate. A compound having a phosphoric acid group and an ethylenically unsaturated group may be contained. The compound is preferably a (meth)acryloyloxy group-containing phosphate, and is one of the following: Those represented by general formulas (g1), (g2) and (g3) are preferred.

[0265] [ka]

[0266] [In the above general formulae (g1), (g2), and (g3), R 51 represents a hydrogen atom or a methyl group. wherein l and l' are integers of 1 to 10, and m is 1, 2, or 3.

[0267] These compounds having a phosphoric acid group and an ethylenically unsaturated group may be used alone. Two or more types may be used in combination.

[0268] <Method for preparing photosensitive resin composition> The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components with a mixer. This can be done. The photosensitive resin composition of the present invention contains a solvent-insoluble component such as a purple pigment as a colorant. Paint conditioner, sand grinder, ball mill, roll mill, stone It is preferable to carry out the dispersion treatment using a mill, a jet mill, a homogenizer, or the like. This causes the colorant to be microparticulated, thereby improving the coating properties of the photosensitive resin composition.

[0269] The dispersion treatment is usually carried out by dispersing a colorant, a solvent, a dispersant, and a part or all of the alkali-soluble resin. It is preferable to use a system in which all of these are used together (hereinafter, the mixture to be subjected to dispersion treatment and the dispersion treatment The composition obtained by this process is sometimes called a "pigment dispersion liquid." The use of a dispersant prevents the resulting pigment dispersion and photosensitive resin composition from increasing in viscosity over time. That is, it is preferable because it has excellent dispersion stability. In this way, in the process of producing a photosensitive resin composition, a colorant, a solvent, and a dispersant are used. It is preferable to produce a pigment dispersion containing at least the above-mentioned component. The colorants, organic solvents, and dispersants that can be used in the pigment dispersion liquid are each Those described as usable for the photosensitive resin composition are preferably used. In addition, the content ratio of each colorant in the pigment dispersion liquid can be adjusted depending on the photosensitive resin composition. The content ratios described above in the composition can be preferably adopted.

[0270] When dispersing colorants using a sand grinder, use sand with particle sizes of 0.1 to 8 mm. Lath beads or zirconia beads are preferably used. The dispersion treatment conditions are usually 0 The dispersion temperature is in the range of from room temperature to 80°C. The appropriate time varies depending on the size of the dispersion treatment device and the like, so adjust as appropriate. The ink is adjusted so that the 20-degree specular gloss (JIS Z8741) is in the range of 50 to 300. The aim of dispersion is to control the gloss of the ink.

[0271] The particle size of the pigment dispersed in the pigment dispersion is usually 0.01 to 1 μm, preferably 0. The particle size is preferably 0.02 to 0.5 μm, more preferably 0.03 to 0.3 μm, and is suitable for dynamic light scattering and the like. It is measured as the median diameter based on the number of particles. Next, the ink obtained by the above dispersion treatment and the above-mentioned The other components are mixed to form a uniform solution. Since dust may be mixed in the liquid, the obtained photosensitive resin composition should be filtered using a filter or the like. It is advisable to over-treat.

[0272] <Cured product and method for forming same> The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention can be used as a color resist, for example. It can be suitably used to form a cured product for partitioning pixel portions in a filter. Cut. The method for forming a cured product using the photosensitive resin composition is not particularly limited, and any conventionally known method can be used. As a method for forming a cured product, for example, a method for curing a photosensitive resin composition by a coating step of applying the composition onto a substrate to form a photosensitive resin composition layer; and a step of exposing the photosensitive resin composition layer to light. Specific examples of the method for forming such a cured product include: Examples of the method include an ink jet method and a photolithography method.

[0273] In the inkjet method, a photosensitive resin composition whose viscosity has been adjusted by diluting it with a solvent is applied to the ink. The ink is then applied by inkjet printing along a predetermined pattern on the cured product. The photosensitive resin composition is applied to a substrate by discharging it onto the substrate, and a pattern of the uncured cured material is formed. Then, the pattern of the uncured cured material is exposed to light, and the cured material is formed on the substrate. The pattern of the uncured cured product is exposed in the same manner as described below, except that a mask is not used. This is carried out in the same manner as the exposure step in photolithography.

[0274] In the photolithography method, a photosensitive resin composition is applied to the entire area of ​​the substrate where a cured product is to be formed. The photosensitive resin composition layer is then applied to a surface of the substrate. After exposure according to the pattern of the partition wall, the exposed photosensitive resin composition layer is developed to form a layer on the substrate. A cured product is formed.

[0275] In the photolithography method, in the coating step of coating a photosensitive resin composition onto a substrate, , and then the cured product is applied to the substrate using a roll coater, reverse coater, or bar coater. Contact transfer type coating equipment, spinners (rotary coating equipment), curtain flow coaters, etc. The photosensitive resin composition is applied using a non-contact type coating device, and the solvent is removed by drying, if necessary. The photosensitive resin composition layer is then removed to form the photosensitive resin composition layer.

[0276] Next, in the exposure step, a negative mask is used to expose the photosensitive resin composition layer to ultraviolet light and electrons. The photosensitive resin composition layer is irradiated with active energy rays such as xenon laser light to form a barrier rib pattern. The exposure is carried out in parts depending on the conditions. For exposure, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a photo A light source that emits ultraviolet light, such as a carbon arc lamp, can be used. The exposure dose depends on the composition of the photosensitive resin. Although it varies depending on the composition of the material, for example, 10 to 400 mJ / cm 2 The degree is preferable.

[0277] Next, in the development step, the exposed photosensitive resin composition layer is developed according to the pattern of the cured product. The partition walls are formed by developing with a developing solution. The developing method is not particularly limited, and may be a dipping method, a spray method, or the like. Specific examples of the developer include dimethylbenzylamine, mono Organic compounds such as ethanolamine, diethanolamine, and triethanolamine, as well as water Sodium oxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salts, etc. The developer may contain an antifoaming agent or a surfactant. A post-exposure process may be performed after development. A light source that emits ultraviolet light, such as a lantern lamp or a carbon arc lamp, can be used. The light source may be the same as or different from that used in the previous step. The exposure dose depends on the composition of the photosensitive resin composition. It varies depending on the situation, but for example, 10 mJ / cm 2 ~5J / cm 2 Post-exposure The process is suitable for increasing the taper angle.

[0278] After that, the developed cured product is post-baked to be cured by heating. Preferably, the temperature is 0 to 250°C for 15 to 60 minutes.

[0279] The substrate used for forming the partition walls is not particularly limited, and the partition walls are manufactured using a substrate on which a cured product has been formed. The substrate material is appropriately selected according to the type of organic electroluminescent device. Examples of resin materials include polyethylene terephthalate (PET) and various resin materials. Polyesters such as polyethylene and polypropylene; polyolefins such as polyethylene and polypropylene; Carbonates; poly(meth)methacrylic resins; polysulfones; polyimides Among these substrate materials, glass and polyimide are preferred because of their excellent heat resistance. In addition, the surface of the substrate on which the cured product is formed is determined according to the type of organic electroluminescent device to be manufactured. A transparent electrode layer such as ITO or ZnO may be provided on the surface in advance.

[0280] The film thickness of the cured product of the present invention is usually 0.1 μm or more, preferably 1 μm or more, and more preferably or 5 μm or more, more preferably 10 μm or more, usually 1 mm or less, preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, and particularly preferably For example, the thickness is 0.1 μm to 1 mm, preferably 1 to 100 μm, more preferably 20 μm or less. Preferably 1 to 50 μm, more preferably 5 to 30 μm, particularly preferably 10 to 20 μm By making the value equal to or greater than the lower limit, the light-blocking property tends to be improved. The thickness of the cured film is affected by the difference in level, surface roughness, and fine features. shape measurement device, scanning white light interference microscope, ellipsometer, reflection spectroscopic film thickness meter, electron microscope To be measured. [Example]

[0281] The photosensitive resin composition of the present invention will be described below with reference to specific examples. The present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0282] (1) Weight average molecular weight (Mw) The weight average molecular weight of the copolymer was measured by GPC under the following conditions. Equipment: Waters "e2695" Column: TSKgel Super H3000+H4000+H manufactured by Tosoh Corporation 6000", Detector: Differential refractive index detector (RI detector / built-in), Solvent: tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: monodisperse polystyrene, Calibration method: Polystyrene equivalent.

[0283] (2) Acid value The acid value can be determined as follows. Acid value (mgKOH / g) = (f × M1 / Mw / M2 × [KOH] × 1,000) f: number of acidic groups in the monomer (Z) [KOH]: Molecular weight of KOH M1: Mass (g) of monomer (Z) M2: Total mass (g) of the raw materials constituting the copolymer (S), excluding the solvent Mw: Molecular weight (g) of monomer (Z)

[0284] (3) Alkali-soluble Add 10 mL of 0.036 mmol / L potassium hydroxide solution at 25°C to 0 mg was added and stirred for 10 minutes using a stirrer and a stirrer. The alkali solubility was evaluated by visual observation of the aqueous solution of ammonium hydroxide. The evaluation criteria were as follows: The higher the evaluation score, the more preferable it is. 4: No white solid remains, and the solution is clear. 3: No white solid remains, but the potassium hydroxide aqueous solution is a milky translucent solution. It is as follows. 2: The potassium hydroxide aqueous solution is a milky white, translucent solution, and a white solid is present. It is settling. 1: Insoluble in aqueous potassium hydroxide, the copolymer precipitates without dissolving at all. are.

[0285] (4) Storage stability 18 mL of unpurified copolymer (S) and comparative copolymer (C) were placed in a 20 mL light-shielding bottle. The viscosity was measured immediately after production and after 10 days in a hot air dryer at a temperature of 40°C. The storage stability was estimated from the viscosity increase rate at 40°C. The viscosity is divided by the viscosity immediately after production, multiplied by 100, and expressed as a percentage. The viscosity is measured according to JIS K7117 using an E-type viscometer (Toki Sangyo TVE-20H type viscometer) The evaluation criteria for storage stability are as follows: The higher the evaluation score, the more preferable it is. 4: The viscosity increase rate over time at 40°C is 100-110%. 3: The viscosity increase rate over time at 40°C is 111 to 130%. 2: The viscosity increase rate over time at 40°C is 131 to 150%. 1: The viscosity increase rate over time at 40°C is 151% or more.

[0286] (5) Thermal crosslinkability The purified copolymer (S) and the comparative copolymer (C) were dissolved in 10% solids solution (PGMEA dilution). The mixture was applied to a 3 mm thick, 15 cm square glass substrate using a #24 bar coater and then dried with hot air. The coating was dried at 100°C for 2 minutes in a dryer to produce a coating film with a thickness of 10 μm after drying. UV control of the Igraphics high-power UV device (model: US5-X1802-X1202) Using bare light, cumulative light intensity 50mJ / cm 2 , illuminance 30mW / cm 2 UV irradiation was performed under the following conditions: After that, this cured film was dried in a hot air dryer at an internal temperature of 230°C for 30 minutes. It was heated and cooled. At this time, the contact angle of PGMEA on the cured film after UV irradiation with a high-pressure mercury lamp was measured as "heat treatment". The contact angle of PGMEA before and after curing was measured by heating for 30 minutes in a hot air dryer at an internal temperature of 230°C. The contact angle of PGMEA with the film was defined as the "PGMEA contact angle after heat treatment." A contact angle (liquid volume 1 μL) was measured using a feeler (Dropmaster 5 manufactured by Kyowa Interface Science Co., Ltd.) The values ​​were measured 2 seconds and 60 seconds after the droplets landed on the surface of the ink. The crosslink density of the coating film increases, making it more insoluble in PGMEA. The difference between the contact angle at 0 seconds and the value at 2 seconds after the droplet was applied was small (PGMEA did not swell or dissolve the droplet). Therefore, the thermal crosslinking property is such that the contact angle is Estimated by subtracting the contact angle difference (b) from the difference (a) (contact angle difference (a) - contact angle difference (b)). It is possible. Contact angle difference (a): The difference between the value 2 seconds after the droplet contact and the value 60 seconds after the droplet contact. The value obtained by subtracting the value of Contact angle difference (b): The difference between the value 2 seconds after the drop of PGMEA contact angle after heat treatment and the value 60 seconds after the drop of PGMEA contact angle after heat treatment The value obtained by subtracting the value of The evaluation criteria for thermal crosslinking are as follows: the higher the evaluation score, the better the thermal crosslinking. Very desirable. 4: The value of the contact angle difference (a) - contact angle difference (b) is 31° or more. 3: The difference in contact angle (a) - the difference in contact angle (b) is 21 to 30° or more. 2: The value of the contact angle difference (a) - contact angle difference (b) is 11 to 20° or more. 1: The value of the contact angle difference (a) - contact angle difference (b) is 0 to 10° or more.

[0287] (6) Appearance The appearance of the cured film made of the photosensitive resin composition obtained by the method described in the examples was evaluated based on the following criteria: The higher the evaluation score, the higher the quality of the cured product, which is preferable. 4: The coating is uniform and there are no uneven colors or foreign matter. 3: There is some uneven coloring, but the coating is done without any foreign matter. 2: There is uneven coloring and 2-3 or more foreign objects are found per 10cm square. 1: The coating is uniform and there is no uneven coloring or foreign matter.

[0288] (7) Liquid repellency 1 PGM of the cured film made of the photosensitive resin composition after heat treatment obtained by the method described in the examples The EA contact angle was taken as liquid repellency 1, and the contact angle was measured using a feeler (Kyowa Interface Science Co., Ltd., "Dropmaster" The value was evaluated by measuring the value 2 seconds after a drop of water (liquid volume 1 μL) was dropped using a r500. The evaluation criteria for liquid repellency 1 were as follows: The higher the evaluation score, the higher the exposure sensitivity. is highly preferable. 4: The water contact angle of the cured film of the photosensitive resin composition is greater than 45°. 3: The cured film of the photosensitive resin composition has a water contact angle of 30 to 45°. 2: The cured film of the photosensitive resin composition has a water contact angle of 20 to 29°. 1: The water contact angle of the cured film of the photosensitive resin composition is less than 20°.

[0289] (8) Liquid repellency 2 The water contact of the cured film made of the photosensitive resin composition after heat treatment obtained by the method described in the examples The corner was treated as liquid repellent 2, and a feeler (Kyowa Interface Science Co., Ltd., "Dropmaster 500") was used. The evaluation was carried out by measuring the value 2 seconds after a drop of water (liquid volume 1 μL) was dropped onto the surface of the device. The evaluation criteria for liquid repellency 2 were as follows: The higher the evaluation score, the higher the exposure sensitivity and the better the result. I wish. 4: The water contact angle of the cured film of the photosensitive resin composition is greater than 100°. 3: The cured film of the photosensitive resin composition has a water contact angle of 91 to 100°. 2: The cured film of the photosensitive resin composition has a water contact angle of 81 to 90°. 1: The water contact angle of the cured film of the photosensitive resin composition is 80° or less.

[0290] (9) Cleanability The glass substrate with the cured film obtained by the method described in the examples was washed with 300 mL of ion-exchanged water. The cleaning performance was evaluated by observing the wetting and spreading of ion-exchanged water during rinsing. The cured product containing the liquid-repellent copolymer forms a salt when it comes into contact with a developer under basic conditions, making it resistant to the developer. Although it shows high wettability, it spreads during rinsing with ion-exchanged water under neutral conditions. This can lead to insufficient cleaning performance and the ion-exchanged water is used up during the rinsing process. First, spreading the coating evenly over the entire surface reduces copolymer residue and eliminates coating defects. The evaluation criteria for cleaning performance are as follows. The higher the evaluation score, the better the cleaning performance. Very desirable. 4: The ion-exchanged water spreads over the entire coating surface, allowing for even cleaning. 3: The ion-exchanged water spreads over about half the surface area of ​​the coating, allowing for cleaning. 2: The ion-exchanged water is repelled by the coating, causing uneven cleaning. 1: The coating repels ion-exchanged water, causing uneven cleaning. Also, copolymer residues remain on the coating. Visible on the film.

[0291] Copolymer (S) was produced with the composition shown in Table 1. The constituent components of copolymer (S) used in the synthesis examples were: The minutes are as follows:

[0292] <Monomer (F)> F-1: 1H,1H,2H,2H-tridecafluorooctyl methacrylate (Daikin (Manufactured by Kogyo Co., Ltd., C6SFMA) <Monomer (X)> X-1: 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy] Ethyl methacrylate (Mitsubishi Chemical Corporation) <Monomer (O)> O-1: (3-ethyloxetan-3-yl)methyl methacrylate (manufactured by UBE Corporation) , ETERNACOLL OXMA) <Monomer (Z)> Z-1: methacrylic acid Z-2: 2-methacryloyloxyethyl hexahydrophthalate (Mitsubishi Chemical Corporation) (Made by Acrylates HH) <Monomer (R)> R-1: Methyl methacrylate (Mitsubishi Chemical Corporation, Acryester M) R-2: Glycidyl methacrylate (Mitsubishi Chemical Corporation, Acryester G) <Monomers and compounds having ethylenic double bonds> A-1: 2-hydroxyethyl methacrylate (Mitsubishi Chemical Corporation, Acrieste) LeHO) B-1: 2-Isocyanatoethyl acrylate (Resonac Holdings Co., Ltd.) (Made by Karenz AOI) <Solvent-1> PGMEA: Propylene glycol monomethyl ether acetate

[0293] The following are synthesis examples of copolymers (S-1) to (S-6), which are examples of copolymer (S), and copolymerization The synthesis examples of (C-1) to (C-4) are shown below as comparative copolymers (C) that do not fall under the category of copolymer (S). .

[0294] <Synthesis example 1: Copolymer (S-1)> In a 500 mL flask equipped with a stirrer, condenser, and thermometer, add propylene glycol Add 46.9 parts of monomethyl ether acetate (hereinafter referred to as solvent-1) to the flask. The inside of the flask was purged with nitrogen and the internal temperature was raised to 90° C. Then, 34.9 mass of the monomer (F-1) was added to the dropping funnel. parts by mass, monomer (O-1) 11.0 parts by mass, monomer (X-1) 34.9 parts by mass, monomer (Z- 2) 9.0 parts by mass, monomer (R-1) 10.0 parts by mass, I-1 (2,2 0.25 parts by weight of 2,4-azobis(2,4-dimethylvaleronitrile) (AMBN), and 103.5 parts by mass of the mixed solution of Solvent-1 was added dropwise over 4 hours to carry out polymerization. During the addition, nitrogen flow (10 mL / min) was continued, and after the end of the addition, the internal temperature was maintained at 90°C for 1.5 minutes. The polymerization was continued for 1 hour. After that, a mixture of nitrogen (6.6 mL / min) and air (3.3 mL / min) was added. The flow was switched to the above, and 0.040 parts by mass of p-methoxyphenol (MEHQ) was added. The internal temperature was cooled to 70°C. Next, the purification step will be described. 50 parts by mass of MIBK was added to the dropping funnel, and then A 1000 mL flask equipped with a stirrer, a condenser, and a thermometer was charged with 400 parts by mass of ethanol. The hexane was added dropwise over 30 minutes to effect hexane reprecipitation. After the addition was completed, the internal temperature was kept at 25°C. After continuing stirring for another hour, the slurry was pressure filtered to recover a white solid. Then, 10 parts by mass of the white solid and 150 parts by mass of normal hexane were added to the flask again, and the same procedure was repeated. After repeating hexane reprecipitation three times, the mixture was dried under reduced pressure (10 torr) at 40°C for 6 hours. The copolymer (S-1) was obtained as a white powder. The weight average molecular weight (Mw ) is 99,400, the number average molecular weight (Mn) is 28,600, and the polydispersity (Mw / Mn ) was 3.48.

[0295] <Synthesis example 2: Copolymer (S-5)> In a 500 mL flask equipped with a stirrer, condenser, and thermometer, add propylene glycol Add 47.0 parts of monomethyl ether acetate (hereinafter referred to as solvent-1) to the flask. The inside of the flask was purged with nitrogen and the internal temperature was raised to 90° C. Then, 34.9 mass of the monomer (F-1) was added to the dropping funnel. parts by mass, monomer (O-1) 19.7 parts by mass, monomer (X-1) 19.0 parts by mass, monomer (Z- 1) 7.3 parts by mass, monomer (A-1) 9.4 parts by mass, I-1(2,2') as a polymerization initiator - 0.25 parts by mass of azobis(2,4-dimethylvaleronitrile) (AMBN), and 103.6 parts by mass of the mixed solution of Agent-1 was added dropwise over 4 hours to carry out polymerization. Nitrogen flow (10 mL / min) was continued inside, and after the dropwise addition, the internal temperature was maintained at 90°C for 1.5 hours. The polymerization was continued for 10 minutes. After that, a mixture of nitrogen (6.6 mL / min) and air (3.3 mL / min) was added. The flow was switched to 0.040 parts by mass of p-methoxyphenol (MEHQ) was added. The temperature was cooled to 70°C. Furthermore, 0.050 ml of dibutyltin dilaurate (DBTDL) was added. parts by mass and 9.6 parts by mass of monomer (B-1) were added, and the reaction was continued for 6 hours while maintaining the internal temperature at 70°C. After that, 0.1 mL of the reaction mixture was sampled and subjected to FT-IR analysis. After confirming that the peak (2255 cm-1) had disappeared, the reaction mixture was cooled to room temperature. . Next, the purification step will be described. 50 parts by mass of MIBK was added to the dropping funnel, and then A 1000 mL flask equipped with a stirrer, a condenser, and a thermometer was charged with 400 parts by mass of ethanol. The hexane was added dropwise over 30 minutes to effect hexane reprecipitation. After the addition was completed, the internal temperature was kept at 25°C. After continuing stirring for another hour, the slurry was pressure filtered to recover a white solid. Then, 10 parts by mass of the white solid and 150 parts by mass of normal hexane were added to the flask again, and the same procedure was repeated. After repeating hexane reprecipitation three times, the mixture was dried under reduced pressure (10 torr) at 40°C for 6 hours. The copolymer (S-1) was obtained as a white powder. The weight average molecular weight (Mw ) is 98,400, the number average molecular weight (Mn) is 29,000, and the polydispersity (Mw / Mn ) was 3.39.

[0296] <Synthesis of Copolymers (S-2) to (S-4) and Comparative Copolymers (C-1) to (C-3)> The copolymer was synthesized in the same manner as in the synthesis of copolymer (S-1), except that the monomers were changed as shown in Table 1. Copolymers (S-2) to (S-4) and comparative copolymers (C-1) to (C-3) were obtained.

[0297] [Table 1]

[0298] The alkali solubility, storage stability, and thermal stability of the obtained copolymer (S) and comparative copolymer (C) were The crosslinkability is as shown in Table 2.

[0299] [Table 2]

[0300] Photosensitive resin compositions were prepared according to the formulations shown in Table 4. The components of the polymeric resin composition are as follows:

[0301] <Acrylic alkali-soluble resin (PA-1)> Dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.30 / 0.10 / 0.60) as constituent monomers, and acrylic acid was added to the copolymer resin. Addition reaction with an equal amount of glycidyl methacrylate, and then tetrahydrophthalic anhydride The alkali was added to the copolymer resin in an amount of 0.39 moles per mole of the copolymer resin. Soluble acrylic copolymer resin. Weight average molecular weight (M) measured by GPC in terms of polystyrene. w) is 9,000, acid value is 80 mg KOH / g, and double bond equivalent is 470 g / mol .

[0302] <Acrylic alkali-soluble resin (PA-2)> Dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.02 / 0.05 / 0.93) as constituent monomers, and acrylic acid was added to the copolymer resin. An equal amount of glycidyl methacrylate is added to the reaction product, and tetrahydrophthalic anhydride is then added to the reaction product. The alkali-soluble alkyl acrylate was added to the copolymer resin in an amount of 0.10 moles per mole of the copolymer resin. The weight average molecular weight (Mw) of the polystyrene equivalent measured by GPC is 7, 700, acid value is 28.5 mg KOH / g, and double bond equivalent is 260 g / mol.

[0303] <Alkali-soluble epoxy resin (PE-1)> "ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 6,500, acid value = 98 mgKOH / g) It has a partial structure represented by the following formula (C2).

[0304] [ka]

[0305] In formula (C2), * represents a linking hand.

[0306] <Pigments> CI Pigment Violet 29 CI Pigment Violet 60 CI Pigment Violet 64

[0307] <Dispersant> BYK-LPN21116 manufactured by BYK-Chemie

[0308] <Crosslinking agent> DPHA: Dipentaerythritol hexaacrylate (weight average) manufactured by Nippon Kayaku Co., Ltd. Average molecular weight Mw:579)

[0309] <Photopolymerization initiator> The compound used had the following chemical structure:

[0310] [ka]

[0311] <Chain transfer agent> Karenz MT PE1 (Pentaerythritol) manufactured by Resonac Holdings Co., Ltd. Tetrakis(3-mercaptobutyrate)

[0312] <Solvent-1> PGMEA: Propylene glycol monomethyl ether acetate <Solvent-2> MB: 3-methoxy-1-butanol

[0313] <Preparation of Colorant> Pigment, dispersant, alkali-soluble resin, and solvent were mixed in the mass ratio shown in Table 3. This solution was dispersed in a paint shaker at a temperature range of 25 to 45°C for 3 hours. The beads used were zirconia beads with a diameter of 0.5 mm, and the mass was 2.5 times that of the dispersion liquid. After the dispersion was completed, the beads and the dispersion were separated using a filter to prepare a colorant.

[0314] [Table 3]

[0315] [Example 1] Mix and stir all ingredients except for the colorant in the proportions shown in Table 4 until fully dissolved. Add the colorant and mix, then stir for 10 minutes using an ultrasonic cleaner to prepare a photosensitive resin composition. Each of the obtained photosensitive resin compositions was evaluated by the methods described below. The blending ratios of copolymer (S), colorant, and alkali-soluble resin (P) in Table 4 are based on solids. This is a minute equivalent value. A 3mm thick, 15cm square glass substrate was coated with a #24 bar coater to a thickness of 1000μm. The composition shown in Table 4 was applied to a thickness of 10 μm, and then heated at 100°C for 2 minutes using a hot air dryer. The solvent was evaporated by drying, and the sample was then exposed to a high-pressure mercury lamp in an air atmosphere with an integrated light intensity of 50 mJ / cm. 2 , Teru degree 30mW / cm 2 The mixture was irradiated with ultraviolet light at 1000 kJ / min to form a cured product. The ultraviolet light was irradiated using an Eye Graphics high-power UV device (model: US5-X1802-X The integrated light intensity was measured using an illuminance meter (eye purple) manufactured by Iwasaki Electric Co., Ltd. The integrated illuminance meter "UVPF-A1" and "PD-365" measures the integrated illuminance of wavelengths between 300 and 390 nm. This is the value when the calculated amount of light is measured. Next, alkaline development was carried out. The glass substrate on which the cured material was laminated was then Immerse the beaker in 2000 mL of 36 mmol / L potassium hydroxide solution. The glass substrate was shaken at 25°C for 90 seconds and then collected. The substrate was rinsed with 1 L of ion-exchanged water and then dried at 40°C for 2 hours using a hot air dryer. At this time, the PGMEA contact angle was measured after exposure. Next, the glass substrate on which the cured product was laminated was subjected to a heat treatment at 230°C for 30 minutes. The surface was cooled to room temperature. After the heat treatment, the PGMEA contact angle was measured. The evaluation results of exposure sensitivity and cleaning property are shown in Table 5.

[0316] [Examples 2 to 5 and Comparative Examples 1 to 3] A cured product was obtained in the same manner as in Example 1, except that the copolymer (S) shown in Table 4 was used instead. The evaluation results of the appearance, liquid repellency (exposure sensitivity) and cleaning properties are shown in Table 5.

[0317] [Table 4]

[0318] [Table 5]

[0319] As shown in Table 2, the copolymer (S) of the present invention has excellent storage stability while maintaining the acid group and oxetane group. Therefore, as shown in Examples 1 to 5, the copolymer of the present invention The cured product of the photosensitive resin composition containing the polymer (S) can be cured even with relatively low ultraviolet irradiation. The crosslinking density can be increased by heat, resulting in high liquid repellency against water and PGMEA. Therefore, the copolymer (S) can be obtained by the method of the present invention. is effective in achieving both high-definition resist patterns and liquid repellency. In Comparative Example 1, the comparative copolymer (C-1) contained an epoxy group instead of the monomer (O) as a thermal crosslinking group. As a result of using a monomer (R-2) having a silyl group, the storage stability is low and it is difficult to incorporate it into a photosensitive resin composition. In Comparative Example 2, the comparative copolymer (C-2) was used. Since the copolymer (O) was not included, thermal crosslinking properties could not be ensured, and the liquid repellency was insufficient. In Comparative Example 3, the comparative copolymer (C-3) contains a monomer (R-2) having an epoxy group. Therefore, although thermal crosslinking with alkali-soluble resin (P) is possible, it does not have an acid group. Therefore, cleaning properties are poor and there is a risk of contamination of the cured film due to copolymer residue. It was.

Claims

1. A structural unit derived from a monomer (F) containing a fluorine atom and a monomer containing an oxetanyl group a structural unit derived from a monomer (O) and a structural unit derived from a monomer (Z) containing an acid group, Furthermore, a monomer (X) having a functional group capable of generating radicals upon irradiation with active energy rays is ) or one or more structural units (E) containing an ethylenically unsaturated group A copolymer containing

2. The content of the fluorine atoms is 10.0 to 35.0% by mass based on the total solid content of the copolymer. The copolymer according to claim 1 .

3. The copolymer according to claim 1, wherein the monomer (X) has a structure represented by the following formula (Ia): 【Chemical 1】 [In the formula, R ２ represents a linear or branched alkylene group having 1 to 5 carbon atoms; R ３ , R ４ may or may not be bonded to each other to form a ring. is R ３ and R ４ each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms; When a ring is formed, R ３ and R ４ represents a cyclic structure having 2 to 10 carbon atoms in total. Also, * indicates a connecting hand.

4. The copolymer according to claim 1 , wherein the structural unit (E) has a structure represented by the following formula (Ib): 【Chemistry 2】 [In the formula, R １ is hydrogen or a methyl group, R ２ is a linear or branched alkyl group having 1 to 5 carbon atoms. represents an aryl group, and * represents a bond.]

5. The copolymer contains an acid group of 5 to 140 mg KOH / g and is alkali-soluble. The copolymer according to claim 1 .

6. The copolymer according to any one of claims 1 to 5, which is used for displays.

7. A photosensitive resin composition comprising the copolymer according to any one of claims 1 to 5.

8. A photosensitive resin composition containing the copolymer according to any one of claims 1 to 5 is cured. The hardened product.

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