TW202409729A - Positive-type photosensitive resin composition, partition wall, and optical element - Google Patents

Abstract

The present invention pertains to a positive-type photosensitive resin composition which contains an alkali-soluble resin (A), a photosensitizer (B), and an ink repellent agent (C), and in which the ink repellent agent (C) has a monovalent group that is represented by formula (c) and that has 2-40 carbon atoms. (c): Rf1-O-Rf2- [Rf1 represents a polyfluoro alkyl group having 1-6 carbon atoms, and Rf2 represents a polyfluoro alkylene group optionally having an etheric oxygen atom between carbon-carbon atoms (however, Rf1-O-Rf2- has at least one -O-CF2-group).].

Description

Positive photosensitive resin composition, barrier rib and optical element

The present invention relates to a positive photosensitive resin composition, a barrier rib and an optical element.

It is known that a photosensitive resin composition is coated on a substrate and used as a barrier rib in a pixel portion of an organic EL (Electro-Luminescence) element as a color filter or an organic EL (Electro-Luminescence) element. method of formation.

In recent years, the industry has proposed a low-cost process using the inkjet method as a method for manufacturing color filters or pixel portions of organic EL elements. For example, in the production of color filters, after the barrier ribs are formed by photolithography, R (red) and G (green) are sprayed on the openings (dots) surrounded by the barrier ribs by the inkjet method. , and B (blue) ink are applied to form pixels.

In addition, in the inkjet method, it is necessary to prevent color mixing of ink between adjacent pixels. Therefore, the barrier rib is required to have a property of repelling ink containing water or an organic solvent as an inkjet ejection liquid, that is, so-called ink repellency. On the other hand, the ink layer formed on the pixel by the inkjet method requires excellent film thickness uniformity. Therefore, it is required that the dots surrounded by the barrier ribs have good wettability to the ejection liquid, that is, so-called ink affinity.

In order to make the surface of the barrier ribs ink-repellent, the industry has developed a technology for adding ink-repellent to the photosensitive resin composition used to form the barrier ribs. In addition, positive photosensitive resins are superior to negative photosensitive resins in that they have less residue after development (hereinafter also referred to as "development residue"), and are sometimes better used.

For example, Patent Document 1 describes a positive photosensitive resin composition that contains an ink repellent derived from polysiloxane having fluorine atoms, and is subjected to plasma treatment or UV (Ultra Violet, ultraviolet) ozone treatment. It also maintains high water repellency and high liquid repellency. [Prior technical literature] [Patent Document]

Patent Document 1: International Publication No. 2019/156000

[Problem to be solved by the invention]

However, the cured film obtained by the positive photosensitive resin composition described in Patent Document 1 still has room for improvement in terms of development residue removal and ink repellency. In addition, it is required that the ink in the dot diffuses evenly to the edge of the barrier wall (hereinafter also referred to as "inkjet coating property"). The cured film obtained by the positive photosensitive resin composition described in Patent Document 1 also has room for improvement in this aspect.

An object of the present invention is to provide a positive photosensitive resin composition capable of obtaining a cured film having excellent ink repellency, less development residue, and excellent inkjet coating properties. [Technical means to solve problems]

The present invention relates to the following positive photosensitive resin composition. [1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B) and an ink repellent (C), wherein the ink repellent (C) has a monovalent group having 2 to 40 carbon atoms represented by the following formula (c): R ^f1 -OR ^f2 - (c) R ^f1 : a polyfluoroalkyl group having 1 to 6 carbon atoms R ^f2 : a polyfluoroalkyl group having an ethereal oxygen atom between carbon atoms, wherein R ^f1 -OR ^f2 - has at least one -O-CF ₂ - group. [Effects of the invention]

According to the positive photosensitive resin composition of the present invention, a hardened film having excellent ink repellency, less developing residue and excellent inkjet coating property can be obtained.

In this specification, the compound represented by formula (c-1) is referred to as "compound (c-1)". The same applies to other compounds. The "total solid content" in this specification refers to the barrier rib forming components among the components contained in the positive photosensitive resin composition, and means all components except for the volatile components such as solvents that evaporate due to heating during the barrier rib formation process. The total solid content is measured in the form of the residue obtained by heating the positive photosensitive resin composition at 140°C for 24 hours and removing the solvent. In addition, the total solid content can also be calculated based on the amount of each component added. In this specification, the film obtained by coating the positive photosensitive resin composition is called a "coated film", the dried state is called a "film", and the film obtained by further curing is called a "cured film".

In this specification, the "surface" of the barrier rib is used as a term that only refers to the surface above the barrier rib. Therefore, the "surface" of the barrier wall does not include the side surfaces of the barrier wall. "Ink" in this specification refers to a general term for liquids that have been dried and hardened, such as optical and electrical functions, and is not limited to the coloring materials that have been used. In addition, "pixels" formed by injecting the above-mentioned ink are also used to represent partitions with optical and electrical functions separated by barrier ribs. "Ink repellency" in this specification refers to the property of having both water repellency and oil repellency moderately in order to repel the above-mentioned ink, and can be evaluated, for example, by the following method. Hereinafter, embodiments of the present invention will be described. In addition, in this specification, unless otherwise specified, % means mass %.

In this specification, the weight average molecular weight (Mw) means the weight average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran as the mobile phase and converted with standard polystyrene as the reference. In addition, the number average molecular weight (Mn) means the number average molecular weight measured by the same GPC.

The positive photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a photosensitive agent (B) and an ink repellent agent (C), and the ink repellent agent (C) has the following formula (c): A monovalent base with a carbon number of 2 to 40. R ^f1 -OR ^f2 - (c) R ^f1 : Polyfluoroalkyl group having 1 to 6 carbon atoms R ^f2 : Polyfluoroalkylene group which may have etheric oxygen atoms between carbon-carbon atoms Among them, R ^f1 -OR ^f2 -Has at least 1 -O-CF ₂ - group. Since the ink repellent agent (C) has a polyfluoroether structure, a cured film excellent in inkjet coating properties, residue removal properties, and ink repellency can be obtained.

[Alkali-soluble resin (A)] Alkali-soluble resin (A) is a resin that dissolves in the alkali used in the development step and is a resin that becomes the main component of the barrier wall used in the pixel part, etc. The alkali-soluble resin (A) functions as a positive photosensitive resin composition by being used together with the photosensitive agent (B) described below. That is, in the positive photosensitive resin composition, when exposed by photolithography, etc., the photosensitive agent (B) is activated in the exposed part, and the solubility in the developer is increased. The exposed part is dissolved in the developer (usually an alkaline developer) during development and is removed. The part that is not irradiated with light (unexposed part) becomes the barrier wall. Furthermore, since the alkali-soluble resin (A) is combined with the photosensitive agent (B) before exposure, there are also resins that are insoluble in the developer.

In order to impart alkali solubility to the alkali-soluble resin (A), it is preferred that the alkali-soluble group be present in the structural unit of the resin and/or at the end of its main chain. The alkali-soluble group refers to a functional group that increases the solubility in an alkaline solution by interacting or reacting with an alkali, and specifically, an acidic group can be cited. Preferred alkali-soluble groups include: a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and the like.

As the alkali-soluble resin (A) in the positive photosensitive resin composition of the present invention, a known alkali-soluble resin used in a positive photosensitive resin composition can be used. As the alkali-soluble resin (A), acrylic resin, polyimide resin, and novolac type phenol resin are preferred.

As the acrylic resin, for example, N-substituted maleimide with a high Tg, benzyl methacrylate, a copolymer of acrylic acid, an acrylic resin containing a phenolic hydroxyl group, and acrylic acid having a sulfonamide group are preferred. Made of resin. Specific examples include Japanese Patent No. 6177495, Japanese Patent No. 5447384, Japanese Patent No. 4770985, Japanese Patent No. 4600477, Japanese Patent No. 5444749, and International Publication No. 2019/156000. Alkali-soluble resins described in, but are not limited to these.

The polyimide resin is preferably a polyimide resin, a polyimide precursor, or a copolymer having two or more types of repeating units. The polyimide resin is preferably obtained by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic diester dicarboxylic acid chloride, etc., with a diamine or diisocyanate compound, trimethylsilylated diamine, etc. Obtained resin. The polyimide resin has tetracarboxylic acid residues and diamine residues. Moreover, the polyamide resin is preferably a resin obtained by reacting tetracarboxylic dianhydride and a diamine, and polyamide acid, which is one type of polyamide precursor, obtained by reacting it. Obtained by heat treatment for dehydration and closed loop. During the heat treatment, a solvent such as m-xylene that azeotropes with water may also be added. Alternatively, the polyimide resin is preferably a resin obtained by adding a dehydration condensation agent such as carboxylic anhydride or dicyclohexylcarbodiimide or an alkali such as triethylamine as a ring-closing catalyst and chemically heat-treated Obtained by dehydration and closed loop. Alternatively, it can also be obtained by adding a weakly acidic carboxylic acid compound and performing dehydration and ring-closure by heating at a low temperature of 100° C. or below.

Examples of the polyamide precursor include polyamide acid, polyamide ester, polyamide acid amide, and polyisoamide imide. For example, polyamic acid can be obtained by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic diester dicarboxylic acid chloride, etc. with a diamine, a diisocyanate compound, or trimethylsilylated diamine. Polyamide imide can be obtained, for example, by dehydrating and ring-closing the polyamide acid obtained by the above method through heating or chemical treatment with acid or alkali.

The novolak-type phenol resin is preferably an unmodified or modified novolak-type phenol resin, which is produced by adding phenols and aldehydes and optionally various modifiers to perform polycondensation.

Examples of phenols used to produce novolak-type phenol resin include: cresols such as phenol, o-cresol, p-cresol, and m-cresol; 3,5-xylenol, 2,5-xylenol Phenol, 2,3-xylenol, 3,4-xylenol and other xylenols; 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,4,5 -Trimethylphenols such as trimethylphenol and 3,4,5-trimethylphenol; tertiary butylphenols such as 2-tert-butylphenol, 3-tert-butylphenol and 4-tert-butylphenol Phenols; 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol Methoxyphenols such as methoxyphenol; 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,3-diethylphenol, 3,5-diethylphenol, 2,3 , ethylphenols such as 5-triethylphenol, 3,4,5-triethylphenol; chlorophenols such as o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, etc.; m-phenylene Diphenols, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol and other resorcinols; 5-methylresorcinol and other catechols ; Pyrogallols such as 5-methylpyrogallol; Bisphenols A, B, C, D, E, F and other bisphenols; Hydroxymethylation of 2,6-dihydroxymethyl p-cresol, etc. Cresols; naphthols such as α-naphthol, β-naphthol, etc. One type of these may be used alone, or two or more types may be used in combination.

Examples of aldehydes used to produce novolac-type phenol resin include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyformaldehyde, trichloroacetaldehyde, furfural, glyoxal, and n-butyraldehyde. , hexanal, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraformaldehyde, phenyl acetaldehyde, o-tolualdehyde, salicaldehyde, etc. One type of these may be used alone, or two or more types may be used in combination.

Among the above-mentioned novolak-type phenol resins, novolak-type phenol resins using cresols, xylenols, etc. as phenols are preferred from the viewpoints of ease of acquisition, low metal impurities, etc., and particularly preferred are those using novolak-type phenol resins. Cresol-based novolak-type phenol resin (hereinafter also referred to as "cresol novolak resin").

Examples of the alkali-soluble resin (A) include, in addition to the above, polyhydroxystyrene, polyhalogenated hydroxystyrene, copolymers of N-(4-hydroxyphenyl)methacrylamide, and hydroquinone. Monomethacrylate copolymer. In addition, various alkali-soluble polymer compounds such as sulfonyl imine polymers, carboxyl group-containing polymers, and urethane resins can also be used.

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably in the range of 500 to 20,000, more preferably in the range of 3,000 to 10,000, and particularly preferably in the range of 3,000 to 8,000. If the mass average molecular weight (Mw) is within the above range, the solubility to the developer after exposure will be excellent.

The alkali-soluble resin (A) in the positive photosensitive resin composition of the present invention may be used alone or in combination of two or more. The content of the alkali-soluble resin (A) in the total solid content of the positive photosensitive resin composition is preferably 10 to 90% by mass, and more preferably 30 to 80% by mass. If the content is within the above range, the developing property of the positive photosensitive resin composition becomes good.

[Photosensitive agent (B)] As the photosensitive agent (B) in the positive photosensitive resin composition of the present invention, a known photosensitive agent used in the positive photosensitive resin composition can be used. As the photosensitizer (B), a compound having a quinonediazide group is preferred. As the compound having a quinonediazide group, it is possible to use acrylic resin, novolak type phenol resin, polyamide imide, polybenzoethazole, polyamide amide imine, any precursor thereof, and the like. A well-known compound having a quinonediazide group is used in combination with polymer resins.

As the photosensitizer (B), there can be exemplified a complete condensate or a partial condensate of the following compound α having a quinone diazide group and a compound β which are capable of condensing with each other.

Compound α has a functional group capable of condensation reaction. Examples of the functional group capable of condensation reaction include sulfo group and chlorosulfo group. Examples of compound α include sulfonic acids such as benzoquinonediazidesulfonic acid, naphthoquinonediazidesulfonic acid, anthraquinonediazidesulfonic acid, and sulfonyl chlorides thereof. Specifically, examples of sulfonyl chloride include 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, and 1,2-benzoquinonediazide-4-sulfonyl chloride.

Compound β has a functional group capable of undergoing a condensation reaction with compound α. Examples of the functional group capable of undergoing a condensation reaction include a hydroxyl group, an amino group, etc., and a hydroxyl group is preferred. As compound β, a compound having an aromatic ring is preferred in terms of excellent heat resistance of the barrier wall obtained. In terms of heat resistance and the ability to introduce more hydroxyl groups, the number of aromatic rings in the aromatic compound is preferably 1 to 6, and more preferably 2 to 4. As compound β, an aromatic compound in which at least one hydrogen atom bonded to the aromatic ring is substituted with a hydroxyl group is particularly preferred. The number of hydroxyl groups in one molecule is preferably 1 to 10, and more preferably 2 to 4. As specific examples of compound β, the compounds shown below can be cited. Phenol and 4-methylphenol as phenols; 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone as polyhydroxybenzophenones; tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-[α,α-dimethyl-α-(4'-hydroxyphenyl)benzyl]ethane and 1,3,5-tris(4-hydroxyphenyldimethylbenzyl)benzene as triphenol compounds; 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(3,4-dihydroxyphenyl)-2-(3',4'-dihydroxyphenyl)propane and 2-(2,4-dihydroxyphenyl)- )-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane;1-[1,1-bis(4-hydroxyphenyl)ethyl]-4-[1',1'-bis(4'-hydroxyphenyl)ethyl]benzene as a multinuclear branched compound; 2-bis(4'-hydroxyphenyl)ethyl as a condensed phenol compound [1,1-Bis(4-hydroxyphenylcyclohexyl)]-2-bis[1',1'-bis(4'-hydroxyphenylcyclohexyl)]propane;1,1'-spirobi[1H-indene]-5,5',6,6'-tetrol, 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxybenzodihydropyran, pentacyclic[19,3,1,1 ^3,7 ,1 ^9,13 ,1 ^15,19 ]octacosane-1,3,5,7,9,11,13,15,17,19,21,23-dodecene-4,6,10,12,16,18,22,24-octaol.

The photosensitive agent (B) in the positive photosensitive resin composition of the present invention may be a mixture of compounds having different numbers of quinone diazide groups in one molecule. Based on the average value of the photosensitive agent (B) as a whole, a compound having 1 to 4 quinone diazide groups in one molecule is preferred, and a compound having 2.5 to 3 quinone diazide groups is particularly preferred.

The content of the photosensitive agent (B) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 0.1 to 50 mass %, and particularly preferably 1.0 to 30 mass %. If it is the said range, the developability of a positive photosensitive resin composition will be excellent. If it is less than the lower limit, sufficient sensitivity as a photosensitive resin composition may not be obtained, and if it exceeds the upper limit, there is a risk of component precipitation.

[Ink repellent agent (C)] The ink repellent agent (C) in the present invention has a monovalent group having 2 to 40 carbon atoms represented by the following formula (c) (hereinafter also referred to as group (c)). R ^f1 -OR ^f2 - (c) R ^f1 : Polyfluoroalkyl group having 1 to 6 carbon atoms R ^f2 : Polyfluoroalkylene group which may have etheric oxygen atoms between carbon-carbon atoms Among them, R ^f1 -OR ^f2 -Has at least 1 -O-CF ₂ - group.

The ink repellent (C) has the property of migrating to the surface during the process of forming a cured film using a positive photosensitive resin composition containing it (surface transfer property) and ink repellency. The upper layer of the surface of the obtained cured film becomes a layer in which the ink repellent (C) is densely present (hereinafter, sometimes referred to as an "ink repellent layer"), and the ink repellency is imparted to the surface of the cured film. Here, as the ink repellent (C), from the perspective of improving the ink repellency, it is preferred that the fluorine content is higher, and from the perspective of improving the removability of residues during development after exposure, it is preferred that the fluorine content is lower. The base represented by the above formula (c) has a fluoroalkyl group at the end, and the fluoroalkyl group at the end is connected to the fluoroalkylene group by an ether oxygen atom. The surface transferability of the ink repellent (C) is higher, and the ink repellency is easily exerted. For example, when compared with a polyfluoroalkylene group having the same chain length and the same fluorine content as the formula (c), the base represented by the formula (c) maintains the residue removal property and obtains an ink repellent with higher ink repellency.

The group represented by formula (c) has at least one -O-CF ₂ - group. The oxygen atom in the -O-CF ₂ - group is an etheric oxygen atom, and the other bonding bond of the oxygen atom is bonded to a carbon atom. The carbon atom bonded to the left side of the group represented by -O-CF ₂ - (bonding bond of the oxygen atom) may be a carbon atom bonded to two fluorine atoms (i.e., CF ₂ ) or a carbon atom bonded to one or more atoms other than fluorine atoms such as CH _2. Specifically, for example, -CF ₂ -O-CF ₂ -, CF ₃ -O-CF ₂ -, -CH ₂ -O-CF ₂ -, -CF(CF ₃ )-O-CF ₂ -, etc. are groups having an -O-CF ₂ - group. Furthermore, -O- _CF2- is the same group as _-CF2 -O-, that is, the same group that differs only in the expression (the order of atoms) in the chemical formula. Therefore, for example, _-CF2 -O- _CH2- , _-CF2 -O-CF( _CF3 )-, _CF3 -O- _CH2- , etc. are also groups having -O- _CF2- .

As ^Rf1 and ^Rf2 , from the viewpoint of improving ink repellency, it is preferred that all hydrogen atoms are substituted by fluorine atoms. That is, as ^Rf1 , it is preferred to be a perfluoroalkyl group having 1 to 6 carbon atoms, and as ^Rf2 , it is preferred to be a perfluoroalkylene group which may have an ethereal oxygen atom between carbon atoms.

The content of fluorine atoms in the ink repellent agent (C) is preferably 1 to 45% by mass. If the fluorine atom content of the ink repellent agent (C) is more than the lower limit of the above range, good ink repellency, especially good ink roll-off properties, can be imparted to the surface of the cured film. If it is less than the upper limit, , the compatibility with other components in the positive photosensitive resin composition becomes good. From the viewpoint of imparting ink repellency, the content of fluorine atoms in the ink repellent agent (C) is more preferably 1.5% by mass or more, and particularly preferably 2% by mass or more. Furthermore, if the content rate of fluorine atoms in the ink repellent agent (C) is high, the storage stability of the positive photosensitive resin composition may decrease. Therefore, the content rate of fluorine atoms in the ink repellent agent (C) is more preferably 35% by mass or less, and more preferably less than 30% by mass. That is, the content rate of fluorine atoms in the ink repellent agent (C) is particularly preferably 2 mass % or more and less than 30 mass %.

R ^f1 is a polyfluoroalkyl group having 1 to 6 carbon atoms, preferably a perfluoroalkyl group having 1 to 6 carbon atoms. The carbon number of R ^f1 is more preferably 1 to 4, particularly preferably 1 to 3. Examples of the structure of R ^f1 include a straight chain structure, a branched chain structure, a ring structure, a structure partially having a ring, etc., and a straight chain structure is preferred. R ^f1 is particularly preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms.

The carbon number of R ^f2 is such that the total of the carbon number and R ^f1 is 2 to 40. The carbon number is preferably 2 to 30, and more preferably 2 to 20.

As R ^f2 , a group represented by the following formula (1) can be preferably exemplified. -[(CY ₂ -O) _n1 (CY ₂ CY ₂ -O) _n2 (CY ₂ CY ₂ CY ₂ -O) _n3 (CY ₂ CY ₂ CY ₂ CY ₂ -O) _n4 ]-(CY ₂ ) _n5 - (1) In formula (1), each symbol is as follows. Y independently represents H, F or CF ₃ , and at least one Y in each repeating unit enclosed by n1, n2, n3, n4 and n5 is F or CF ₃ . n1, n2, n3 and n4 each independently represent an integer above 0, and n1+n2+n3+n4 is at least 1 or above. n5 represents an integer from 1 to 4. The total number of all carbon atoms in the formula (1) and R ^f1 is a number from 2 to 40. The order of existence of the repeating units enclosed by n1, n2, n3 and n4 is not limited in formula (1).

In formula (1), (CY ₂ ) _n5 is a linear or branched polyfluoroalkylene group, preferably a perfluoroalkylene group in which all Y are F or CF ₃ , and particularly preferably CF(CF ₃ )(CF ₂ ) _n6 (n6 is an integer represented by n5-1, preferably 0 or 1) or (CF ₂ ) _n5 (n5 is the same integer as above, preferably 1 or 2). As R ^f2 , a perfluoroalkylene group in which all Y in formula (1) are F or CF ₃ and contains an ethereal oxygen atom is preferred.

When R ^f2 is any of the groups exemplified above, the ink repellent (C) has good ink repellency, especially ink rolling property, and the solubility of the compound (s1) described below in the solvent is excellent.

As specific examples of R ^f2 , the following groups can be cited. -(CF ₂ O) _n1 -(CY ₂ ) _n5 -, -(CF ₂ CF ₂ O) _n2 -(CY ₂ ) _n5 -, -{CF(CF ₃ )CF ₂ O} _n2 -(CY ₂ ) _n5 -, -(CF ₂ CF ₂ CF ₂ O) _{n3 -} (CY ₂ ) _n5 -, -[(CF ₂ O) _n1 -(CF ₂ CF ₂ O) _n2 ] _{-(CY 2 ) n5 -, -[(CF 2 O ) n1 - {} CF ₂ CF(CF ₃ )O} _n2 ]-( _{CY 2 ) n5 -} , _- [(CF _{2 O} ) _n1 -{CF(CF ₃ )CF _{2 O} n2 ]} -(CY ₂ ) _n5 -, -[(CF ₂ CF ₂ O) _n2 -(CF ₂ CF ₂ CF ₂ CF ₂ O) _n4 ]-(CY ₂ ) _n5 -, -[(CF ₂ CF ₂ CF ₂ O) _n3 -{CF(CF ₃ )CF ₂ O} _n2 ]-(CY ₂ ) _n5 -. (In each formula, n1 to n5 and Y in each formula independently have the same meanings as in the above formula (1), and the preferred embodiments are also the same.)

Among them, the following groups are preferred as R ^f2 . -CF ₂ CF ₂ O-CF ₂ -, -CF ₂ CF ₂ O-CF ₂ CF ₂ -, -(CF ₂ CF ₂ O) ₂ -CF ₂ -, -(CF ₂ CF ₂ O) ₂ -CF ₂ CF ₂ -, -(CF ₂ CF ₂ O) ₄ -CF ₂ -, -(CF ₂ CF ₂ O) ₄ -CF ₂ CF ₂ -, -(CF ₂ CF ₂ O) ₇ -CF ₂ -, -(CF ₂ CF ₂ O) ₇ -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ O-CF ₂ -, -CF ₂ CF ₂ CF ₂ O-CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ O-CF(CF ₃ )-, -CF ₂ CF ₂ CF ₂ O-CF(CF ₃ )CF ₂ -, _-CF2O -CF _{( CF3 )} CF2O-CF( _CF3 ) _- , -CF2CF2O-CF _{( CF3} ) _{CF2O -} CF( _CF3 )-, -CF2CF2CF2O-CF( _CF3 )CF2O-CF2CF2- _{, -CF2CF2CF2O} -CF( _CF3 ) _{CF2O -} CF( _CF3 ) _- , _-CF2CF2CF2O - _{CF ( CF3 ) CF2O} -CF ₍ CF3 _{) CF2- ,} -CF( _CF3 ) _{CF2O - CF2CF2- ,} -CF( _CF3 ) _CF2O -CF _{( CF3 ) CF2-} .

The ink repellent agent (C) is preferably the ink repellent agent (C1) having the above-mentioned group (c) and a silane-based skeleton, or the ink repellent agent (C2) having the above-mentioned group (c) and an acrylic-based skeleton. Hereinafter, the ink repellent agent (C1) and the ink repellent agent (C2) will be described.

＜Ink repellent(C1)＞ The ink repellent agent (C1) is a partially hydrolyzed condensate of a mixture (M) containing a hydrolyzable silane compound, and as the hydrolyzable silane compound, it is necessary to contain a hydrolyzable silane compound (s1) having a group represented by the above formula (c). Element.

<Hydrolyzable silane compound (s1)> The hydrolyzable silane compound (s1) is a silane compound having a group represented by the above formula (c) and a hydrolyzable group. By using the hydrolyzable silane compound (s1), the ink repellent (C1) has a polyfluoroether structure, maintains the residue removal property, and has excellent surface transferability and ink repellency, especially ink rolling property.

Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a acyl group, an isocyanato group, an amino group, and a group in which at least one hydrogen of the amino group is substituted by an alkyl group. Alkanes having 1 to 4 carbon atoms are preferred because the reaction of forming a hydroxyl group (silanol group) through a hydrolysis reaction and further condensation reaction between molecules to form a Si-O-Si bond proceeds easily and smoothly. Oxygen group and halogen atom are more preferably methoxy group, ethoxy group and chlorine atom, especially methoxy group and ethoxy group. One type of hydrolyzable silane compound (s1) may be used alone, or two or more types may be used in combination.

As the hydrolyzable silane compound ( ^s1 ), a compound represented by the following formula (s1) is preferred. ( ^Rf1ORf2 - ^Q1 ) _a -Si( ^RH1 ) _{bX1 (4} ^- _{a - b )} (s1) In formula (s1), the symbols are as follows. ^Rf1 and ^Rf2 are respectively the same as ^Rf1 and ^Rf2 in the above formula (c), and preferred embodiments are also the same. ^Q1 is a divalent organic group having 1 to 10 carbon atoms and not containing fluorine atoms. ^RH1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms. a is 1 or 2, b is 0 or 1, and a+b is 1 or 2. ^X1 is a hydrolyzable group. When there are plural ^X1s , they may be different from each other or the same. When there are plural ^{Rf1ORf2 -Q1s ,} they may be different from each other or the same.

Compound (s1) is a fluorine-containing hydrolyzable silane compound having one difunctional or trifunctional hydrolyzable silane group. R ^H1 is preferably a alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. In formula (s1), a is more preferably 1, and b is 0 or 1, and more preferably b is 0. Specific examples and preferred aspects of X ¹ are as described above for the hydrolyzable group.

In the formula (s1), Q ¹ is a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom. As Q ¹ , when Si is bonded to the bond on the right side and R ^f2 is bonded to the bond on the left side, for example, -(CH ² ) _i1 -A-(CH ₂ ) _i2 can be mentioned. -(A is a single bond, amide bond, urethane bond, sulfonamide bond, ether bond or ester bond, i1 and i2 are independently integers from 0 to 10, and the number of carbon atoms in the entire group is 1 ~10) represents the base.

Q ¹ is preferably the following: -(CH ₂ ) _i1 -, -CH ₂ O(CH ₂ ) _i2 -, -O(CH ₂ ) _i2 -, -SO ₂ NR ¹ -(CH ₂ ) _i2 -, -(C=O)-NR ¹ -(CH ₂ ) _i2 -, -(CH ₂ ) _i1 -OC(=O)-NR ₁ -(CH ₂ ) _i2 -, -(CH 2 ) _i1 -OC(=O)-(CH ₂ ) _i2 -, -(CH ₂ ) _i1 -C(=O)-O-(CH ₂ ) _i2 -. (In each group, i1 is an integer of 1 to 5, i2 is an integer of 1 to 4, R ¹ is a hydrogen atom, a methyl group, or an ethyl _group , and the number of carbon atoms in the entire group is 1 to 10. The number of carbon atoms in the entire group is preferably 1 to 5.)

Hereinafter, -C(=O)N... is represented as -CON... For example, -C(=O)NH- is represented as -CONH-. Similarly, -O-C(=O)... is represented as -OCO..., and -C(=O)-O... is represented as -COO....

Particularly preferred as Q ¹ are -(CH ₂ ) _i1 -, -O(CH ₂ ) _i2 -, and -CONH(CH ₂ ) _i2 - (i1 and i2 include preferred aspects and are the same as described above). Furthermore, i1 and i2 are each independently preferably 1 to 3, and particularly preferably 2 or 3.

Specific examples of the compound (s1) include the following compounds. CF ₃ CF ₂ O(CF ₂ CF ₂ O)(CF ₂ ) ₂ O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ 、CF ₃ CF ₂ O(CF ₂ CF ₂ O)(CF ₂ )CONH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O)(CF ₂ ) ₂ (CH ₂ ) ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ O(CF ₂ CF ₂ O)(CF ₂ ) ₂ (CH ₂ ) ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O)(CF(CF ₃ ))CONH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O)(CF(CF ₃ )CF ₂ )O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O)(CF ₂ ) ₂ CONH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ .

The above compound (s1) can be produced by a known method, for example, the method described in International Publication No. 2009/008380.

The content ratio of the hydrolyzable silane compound (s1) in the mixture (M) is preferably such that the content ratio of fluorine atoms in the partially hydrolyzed condensate obtained from the mixture is 1 to 45 mass %, more preferably 2 mass % or more and less than 25 mass %. If the content ratio of the hydrolyzable silane compound (s1) is at least the lower limit of the above range, good ink repellency, especially good ink rolling property, can be imparted to the surface of the cured film. If it is below the upper limit, the compatibility with other hydrolyzable silane compounds in the mixture becomes good, and the storage stability in the photosensitive resin composition is hardly reduced.

The mixture (M) in the ink repellent agent (C1) contains the above-mentioned hydrolyzable silane compound (s1) as an essential component, and optionally contains a hydrolyzable silane compound other than the hydrolyzable silane compound (s1). Examples of the hydrolyzable silane compound optionally included in the mixture (M) include the following hydrolyzable silane compounds (s2) to (s6).

Hydrolyzable silane compound (s2); a hydrolyzable silane compound containing a group having an epoxy group and a hydrolyzable group, and containing no fluorine atom. Hydrolyzable silane compound (s3); a hydrolyzable silane compound containing a phenyl group and a hydrolyzable group, and containing no fluorine atom. Hydrolyzable silane compound (s4); a hydrolyzable silane compound in which four hydrolyzable groups are bonded to a silicon atom. Hydrolyzable silane compound (s5); a hydrolyzable silane compound containing a group having an ethylene double bond and a hydrolyzable group, and containing no fluorine atom. Hydrolyzable silane compound (s6); a hydrolyzable silane compound having a hydrolyzable group and an organic group having a fluorine atom and not having an ethereal oxygen atom.

As the hydrolyzable group in the hydrolyzable silane compounds (s2) to (s6), the same hydrolyzable group as that of the hydrolyzable silane compound (s1) can be used.

<Hydrolyzable silane compound (s2)> The hydrolyzable silane compound (s2) is a hydrolyzable silane compound represented by the following formula (s2) (hereinafter, also referred to as "compound (s2)"). R ⁴ Si(R ⁵ ) _n (X ² ) _3-n (s2) R ⁴ is an organic group having 2 to 12 carbon atoms having an epoxy group. Among them, an organic group having 3 to 12 carbon atoms having a glycidyl group or an organic group having 6 to 12 carbon atoms having an epoxycyclohexyl group is preferred. R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred. X ² is a hydrolyzable group and is the same as X ¹ in the above formula (s1) including preferred aspects. n is 0 or 1.

As specific examples of compound (s2), the following compounds can be cited. Diethoxy(3-glycidyloxypropyl)methylsilane 3-glycidyloxypropyl(dimethoxy)methylsilane 3-glycidyloxypropyl(diethoxy)methylsilane 3-glycidyloxypropyltrimethoxysilane 3-glycidyloxypropyltriethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane

The above compound (s2) can be produced by a known method, for example, the method described in International Publication No. 2019/156000.

One type of compound (s2) contained in the mixture (M) may be used alone, or two or more types may be used in combination. The compounding amount of the compound (s2) in the mixture (M) is preferably 5 to 15 moles, and particularly preferably 7 to 13 moles per 1 mol of the hydrolyzable silane compound (s1). If the content ratio is within this range, the solvent resistance of the ink repellent layer is improved, so it is preferable.

<Hydrolyzable silane compound (s3)> The hydrolyzable silane compound (s3) is a hydrolyzable silane compound represented by the following formula (s3) (hereinafter, also referred to as "compound (s3)"). ( ^YQ2 ) _q -Si( ^RH2 ) _{rX3 (4 - q - r)} (s3) In the formula (s3), ^X3 representing a hydrolyzable group is the same as ^X1 in the above formula (s1), including preferred aspects. ^RH2 is preferably an alkyl group ^having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. In the formula (s3), Y represents a phenyl group in which a hydrogen atom may be substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a nitro group. ^Q2 is a group linking the silicon atom and the phenyl group, and is a single bond or a divalent organic group.

q is 1 or 2, r is 0 or 1, and q+r is 1 or 2. Furthermore, in formula (s3), when q is 2, the two Q ² can be different from each other or the same. When q + r is 1, the three X ³ can be different from each other or the same. , when q+r is 2, the two X ³ can be different from each other or the same. In formula (s3), it is preferable that q is 1 and r is 1, or q is 1 and r is 0.

In formula (s3), Y may be exemplified by phenyl, fluorophenyl, chlorophenyl, dichlorophenyl, etc., and phenyl is particularly preferred. By using such compound (s3), a barrier wall with higher resolution and less residue in the dot portion can be obtained. The reason is presumed to be that after the ink repellent (C1) is transferred to the film surface of the positive photosensitive resin composition, the phenyl group derived from compound (s3) undergoes an azo coupling reaction with the diazonium group of the photosensitive agent in the developer, thereby making it easy for the ink repellent (C1) to remain on the film surface of the positive photosensitive resin composition. Thus, even after development, post-baking, etc., the surface of the barrier wall obtained can be kept ink-repellent, and the side surface can be kept ink-affinity.

In formula (s3), when Q ² is a divalent organic group, -(CH ₂ )j-(j is an integer from 1 to 6), -NH-, -NH-(C _k H _2k )-( k is an integer from 1 to 6) and -N(C _g H _{2g + 1} )- (g is an integer from 1 to 6) are electron-donating groups and are preferable in terms of ease of acquisition. Q ² is particularly preferably a single bond or -NH-.

Specific examples of the compound (s3) include the following compounds. (C ₆ H ₅ )Si(OC ₂ H ₅ ) ₃ (C ₆ H ₅ )NH(CH ₂ ) ₃ Si(OCH ₃ ) ₃

The compound (s3) can be produced by a known method, for example, the method described in International Publication No. 2013/133392.

The compound (s3) contained in the mixture (M) may be used alone or in combination of two or more. The amount of the compound (s3) in the mixture (M) is preferably 20 mol or less, and more preferably 15 mol or less, relative to 1 mol of the hydrolyzable silane compound (s1). If the content ratio is within this range, the ink repellency can be maintained during development, which is preferred.

<Hydrolyzable silane compound (s4)> By including a hydrolyzable silane compound (s4) in the mixture (M) of the present invention, the film-forming property of the ink repellent (C1) after it migrates to the surface can be improved in the cured film formed by curing the positive photosensitive resin composition containing the ink repellent (C1). That is, it is considered that since the hydrolyzable bases in the hydrolyzable silane compound (s4) are relatively large, the ink repellent (C1) is well condensed with each other after migrating to the surface, forming a thin film on the entire surface to form an ink repellent layer. In addition, by including a hydrolyzable silane compound (s4) in the mixture (M), the ink repellent (C) is easily dissolved in a hydrocarbon solvent. The hydrolyzable silane compound (s4) may be used alone or in combination of two or more.

The hydrolyzable silane compound (s4) can be represented by the following formula (s4). The hydrolyzable silane compound (s4) may also be an oligomer of the compound (s4). Si(X ⁴ ) ₄ (s4) In the formula (s4), X ⁴ represents a hydrolyzable group, and the four X ⁴ may be different from each other or the same. As X ⁴ , the same hydrolyzable group as X ¹ mentioned above can be used.

Specific examples of the hydrolyzable silane compound (s4) include the following compounds. Si(OCH ₃ ) ₄ Si(OC ₂ H ₅ ) ₄ Partial hydrolysis condensation product of Si(OCH ₃ ) ₄ (for example, Methyl Silicate 51 (trade name) manufactured by COLCOAT) Partial hydrolysis of Si(OC ₂ H ₅ ) ₄ Condensate (for example, Ethyl Silicate 40 and Ethyl Silicate 48 (both trade names) manufactured by COLCOAT).

The compound (s4) can be produced by a known method, for example, the method described in International Publication No. 2015/093415.

The content ratio of the hydrolyzable silane compound (s4) in the mixture (M) is preferably 1 to 25 moles, and particularly preferably 3 to 20 moles per 1 mol of the hydrolyzable silane compound (s1). If the content ratio is more than the lower limit of the above range, the film-forming property of the ink repellent agent (C1) is good, and if it is less than the upper limit, the ink repellent property of the ink repellent agent (C1) is good.

<Hydrolyzable silane compound (s5)> By including a hydrolyzable silane compound (s5) in the mixture (M) of the present invention, an ink repellent (C1) having a group having an ethylenic double bond in the side chain can be obtained as a partial hydrolysis condensate of the mixture (M). In this way, the ink repellent (C1) can be preferably (co)polymerized with each other or with other components having an ethylenic double bond contained in the positive photosensitive resin composition through the group having an ethylenic double bond. In this way, the effect of improving the fixation of the ink repellent (C1) in the ink repellent layer can be obtained. The hydrolyzable silane compound (s5) may be used alone or in combination of two or more. As the group having an ethylenic double bond, (meth)acryloyloxy and vinylphenyl are preferred, and (meth)acryloyloxy is particularly preferred.

As the hydrolyzable silane compound (s5), a compound represented by the following formula (s5) is preferred. (ZQ ³ ) _g -Si(R ^H3 ) _h X ⁵ _{(4 - g - h)} (s5) The symbols in formula (s5) are as follows. Z is a group with an ethylenic double bond. Q ³ is a divalent organic group containing 1 to 6 carbon atoms and does not contain fluorine atoms. R ^H3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms. X ⁵ is a hydrolyzable group. g is 1 or 2, h is 0 or 1, and g+h is 1 or 2. When there are multiple ZQ ^3s , they may be different from each other or they may be the same. When there are multiple X ^5s , they may be different from each other or they may be the same.

As R ^H3 , specifically, the same groups as those for R ^H1 described above can be used. As X ⁵ , specifically, the same groups as those for X ¹ described above can be used.

As Z, for example, a (meth)acryloyloxy group and a vinylphenyl group are preferred, and a (meth)acryloyloxy group is particularly preferred.

Specific examples of Q ³ include -(CH ₂ )j- (j is an integer of 1 to 6). Preferably, g is 1, and h is 0 or 1. Compound (s5) may be used alone or in combination of two or more.

Specific examples of compound (s5) include the following compounds. _CH2 =C( _CH3 )COO( _CH2 ) _3Si ( _OCH3 ) ₃ , _CH2 =C( _CH3 )COO(CH2)3Si( _{OC2H5 ) 3} , _{CH2 =CHCOO(CH2)3Si(OCH3)3, CH2=CHCOO(CH2)3Si(OC2H5 ) 3 , [ CH2 = C ( CH3 ) COO} ( _CH2 ) ₃ ] _{CH3Si ( OCH3} ) ₂ , [ _CH2 =C _{( CH3} )COO( _CH2 ) ₃ ] _CH3Si ( _{OC2H5 ) 2} ,

The above compound (s5) can be produced by a known method, for example, the method described in International Publication No. 2015/093415.

The content ratio of the hydrolyzable silane compound (s5) in the mixture (M) is preferably 0.1 to 25 mol, and more preferably 0.5 to 20 mol, relative to 1 mol of the hydrolyzable silane compound (s1). If the content ratio is at least the lower limit of the above range, the surface transferability of the ink repellent (C1) is good, and the fixation of the ink repellent (C1) in the ink repellent layer including the surface after the surface transfer is good, and further, the storage stability of the ink repellent (C1) is good. If it is at most the upper limit, the ink repellent (C1) has good ink repellency.

<Hydrolyzable silane compound (s6)> The hydrolyzable silane compound (s6) is a hydrolyzable silane compound having a hydrolyzable group and an organic group having a fluorine atom and not having an etheric oxygen atom. The organic group having a fluorine atom is an organic group bonded to a silicon atom of the polysiloxane main chain, and is an organic group partially or completely substituted with a fluorine atom. The organic group having a fluorine atom is not particularly limited as long as it does not impair the effect of the present invention, as long as it has a fluorine atom. It is particularly preferred to be an alkyl group in which a part or all of the hydrogen atoms are substituted with a fluorine atom. In addition, the number of fluorine atoms possessed by the organic group is not particularly limited. Among them, the organic group does not have an etheric oxygen atom. As the hydrolyzable silane compound (s6), the compound represented by the following formula (s6) is preferred. [ _CF3 ( _CF2 ) _xCH2CH2 ] _y - ^Si ( _RH6 ) _{zX6 (4 - y - z) (} s6) The symbols in formula (s6) are as follows. ^RH6 is a monovalent hydrocarbon group having 1 ^to 6 carbon atoms. ^X6 is a hydrolyzable group. x is 0 to 12. y is 1 or 2, z is 0 or 1, and y+z is 1 or 2. When there are a plurality of _CF3 ( _CF2 ) _{xCH2CH2- ,} they may be different from each other or _the same.

As R ^H6 , specifically, the same groups as those for R ^H1 described above can be used. As X ⁶ , specifically, the same groups as those for X ¹ described above can be used.

Specific examples of the compound (s6) include the following compounds. nC ₆ F ₁₃ (CH ₂ ) ₂ Si(OCH ₃ ) ₃ .

The above compound (s6) can be produced by a known method, for example, the method described in International Publication No. 2019/156000.

The compound (s6) contained in the mixture (M) may be used alone or in combination of two or more. The amount of the compound (s6) in the mixture (M) is preferably 5 mol or less, and particularly preferably 1 mol or less, relative to 1 mol of the hydrolyzable silane compound (s1). If the content ratio is within this range, the surface transferability of the ink-repellent layer is stabilized, and the distribution of the fluoride in the ink-repellent layer becomes uniform, which is preferred.

The hydrolyzable silane compound optionally included in the mixture (M) is preferably the following: a hydrolyzable silane compound (s2) which acts as a component for improving the fixation of the ink repellent (C1) in the upper layer portion, i.e., the ink repellent layer, of the cured film formed by curing the positive photosensitive resin composition after the ink repellent (C1) has moved to the surface; and a hydrolyzable silane compound (s3) which acts as a component for improving the stability and film-forming property of the ink repellent (C1).

In addition, as the hydrolyzable silane compounds (s1) to (s6), in addition to the monomers classified into each hydrolyzable silane compound, partial hydrolysis condensates (low hydrolysis condensates) obtained by hydrolyzing and condensing a plurality of parts in advance can also be used. polymer).

The ink repellent (C1) is a hydrolytic condensate of a mixture (M) containing compound (s1) and optionally containing compounds (s2) to (s6), but is actually a product (part of which remains of a hydrolyzable group or silanol group). Hydrolysis condensation product), so it is difficult to express this product with a chemical formula.

The ink repellent (C1) can be produced by subjecting the above mixture (M) to hydrolysis and condensation reaction using a known method. In the reaction, it is preferred to use as a catalyst a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; or an organic acid such as acetic acid, oxalic acid and maleic acid. A known solvent can be used in the above reaction. The ink repellent (C1) obtained in the above reaction can be mixed with a solvent and formulated into a positive photosensitive resin composition in the form of a solution.

<Ink repellent (C2)> The ink repellent (C2) is a polymer having the above-mentioned group (c) and an acrylic skeleton, preferably a polymer having a side chain containing a group represented by the above-mentioned formula (c) and a side chain containing an ethylene double bond. The side chain containing an ethylene double bond can be formed by chemical conversion after a polymerization reaction. By having a side chain containing an ethylene double bond, a curing reaction of the ink repellent (C2) occurs during post-baking, and it is easy to fix it on the surface of the barrier wall. It is not easy for unreacted residual molecules to migrate to the point and contaminate the point during post-baking.

Examples of the ethylenic double bond include (meth)acryl, allyl, vinyl, vinyloxy, vinyloxyalkyl and other double bonds having addition polymerizability, which may be used alone or in combination of two or more. Furthermore, part or all of the hydrogen atoms of the addition polymerizability group may be substituted by an alkyl group, preferably a methyl group.

The ink repellent (C2) is preferably a polymer containing a side chain having an acidic group. Some molecules of the ink repellent (C2) that do not undergo a hardening reaction in the exposure step are washed away from the surface of the exposed substrate during development because they contain a side chain having an acidic group, and are unlikely to leave residual molecules. Therefore, the ink affinity of the dots can be further improved.

Examples of the above-mentioned acidic group include a carboxyl group, a sulfo group, and the like. One type of these may be used alone, or two or more types may be used in combination. Side chains with acidic groups can be formed by polymerization of monomers with acidic groups, or by chemical conversion after polymerization.

The ink repellent (C2) can be produced by reacting a polymer obtained by homopolymerizing the following monomer (a1) with a compound (z1) having a functional group capable of bonding to the above-mentioned reactive group and an ethylenic double bond.

When the ink repellent (C2) contains a polymer having a side chain further having an acidic group, it can be produced by copolymerizing the following monomer (a1) and a monomer (a4) having an acidic group, and then reacting the obtained copolymer with the compound (z1).

The monomer (a1) is a monomer having a group (c) and is represented by the following formula (a1). CH ₂ =CR ²¹ COO-YR ^f2 -OR ^f1 (a1) In the above formula, R ²¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and Y represents a divalent organic carbon number of 1 to 6 that does not contain a fluorine atom. base. R ^f1 and R ^f2 are respectively the same as R ^f1 and R ^f2 in the above formula (c), and the preferred aspects are also the same.

In the monomer (a1), Y is preferably a group represented by the following formula from the viewpoint of availability: -R ²² - -R ²² NR ²³ SO ₂ - -R ²² NR ²³ CO- -CH ₂ CH(OH)R ²⁴ - R ²² : Alkylene having 1 to 6 carbon atoms R ²³ : Hydrogen atom or methyl group R ²⁴ : Single bond or Alkylene having 1 to 4 carbon atoms

Specific examples of R ²² include -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -C(CH ₃ ) ₂ -, - CH(CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH ₂ ) ₃ CH ₂ -, -CH(CH ₂ CH (CH ₃ ) ₂ )-etc.

Specific examples of ^R24 include _-CH2- , _-CH2CH2- , -CH( _CH3 ) _{- ,} -CH2CH2CH2- _{, -C} ( _{CH3 ) 2- , -CH ( CH2CH3} ) _- , -CH2CH2CH2CH2-, -CH( _CH2CH2CH3 )-, _{-CH2CH2CH2CH2-, and -CH(CH2CH2CH3 )} -.

Specific examples of the monomer (a1) include: CF ₃ O (CF ₂ CF ₂ O) _p CF ₂ CH ₂ OCOCH=CH ₂ (p=2 to 7) and the like. One type of monomer (a1) may be used, or two or more types may be used in combination.

The monomer (a3) is a monomer having a reactive group, and examples thereof include a monomer having a hydroxyl group, a monomer having an acid anhydride group, a monomer having a carboxyl group, a monomer having an epoxy group, and the like. Examples of the reactive group include a hydroxyl group, an acid anhydride group, a carboxyl group, and an epoxy group. Furthermore, it is preferable that the monomer (a3) substantially does not contain the group (c).

Specific examples of the monomer having a hydroxyl group include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylate ) 4-hydroxybutyl acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono(methyl ) Acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glyceryl mono(meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monoethylene Ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, etc.

Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain having a hydroxyl group at the end. For example, CH ₂ =CHOCH ₂ C ₆ H ₁₀ CH ₂ O(C ₂ H ₄ O) _h H (here, h is an integer from 1 to 100, the same below), CH ₂ =CHOC ₄ H ₈ O (C ₂ H ₄ O) _h H, CH ₂ =CHCOOC ₂ H ₄ O(C ₂ H ₄ O) _h H, CH ₂ =C(CH ₃ )COOC ₂ H ₄ O(C ₂ H ₄ O) _h H , CH ₂ =CHCOOC ₂ H ₄ O(C ₂ H ₄ O) _i (C ₃ H ₆ O) _g H (here, i is an integer from 0 to 100, g is an integer from 1 to 100, m+j is 1 to 100. The same below), CH ₂ =C(CH ₃ )COOC ₂ H ₄ O(C ₂ H ₄ O) _i (C ₃ H ₆ O) _g H, etc. As the monomer having a hydroxyl group, commercially available products can be used.

Specific examples of the monomer having an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4, 5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, etc. Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and the like. of salt. Specific examples of the monomer having an epoxy group include glycidyl (meth)acrylate and 3,4-epoxycyclohexyl methacrylate.

The monomer (a3) is preferably a compound having a hydroxyl group at the terminal, more preferably a (meth)acrylate having a hydroxyl group at the terminal, and particularly preferably 2-hydroxyethyl (meth)acrylate.

The compound (z1) is preferably selected based on the reactive group of the monomer (a3). Examples of the combination of the reactive group and the compound (z1) include the following. (1) an acid anhydride having an ethylenic double bond relative to the hydroxyl group as the reactive group; (2) a compound having an isocyanate group and an ethylenic double bond relative to the hydroxyl group as the reactive group; (3) a compound having an acyl chloride group and an ethylenic double bond relative to the hydroxyl group as the reactive group; (4) a compound having an acyl chloride group and an ethylenic double bond relative to the hydroxyl group as the reactive group; 4) a compound having a hydroxyl group and an ethylenic double bond relative to the acid anhydride group as the reactive group of the compound (z1); (5) a compound having an epoxide group and an ethylenic double bond relative to the carboxyl group as the reactive group of the compound (z1); (6) a compound having a carboxyl group and an ethylenic double bond relative to the epoxide group as the reactive group of the compound (z1).

As specific examples of the acid anhydride having an ethylenic double bond as the compound (z1), the same compounds as the above-mentioned monomers having an acid anhydride group can be cited. As specific examples of the compound having an isocyanate group and an ethylenic double bond as the compound (z1), 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, and 2-acryloyloxyethyl isocyanate can be cited. As specific examples of the compound having an acyl chloride group and an ethylenic double bond as the compound (z1), (meth)acryloyl chloride can be cited. As specific examples of the compound having a hydroxyl group and an ethylenic double bond as the compound (z1), the above-mentioned examples of the monomers having a hydroxyl group can be cited. As specific examples of compounds having an epoxy group and an ethylenic double bond as compound (z1), the above-mentioned examples of monomers having an epoxy group can be cited. As specific examples of compounds having a carboxyl group and an ethylenic double bond as compound (z1), the above-mentioned examples of monomers having a carboxyl group can be cited. As the above combination, combination (2) is preferred, and it is particularly preferred to use 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate as compound (z1). The reason for this is that by using this combination, the ink repellent (C2) has a side chain having two or more ethylenic double bonds per side chain, and the ink repellent (C2) is excellently fixed to the barrier wall surface, and a barrier wall with excellent ink repellency can be obtained.

As the monomer (a4) having an acidic group, there can be exemplified a monomer having a carboxyl group, a monomer having a sulfonic group, and the like. As the monomer having a carboxyl group, there can be exemplified the same monomers as those exemplified in the above-mentioned monomer (a3). When a monomer having a carboxyl group is used as the monomer (a4) having an acidic group, and a monomer having a carboxyl group is also used as the above-mentioned monomer (a3) having a reactive group, the monomer (a4) is considered to be the one that does not introduce an ethylenic double bond and remains in the form of a carboxyl group.

Examples of the monomer having a sulfonic group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, 2-hydroxy-3-(meth)allyloxypropanesulfonic acid, 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropanesulfonic acid, and 2-(meth)acrylamide-2-methylpropanesulfonic acid.

As the monomer used in the polymerization in the present invention, other monomers (a5) and monomers (a6) other than the monomers (a1), (a3), and (a4) can also be used.

As the other monomer (a5), the monomer (a5) described in Japanese Patent Application Laid-Open No. 2013-05049 is preferred. As the other monomer (a6), a compound having an acryl group and an organic group having a fluorine atom and not having an etheric oxygen atom is preferred. Specifically, a compound having a fluorine-containing alkyl group and not having an etheric property can be mentioned. Oxygen atom acrylic compound.

The ink repellent agent (C2) can be synthesized by the following method, for example. First, a monomer used to obtain a desired polymer is dissolved in a solvent and heated, a polymerization initiator is added, and polymerization is performed to obtain a polymer. In the polymerization reaction, it is preferred that a chain transfer agent is present if necessary. Monomers, polymerization initiators, solvents and chain transfer agents can be added continuously.

Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, azo compounds, and the like. Organic peroxides and inorganic peroxides can also be combined with reducing agents and used as redox catalysts.

Examples of organic peroxides include benzyl peroxide, lauryl peroxide, isobutyl peroxide, tert-butyl hydroperoxide, tert-butyl-α-cumyl peroxide, etc. . Examples of inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate, and the like. Examples of azo compounds include: 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2 ,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyric acid dimethyl ester , 2,2'-Azobis(2-amidinopropane) dihydrochloride, etc. In addition, as the azo polymerization initiator, commercially available V-65 (trade name, manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.), etc. can also be used.

Examples of the above solvent include: alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, etc. Ketones; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and other cyclosuoids; 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxy) ethanol, 2-(2-butoxyethoxy)ethanol and other carbitols; methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethyl Glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl 3-ethoxypropionate, cyclohexanol acetate, γ- Butyrolactone, 3-methyl 3-methoxybutylacetate, glycerol triacetate and other esters; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, etc. Ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether, etc.

Examples of the chain transfer agent include n-butyl mercaptan, n-dodecyl mercaptan, tert-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and 2-mercaptoethanol. Thiols such as chloroform, carbon tetrachloride, carbon tetrabromide and other haloalkyl groups.

The ink repellent agent (C2) first polymerizes the monomer (a1) through the above-mentioned polymerization reaction. When monomer (a1) is copolymerized with at least one selected from the group consisting of monomer (a3), monomer (a4), monomer (a5), and monomer (a6), each monomer is added at that point And make it coaggregate. Next, the obtained polymer or copolymer is reacted with compound (z1). It is preferred to use a solvent in this reaction. As the solvent, the solvent used in the above-mentioned polymerization reaction can be used. Furthermore, it is preferable to prepare a polymerization inhibitor. Examples of the polymerization inhibitor include 2,6-di-tert-butyl-p-cresol. In addition, a catalyst or neutralizing agent may also be added. For example, when a copolymer having a hydroxyl group is reacted with a compound having an isocyanate group and an ethylenic double bond, tin compounds such as dibutyltin dilaurate can be used. When reacting a copolymer having a hydroxyl group with a compound having a chloride group and an vinyl double bond, an alkaline catalyst can be used.

In this case, the preferred ratio of each monomer to the total mass of copolymerized monomers is as follows. The ratio of the monomer (a1) is preferably 5 to 50 mass%, particularly preferably 10 to 40 mass%. If the ratio is more than the lower limit of the above range, the surface tension of the barrier wall including the cured film can be reduced, and high ink repellency can be imparted to the barrier wall. If it is below the upper limit of the above range, the adhesion between the barrier rib and the base material will be good. The ratio of the monomer (a3) is preferably 10 to 70% by mass, particularly preferably 20 to 50% by mass. If it is within this range, the immobilization of the ink repellent agent (C2) to the barrier rib by introduction of the ethylenic double bond will be favorable.

The ratio of the monomer (a4) having an acidic group is preferably 1 to 20% by mass, and more preferably 1 to 15% by mass. If it is within this range, it is easily washed away from the substrate surface during the development step.

When the ink repellent (C2) contains both a side chain having an vinyl double bond and a side chain having an acidic group, first, the monomer (a1), the monomer (a3) and the monomer having an acidic group ( a4) Copolymerization. Next, the ink repellent agent (C) can be obtained by reacting the obtained copolymer with the compound (z1). The ratio of the monomer (a1) is preferably 5 to 50% by mass, particularly preferably 10 to 40% by mass, as described above. The ratio of the monomer (a3) is preferably 10 to 70% by mass, particularly preferably 20 to 50% by mass, as described above. The ratio of the monomer (a4) is preferably 1 to 20% by mass, particularly preferably 1 to 15% by mass. If it is within this range, it will be easily washed away from the substrate surface during the development step.

When using another monomer (a5), the ratio is preferably 5 to 45 mass%, particularly preferably 5 to 25 mass%. If it is within this range, the storage stability of the ink repellent agent is good. When using another monomer (a6), the ratio is preferably 0 to 15% by mass, particularly preferably 0 to 10% by mass. If it is within this range, the surface transfer property of the ink repellent layer will be more stable, and the distribution of fluoride in the ink repellent layer will become uniform and better.

Preferred combinations of monomers are as follows. Monomer (a1): Monomer (a3): Monomer (a4): Monomer (a5) = 5 to 50 mass %: 10 to 70 mass %: 1 to 20 mass %: 5 to 45 mass %

The polymer and compound (z1) are preferably added so that the equivalent ratio of [functional group of compound (z1)]/[reactive group of polymer] becomes 0.5 to 2, particularly preferably 0.6 to 1.5. If the equivalent ratio is more than the lower limit of the above range, the ink repellent agent (C2) will be better fixed to the barrier ribs. If it is below the upper limit of the above range, the amount of unreacted compound (z1) present as an impurity can be suppressed to a low level, and the appearance of the coating film can be maintained favorably. Furthermore, when a monomer having a carboxyl group is used as both the monomer (a3) and the monomer (a4), it is only necessary to adjust the copolymer and The addition amount of compound (z1) is sufficient.

When the ink repellent (C2) has an ethylenic double bond, the amount is preferably 1.0×10 ^-3 to 5.0×10 ^-3 mol/g, and more preferably 2.0×10 ^-3 to 4.0×10 ^-3 mol/g. Within the above range, the ink repellent (C2) is well fixed to the barrier ribs.

When the ink repellent agent (C2) has an acidic group, its acid value is preferably 100 mgKOH/g or less, and particularly preferably 10 to 50 mgKOH/g. If it is within the above range, residual molecules on the substrate will be easily washed away from the barrier ribs during the development step.

The weight average molecular weight (Mw) of the ink repellent agent (C1) is preferably 500 to 2000, particularly preferably 500 to 1500. If the weight average molecular weight (Mw) is 500 or more, when the positive photosensitive resin composition is used to form a cured film, the ink repellent agent (C1) is likely to migrate to the surface. If it is 2000 or less, storage stability will be excellent. The weight average molecular weight (Mw) of the ink repellent agent (C1) can be adjusted by manufacturing conditions.

The weight average molecular weight (Mw) of the ink repellent agent (C2) is preferably 6000 to 200000, more preferably 6000 to 180000, further preferably 6000 to 150000, particularly preferably 30000 to 150000, most preferably 50000 to 150000. If the weight average molecular weight (Mw) is 6000 or more, the ink repellent agent (C2) will easily migrate to the surface when the positive photosensitive resin composition is used to form a cured film. In particular, if it is 50,000 or more, the ink repellent agent (C2) is more likely to move to the surface, and liquid repellency is easily expressed even with a small amount added. When the weight average molecular weight (Mw) is 200,000 or less, the development residue removability is excellent. The weight average molecular weight (Mw) of the ink repellent agent (C2) can be adjusted by manufacturing conditions.

In addition, from the viewpoint of surface transferability, the ratio of the molecular weight of the alkali-soluble resin (A) to the molecular weight of the ink repellent (C) is preferably within a specific range. In particular, from the viewpoint of phase separation, the molecular weight balance of the ink repellent (C2) having an acrylic skeleton and the alkali-soluble resin (A) is important. The ratio of the molecular weight (Mw) of the alkali-soluble resin (A) to the molecular weight (Mw) of the ink repellent (C2) is preferably 1:2 to 1:30, and more preferably 1:3 to 1:20.

The content ratio of the ink repellent (C) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 0.01 to 15% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.03 to 1.5% by mass. If the content ratio is 0.01% by mass or more, the surface of the cured film formed by the positive photosensitive resin composition has excellent ink repellency, especially excellent ink rolling property. If it is 15% by mass or less, the adhesion between the cured film and the substrate becomes good. In addition, the positive photosensitive resin composition has excellent storage stability.

Furthermore, the content ratio of the ink repellent (C1) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass, from the perspective of ink repellency. Furthermore, the content ratio of the ink repellent (C2) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass, from the perspective of ink repellency.

[Solvent (D)] The positive photosensitive resin composition of the present invention may also contain a solvent (D). By containing the solvent (D), the coating property of the composition to the substrate and the adhesiveness to the substrate surface are further improved. Furthermore, by containing the solvent (D), the ink repellent agent (C) can stably exist in the composition. The solvent (D) may be an alkali-soluble resin (A), a photosensitive agent (B), an ink repellent agent (C), or a thermosetting agent (E) contained as an optional component so that the positive photosensitive resin composition contains it as an essential component. ), the thermosetting accelerator (F) and other additives are uniformly dissolved or dispersed, and have no reactivity with the components contained in the positive photosensitive resin composition.

Specific examples of the solvent (D) include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; celulose such as 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; carbitols such as 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, and 2-(2-butoxyethoxy)ethanol; methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. , ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, 3-ethoxyethyl propionate, cyclohexanol acetate, butyl lactate, γ-butyrolactone, 3-methyl 3-methoxybutyl acetate, glycerol triacetate and other esters; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether and the like. In addition, chain hydrocarbons such as n-butane and n-hexane; cyclic saturated hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene, xylene, benzyl alcohol and the like can be cited. These can be used alone or in combination of two or more.

The content of the solvent (D) in the positive photosensitive resin composition of the present invention is preferably 5 to 2,000 mass %, and more preferably 100 to 500 mass %, relative to 100 mass % of the total solid content of the positive photosensitive resin composition.

[Thermosetting agent (E)] The positive photosensitive resin composition of the present invention may contain a thermosetting agent (E) as an optional component for promoting thermosetting. As the thermosetting agent (E), at least one selected from the group consisting of amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, and polycarbodiimide compounds is preferred.

Examples of the amino resin include compounds obtained by methylating a part or all of the hydroxyl groups of melamine compounds, guanamine compounds, urea compounds, etc., or compounds obtained by etherifying a part or all of the hydroxyl groups of the compounds obtained by methylating the hydroxyl groups using methanol, ethanol, n-butanol, 2-methyl-1-propanol, etc., such as hexamethoxymethylmelamine.

Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol-novolak type epoxy resin, cresol-novolac type epoxy resin, and trisphenolmethane type epoxy. Resins, brominated epoxy resins and other glycidyl ethers; 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, bis(2,3-epoxycyclopentyl) ether and other esters Cyclic epoxy resin; glycidyl esters such as hexahydrophthalic diglycidyl ester, tetrahydrophthalic diglycidyl ester, and diglycidyl phthalate; tetrahydroglycidyl diamine diamine Glycidyl amines such as phenylmethane and triglycidyl p-aminophenol; heterocyclic epoxy resins such as triglycidyl isocyanurate, etc. Furthermore, an epoxy compound having a cyclic olefin oxide structure can be exemplified.

Examples of the oxazoline compound include copolymers of polymerizable monomers such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and 2-isopropenyl-4-methyl-2-oxazoline.

Furthermore, as the heat curing agent (E), a crosslinking compound having two or more substituents selected from alkoxymethyl and hydroxymethyl groups may be used, such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine and phenoplast compounds.

These compounds may be used alone or in combination of two or more.

As the thermosetting agent (E), a compound having two or more epoxy groups in one molecule is particularly preferred. When the positive photosensitive resin composition includes the thermosetting agent (E), the curability of the positive photosensitive resin composition during exposure is more excellent, and a barrier wall having a stable shape after thermosetting can be formed.

The content of the thermosetting agent (E) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 2-40 mass %, and more preferably 3-30 mass %. If it is within the above range, when a cured film having barrier walls is formed using the positive photosensitive resin composition, the wettability of the ink (dots) other than the barrier wall surface is better.

[Thermal hardening accelerator (F)] The positive photosensitive resin composition of the present invention may contain a thermosetting accelerator (F) as an optional component that accelerates thermosetting.

The thermosetting accelerator (F) is a compound that has the function of forming a crosslinked structure in the positive photosensitive resin composition by heating. As the thermosetting accelerator (F), for example, there can be mentioned: a compound that reacts with the thermosetting agent (E) and crosslinks to form a crosslinked structure; or a compound that does not crosslink itself but has a catalytic effect on the thermosetting agent (E). In the case of using an epoxy compound as the thermosetting agent (E), as the thermosetting accelerator (F) that forms a crosslinked structure, there can be mentioned: polyamines, polythiols, and polycarboxylic anhydrides. More specifically, examples of polyamines include ethylenediamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylenepolyamine, isophoronediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane. Examples of polythiols include polyether polythiols, and examples of polycarboxylic anhydrides include succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, etc. Examples of catalysts include tertiary amines, imidazoles, Lewis acids, onium salts, dicyandiamides, organic acid dihydrazides, phosphines, and other hardening catalysts. More specifically, examples include: 2-methylimidazole, 2-ethyl-4-methylimidazole, tris(dimethylaminomethyl)phenol, boron trifluoride-amine complex, dicyandiamide, diphenyliodonium hexafluorophosphate, triphenylcopperium hexafluorophosphate, etc. The heat curing accelerator (F) may be used alone or in combination of two or more.

When the thermal hardening agent (E) is a compound having two or more epoxy groups in one molecule, the thermal hardening accelerator (F) is particularly preferably 2-methylimidazole or 4-methyl-2- Phenylimidazole. The content of the thermosetting accelerator (F) in the total solid content of the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass, particularly preferably 0.5 to 3% by mass.

[Colorant (G)] When the positive photosensitive resin composition of the present invention is used to form a black matrix, which is a lattice-shaped black portion of the pixels of the three colors of R, G, and B surrounding the color filter of the liquid crystal display element, it is preferred to contain a colorant (G). Examples of the colorant (G) include carbon black, aniline black, anthraquinone-based black pigments, and perylene-based black pigments. Specifically, C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc. As the colorant (G), a mixture of organic pigments or inorganic pigments such as red pigments, blue pigments, and green pigments can also be used.

When the positive photosensitive resin composition of the present invention contains a colorant (G) and is used to form a black matrix, etc., the colorant (G) in the total solid content of the positive photosensitive resin composition is The content is preferably 15 to 65% by mass, particularly preferably 20 to 50% by mass. If it is the said range, the sensitivity of a positive photosensitive resin composition will be excellent, and the barrier rib formed will be excellent in light-shielding property.

When the positive photosensitive resin composition of the present invention contains dispersible materials such as the above-mentioned colorant (G), in order to improve its dispersibility, it may further contain a polymer dispersant, a dispersion aid, and the like. These can be contained in the positive photosensitive resin composition in the content within the range which does not impair the effect of the present invention.

[Silane coupling agent (H)] The positive photosensitive resin composition of the present invention may also contain a silane coupling agent (H) as needed. By containing the silane coupling agent (H), the substrate adhesion of the formed cured film is better. As the silane coupling agent (H), there can be cited: tetraethoxysilane, 3-glyceryloxypropyl trimethoxysilane, methyl trimethoxysilane, vinyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-chloropropyl trimethoxysilane, 3-butyl propyl trimethoxysilane, 3-aminopropyl triethoxysilane, heptadecafluorooctylethyl trimethoxysilane, triethoxysilane containing a polyoxyalkylene chain, etc. These can be used alone or in combination of two or more.

The content of the silane coupling agent (H) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 0.1 to 20 mass%, and more preferably 1 to 10 mass%. If it is above the lower limit of the above range, the substrate adhesion of the cured film formed by the positive photosensitive resin composition is better, and if it is below the upper limit of the above range, the ink repellency of the cured film is good.

[Fine particles (I)] The positive photosensitive resin composition of the present invention may optionally contain fine particles (I). By containing the fine particles (I), heat sagging of the barrier rib formed using the positive photosensitive resin composition can be prevented.

The fine particles (I) are not particularly limited, and examples thereof include inorganic fine particles such as silicon dioxide, zirconium oxide, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO); polyethylene, polyethylene, etc. Organic fine particles such as methyl methacrylate (PMMA), etc. From the viewpoint of heat resistance, inorganic fine particles are preferred, and from the viewpoint of ease of acquisition and dispersion stability, silica or zirconium oxide is particularly preferred. Moreover, when the positive photosensitive resin composition contains a colorant (G) and a polymer dispersant, considering the adsorption capacity of the polymer dispersant, it is preferable that the fine particles (I) be negatively charged. Furthermore, considering the exposure sensitivity of the positive photosensitive resin composition, it is preferable that the fine particles (I) do not absorb the light irradiated during exposure, and it is particularly preferable that they do not absorb the i-ray (365) which is the main emission wavelength of the ultrahigh-pressure mercury lamp. nm), h-rays (405 nm), and g-rays (436 nm).

Regarding the average particle size of the microparticles (I), from the perspective of improving the surface smoothness of the barrier wall, the average particle size is preferably 1 μm or less, and more preferably 200 nm or less. Among them, the best average particle size is 5 to 100 nm. The content of the microparticles (I) in the total solid content of the positive photosensitive resin composition of the present invention is preferably 5 to 35% by mass, and more preferably 10 to 30% by mass. If the content is above the lower limit of the above range, there is an effect of suppressing the reduction of ink repellency, and if it is below the upper limit of the above range, the storage stability of the positive photosensitive resin composition is excellent.

[Other additives] In the positive photosensitive resin composition of the present invention, other additives may be selected from the group consisting of tackifiers, plasticizers, defoaming agents, leveling agents, and anti-foaming agents as needed within the scope that does not impair the effects of the present invention. One or more of the group consisting of shrinkage agents and ultraviolet absorbers.

[Production method of positive photosensitive resin composition] As a method for producing a positive photosensitive resin composition, it is preferable to use an alkali-soluble resin (A), a photosensitive agent (B), an ink repellent agent (C), an optional solvent (D), and a thermosetting agent (E). , method of mixing thermal hardening accelerator (F), colorant (G), silane coupling agent (H), microparticles (I), and other additives. Mixing is performed using a mixer at a temperature of 20°C to 25°C and a time of 3 hr to 6 hr, and the obtained composition is used directly.

The positive photosensitive resin composition of the present invention can be used as a material for photolithography, etc., similarly to a conventional positive photosensitive resin composition, and the obtained cured film can be used as a component of an optical element using a conventional cured film of a positive photosensitive resin composition.

[Barrier and its manufacturing method] The barrier of the present invention is formed by setting a partition on a substrate, and includes a cured film formed by applying the positive photosensitive resin composition of the present invention, drying it, and curing it. The barrier of the present invention can be suitably used for optical elements. When the positive photosensitive resin composition contains a coloring agent (G), the obtained barrier can be used as a black matrix. The barrier of the present invention is used, for example, as a barrier for an optical element having a plurality of pixels on a substrate and barrier between adjacent pixels.

As a method for manufacturing a barrier rib for an optical element using the positive photosensitive resin composition of the present invention, for example, the following method can be cited.

The positive photosensitive resin composition of the present invention is coated on a substrate to form a coating film (coating film forming step), and then the coating film is dried to form a film (prebaking step), and then only this coating film is The portion of the film that has not become the barrier rib is exposed (exposure step), and then the coating film on the exposed portion is removed to form a barrier rib including the unexposed portion of the coating film (development step). Then, if necessary, the barrier ribs formed above are further thermally cured (post-baking step), whereby the barrier ribs for the optical element of the present invention can be manufactured.

The material of the substrate is not particularly limited, and various glass plates; thermoplastic plastic sheets such as polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, polymethacrylate, acrylic resin, etc.; hardened sheets of thermosetting resins such as epoxy resin and unsaturated polyester, etc. can be used. In particular, from the perspective of heat resistance, heat-resistant plastics such as glass plates and polyimide are preferred. In addition, a transparent substrate is preferred.

There is no particular restriction on the shape of the substrate or the surface on which the barrier ribs are formed, and they are appropriately selected according to the application. When the substrate is in the form of a plate, it may be a flat plate, or the entire surface or a portion thereof may have a curvature. The thickness of the substrate may be appropriately selected according to the application of the barrier ribs, and is generally preferably 0.5 to 10 mm.

For the substrate used in the present invention, it is preferred that the surface on which the positive photosensitive resin composition is coated has been cleaned in advance by alcohol cleaning, ultraviolet ray/ozone cleaning, or the like.

Hereinafter, the method for manufacturing a barrier wall for an optical element using the positive photosensitive resin composition of the present invention will be specifically described using FIG. FIG. 1 is a cross-sectional view schematically showing an example of manufacturing a barrier wall for an optical element using the positive photosensitive resin composition of the present invention. FIG. 1 (I) is a view schematically showing a step of forming a coating film 2 containing the positive photosensitive resin composition of the present invention on a substrate 1. FIG. 1 (II) is a view schematically showing an exposure step. FIG. 1 (III) is a cross-sectional view showing a substrate 1 after a development step and a barrier wall 6 formed on the substrate.

(Coating film formation step) As shown in cross section in (I) of FIG. 1 , the above-mentioned positive photosensitive resin composition of the present invention is applied on the substrate 1 to form a coating film 2 including the positive photosensitive resin composition.

The coating method of the positive photosensitive resin composition is not particularly limited as long as it forms a coating film with a uniform film thickness. Examples thereof include spin coating, spray coating, slit coating, and roll coating. Methods commonly used for coating film formation, such as coating, spin coating, and rod coating. The film thickness of the coating film 2 is determined taking into consideration the height of the barrier wall finally obtained. The film thickness of the coating film 2 is preferably 100 to 200% of the height of the barrier wall finally obtained, particularly preferably 100 to 130%. The film thickness of the coating film 2 is preferably 0.3 to 325 μm, particularly preferably 0.5 to 65 μm.

(pre-baking step) The coating film 2 formed on the substrate 1 in the above-mentioned coating film forming step is heated to obtain the film 2 . By heating, the volatile components including the solvent contained in the positive photosensitive resin composition constituting the coating film are volatilized and removed, and a non-adhesive film is obtained. Furthermore, the ink repellent agent (C) is transferred to the vicinity of the film surface. An example of the heating method is the following method: Using a heating device such as a hot plate or an oven, the substrate 1 and the coating film 2 are heated together at 50 to 120°C, preferably 70 to 110°C for 10 to 2,000 seconds. , preferably about 30 to 180 seconds.

In order to remove volatile components such as solvents, an additional drying step such as vacuum drying in addition to heating (drying) can be provided before the pre-baking step. Furthermore, in order to prevent unevenness in the appearance of the coating film and to perform drying efficiently, it is more preferable to use both heating and vacuum drying in the above-mentioned prebaking step. The conditions for vacuum drying vary depending on the type of each component, the mixing ratio, etc., but can be carried out within a wide range of 500 to 10 Pa and 10 to 300 seconds.

(exposure step) As shown in (II) of FIG. 1 , the film 2 is irradiated with light 5 through a mask 4 with a predetermined pattern interposed therebetween. The light 5 only passes through the predetermined pattern portion divided by the above-mentioned photomask 4 and reaches the film 2 on the substrate 1 . Since only the exposed portion is alkali-solubilized, the above-mentioned predetermined pattern is provided in a form suitable for the shape of the barrier rib. After the post-baking step, the average barrier rib width is preferably 100 μm or less, and more preferably 20 μm or less. In addition, the average distance between adjacent barrier ribs is preferably 300 μm or less, more preferably 100 μm or less. As the photomask 4, it is preferable to use one in which a pattern is formed so as to fall within this range.

In Figure 1 (II), the exposed portion of the film irradiated with light becomes the soluble portion of the positive photosensitive resin composition. On the other hand, the unexposed portion 3 is the film 2 itself of the positive photosensitive resin composition. condition.

Examples of the irradiated light 5 include: visible light; ultraviolet rays; far ultraviolet rays; KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Excimer lasers such as Ar ₂ excimer laser; X-rays; electron beams, etc. In addition, the irradiation light 5 is preferably an electromagnetic wave with a wavelength of 100 to 600 nm, more preferably a light with distribution in the range of 300 to 500 nm, and particularly preferably an i-ray (365 nm) or an h-ray (405 nm). and g-rays (436 nm).

As the irradiation device (not shown), a known ultrahigh-pressure mercury lamp or deep UV lamp can be used. The exposure amount is preferably 5 to 1,000 mJ/cm ² , particularly preferably 50 to 400 mJ/cm ² . If the exposure amount is more than the lower limit of the above range, the soluble part of the positive photosensitive resin composition becomes sufficiently soluble in the developer, and the development residue disappears. If it is below the upper limit of the above range, a higher resolution can be obtained. The exposure time also depends on the exposure amount, the composition of the photosensitive composition, the thickness of the coating film, etc., but is preferably 1 to 60 seconds, and particularly preferably 5 to 20 seconds.

(Development step) Develop using a developer, and remove the exposed portion of the substrate 1 shown in (II) of Figure 1 . Thereby, the structure of the substrate 1 as shown in the cross-sectional view in (III) of FIG. 1 , and the barrier rib 6 formed of a film of a positive photosensitive resin composition on the substrate can be obtained. In addition, the portion surrounded by the barrier rib 6 and the substrate 1 is a portion called a dot 7 where a pixel is formed by ink injection or the like. The obtained substrate 10 can be used for optical elements using the inkjet method through the following post-baking steps.

As the developer, an alkaline aqueous solution containing alkali such as inorganic alkalis, amines, alcoholamines, and quaternary ammonium salts, preferably an alkaline aqueous solution containing alkali such as tetramethylammonium hydroxide, can be used. In addition, in order to improve solubility or remove residues, a surfactant or an organic solvent such as alcohol may be added to the developer.

The development time (time of contact with the developer) is preferably 5 to 180 seconds, more preferably 10 to 60 seconds. Examples of the development method include: overflow method, dipping method, spray method, etc. After development, perform high-pressure water washing or running water washing, and use compressed air or compressed nitrogen to air-dry, thereby removing moisture on the substrate 1 and barrier ribs 6 .

(post-baking step) As a post-baking step, the barrier ribs 6 on the substrate 1 are heated. An example of the heating method is the following method: using a heating device such as a hot plate or an oven, the substrate 1 and the barrier rib 6 are heated together at 150 to 250° C. for 5 to 90 minutes. By heating, the barrier rib 6 including the cured film of the positive photosensitive resin composition on the substrate 1 is further hardened, and the shape of the point 7 surrounded by the barrier rib 6 and the substrate 1 is further fixed. Furthermore, the above-mentioned heating temperature is particularly preferably 180°C or higher. If the heating temperature is too low, the barrier rib 6 will not be sufficiently hardened and sufficient chemical resistance will not be obtained. When ink is injected into the dots 7 by the ink injection step described below, there is a risk that the barrier rib 6 may swell or the ink may bleed depending on the solvent contained in the ink. On the other hand, if the heating temperature is too high, there is a risk of thermal decomposition of the barrier rib 6 .

The average width of the formed barrier ribs is preferably 100 μm or less, particularly preferably 20 μm or less. Among them, the optimum range is 5 to 20 μm. Furthermore, the average distance (width of dots) between adjacent barrier ribs is preferably 300 μm or less, particularly preferably 100 μm or less. Among them, the optimum range is 30 to 80 μm. Moreover, the average value of the barrier rib height is preferably 0.05 to 50 μm, particularly preferably 0.2 to 10 μm.

[Manufacturing method of optical components] The optical element of the present invention can be obtained by the following method: after forming the barrier rib on the substrate by the above-mentioned manufacturing method, for example, the exposed substrate surface in the area surrounded by the above-mentioned substrate and the above-mentioned barrier rib is subjected to an ink-receptive treatment. (Ink adhesion processing step), and then, ink is injected into the above-mentioned area by an inkjet method to form the above-mentioned pixels (ink injection step).

(Ink affinity treatment step) As methods for ink affinity treatment, there can be cited: cleaning treatment using alkaline aqueous solution, ultraviolet cleaning treatment, ultraviolet/ozone cleaning treatment, excimer cleaning treatment, corona discharge treatment, oxygen plasma treatment and the like. Cleaning treatment using alkaline aqueous solution is a wet treatment using an alkaline aqueous solution (potassium hydroxide, tetramethylammonium hydroxide aqueous solution, etc.) to clean the surface of the substrate. Ultraviolet cleaning treatment is a dry treatment using ultraviolet light to clean the surface of the substrate. Ultraviolet/ozone cleaning treatment is a dry treatment using a low-pressure mercury lamp emitting light of 185 nm and 254 nm to clean the surface of the substrate. Excimer cleaning is a dry process that uses a xenon excimer lamp that emits 172 nm light to clean the substrate surface. Corona discharge treatment is a dry process that uses high frequency and high voltage to generate corona discharge in the air and clean the substrate surface. Oxygen plasma treatment is a dry process that uses a high frequency power source as a trigger in a vacuum to excite oxygen and make it a more reactive "plasma state", thereby cleaning the substrate surface.

As a method of ink adhesion treatment, a dry treatment method such as ultraviolet/ozone cleaning treatment is preferred in terms of simplicity. UV/ozone can be generated using commercially available devices. The substrate with the barrier ribs is placed inside the ultraviolet/ozone device, and is processed in the air at room temperature for about 1 to 10 minutes within a range that does not impair the oil repellency of the barrier ribs. This allows the ink adhesion treatment to be performed. . Furthermore, the treatment time can be adjusted in a range that does not impair the ink repellency of the barrier rib in conjunction with each ultraviolet/ozone device.

By the ink affinity treatment, the development residues remaining in the dots after the formation of the barrier ribs are fully removed, thereby achieving sufficient ink affinity of the dots and preventing hollowing of the color display device using the obtained optical element. In addition, if the barrier ribs are formed using the positive photosensitive resin composition of the present invention, the ink affinity can be performed without reducing the ink repellency of the barrier ribs by the above-mentioned ultraviolet cleaning treatment.

Here, the ink repellency (water repellency and oil repellency) of the cured film formed by the positive photosensitive resin composition can be estimated by the contact angle between water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent that is often used as a solvent for ink). When a substrate having a barrier wall formed using the positive photosensitive resin composition of the present invention is used to manufacture an optical element, the barrier wall is required to have sufficient ink repellency after the above-mentioned ink affinity treatment. The contact angle of water of the barrier wall is preferably 90 degrees or more, and more preferably 95 degrees or more. In addition, the contact angle of PGMEA of the barrier wall is preferably 30 degrees or more, and more preferably 35 degrees or more. On the other hand, when using a substrate having a barrier wall formed using the positive photosensitive resin composition of the present invention to manufacture an optical element, it is required to be ink-affinity and its water contact angle is preferably less than 20 degrees, and more preferably less than 10 degrees.

(Ink injection step) This step is a step of injecting ink into the dots after the ink adhesion treatment step by an inkjet method to form pixels. This step can be performed in the same manner as a normal method using an inkjet device commonly used in the inkjet method. The inkjet device used for forming such pixels is not particularly limited, and an inkjet device using various methods such as the following can be used: a method of continuously ejecting charged ink and controlling it using a magnetic field; a method using piezoelectric A method of intermittently ejecting ink from an element; a method of heating the ink and utilizing its foaming to eject intermittently.

Examples of optical elements produced using the positive photosensitive resin composition of the present invention include color filters, organic EL elements, organic TFT (Thin Film Transistor, thin film transistor) arrays, and the like.

[Manufacturing of color filter] The formation of barrier walls, ink affinity treatment of dots, and ink injection using the inkjet method are as described above. In the color filter, the shape of the pixels formed can also be any known arrangement such as stripe type, mosaic type, triangle type, 4-pixel configuration type, etc.

The ink used for forming pixels mainly includes a coloring component, a binder resin component, and a solvent. As the coloring component, it is preferred to use a pigment or dye with excellent heat resistance and light resistance. As the binder resin component, it is preferred to use a transparent resin with excellent heat resistance, such as acrylic resin, melamine resin, polyurethane resin, etc. The water-based ink includes water and a water-soluble organic solvent as a solvent, a water-soluble resin or a water-dispersible resin as a binder resin component, and various additives as needed. Furthermore, the oil-based ink contains an organic solvent as a solvent, contains a resin soluble in the organic solvent as a binder resin component, and contains various additives as needed. It is preferred that the ink is injected by inkjet method and then dried, heat-cured, and/or UV-cured as needed.

After forming the pixel, a protective coating liquid is used to form a protective film layer as needed. The protective film layer is preferably formed for the purpose of improving the surface flatness and blocking the dissolution of the ink from the barrier wall or the pixel portion from reaching the liquid crystal layer. When forming the protective film layer, it is preferred to remove the ink repellency of the barrier wall in advance. If the ink repellency is not removed, the protective coating liquid will be repelled, and a uniform film thickness cannot be obtained, which is not preferred. As a method for removing the ink repellency of the barrier wall, plasma ashing or optical ashing can be cited. Furthermore, in order to improve the quality of the liquid crystal panel manufactured using the color filter, it is preferred to form a photosensitive spacer on the black matrix including the barrier ribs.

[Manufacturing of organic EL elements] Before forming barrier ribs using the positive photosensitive resin composition of the present invention, a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by sputtering, and the transparent electrode is etched if necessary. for the desired pattern. Secondly, the positive photosensitive resin composition of the present invention is used to form barrier ribs, and after the dots are treated with ink adhesion, the solution of the hole transport material and the luminescent material is sequentially coated on the dots using the inkjet method, and dried. A hole transport layer and a luminescent layer are formed. Thereafter, electrodes such as aluminum are formed by evaporation, etc., thereby obtaining pixels of organic EL elements.

[Manufacturing of organic TFT array] An organic TFT array can be manufactured through the following steps (1) to (3). (1) A barrier wall is formed on a transparent substrate such as glass using the positive photosensitive resin composition of the present invention. Then, after the dots are subjected to ink-receptive treatment, a solution of a gate electrode material is applied to the dots using an inkjet method to form a gate electrode. (2) After the gate electrode is formed, a gate insulating film is formed thereon. Next, on the gate insulating film, a barrier wall is formed using the positive photosensitive resin composition of the present invention, and after the dots are subjected to ink-receptive treatment, a solution of source and drain electrode materials is applied to the dots using an inkjet method to form source and drain electrodes. (3) After the source and drain electrodes are formed, a barrier wall is formed using the positive photosensitive resin composition of the present invention in a manner surrounding a pair of source and drain electrodes. Next, after the dots are subjected to ink-receptive treatment, an organic semiconductor solution is applied to the dots using an inkjet method to form an organic semiconductor layer between the source and drain electrodes. Furthermore, steps (1) to (3) can be used in only one step to form a barrier wall using the positive photosensitive resin composition of the present invention, or can be used in two or more steps to form a barrier wall using the positive photosensitive resin composition of the present invention.

Based on the above, the present specification discloses the following positive photosensitive resin composition, barrier rib and optical element. [1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B) and an ink repellent (C), wherein the ink repellent (C) has a monovalent group having 2 to 40 carbon atoms represented by the following formula (c). ^Rf1 - ^ORf2- (c) ^Rf1 : a polyfluoroalkyl group having 1 to 6 carbon atoms ^Rf2 : a polyfluoroalkyl group having an ethereal oxygen atom between carbon atoms, wherein ^Rf1 - ^ORf2- has at least one -O- _CF2- group. [2] The positive photosensitive resin composition as described in [1], wherein in the above formula (c), ^Rf1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and ^Rf2 is a perfluoroalkylene group which may have an ethereal oxygen atom between carbon atoms. [3] The positive photosensitive resin composition as described in [1] or [2], wherein the ink repellent (C) has a silane skeleton and a weight average molecular weight (Mw) of 500 to 2000. [4] The positive photosensitive resin composition as described in any one of [1] to [3], wherein the ink repellent (C) has an acrylic skeleton and a weight average molecular weight (Mw) of 6000 to 200000. [5] The positive photosensitive resin composition as described in any one of [1] to [4], wherein the fluorine atom content of the ink repellent (C) is 1 to 45% by mass. [6] The positive photosensitive resin composition as described in any one of [1] to [5], wherein the photosensitive agent (B) is a compound having a quinonediazide group. [7] The positive photosensitive resin composition as described in any one of [1] to [6], further comprising a solvent (D). [8] The positive photosensitive resin composition as described in any one of [1] to [7], further comprising a thermosetting agent (E). [9] The positive photosensitive resin composition as described in any one of [1] to [8], further comprising a thermosetting accelerator (F). [10] A positive photosensitive resin composition as described in any one of [1] to [9], further comprising a colorant (G). [11] A barrier wall, which is formed in a morphology of dividing a substrate surface into a plurality of zones for forming pixels, and comprises a cured film of the positive photosensitive resin composition as described in any one of [1] to [10]. [12] An optical element, which comprises a substrate, a plurality of pixels formed on the surface of the substrate, and barrier walls located between adjacent pixels, and the barrier walls comprise a cured film of the positive photosensitive resin composition as described in any one of [1] to [10]. [13] An optical element as described in [12], wherein the optical element is a color filter, a TFT array, or an organic EL element. [Examples]

The present invention is described in more detail using the following examples, but the present invention is not limited to these examples.

Each measurement was performed by the following method. [Number average molecular weight (Mn) and weight average molecular weight (Mw)] Using a commercially available GPC measuring apparatus (manufactured by Tosoh Corporation, apparatus name: HLC-8320GPC), several commercially available monodisperse polystyrene polymers with different polymerization degrees were measured by gel permeation chromatography (GPC) as standard samples for molecular weight measurement, and a calibration curve was prepared based on the relationship between the molecular weight and retention time (retention time) of polystyrene. After diluting the sample to 1.0 mass % with tetrahydrofuran and passing it through a 0.5 μm filter, the GPC related to the sample was measured using the above-mentioned GPC measuring apparatus. Using the above calibration curve, the GPC spectrum of the sample is analyzed by computer to obtain the number average molecular weight (Mn) and weight average molecular weight (Mw) of the sample.

[Alkali-soluble resin (A)] A1: Copolymer of N-phenylmaleimide, benzyl methacrylate, and acrylic acid (Mw6200, solid content 20%) A2: Copolymer of N-cyclohexylmaleimide, methyl methacrylate, 4-hydroxyphenyl methacrylate, and acrylic acid (Mw4800, solid content 20%)

[Photosensitive agent (B)] B1: (4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α,α-dimethylbenzyl}phenol and 6-diazo-5,6-dihydro-5 -Oxo-naphthalene-1-sulfonic acid (mono-tetra)ester)

[Ink repellent (C)] The hydrolyzable silane compounds used in ink repellents C1-1 to C1-4 are shown below.

[Chemistry 1]

Ink repellent C1-1: Use those synthesized by the following method. Mix the hydrolyzable silane compound shown in Table 1 and propylene glycol monomethyl ether (PGME) in the amounts shown in Table 1 until uniform. Add 6.29 g of 1% nitric acid aqueous solution dropwise to the mixed solution. After the dropwise addition, the mixture was stirred at 40° C. for 5 hours to react, and a PGME solution of the ink repellent agent (C1-1) was obtained (ink repellent agent (C1-1) concentration: 10 mass%, also referred to as "ink repellent agent (C1-1)" below). Agent (C1-1) solution").

Ink repellent C1-2~C1-4: Prepare in the same order as ink repellent C1-1, but change the materials and mixing amounts listed in Table 1.

[Table 1] Table 1 Ink repellent Ink repellent Ink repellent Ink repellent C1-1 C1-2 C1-3 C1-4 Blending amount (g) Hydrolyzable silane compound (s1-1) CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O)(CF(CF ₃ ))CONH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ 1.63 - 1.63 - (s1-2) CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O)(CF(CF ₃ )CF ₂ )O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ - 2.55 - - (s2-1) C ₆ H ₉ O(CH ₂ ) ₂ Si(OCH ₃ ) ₃ 6.87 6.17 - 4.87 (s3-1) (C ₆ H ₅ )Si(OCH ₃ ) ₃ 5.53 4.97 - 3.92 (s4-1) Si(OC ₂ H ₅ ) ₄ - - 8.02 - (s5-1) CH ₂ =CH(C=O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ - - 8.84 - (s6-1) nC ₆ F ₁₃ (CH ₂ ) ₂ Si(OCH ₃ ) ₃ - - - 4.63 1% nitric acid 6.29 5.77 9.88 1.76 PGME 79.69 80.54 71.63 84.83 Addition molar ratio of hydrolyzable silane compounds Hydrolyzable silane compounds (s1-1) CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O)(CF(CF ₃ ))CONH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ 0.043 - 0.030 - (s1-2) CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O)(CF(CF ₃ )CF ₂ )O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ - 0.062 - - (s2-1) C ₆ H ₉ O(CH ₂ ) ₂ Si(OCH ₃ ) ₃ 0.479 0.469 - 0.400 (s3-1) (C ₆ H ₅ )Si(OCH ₃ ) ₃ 0.479 0.469 - 0.400 (s4-1) Si(OC ₂ H ₅ ) ₄ - - 0.490 - (s5-1) CH ₂ =CH(C=O)O(CH ₂ ) ₃ Si(OCH ₃ ) ₃ - - 0.480 - (s6-1) nC ₆ F ₁₃ (CH ₂ ) ₂ Si(OCH ₃ ) ₃ - - - 0.200 Ink repellent reviews Number average molecular weight (Mn) 1050 1100 1020 1330 Mass average molecular weight (Mw) 1210 1370 1090 1680 Content rate of F atoms (mass %) 8.0 12.0 8.0 24.4

The fluorine-containing monomers used in ink repellents C2-1 to C2-4 are shown below. a1-1: CF ₃ O(CF ₂ CF ₂ O) ₇ CF ₂ CH ₂ OCOCH=CH ₂ a1-2: CF ₃ O(CF ₂ CF ₂ O) ₂ CF ₂ CH ₂ OCOCH=CH ₂ a6-1: nC ₆ F ₁₃ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂

Ink repellent C2-1: Use those synthesized by the following method. (Step 1) While stirring each raw material (unit: g) shown in Table 2 in a nitrogen atmosphere, polymerization was performed at 50° C. for 24 hours. Furthermore, the mixture was heated at 70° C. for 5 hours to inert the polymerization initiator, thereby obtaining a solution of the copolymer. The number average molecular weight of the copolymer is 5300, and the mass average molecular weight is 13100. (Step 2) Next, add the solution of the above copolymer (130.0 g), 1,1-(bisacryloxymethyl)ethyl isocyanate (33.5 g), and dibutyltin dilaurate (0.13 g). , tert-butyl-p-benzoquinone (1.5 g) was stirred while polymerizing at 40°C for 24 hours. The polymer was purified using hexane and then dried to obtain 65.6 g of ink repellent agent (C2-1). Thereafter, PGMEA was diluted with PGMEA to obtain a PGMEA solution of the ink repellent agent (C2-1) (ink repellent agent (C2-1) concentration: 10 mass %. Hereinafter, it is also referred to as "ink repellent agent (C2-1) solution" ).

Ink repellent C2-2:

The same sequence as ink repellent C2-1 was used, except that the materials and amounts listed in Table 2 were used. The number average molecular weight of the copolymer obtained in step 1 was 5570, and the mass average molecular weight was 13700.

Ink repellent C2-3: It was produced by following the same procedure as the ink repellent agent C2-1, except that the materials and preparation amounts described in Table 2 were changed. The number average molecular weight of the copolymer obtained in step 1 is 5540, and the mass average molecular weight is 13200.

Ink repellent C2-4: It was produced by following the same procedure as the ink repellent agent C2-1, except that the materials and preparation amounts described in Table 2 were changed. The number average molecular weight of the copolymer obtained in step 1 was 2990, and the mass average molecular weight was 121000.

[Table 2] Table 2 Ink repellent Ink repellent Ink repellent Ink repellent C2-1 C2-2 C2-3 C2-4 Step 1 Mixing amount (g) Fluorine-containing monomer (a1-1) CF ₃ O(CF ₂ CF ₂ O) ₇ CF ₂ CH ₂ OCOCH=CH ₂ 45.0 - - - (a1-2) CF ₃ O(CF ₂ CF ₂ O) ₂ CF ₂ CH ₂ OCOCH=CH ₂ - 63.0 - 102.5 (a6-1) nC ₆ F ₁₃ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ - - 81.0 - Monomers containing reactive groups (a3-1) 2-hydroxyethyl methacrylate 81.0 81.0 81.0 63.2 Monomers containing acidic groups (a4-1) Methacrylate 18.0 18.0 18.0 12.2 Other monomers (a5-1) Methyl methacrylate 36.0 18.0 - - starter (2,2'-Azobis(2,4-dimethylvaleronitrile)) 5.0 5.0 5.0 2.0 chain transfer agent n-dodecanethiol 4.7 4.7 4.7 - Solvent 2-Butanone 415.1 415.1 415.1 415.1 Step 1 Ratio of each monomer relative to the total mass of the monomer (mass %) Fluorine-containing monomer (a1-1) CF ₃ O(CF ₂ CF ₂ O) ₇ CF ₂ CH ₂ OCOCH=CH ₂ 25 - - - (a1-2) CF ₃ O(CF ₂ CF ₂ O) ₂ CF ₂ CH ₂ OCOCH=CH ₂ - 35 - 61 (a6-1) nC ₆ F ₁₃ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ - - 45 - Monomers containing reactive groups (a3-1) 2-hydroxyethyl methacrylate 45 45 45 33 Monomers containing acidic groups (a4-1) Methacrylate 10 10 10 6 Other monomers (a5-1) Methyl methacrylate 20 10 - - Step 2 Mixing amount (g) Compound(z1) 1,1-(bisacrylyloxymethyl)ethyl isocyanate 33.5 33.5 33.5 - 2-propenyloxyethyl isocyanate - - - 8.3 catalyst dibutyltin dilaurate 0.13 0.13 0.13 0.16 polymerization inhibitor 3-Butyl-p-benzoquinone 1.5 1.5 1.5 0.95 Ink repellent reviews Number average molecular weight (Mn) 7370 7650 7540 29900 Mass average molecular weight (Mw) 15800 17200 16200 121000 Content rate of F atoms (mass %) 8.3 10.5 14.1 27.3

[Hardener (E)] E1: 2-[4-(2,3-glycidyloxy)phenyl-2-[4-[1,1-bis[4-([2,3-glycidyloxy]phenyl]ethyl]phenyl]propane E2: Glycidyl etherification product of 1,4-cyclohexanedimethanol diallyl ether with hydrogen peroxide E3: N,N,N',N'-tetraglycidyl-m-phenylenediamine E4: Epoxybutanetetracarboxylic acid tetra-(3-cyclohexenylmethyl) modified ε-caprolactam

[Solvent (D)] EDM: diethylene glycol ethyl methyl ether (boiling point 176°C) EDEGAC: diethylene glycol monoethyl ether acetate (boiling point 217°C) PGME: propylene glycol monomethyl ether (boiling point 120°C) PGMEA: propylene glycol monomethyl ether acetate (boiling point 146°C)

<Example 1 to Example 10> The raw materials were stirred at the ratios listed in Table 3 until they became uniform (about 30 minutes) to prepare a positive photosensitive resin composition. The positive photosensitive resin composition was used and evaluated by the following methods. In addition, Examples 1 to 8 are implementation examples, and Examples 9 to 10 are comparative examples.

<Measurement conditions, evaluation conditions> [Sample for evaluation] Using the positive photosensitive resin composition described in Table 3, a cured film was produced on an ITO substrate and used as a sample for evaluation. Two types of evaluation samples, 1 and 2, were prepared as evaluation samples. Sample 1 for evaluation was used to evaluate IJ (Ink Jet) coating properties and residue. The ink repellency was evaluated using Sample 2 for evaluation.

[Sample 1 for evaluation] An ITO substrate (ITO product with a resistance value of 10 Ω/sq or less manufactured by Kuramoto Seisakusho Co., Ltd., size 7.5 cm×7.5 cm×0.7 mm) was ultrasonically cleaned in ethanol (30 seconds). Then, ultraviolet/ozone cleaning is performed for 5 minutes (device: PL7-200 manufactured by Sen Engineering Co., Ltd.). On the surface of the above-cleaned glass substrate, use a spinner (Mikasa Co., Ltd. IH-DX2) to hold the positive photosensitive resin composition at a rotation speed of 610 rpm for 10 seconds, and spin-coat (at a rotation speed of 610 rpm 10 seconds). Next, it was dried on a hot plate at 100° C. for 2 minutes to prepare a film with a thickness of 1.3 μm. The surface of the obtained film was exposed under the following conditions. <Conditions> [Mask]: It has openings in the following pattern within the range of 20 mm × 20 mm. Opening shape: 100 μm × 200 μm Pattern spacing of light shielding part: 20 μm [Lamp]: USH-255BY manufactured by Ushio Electric Co., Ltd., exposure power (exposure output) converted to 365 nm is 25 mW/cm ² [Irradiation conditions] : Cut off light below 330 nm, separate a gap of 50 μm, and irradiate for 8 seconds at 25 mW/ ^cm2 . The exposed and treated ITO substrate was immersed in an aqueous tetramethylammonium hydroxide solution (0.4% by mass) for 40 seconds to develop. Thereafter, water washing and drying are performed. The dried substrate was heated on a hot plate (at 220° C. for 60 minutes) to prepare an ITO substrate (evaluation sample 1) including a cured film having a specific pattern.

[Sample 2 for evaluation] An evaluation sample 2 was produced in the same manner as the evaluation sample 1 except for the step of exposure.

[IJ coating properties] Using an IJ device (manufactured by LaboJET 500 Microjet), 20 pl of a cyclohexylbenzene solution of 1% TPD (triphenyldiamine) was added dropwise inside the point surrounded by the barrier wall of sample 1 for evaluation. Check the spread of dry matter inside the dried spot. In addition, the following criteria were used for judgment. ○: Spread evenly within the point, and the material reaches the edge of the barrier rib. ×: Not spread within the point.

[Development residue] The residue amount was measured inside the point surrounded by the barrier wall of Sample 1 for evaluation. The amount of residue on the ITO surface of the barrier removal part was measured by the μ-XPS method (X-ray photoelectron spectroscopy, X-ray photoelectron spectroscopy). ＜Measurement conditions＞ Measuring device: QuanteraSXM manufactured by ULVAC-PHI X-ray conditions: 50 μmΦ 12.5 W 15 kV Raster size: point Sample angle: 45 degrees Acquisition cycle: 18 Pass Energy Step: Measure at 0.4 eV, and digitize the measurement data as C/In. ◎：4 or less ○: More than 4 and less than 5 △: Greater than 5 and less than 8 ×: greater than 8 ◎, ○, and △ were evaluated as passing.

[Ink repellency] For the above evaluation sample 2, the contact angle of the film surface with respect to PGMEA was measured by the θ/2 method. The evaluation is based on the following criteria. ◎：Above 45° ○：Above 40° and less than 45° △: More than 30° and less than 40° ×: Less than 30° ◎, ○, and △ were evaluated as passing.

The evaluation results are shown in Table 3.

[table 3] table 3 Positive photosensitive resin composition example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Mixing amount (mass%) Alkaline soluble resin (A) (A1) 53.57 - 53.57 53.57 53.57 53.57 53.57 53.78 53.57 53.57 (A2) - 53.57 - - - - - - - - Photosensitizer (B) (B1) 2.98 - 2.98 2.98 2.98 2.98 2.98 2.99 2.98 2.98 Ink remover (C) (C1-1) 1.19 1.19 - - - - - - - - (C1-2) - - 1.19 - - - - - - - (C1-3) - - - 1.19 - - - - - - (C1-4) - - - - - - - - 1.19 - (C2-1) - - - - 1.19 - - - - - (C2-2) - - - - - 1.19 - - - - (C2-3) - - - - - - - - - 1.19 (C2-4) - - - - - - 1.19 0.60 - - Crosslinking agent (E) (E1) 1.19 - - - - - - - 1.19 1.19 (E2) - - 1.19 - 1.19 - - - - - (E3) - - - 1.19 - 1.19 1.19 1.20 - - (E4) - 1.19 - - - - - - - - Solvent (D) EDM 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 EDEGAC 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 PGMEA 6.07 6.07 6.07 6.07 6.07 6.07 6.07 6.43 6.07 6.07 Solid content conversion amount (mass %) Alkaline soluble resin (A) (A1) 71.43 - 71.43 71.43 71.43 71.43 71.43 71.71 71.43 71.43 (A2) - 71.43 - - - - - - - - Photosensitizer (B) (B1) 19.84 - 19.84 19.84 19.84 19.84 19.84 19.92 19.84 19.84 Ink remover (C) (C1-1) 0.79 0.79 - - - - - - - - (C1-2) - - 0.79 - - - - - - - (C1-3) - - - 0.79 - - - - - - (C1-4) - - - - - - - - 0.79 - (C2-1) - - - - 0.79 - - - - - (C2-2) - - - - - 0.79 - - - - (C2-3) - - - - - - - - - 0.79 (C2-4) - - - - - - 0.79 0.40 - - Crosslinking agent (E) (E1) 7.94 - - - - - - - 7.94 7.94 (E2) - - 7.94 - 7.94 - - - - - (E3) - - - 7.94 7.94 7.94 7.97 - - (E4) - 7.94 - - - - - - - - Reviews Inkjet coating ○ ○ ○ ○ ○ ○ ○ ○ × × Development residue ○ ○ ○ ◎ △ △ △ ○ △ × Ink repellency ○ △ ◎ ○ ◎ ◎ ○ ○ × △

According to the above results, in the positive photosensitive resin compositions of Examples 1 to 8 using ink repellents having a polyfluoroether structure, the cured films obtained were above the pass standard in all evaluations of IJ coating, residue removal, and ink repellency. In the positive photosensitive resin compositions of Examples 9 and 10 in which the ink repellents did not have a polyfluoroether structure, the cured films obtained had lower IJ coating, and either the residue removal or ink repellency. If the fluorine content of the ink repellents in Examples 1, 3, 4, and 9 is compared, the ink repellents C1-1 to C1-3 in Examples 1, 3, and 4 have lower fluorine content than the ink repellent C1-4 in Example 9, but Examples 1, 3, and 4 have good results in terms of coating properties. If the fluorine content of the ink repellents in Examples 5 to 6 and 10 is compared, the ink repellents C2-1 to C2-2 in Examples 5 to 6 have lower fluorine content than the ink repellent C2-3 in Example 10, but Examples 5 to 6 have good results in terms of coating properties. Furthermore, according to the comparison between Example 1 and Example 4, the ink repellent C1-3 obtained by using the fluorine-containing silane compound and the fluorine-free silane compound in Example 4 has improved residue removal performance compared with Example 1. It is believed that the reason is that by using the fluorine-free silane compound, the residue of the hydrolyzed silanol group is easy to remain, the hydrophilicity is improved, the permeability of the developer is increased, and the residue is easy to remove.

In addition, the present invention has been described in detail with reference to specific implementation modes, but the industry understands that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on the Japanese patent application (Japanese Patent Application No. 2022-131378) filed on August 19, 2022, and its contents are incorporated into this article by reference. [Industrial Applicability]

The positive photosensitive resin composition of the present invention can produce barrier ribs with excellent ink repellency and less residue in dots, and can be suitably used for the production of color filters and organic EL using inkjet recording technology. The formation of barrier ribs in the manufacture of components and organic TFT arrays is particularly suitable for the formation of barrier ribs on large-area substrates.

1:Substrate 2: Coating film of positive photosensitive resin composition 3: The unexposed part of the coating film 4: Photomask 5:Light 6: Barrier wall 7:00 10: Substrate for optical components used in inkjet method

1(I) to 1(III) are step diagrams schematically showing an example of manufacturing a barrier rib for an optical element using the positive photosensitive resin composition of the present invention, and FIG. 1(I) is shown in The step of forming a coating film containing the positive photosensitive resin composition of the present invention on a substrate. (II) of Figure 1 shows the exposure step, and (III) of Figure 1 shows the substrate after the development step and the formation on the substrate. Sectional view of the barrier wall.

Claims (13)

A positive photosensitive resin composition, which contains an alkali-soluble resin (A), a photosensitive agent (B) and an ink repellent agent (C), and the above-mentioned ink repellent agent (C) is represented by the following formula (c) A monovalent group with 2 to 40 carbon atoms, R ^f1 -OR ^f2 - (c) R ^f1 : Polyfluoroalkyl group with 1 to 6 carbon atoms. R ^f2 : A polymer that may have an etheric oxygen atom between carbon and carbon atoms. Fluoroalkylene group wherein R ^f1 -OR ^f2 - has at least 1 -O-CF ₂ - group. The positive photosensitive resin composition of claim 1, wherein in the above formula (c), R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ^f2 is an etheric oxygen atom that may have between carbon and carbon atoms. of perfluoroalkyl. The positive photosensitive resin composition of claim 1, wherein the ink repellent agent (C) has a silane-based skeleton and a weight average molecular weight (Mw) of 500 to 2,000. The positive photosensitive resin composition of claim 1, wherein the ink repellent agent (C) has an acrylic skeleton and a weight average molecular weight (Mw) of 6,000 to 200,000. In the positive photosensitive resin composition of claim 1, the fluorine atom content of the ink repellent (C) is 1 to 45% by mass. The positive photosensitive resin composition of claim 1, wherein the photosensitizer (B) is a compound having a quinonediazide group. The positive photosensitive resin composition of claim 1, which further contains a solvent (D). The positive photosensitive resin composition of claim 1 further contains a thermosetting agent (E). The positive photosensitive resin composition of Claim 1, which further contains a thermosetting accelerator (F). The positive photosensitive resin composition of Claim 1, which further contains a colorant (G). A barrier wall is formed in a shape that divides a substrate surface into a plurality of zones for forming pixels, and comprises a cured film of a positive photosensitive resin composition as described in any one of claims 1 to 10. An optical element having a substrate, a plurality of pixels formed on the surface of the substrate, and barrier ribs located between the adjacent plurality of pixels, and The barrier rib includes a cured film of the positive photosensitive resin composition according to any one of claims 1 to 10. The optical element of claim 12, wherein the optical element is a color filter, a TFT array or an organic EL element.