JP6468853B2 - Positive photosensitive resin composition and cured film - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition and a cured film.

  Conventionally, an optical element such as an organic EL display element, a liquid crystal element, an organic TFT array, and a color filter is a region surrounded by a bank after a cured film pattern is formed on a substrate as a bank (partition) surrounding the pixel. It is manufactured by laminating various functional layers. The cured film pattern is preferably formed by a photolithography method using a positive photosensitive resin composition because a fine pattern with good dimensional accuracy can be easily formed. In this case, the positive photosensitive resin composition is required to be able to form a cured film pattern having excellent adhesion to the substrate even after undergoing a development process and a baking process.

  As a method of laminating various functional layers in a region such as a pixel region surrounded by a bank, a method of injecting a material such as ink constituting the functional layer into a region surrounded by the bank is known. It has been. In this method, an ink jet method is often employed because a predetermined amount of material is easily injected accurately into a predetermined location.

  When forming pixels using ink, the bank is provided with ink repellency or liquid repellency for the purpose of preventing ink from adhering to the bank or preventing ink from overflowing to the adjacent pixels beyond the bank. Is required. As a method for imparting liquid repellency to a bank, a method in which a positive photosensitive resin composition contains a fluorine-based liquid repellent material has been proposed (for example, Patent Documents 1 and 2).

JP 2009-251327 A JP 2012-220855 A

  However, with respect to the ink injected into the area surrounded by the bank, the substrate is required to have ink affinity or lyophilicity so as not to cause pixel repellency or the like. It has been difficult to achieve both the liquid repellency of the bank and the lyophilicity of the substrate.

  In view of the above-mentioned problems, the present invention can achieve both the liquid repellency of the bank and the lyophilicity of the substrate, and preferably has excellent storage stability and changes in liquid repellency over time. An object is to provide a positive photosensitive resin composition and a cured film capable of forming a small bank.

  The present inventors include a positive type photosensitive resin composition containing a novolak resin (A) and a photosensitizer (B) by containing a fluororesin (C) having a specific structure and a crosslinking agent (D). The present inventors have found that the above problems can be solved and have completed the present invention.

The first aspect of the present invention contains a novolac resin (A), a photosensitive agent (B), a fluororesin (C), and a crosslinking agent (D),
1 wherein the fluororesin (C) is selected from a unit derived from an unsaturated compound containing a perfluoroalkylene ether group represented by the following formula (1) and a unit derived from a fluorinated alkyl ester of an unsaturated carboxylic acid A positive containing a fluorine-containing unit (C1) of at least species and a unit (C2) derived from an unsaturated compound having a carboxyl group protected by an acid-dissociable group or a phenolic hydroxyl group protected by an acid-dissociable group Type photosensitive resin composition.
-(X-O) _n -X- (1)
(In the formula (1), X is a perfluoroalkylene group having 1 to 3 carbon atoms, and a plurality of X contained in the formula (1) may be the same or different, and n is (It is an integer of 1 or more.)

  The second aspect of the present invention is a cured film formed using the positive photosensitive resin composition according to the first aspect.

  According to the present invention, both the liquid repellency of the bank and the lyophilicity of the substrate can be achieved. Preferably, a bank having excellent storage stability and small change in liquid repellency with time is formed. A positive photosensitive resin composition and a cured film can be provided.

≪Positive photosensitive resin composition≫
The positive photosensitive resin composition contains a novolak resin (A), a photosensitive agent (B), a fluororesin (C), and a crosslinking agent (D). The absolute value of the difference between the log P value of the fluororesin (C) and the log P value of the positive photosensitive resin composition is preferably 3.0 or less, more preferably 2.0 or less, It is particularly preferably 1.8 or less, more preferably 1.7 or less, and most preferably 1.5 or less. Furthermore, the log P value of the fluororesin (C) is preferably 4.0 to 0.5, and more preferably 3.0 to 1.0. Here, the log P value is an octanol / water partition coefficient, and the log P value can be calculated by using parameters such as Gose, Pritchett, and Crippen (J. Comp. Chem., 9, 80). (1998)). This calculation can be performed using software such as CAChe 6.1 (manufactured by Fujitsu Limited).

  When the positive photosensitive resin composition is stored for a long period of time, fine foreign matter may be generated in the composition, but the log P value of the fluororesin (C), the log P value of the fluororesin (C), and the positive By making the difference from the log P value of the type photosensitive resin composition within the above range, it is easy to suppress the generation of foreign matter.

  The log P value of the fluororesin (C) is adjusted by adjusting the type and content of the constituent units constituting the fluororesin (C) or by adjusting the content of fluorine atoms in the fluororesin (C). it can. The log P value of the positive photosensitive resin composition is adjusted by adjusting the log P value of each component contained in the composition. When the positive photosensitive resin composition contains a solvent, it is easy to adjust the log P value of the positive photosensitive resin composition by adjusting the log P value of the solvent.

  Hereinafter, the essential or optional components contained in the positive photosensitive resin composition will be described.

<Novolac resin (A)>
As the novolak resin (A), various novolak resins conventionally blended in photosensitive resin compositions can be used. As the novolak resin (A), those obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst are preferable.

〔Phenols〕
Examples of phenols include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3 , Xylenols such as 4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, alkylphenols such as o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcino Polyhydric phenols such as alkyl, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phlorogricinol; alkyl polyhydric phenols such as alkyl resorcin, alkyl catechol, and alkyl hydroquinone (all alkyl groups have 1 to 4 carbon atoms) Α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A and the like. These phenols may be used alone or in combination of two or more.

  Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various characteristics such as sensitivity as a positive photosensitive resin composition and heat resistance of a formed cured film can be adjusted by adjusting the blending ratio of the two. The blending ratio of m-cresol and p-cresol is not particularly limited, but the mass ratio of m-cresol / p-cresol is preferably 3/7 or more and 8/2 or less. The sensitivity as a positive photosensitive resin composition can be improved as the ratio of m-cresol is 3/7 or more, and the heat resistance of a cured film can be improved as it is 8/2 or less. .

[Aldehydes]
Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

[Acid catalyst]
Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and paratoluenesulfonic acid; and zinc acetate Metal salts etc. are mentioned. These acid catalysts may be used alone or in combination of two or more.

[Molecular weight]
The polystyrene-reduced mass average molecular weight (Mw; hereinafter, also simply referred to as “mass average molecular weight”) of the novolak resin (A) is a lower limit value from the viewpoints of developability and resolution of the positive photosensitive resin composition. 1000 is preferable, 2000 is more preferable, 3000 is further preferable, and the upper limit is 50000, 40000 is more preferable, 30000 is further preferable, and 20000 is even more preferable.

As the novolak resin (A), those having different mass average molecular weights in terms of polystyrene can be used in combination. By using a combination of different mass average molecular weights, the positive photosensitive resin composition can be provided with excellent multifaceted characteristics such as developability, resolution, and film formability.
As a novolak resin (A), the combination of resins having different mass average molecular weights is not particularly limited, but is a resin having a mass average molecular weight of 1000 to 10,000 and a mass average molecular weight of 5000 to 50000. A combination with a resin having a high mass average molecular weight is preferred, and a combination of a resin having a mass average molecular weight of 2000 to 8000 and a resin having a mass average molecular weight of 8000 to 40000 and a resin having a mass average molecular weight of 8000 to 40000 More preferred is a combination of a low mass average molecular weight resin having a mass average molecular weight of 3000 to 7000 and a high mass average molecular weight side resin having a mass average molecular weight of 10,000 to 20000.

  When the resins having different mass average molecular weights are used in combination as the novolak resin (A), each content is not particularly limited, but the content of the resin on the low mass average molecular weight side in the total amount of the novolak resin (A) is the lower limit. The value is preferably 5% by mass, more preferably 10% by mass, further preferably 15% by mass, and the upper limit is preferably 50% by mass, more preferably 40% by mass.

  The content of the novolak resin (A) in the positive photosensitive resin composition of the present invention is preferably 50% by mass, more preferably 60% by mass, still more preferably 70% by mass, and 90% by mass as the upper limit. Is preferable, and 85 mass% is more preferable. By making it within the above-mentioned range, a positive photosensitive film capable of forming a cured film having excellent adhesion to the base material while achieving both the liquid repellency of the bank and the lyophilicity of the substrate due to other components. It is easy to obtain a functional resin composition.

<Photosensitive agent (B)>
The positive photosensitive resin composition of the present invention contains a photosensitive agent (B). Although it does not specifically limit as a photosensitive agent (B), A quinonediazide group containing compound is preferable. Examples of the quinonediazide group-containing compound include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4,4 ', 6-pentahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,2 ', 3,4,5-pentahydroxybenzophenone, 2,3', 4,4 ', 5 Polyhydroxybenzoes such as', 6-hexahydroxybenzophenone, 2,3,3 ', and 4,4', 5'-hexahydroxybenzophenone Phenones; bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-tri Hydroxyphenyl) propane, 4,4 ′-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, and 3,3′-dimethyl- {1- [4- Bis [(poly) hydroxyphenyl] alkanes such as [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol; Tris (4-hydride Xylphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy- 3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3, Tris (hydroxyphenyl) methanes such as 4-dihydroxyphenylmethane and bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane or methyl-substituted products thereof; bis (3-cyclohexyl-4 -Hydroxyphenyl) -3-hydroxyphenylmethane, bis ( 3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl)- 2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, Bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-) 3-methyl Phenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, and bis (5-cyclohexyl-2-hydroxy-) Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as 4-methylphenyl) -4-hydroxyphenylmethane or methyl-substituted products thereof; phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphtho , Pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and compounds having a hydroxyl group or an amino group such as 4,4′-diaminobenzophenone; and novolak, pyrogallol -Complete ester compound, partial ester compound, amidated product, or partially amidated product of acetone resin, copolymer of p-hydroxystyrene homopolymer or a monomer copolymerizable therewith, and quinonediazide group-containing sulfonic acid Etc. These photosensitizers may be used alone or in combination of two or more.

  The quinonediazide group-containing sulfonic acid is not particularly limited. For example, naphthoquinonediazidesulfonic acid such as naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid; orthoanthra A quinone diazide sulfonic acid etc. are mentioned, A naphthoquinone diazide sulfonic acid is preferable. The above-mentioned ester compound of quinonediazide group-containing sulfonic acid, preferably naphthoquinonediazidesulfonic acid, dissolves well in a solvent usually used when a positive photosensitive resin composition is used as a solution, and is in a phase with novolak resin (A). Good solubility. When these compounds are blended in a positive photosensitive resin composition as a photosensitive agent (B), a highly sensitive positive photosensitive resin composition can be easily obtained.

  The method for producing the ester compound as the photosensitive agent (B) is not particularly limited, and for example, a quinonediazide group-containing sulfonic acid is added as a sulfonyl chloride such as naphthoquinone-1,2-diazide-sulfonyl chloride, and the like. Examples thereof include a method of condensing in a solvent such as dioxane in the presence of an alkali such as triethanolamine, alkali carbonate, alkali hydrogencarbonate, and the like to complete esterification or partial esterification.

  The content of the photosensitive agent (B) is preferably 5 parts by mass as the lower limit with respect to 100 parts by mass of the novolak resin (A), more preferably 10 parts by mass, from the viewpoint of the sensitivity of the positive photosensitive resin composition. The upper limit is preferably 100 parts by mass, more preferably 50 parts by mass, and even more preferably 30 parts by mass.

<Fluororesin (C)>
The positive photosensitive resin composition is selected from a unit derived from an unsaturated compound containing a perfluoroalkylene ether group represented by the following formula (1) and a unit derived from a fluorinated alkyl ester of an unsaturated carboxylic acid. Unsaturated group having one or more fluorine-containing units (C1) (hereinafter also referred to as unit (C1)) and a carboxyl group protected by an acid-dissociable group or a phenolic hydroxyl group protected by an acid-dissociable group A fluororesin (C) containing a unit (C2) derived from a compound (hereinafter also referred to as a unit (C2)) is included.
-(X-O) _n -X- (1)
(In the formula (1), X is a perfluoroalkylene group having 1 to 3 carbon atoms, and a plurality of X contained in the formula (1) may be the same or different, and n is (It is an integer of 1 or more.)

  When the positive photosensitive resin composition contains the fluororesin (C) having the above-mentioned predetermined structure, when forming a bank using the positive photosensitive resin composition, good liquid repellency of the bank, It is possible to achieve both good lyophilicity of the substrate. The unit (C1) mainly contributes to the liquid repellency of the bank, and the unit (C2) contributes to the lyophilicity of the substrate. When the fluororesin contains the unit (C2), when the coating film of the positive photosensitive resin composition is exposed, the solubility of the exposed portion in the developer is increased by the action of the acid generated from the photosensitive agent (B) and the like. Cheap. For this reason, when the fluororesin (C) contains the unit (C2), the positive photosensitive resin composition hardly remains on the substrate, and the lyophilicity of the substrate portion after the bank formation is improved. be able to.

[Unit (C1)]
The unit (C1) is a unit selected from a unit derived from an unsaturated compound containing a perfluoroalkylene ether group represented by the formula (1) and a unit derived from a fluorinated alkyl ester of an unsaturated carboxylic acid. .

  The unit derived from the unsaturated compound containing a perfluoroalkylene ether group represented by the formula (1) is a compound having a perfluoroalkylene ether group represented by the formula (1) and a radically polymerizable unsaturated group If it is, it will not specifically limit.

Specific examples of the perfluoroalkylene group having 1 to 3 carbon atoms represented by X in the formula (1) include the following groups a to d.
-CF ₂ -... a
-CF ₂ CF ₂ - ··· b
_{-CF 2 -C (CF 3) F-} ··· c
_{-C (CF 3) F-CF} 2 - ··· d

  Among the perfluoroalkylene ether groups represented by the formula (1), it is easy to obtain and synthesize, and it is easy to improve the liquid repellency of the bank formed using the positive photosensitive resin composition. A group containing a combination of the group a (difluoromethylene group) and the group b (tetrafluoroethylene group) is preferred, and a group containing only the group a and the group b is more preferred. When the perfluoroalkylene tail group represented by the formula (1) contains only the group a and the group b as X, the abundance ratio of the group a and the group b (molar ratio, group a / group b) is 1. It is preferably / 4 to 4/1. In this case, the value of n is preferably 3 to 40, and more preferably 6 to 30.

  Further, the number of fluorine atoms in the perfluoroalkylene ether group represented by the formula (1) is from 18 to 18 because the bank formed using the positive photosensitive resin composition has good liquid repellency. 200 are preferable and 25-80 are preferable.

As the unsaturated compound containing a perfluoroalkylene ether group represented by the formula (1), a functional group containing a radically polymerizable unsaturated group is present at both ends of the perfluoroalkylene ether group represented by the formula (1). Bound compounds are preferred. Preferable examples of the functional group containing the radical polymerizable unsaturated group include groups represented by the following formulas (C1-1) to (C1-4).

  Among the groups represented by the formulas (C1-1) to (C1-4), an unsaturated compound containing a perfluoroalkylene ether group represented by the formula (1) can be easily obtained or manufactured. A group represented by the formula (C1-1) or a group represented by the formula (C1-2) is preferable because of excellent polymerization reactivity.

Among unsaturated compounds containing a perfluoroalkylene ether group represented by the formula (1), a compound having a group represented by the formula (C1-1) or a group represented by the formula (C1-2) at the amount terminal Preferable examples of include compounds represented by the following formulas (C1-5) to (C1-14). In formulas (C1-5) to (C1-14), R ^c1 represents a perfluoroalkylene ether group represented by formula (1).

In addition, a group represented by the formula (C1-1) or a group represented by the formula (C1-2) is bonded to the end of the perfluoroalkylene ether group represented by the formula (1), and the other end is bonded to the other end. A compound to which a perfluoroalkoxy group is bonded is also preferable as the unsaturated compound containing a perfluoroalkylene ether group represented by the formula (1). The number of carbon atoms of the perfluoroalkoxy group is not particularly limited, but is preferably 1 to 6, and particularly preferably 1 to 4. Specific examples of such compounds include those shown below. In the following formula, R ^c1 is a perfluoroalkylene ether group represented by the formula (1).

CF ₃ —O—R ^c1 —CH ₂ —O—C (═O) —CH═CH ₂
CF ₃ —O—R ^c1 —CH ₂ —O—C (═O) —C (CH ₃ ) ═CH ₂
CF ₃ —O—R ^c1 —CH ₂ CH ₂ —O—C (═O) —CH═CH ₂
CF ₃ —O—R ^c1 —CH ₂ CH ₂ —O—C (═O) —C (CH ₃ ) ═CH ₂
C ₂ F ₅ —O—R ^c1 —CH ₂ —O—C (═O) —CH═CH ₂
C ₂ F ₅ —O—R ^c1 —CH ₂ —O—C (═O) —C (CH ₃ ) ═CH ₂
C ₂ F ₅ —O—R ^c1 —CH ₂ CH ₂ —O—C (═O) —CH═CH _{2
^{C 2 F 5 -O-R c1}} -CH 2 CH 2 -O-C (= O) -C (CH 3) = CH 2
C ₃ F ₇ —O—R ^c1 —CH ₂ —O—C (═O) —CH═CH ₂
C ₃ F ₇ —O—R ^c1 —CH ₂ —O—C (═O) —C (CH ₃ ) ═CH ₂
C ₃ F ₇ —O—R ^c1 —CH ₂ CH ₂ —O—C (═O) —CH═CH ₂
C ₃ F ₇ —O—R ^c1 —CH ₂ CH ₂ —O—C (═O) —C (CH ₃ ) ═CH ₂

  The fluorinated alkyl ester of unsaturated carboxylic acid is not particularly limited as long as it is a compound that can be generated by the reaction of unsaturated carboxylic acid and fluoroalkanol. Examples of fluorinated alkyl esters of unsaturated carboxylic acids include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid And a compound containing at least one fluoroalkoxycarbonyl group.

  Of these, fluorinated alkyl esters of (meth) acrylic acid are preferred. The number of carbon atoms of the fluorinated alkyl group contained in the fluorinated alkyl ester of (meth) acrylic acid is not particularly limited. For example, 1 to 20 is preferable, 1 to 12 is more preferable, and 1 to 8 is particularly preferable. The fluorinated alkyl group contained in the fluorinated alkyl ester of (meth) acrylic acid may be linear or branched, and is preferably linear.

As the fluorinated alkyl group contained in the fluorinated alkyl ester of (meth) acrylic acid, suitable groups include —CF ₃ , —CF ₂ CF ₃ , — (CF ₂ ) ₂ CF ₃ , — (CF ₂ ) _3. Perfluoroalkyl groups such as CF ₃ , — (CF ₂ ) ₄ CF ₃ , — (CF ₂ ) ₅ CF ₃ , — (CF ₂ ) ₆ CF ₃ , and — (CF ₂ ) ₇ CF ₃ , and —CH _{2 CH 2 CF 3, -CH 2 CH} 2 CF 2 CF 3, -CH 2 CH 2 (CF2) 2 CF 3, -CH 2 CH 2 (CF2) 3 CF 3, -CH 2 CH 2 (CF2) 4 CF 3 And a perfluoroalkylethyl group such as —CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ .

  Although content of the unit (C1) in a fluororesin (C) is not specifically limited, 1-90 mass% is preferable, 1-50 mass% is more preferable, 1-40 mass% is especially preferable, 5-30 mass % Is most preferred.

[Unit (C2)]
The fluororesin (C) is a unit derived from an unsaturated compound having a carboxyl group protected by an acid dissociable group or a phenolic hydroxyl group protected by an acid dissociable group in addition to the unit (C1) described above (C2). )including. The monomer giving the unit (C2) has an unsaturated carboxylic acid having a carboxyl group protected by an acid-dissociable group, a phenolic hydroxyl group protected by an acid-dissociable group, and a radically polymerizable unsaturated group. It is an aromatic compound. Examples of the aromatic compound having a phenolic hydroxyl group and a radically polymerizable unsaturated group include hydroxystyrenes and vinylhydroxynaphthalenes. Among the units (C2), a unit derived from an unsaturated compound having a carboxyl group protected by an acid dissociable group is preferable.

  Examples of the acid dissociable group include groups represented by the following formulas (C2-1) and (C2-2), linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, vinyloxy Examples include an ethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the above formulas (C2-1) and (C2-2), R ^c2b and R ^c3 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ^c4 Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ^c5 represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, o represents 0 or 1.

  Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. . Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

  Here, specific examples of the acid dissociable, dissolution inhibiting group represented by the above formula (C2-1) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, and an n-butoxyethyl group. Group, isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. . Specific examples of the acid dissociable, dissolution inhibiting group represented by the above formula (C2-2) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

As the unit derived from an unsaturated carboxylic acid having a carboxyl group protected by an acid-dissociable group, units represented by the following formulas (C2-3) to (C2-5) are preferable.

In the above formulas (C2-1) to (C2-3), R ^c6 and R ^{c10 to} R ^c15 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, fluorine Represents an atom or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, and R ^{c7 to} R ^c9 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms. Or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, wherein R ^c8 and R ^c9 are bonded to each other and have 5 to 20 carbon atoms together with the carbon atom to which both are bonded. A hydrocarbon ring may be formed, Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, p represents an integer of 0 to 4, and q represents 0 or 1. Represent.

  Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and the like. Can be mentioned. The fluorinated alkyl group is one in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

When R ^c8 and R ^c9 are not bonded to each other to form a hydrocarbon ring, the R ^c7 , R ^c8 , and R ^c9 are each a linear or branched alkyl group having 2 to 4 carbon atoms. It is preferable. R ^c11 , R ^c12 , R ^c14 and R ^c15 are preferably a hydrogen atom or a methyl group.

R ^1c8 and R ^c9 may form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atom to which both are bonded. Specific examples of such an aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Further, when the aliphatic cyclic group formed by R ^c8 and R ^c9 has a substituent on the ring skeleton, examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (═O And a polar group such as 1) or a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

Y ^b is an aliphatic cyclic group or an alkyl group, and examples thereof include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. . Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups and the like. In particular, a group in which one or more hydrogen atoms are removed from adamantane (which may further have a substituent) is preferable.

Furthermore, the alicyclic group of the abovementioned Y ^b is, if they have a substituent on the ring skeleton, examples of the substituents include a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (= O) polar groups such as And a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

Also, if Y ^b is an alkyl group, having 1 to 20 carbon atoms, it is preferred that preferably a linear or branched alkyl group having 6 to 15. Such an alkyl group is particularly preferably an alkoxyalkyl group. Examples of the alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxy group. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -Ethoxy-1-methylethyl group etc. are mentioned.

  Preferable specific examples of the structural unit represented by the above formula (C2-3) include those represented by the following formulas (C2-3-1) to (C2-3-33).

In the above formulas (C2-3-1) to (C2-3-33), R ^c16 represents a hydrogen atom or a methyl group.

  Preferable specific examples of the structural unit represented by the above formula (C2-4) include those represented by the following formulas (C2-4-1) to (C2-4-25).

In the above formulas (C2-4-1) to (C2-4-25), R ^c16 represents a hydrogen atom or a methyl group.

  Preferable specific examples of the structural unit represented by the above formula (C2-5) include those represented by the following formulas (C2-5-1) to (C2-5-15).

In the above formulas (C2-5-1) to (C2-5-15), R ^c16 represents a hydrogen atom or a methyl group.

[Other units]
The fluororesin (C) preferably comprises only the units (C1) and (C2) described above from the viewpoint of the liquid repellency of the bank formed using the positive photosensitive resin composition. Units other than the unit (C1) and the unit (C2) may be included. The type of other units is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately selected from units derived from monomers having various unsaturated bonds.
It is also possible to adjust the log P value of the fluororesin (C) by changing the type and content of other units.

  Examples of the monomer that gives units other than the aforementioned units (C1) and (C2) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; (Meth) acrylic acid alkyl esters such as (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate; (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Hydroxyal (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloro Vinyl group-containing aromatic compounds such as methylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene Nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; Kill.

  When the fluororesin (C) contains other units, the total amount of the units (C1) and units (C2) in the fluororesin is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass. The above is particularly preferable.

  Although the mass average molecular weight of a fluororesin (C) is not specifically limited, 2000 is preferable as a lower limit, 5000 is more preferable, 50000 is preferable as an upper limit, and 20000 is more preferable. When the mass average molecular weight is 2000 or more, the heat resistance and film strength of the resulting cured film can be improved, and when it is 50000 or less, sufficient solubility in a developer can be obtained.

  The content of the fluororesin (C) is preferably 0.1 parts by weight, more preferably 0.5 parts by weight, further preferably 1 part by weight, based on 100 parts by weight of the novolak resin (A). More preferably, 5 mass parts is more preferable, 10 mass parts is preferable as an upper limit, 8 mass parts is more preferable, 6 mass parts is further more preferable, and 4 mass parts is still more preferable. By adjusting the content of the fluororesin (C), it is easy to balance sensitivity, developability, resolution, and liquid repellency.

<Crosslinking agent (D)>
The positive photosensitive resin composition of the present invention contains a crosslinking agent (D). The cross-linking agent (D) is not particularly limited as long as it is a compound capable of cross-linking the novolak resin (A) by the operation of forming a cured film, but is an amine-based cross-linking agent such as a melamine compound, hexamethylenetetramine, or a urea derivative; epoxy Compounds are preferred, amine-based crosslinking agents are more preferred, and melamine compounds are even more preferred. By containing the crosslinking agent (D), the positive photosensitive resin composition of the present invention can form a cured film excellent in water resistance, heat resistance, and solvent resistance.

  The melamine compound is not particularly limited as long as it is a compound having a chemical structure that can be derived from melamine and acts as a crosslinking agent for the novolak resin (A), but is represented by the following formula (d1). Compounds are preferred.

（式中、Ｒ^ｄ１〜Ｒ^ｄ６はそれぞれ独立に水素原子又は−ＣＨ_２−Ｏ−Ｒ^ｄ７で表される基を示し、Ｒ^ｄ７は水素原子又は炭素原子数１〜１０のアルキル基であり、Ｒ^ｄ１〜Ｒ^ｄ６の少なくとも１つは−ＣＨ_２−Ｏ−Ｒ^ｄ７で表される基である。）

^(Wherein, R d1 ^{to R d6} each independently represent a hydrogen atom or a group represented by _{^{-CH 2 -O-R d7, R}} d7 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, At least one of R ^{d1 to} R ^d6 is a group represented by —CH ₂ —O—R ^d7 .

In the above formula (d1), the number of groups represented by —CH ₂ —O—R ^d7 is preferably two or more of R ^{d1 to} R ^d6 .
^Examples of the alkyl group represented by R ^d7 include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, and n-hexyl group. preferable.

  Examples of the melamine compound represented by the formula (d1) include hexamethylol melamine, hexabutyrol melamine, partially methylolated melamine and alkylated products thereof; tetramethylol benzoguanamine, partially methylolated benzoguanamine and alkylated thereof; Can be mentioned.

  The epoxy compound is not particularly limited as long as it is a compound having an epoxy group and acts as a crosslinking agent for the novolak resin (A). As the epoxy compound, a polyfunctional epoxy compound having two or more epoxy groups in one molecule is preferable. In addition, the below-mentioned silane coupling agent (E) is not included in the epoxy compound used as a crosslinking agent (D).

  As the epoxy compound, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a polyfunctional alicyclic epoxy resin, an aliphatic polyglycidyl ether, and the like are preferable.

The said crosslinking agent (D) may be used independently and may be used in combination of 2 or more type.
The content of the crosslinking agent (D) is preferably 3 parts by weight, more preferably 10 parts by weight, further preferably 15 parts by weight, and 40 parts by weight as the upper limit with respect to 100 parts by weight of the novolak resin (A). Part is preferred, 30 parts by weight are more preferred, and 25 parts by weight are even more preferred. When the content of the crosslinking agent is 3 parts by mass or more, the resin is sufficiently crosslinked, and when it is 40 parts by mass or less, the colorless transparency of the cured film and the storage stability of the resulting composition can be maintained. it can.

<Silane coupling agent (E)>
The positive photosensitive resin composition of the present invention preferably contains a silane coupling agent (E).
The silane coupling agent (E) is a phenolic hydroxyl group that the novolac resin (A) has, an epoxy group and / or oxetanyl that the fluororesin (C) has via an alkoxy group and / or a reactive group bonded to a silicon atom. Since it can react with a group, it can act as a cross-linking agent, can close a cured film formed using a positive photosensitive resin composition, and can improve the water resistance, solvent resistance, heat resistance, etc. of the cured film. In addition to the improvement, the adhesion of the cured film to the substrate can be improved, and the liquid repellency of the cured film and the lyophilicity of the base material can also be improved.

  The silane coupling agent (E) is not particularly limited. For example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane. Monoalkyltrialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; monophenyls such as phenyltrimethoxysilane and phenyltriethoxysilane Trialkoxysilane; diphenyldialkoxysilane such as diphenyldimethoxysilane and diphenyldiethoxysilane; monovinyltrialkoxy such as vinyltrimethoxysilane and vinyltriethoxysilane Lan; (meth) acryloxyalkyl monoalkyl dialkoxy such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane Silane; (Meth) acryloxyalkyltrialkoxysilane such as 3-acryloxypropyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 -Dimethyl-butylidene) propylamine, amino group-containing trialkoxysilanes such as N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Non-alicyclic epoxy group-containing alkyltrialkoxysilane such as reethoxysilane; Non-alicyclic epoxy group-containing alkyl monoalkyldialkoxysilane such as 3-glycidoxypropylmethyldiethoxysilane; 2- (3,4- Alicyclic epoxy group-containing alkyltrialkoxysilanes such as epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane Alicyclic epoxy group-containing alkyl monoalkyl dialkoxysilanes such as [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, etc. Oxetanyl group-containing alkyl Trialkoxysilane; mercaptoalkyltrialkoxysilane such as 3-mercaptopropyltrimethoxysilane; mercaptoalkylmonoalkyldialkoxysilane such as 3-mercaptopropylmethyldimethoxysilane; ureidoalkyltrialkoxysilane such as 3-ureidopropyltriethoxysilane Isocyanate alkyl trialkoxysilanes such as 3-isocyanatopropyltriethoxysilane; acid anhydride group-containing alkyltrialkoxysilanes such as 3-trimethoxysilylpropyl succinic anhydride; Nt-butyl-3- (3-tri Imido group-containing alkyltrialkoxysilanes such as methoxysilylpropyl) succinimide; and the like. A silane coupling agent (E) may be used independently and may be used in combination of 2 or more type.

  The silane coupling agent (E) is not particularly limited. For example, in addition to a silane coupling agent having an alkoxy group bonded to a silicon atom, an alkoxy group, an epoxy group, an oxetanyl group, a vinyl group, (meth) acryloyl A silane coupling agent having at least one reactive group selected from the group consisting of a group, a mercapto group, a ureido group, an isocyanate group, an acid anhydride group, an imide group and an amino group. A silane coupling agent having a reactive group is preferred. As the silane coupling agent having a reactive group, a silane coupling agent having a vinyl group, an amino group, an epoxy group or an oxetanyl group is preferable, and the compatibility with the developer is high, and the residue (undissolved) can be reduced. Moreover, the silane coupling agent which has an epoxy group is more preferable from a viewpoint which is excellent in the liquid repellency of a cured film, and the lyophilic property of a base material, and especially excellent in adhesiveness with the base material of a cured film.

  As the silane coupling agent having an epoxy group, any of a silane coupling agent having a non-alicyclic epoxy group and a silane coupling agent having an alicyclic epoxy group can be preferably used.

  The content of the silane coupling agent (E) is preferably 0.1 parts by weight, more preferably 0.5 parts by weight, and even more preferably 1 part by weight with respect to 100 parts by weight of the novolak resin (A). The upper limit is preferably 10 parts by mass, more preferably 7 parts by mass, further preferably 5 parts by mass, and even more preferably 3 parts by mass. When it is above the above lower limit, the adhesion to the substrate, the liquid repellency of the cured film, and the lyophilicity of the substrate are sufficient, and when it is below the above upper limit, between the silane coupling agents in storage Residues during development due to the condensation reaction can be prevented.

<Photoacid generator (F)>
The positive photosensitive resin composition may contain a photoacid generator (F). When the positive photosensitive resin composition contains a photoacid generator (F), the protective group in the unit (C2) contained in the fluororesin (C) at the location where the positive photosensitive resin composition is exposed. Detachment is promoted. If it does so, after exposing the coating film which consists of positive photosensitive resin compositions, an exposure part will melt | dissolve favorably with respect to a developing solution. Thereby, the lyophilic property is improved in the portion where the substrate in the region surrounded by the bank is exposed.

  In the positive photosensitive resin composition, a photoacid generator (F) that has been conventionally blended in various photosensitive compositions can be blended without particular limitation. Specific examples of photoacid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, halogen-containing triazine compounds, diazomethane acid generators, nitrobenzyl sulfonate acid generators ( Nitrobenzyl derivatives), iminosulfonate acid generators, disulfone acid generators and the like.

  The content of the photoacid generator (F) is preferably 0.1 parts by mass, more preferably 0.2 parts by mass, and 0.5 parts by mass with respect to 100 parts by mass of the novolak resin (A). More preferably, the upper limit is preferably 20 parts by mass, more preferably 10 parts by mass, further preferably 5 parts by mass, and most preferably 3 parts by mass.

<Other ingredients>
The positive photosensitive resin composition of the present invention may contain various additives such as a sensitizer, a surfactant, and a plasticizer as long as the object of the present invention is not impaired.

[Sensitizer]
The sensitizer is not particularly limited, and can be arbitrarily selected from sensitizers usually used in positive resist compositions. Examples of the sensitizer include compounds having a phenolic hydroxyl group with a molecular weight of 1000 or less.

[Surfactant]
The positive photosensitive resin composition of the present invention may contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties and the like. Examples of the surfactant include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, MegaFuck F172, MegaFac F173, MegaFuck F183 (Dainippon Ink Chemical Co., Ltd.), Florard FC-135, Fluoraro FC-170C, Fluorado FC-430, Fluorado FC-431 (Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (Asahi Glass Co., Ltd.) , SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray Silicone), BYK-310, BYK-330 (manufactured by BYK Japan Japan), etc. Or fluorinated surfactants can be used Yes.

  The surfactant content is preferably 5 parts by mass or less with respect to 100 parts by mass of the novolak resin (A).

[Plasticizer]
The positive photosensitive resin composition of the present invention may contain an alkali-soluble acrylic resin as a plasticizer in order to suppress the occurrence of cracks. Generally as an alkali-soluble acrylic resin, what is mix | blended with the positive photoresist composition as a plasticizer can be used.

  More specifically, as the alkali-soluble acrylic resin, 30 to 90% by mass of a structural unit based on a polymerizable compound having an ether bond and 2 parts by mass of a structural unit based on a polymerizable compound having a carboxy group And those containing 50 parts by mass or less.

  Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meta ), Radically polymerizable compounds such as (meth) acrylic acid derivatives having an ether bond and an ester bond such as methoxypolypropylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. Among these, it is preferable to use 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate. These compounds may be used independently and may be used in mixture of 2 or more types.

  Examples of the polymerizable compound having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and 2-methacryloyloxyethyl succinic acid, 2- Examples thereof include radical polymerizable compounds such as methacrylic acid derivatives having a carboxy group and an ester bond such as methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid. Among these, it is preferable to use acrylic acid and methacrylic acid. These compounds may be used alone or in combination of two or more.

  30-90 mass% is preferable and, as for content of the polymeric compound which has an ether bond in an alkali-soluble acrylic resin component, 40-80 mass% is more preferable. By blending an amount of the alkali-soluble acrylic resin component in such a range into the positive photosensitive resin composition as a plasticizer, it is easy to form a homogeneous cured film while suppressing the occurrence of cracks in the cured film.

  2-50 mass% is preferable and, as for content of the structural unit based on the polymeric compound which has a carboxy group in an alkali-soluble acrylic resin component, 5-40 mass% is more preferable. By developing an alkali-soluble acrylic resin component containing a structural unit based on a polymerizable compound having a carboxy group in an amount within the above range as a plasticizer, the positive photosensitive resin composition is developed. Property can be improved.

  The polystyrene-reduced mass average molecular weight of the alkali-soluble acrylic resin component is preferably 10,000 to 800,000, and more preferably 30,000 to 500,000.

  The alkali-soluble acrylic resin component may contain structural units based on other radical polymerizable compounds for the purpose of appropriately controlling physical and chemical properties. Here, the “other radical polymerizable compound” means a radical polymerizable compound other than the above-described polymerizable compound.

  Such other radically polymerizable compounds include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, And (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate and (meth) acrylic aryl esters such as benzyl (meth) acrylate; diethyl maleate and fumarate Dicarboxylic acid diesters such as dibutyl acid; vinyl group-containing aromatic compounds such as styrene and α-methylstyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile and methacrylo Nitrile group-containing polymerizable compounds tolyl; can be used as well as amide-bond-containing polymerizable compounds such as acrylamide and methacrylamide; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride. These compounds may be used alone or in combination of two or more. Among these compounds, it is particularly preferable to use n-butyl acrylate, benzyl methacrylate, methyl methacrylate, and the like. The content of structural units based on other radically polymerizable compounds in the alkali-soluble acrylic resin component is preferably less than 50% by mass, and more preferably less than 40% by mass.

  Examples of the polymerization solvent used for synthesizing the alkali-soluble acrylic resin component include alcohols such as ethanol and diethylene glycol; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol ethyl methyl ether; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl isobutyl ketone; and ethyl acetate and butyl acetate Ester etc. can be used. Among these polymerizable solvents, it is particularly preferable to use polyhydric alcohol alkyl ethers and polyhydric alcohol alkyl ether acetates.

  As a polymerization catalyst used when synthesizing the alkali-soluble acrylic resin component, a normal radical polymerization initiator can be used, for example, an azo compound such as 2,2′-azobisisobutyronitrile; and benzoyl peroxide, and An organic peroxide such as di-tert-butyl peroxide can be used.

  30 mass parts or less are preferable with respect to 100 mass parts of novolak resin (A), and, as for the compounding quantity of the alkali-soluble acrylic resin component in a positive photosensitive resin composition, 20 mass parts or less are more preferable.

<Solvent>
The positive photosensitive resin composition of the present invention is preferably used in the form of a solution by dissolving the above components in a suitable solvent. Such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol alkyl ethers such as ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and Diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopro Propylene glycol alkyl ether acetates such as ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and 2-hydroxypropion Acid methyl, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3 -Esters such as methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These solvents may be used alone or in combination of two or more.

  The content of the solvent in the positive photosensitive resin composition is appropriately adjusted in consideration of the viscosity and applicability of the positive photosensitive resin composition. Specifically, the solvent is used so that the solid content concentration of the positive photosensitive resin composition is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.

  The positive photosensitive resin composition of the present invention may further contain a colorant and various additives as long as the object of the present invention is not impaired. Examples of the additive include a sensitizer, a surfactant, and a plasticizer.

<Preparation method of positive photosensitive resin composition>
The positive photosensitive resin composition can be prepared by blending the above-mentioned components at a predetermined ratio, and then mixing and stirring by a usual method. Moreover, you may further filter using a mesh, a membrane filter, etc. as needed.

<Method for forming cured film>
The cured film includes a coating process for forming a coating film of a positive photosensitive resin composition on a substrate, an exposure process for exposing the coating film to position selective irradiation with active rays, and developing the exposed coating film. And a developing step.

[Coating process]
In the coating step, a positive type photosensitive resin composition is applied using a spinner or the like on a substrate having various functional layers as necessary to form a coating film. The thickness of the coating film is typically preferably 0.5 to 10 μm. If necessary, the coating film is pre-baked (post-apply bake (PAB)) at a temperature of 80 to 150 ° C. for 40 to 600 seconds, preferably 60 to 360 seconds.

[Exposure process]
For example, a low pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp, which are light sources that emit light in the vicinity of a wavelength of 365 nm (i-line), 405 nm (h-line), and 435 nm (g-line), are used for the coating film. The exposure is selectively performed through the mask pattern. The active rays used for exposure include ArF excimer laser, KrF excimer laser, F2 excimer laser, extreme ultraviolet rays (in addition to G-line, H-line, and I-line from the low-pressure mercury lamp, high-pressure mercury lamp, and ultra-high-pressure mercury lamp. Radiation such as EUV), vacuum ultraviolet (VUV), electron beam (EB), X-ray, and soft X-ray can also be used. After the exposure, post-exposure heating (PEB) may be performed under a temperature condition of 80 to 150 ° C., if necessary, for 40 to 600 seconds, preferably 60 to 360 seconds.

[Development process]
In the development step, the exposed coating film was subjected to development treatment at a temperature of 20 to 30 ° C. using an alkaline developer, for example, an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.1 to 10% by mass. Thereafter, water rinsing with pure water and drying are performed as necessary.

  After the development, preferably, the patterned coating film is baked (post-baked). By performing post-baking, a cured film can be formed, and a cured film having excellent water resistance, heat resistance, and solvent resistance can be obtained. The baking temperature is preferably from 100 to 400 ° C, more preferably from 150 to 300 ° C. The baking time is preferably 15 to 60 minutes, and more preferably 30 minutes or less.

<Curing film>
The resulting cured film is excellent in liquid repellency, and when it is formed on a substrate, for example, adjacent to the cured film, such as in a pixel region, where the cured film is not desired, the lyophilic property of the base material For example, it can be used as a cured film for a liquid crystal element or an organic EL element, and is suitable as a cured film for an organic EL element. In a light emitting device such as a liquid crystal device or an organic EL device, for example, if the transmittance of ultraviolet light of 300 to 400 nm is too high, the transmitted light may damage the TFT metal wiring. From this point of view, the cured film is preferable because it can optimize the light transmittance. As the cured film, an insulating film, a planarizing film, a partition (bank), and the like are preferable, and a partition is particularly preferable. As a partition, the partition at the time of forming a pixel by the inkjet method is suitable.
A cured film formed using the positive photosensitive resin composition of the present invention is also one aspect of the present invention.
The positive photosensitive resin composition of the present invention is particularly useful as a material for forming the above various cured films such as a partition material for an organic EL device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

(Resin component)
In Examples and Comparative Examples, the novolak resin (A) is a cresol novolak resin (m-cresol: p-cresol = 6: 4) obtained in Synthesis Example 1 and has a polystyrene-reduced weight average molecular weight of 3000. And a novolak resin A2 having a mass average molecular weight of 7000 were used in the amounts shown in Table 1.

[Synthesis Example 1] Synthesis of Novolak Resin A1 and A2 Using m-cresol and p-cresol in a ratio of 6: 4, charging formaldehyde and a catalytic amount of oxalic acid, reacting under reflux, and adjusting the reaction time Thus, a novolak resin A1 having a weight average molecular weight of 3000 in terms of polystyrene and a novolak resin A2 having a weight average molecular weight of 7000 were obtained.

  The weight average molecular weight in terms of polystyrene was measured by using a measuring device (Shodex SYSTEM21, manufactured by Shodex), and 20 μl of a sample having a concentration of 0.02 g / 10 ml THF was injected into a column (Shodex KF-G, KF-801, manufactured by Shodex). The measurement was performed by detecting tetrahydrofuran 280 nm absorption at a flow rate of 1.0 mL / min by flowing tetrahydrofuran (THF) as an eluent at 40 ° C. in a column oven.

(Photosensitive agent)
In Examples and Comparative Examples, the following B1 was used as a photosensitive agent.
B1: Partial ester of 1,2-naphthoquinonediazide-5-sulfonic acid of 2,3,4,4′-tetrahydroxybenzophenone (one of R is H)

(Fluorine resin)
In the examples, fluororesins F1 to F8 obtained in Synthesis Examples 2 to 9 below were used as the fluororesin (C). Moreover, in the comparative example 1, resin comprised from the unit of the following Formula was used as the fluororesin F9. In the following formula, the numerical value at the lower right of the parenthesis is the content (% by mass) of each unit in the fluororesin F9. The weight average molecular weight Mw of the fluororesin F9 is 10,000, and the ratio Mw / Mn between the mass average molecular weight Mw and the number average molecular weight Mn is 2. The log P value of the fluororesin F9 is 2.80.

[Synthesis Example 2]
Synthesis of fluororesin F1 A glass flask equipped with a stirrer, a thermometer, a condenser tube, and a dropping device was polymerized with 20 g of a hydroxyl group-containing perfluoropolyether compound represented by the following formula and 10 g of diisopropyl ether. 0.006 g of p-methoxyphenol as an inhibitor and 3.3 g of triethylamine as a neutralizer were charged.

HOCH ₂ CF ₂ O (—CF ₂ O—) _a (—CF ₂ CF ₂ O—) _b CF ₂ CH ₂ OH
(In the above formula, the average value of a is 5 and the average value of b is 8. The average value of the number of fluorine atoms in the compound of the above formula is 46. Also, the number average of GPC of the compound of the above formula is The molecular weight is 1,500.)

While maintaining the flask internal temperature at 10 ° C., 3.1 g of methacrylic acid chloride was added dropwise over 2 hours with stirring. After completion of the dropwise addition, the contents of the flask were stirred and reacted under the conditions of 10 ° C. for 1 hour, 30 ° C. for 1 hour, and 50 ° C. for 10 hours. When the reaction solution was partially collected and analyzed by gas chromatography, methacrylic acid chloride was lost in the reaction solution.
Next, 72 g of diisopropyl ether and 72 g of ion exchange water were added to the flask, and then the contents of the flask were stirred to wash the organic layer. After washing, the contents of the flask were allowed to stand and separated into two layers, and the aqueous layer was removed. This washing operation using 72 g of ion-exchanged water was repeated a total of 3 times.
After washing the organic layer with water, 8 g of magnesium sulfate was added to the organic layer to remove water in the organic layer. After filtering off magnesium sulfate, the solvent was distilled off from the filtrate under reduced pressure to obtain 18.7 g of a monomer (M1) represented by the following formula.

_{CH 2 = C (CH 3)} -C (= O) -OCH 2 CF 2 O (-CF 2 O-) a (-CF 2 CF 2 O-) b CF 2 CH 2 O- C (= O) - C (CH ₃ ) = CH ₂
(In the above formula, a and b are as described above.)

  Next, 260 g of methyl isobutyl ketone was charged into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device. After introducing a nitrogen stream into the flask, the methyl isobutyl ketone was heated to 105 ° C. Next, 20 g of monomer (M1), a monomer solution consisting of 80 g of t-butyl methacrylate and 80 g of methyl isobutyl ketone, polymerization initiation consisting of 15 g of t-butyl peroxy-2-ethylhexanoate and 60 g of methyl isobutyl ketone Three types of dropping solutions with the agent solution were set in separate dropping devices, respectively, and dropped simultaneously over 2 hours while maintaining the flask internal temperature at 105 ° C. After completion of the dropwise addition, the contents of the flask were stirred at 105 ° C. for 10 hours to obtain a fluororesin (F1) solution. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a fluororesin (F1). The fluororesin (F1) had a number average molecular weight of 1,400 and a weight average molecular weight of 2,300.

[Synthesis Example 3]
-Synthesis | combination of fluororesin F2 Methyl isobutyl ketone 260g was prepared to the glass-made flask provided with the stirring apparatus, the thermometer, the cooling tube, and the dripping apparatus. A nitrogen stream was introduced into the flask, and then methyl isobutyl ketone was heated to 105 ° C. Next, 20 g of monomer (M1), 80 g of 2-methyl-2-adamantyl methacrylate and 80 g of methyl isobutyl ketone, 15 g of t-butylperoxy-2-ethylhexanoate and 60 g of methyl isobutyl ketone Three kinds of dropping solutions with a polymerization initiator solution consisting of the above were set in separate dropping devices, and dropped simultaneously over 2 hours while keeping the flask internal temperature at 105 ° C. Two hours after the completion of dropping, 2 g each of t-butylperoxy-2-ethylhexanoate was added. Thereafter, the contents of the flask were stirred at 105 ° C. for 10 hours to obtain a fluororesin F2 solution. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a fluororesin (F2). The fluororesin (F2) had a number average molecular weight of 650 and a weight average molecular weight of 1200.

[Synthesis Example 4]
-Synthesis | combination of fluororesin F3 Methyl isobutyl ketone 420g was prepared to the glass flask provided with the stirring apparatus, the thermometer, the cooling tube, and the dripping apparatus. A nitrogen stream was introduced into the flask, and then methyl isobutyl ketone was heated to 105 ° C. Next, 52 g of 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate, 98 g of t-butyl methacrylate and 15 g of t-butylperoxy-2-ethylhexanoate were added to 165 g of methyl isobutyl ketone. The dissolved dropping solution was set in a dropping device and dropped over 2 hours while maintaining the temperature inside the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a fluororesin (F3). The fluororesin (F3) had a number average molecular weight of 2180 and a weight average molecular weight of 2950.

[Synthesis Example 5]
-Synthesis | combination of fluororesin F4 Methyl isobutyl ketone 420g was prepared to the glass flask provided with the stirring apparatus, the thermometer, the cooling tube, and the dripping apparatus. A nitrogen stream was introduced into the flask, and then methyl isobutyl ketone was heated to 105 ° C. Next, 52 g of 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate, 98 g of 2-methyl-2-adamantyl methacrylate and 15 g of t-butylperoxy-2-ethylhexanoate were methylated. A dropping solution dissolved in 165 g of isobutyl ketone was set in a dropping device and dropped over 2 hours while keeping the inside of the flask at 105 ° C. Six hours after the completion of dropping, 2 g of t-butylperoxy-2-ethylhexanoate was added. Then, it stirred at 105 degreeC for 10 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a fluororesin (F4). The fluororesin (F4) had a number average molecular weight of 1050 and a weight average molecular weight of 1780.

[Synthesis Example 6]
Synthesis of fluororesin F5 The monomer solution consisting of 80 g of t-butyl methacrylate and 80 g of methyl isobutyl ketone is changed to a monomer solution consisting of 60 g of t-butyl methacrylate, 20 g of 1-ethoxyethyl methacrylate and 80 g of methyl isobutyl ketone. Otherwise, a fluororesin (F5) was obtained in the same manner as in Synthesis Example 2. The fluororesin (F5) had a number average molecular weight of 1650 and a weight average molecular weight of 2850.

[Synthesis Example 7]
Synthesis of fluororesin F6 A monomer solution consisting of 80 g of 2-methyl-2-adamantyl methacrylate and 80 g of methyl isobutyl ketone was prepared from 60 g of 2-methyl-2-adamantyl methacrylate, 20 g of 1-ethoxyethyl methacrylate and 80 g of methyl isobutyl ketone. A fluororesin (F6) was obtained in the same manner as in Synthesis Example 3 except that the monomer solution was changed to. The fluororesin (F6) had a number average molecular weight of 700 and a weight average molecular weight of 1150.

[Synthesis Example 8]
・ Synthesis of fluororesin F7 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate 52 g, t-butyl methacrylate 98 g and t-butylperoxy-2-ethylhexanoate 15 g A dripping solution dissolved in 165 g of isobutyl ketone was added to 37.5 g of 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate, 75 g of t-butyl methacrylate and 1-ethoxyethyl methacrylate. A fluororesin (F7) was obtained in the same manner as in Synthesis Example 4 except that 5 g was changed to a dripping solution dissolved in 165 g of methyl isobutyl ketone. The fluororesin (F7) had a number average molecular weight of 2350 and a weight average molecular weight of 3200.

[Synthesis Example 9]
Synthesis of fluororesin F8 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate 52 g, 2-methyl-2-adamantyl methacrylate 98 g and t-butylperoxy-2-ethylhexano A dropping solution prepared by dissolving 15 g of ate in 165 g of methyl isobutyl ketone was added to 37.5 g of 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate, 75 g of 2-methyl-2-adamantyl methacrylate. In addition, a fluororesin (F8) was obtained in the same manner as in Synthesis Example 5 except that 37.5 g of 1-ethoxyethyl methacrylate was changed to a dropping solution in which 165 g of methyl isobutyl ketone was dissolved. The fluororesin (F8) had a number average molecular weight of 1050 and a weight average molecular weight of 1800.

(Crosslinking agent)
In Examples and Comparative Examples, a methylated product of hexamethylolmelamine (Nicalac MW-100LM, manufactured by Sanwa Chemical Co., Ltd.) having the following chemical structure was used as a crosslinking agent.

(Additive (Silane coupling agent))
In Examples and Comparative Examples, 3-glycidyloxypropyltrimethoxysilane was used as the additive E1.

[Examples 1 to 19, Comparative Example 1 and Comparative Example 2]
After mixing a resin component, a photosensitizer, a fluororesin, a crosslinking agent, and an additive (silane coupling agent) of the types and amounts (parts by mass) shown in Table 1, 100 parts by mass of propylene glycol monomethyl ether acetate (PM) The positive photosensitive resin composition of each Example and Comparative Example was obtained.

  A positive photosensitive resin composition was applied onto an ITO glass substrate using a spin coater and then pre-baked at 70 ° C. for 120 seconds to form a coating film having a thickness of 2.00 μm. The obtained coating film was exposed using an exposure apparatus (MPA-600FA, 365 mW, 100 mJ, manufactured by Canon Inc.) through a lattice photomask, and then tetramethylammonium hydroxide having a concentration of 2.38% by mass ( Development was performed using a TMAH) aqueous solution as a developer, followed by post-baking at 220 ° C. for 60 seconds to form a cured film.

<Evaluation>
1. Liquid repellency on cured film The contact angle of methoxybenzene on the cured film obtained was dropped by 2.0 μL of propylene glycol monomethyl ether acetate (PM) onto the cured film, and a contact angle meter (DROP MASTER-700, Kyowa Interface Science) The measurement was performed using Evaluation was made according to the following criteria, and the results are shown in Table 2.
◎: Contact angle 30 ° or more ○: Contact angle 15 ° or more and less than 30 ° ×: Contact angle less than 15 °

2. Lipophilicity on the substrate The contact angle of propylene glycol monomethyl ether acetate (PM) in the formed lattice (in the pixel region) is as described in 1. above. Was measured by the same method as above and evaluated according to the following criteria. The results are shown in Table 2.
◎: Contact angle of 10 ° or less ○: Contact angle of more than 10 ° and 15 ° or less ×: Contact angle of more than 15 °

Further, the storage stability of the positive photosensitive resin composition was evaluated according to the following method.
Specifically, after storing the positive photosensitive resin compositions of Examples and Comparative Examples at 25 ° C. for 7 days, the number of foreign matters having a diameter of 0.3 μm or more in the positive photosensitive composition (number / ML) was measured and storage stability was evaluated. In the case where the number of foreign matters after storage under predetermined conditions is 200 / mL, the storage stability is particularly good. The measurement results of the number of foreign matters are shown in Table 2.

  From Table 2, the novolak resin (A), the photosensitive agent (B), and the cross-linking agent (D), and a fluororesin (C) containing a unit (C1) and a unit (C2) having a predetermined structure are contained. When forming the lattice-shaped cured film (bank) using the positive photosensitive resin composition of the example, it can be seen that both the liquid repellency of the bank and the lyophilicity of the substrate can be achieved.

  On the other hand, according to Comparative Examples 1 and 2, using a positive photosensitive resin composition that does not contain the fluororesin (C) or contains a fluororesin having a structure other than the predetermined structure, ), It is understood that the liquid repellency of the bank and the lyophilicity of the substrate cannot be compatible.

Claims (8)

Containing novolac resin (A), photosensitive agent (B), fluororesin (C), and crosslinking agent (D),
The fluororesin (C) is selected from a unit derived from an unsaturated compound containing a perfluoroalkylene ether group represented by the following formula (1) and a unit derived from a fluorinated alkyl ester of an unsaturated carboxylic acid. with one or more fluorine-containing units (C1), it contains a unit (C2) derived from an unsaturated compound having a phenolic hydroxyl group protected by a carboxyl group or an acid-dissociable group protected by an acid dissociable group ,
The total amount, der Ru positive photosensitive resin composition 90% by mass or more of the fluorine-containing units of the fluorine resin (C) (C1) and the unit (C2).
-(X-O) _n -X- (1)
(In the formula (1), X is a perfluoroalkylene group having 1 to 3 carbon atoms, and a plurality of X contained in the formula (1) may be the same or different, and n is (It is an integer of 1 or more.)   2. The positive photosensitive resin composition according to claim 1, wherein an absolute value of a difference between a log P value of the fluororesin (C) and a log P value of the positive photosensitive resin composition is 3.0 or less.   The positive photosensitive resin composition of Claim 1 or 2 whose log P value of the said fluororesin (C) is 4.0-0.5.   The positive photosensitive resin composition of any one of Claims 1-3 whose said photosensitive agent (B) is a quinonediazide containing compound.   Furthermore, the positive photosensitive resin composition of any one of Claims 1-4 containing a silane coupling agent (E).   The positive photosensitive resin composition according to claim 5, wherein the silane coupling agent (E) has an epoxy group.   The positive photosensitive resin composition of any one of Claims 1-6 whose content of the said fluorine-containing unit (C1) in the said fluororesin (C) is 1-40 mass%. Cured film formed using the positive photosensitive resin composition according to any one of claims 1-7.