WO2013133392A1 - Positive photosensitive resin composition, partition wall and optical element - Google Patents

Abstract

To provide: a positive photosensitive resin composition which has excellent ink repellency and still has the excellent ink repellency after an ultraviolet/ozone irradiation treatment, while being capable of providing a partition wall that has less residue in the dot, said positive photosensitive resin composition having sufficient storage stability; a partition wall which is formed using the resin composition; and an optical element. A positive photosensitive resin composition containing (A) an alkali-soluble resin, (B) a sensitizer and (C) an ink repellent agent, which is characterized in that the ink repellent agent (C) is composed of a partial hydrolysis-condensation product of a mixture that contains a fluorine-containing hydrolyzable silane compound and the ratio of the fluorine atom content in the hydrolyzable silane compound is 10-55% by mass; a partition wall which is formed using the resin composition; and an optical element.

Description

Positive photosensitive resin composition, partition and optical element

The present invention relates to a positive photosensitive resin composition, a partition formed using the same, and an optical element having the partition.

A partition used for a pixel portion of a color filter or an organic EL (Electro-Luminescence) element, which is an optical element, is known to be formed by applying a photosensitive resin composition to a substrate and using a photolithography technique.

In recent years, a cost reduction process using an inkjet method has been proposed as a method for manufacturing a pixel portion of a color filter or an organic EL element.
For example, in the manufacture of a color filter, after the partition walls are formed by photolithography, R (red), G (green), and B (blue) inks are applied to the openings (dots) surrounded by the partition walls by an inkjet method. Spray and apply to form pixels.

In the inkjet method, it is necessary to prevent color mixing of ink between adjacent pixels. Therefore, the partition wall is required to have a property of repelling ink containing water or an organic solvent which is an inkjet discharge liquid, so-called ink repellency. On the other hand, the ink layer formed on the pixel by the inkjet method needs to have excellent film thickness uniformity. Therefore, the dots surrounded by the partition walls are required to have good wettability with respect to the discharge liquid, so-called ink affinity.

In order to make the surface of the partition wall ink repellent, a technique for adding an ink repellent agent to the photosensitive resin composition used for forming the partition wall has been developed.
The positive photosensitive resin is superior to the negative photosensitive resin in that it has less residue after development (hereinafter also referred to as “development residue”) and may be preferably used. For example, Patent Document 1 describes a technique for imparting ink repellency to a partition wall surface using a positive photosensitive resin composition containing an ink repellent agent having a small surface free energy.

Japanese Unexamined Patent Publication No. 2009-251327

However, in the positive photosensitive resin composition described in Patent Document 1, there is a problem that the surface transferability of the ink repellent agent is not sufficient, and the ink repellent agent remains inside the partition walls, resulting in poor ink affinity on the side surfaces of the partition walls. was there. There is also a problem that ink repellent remains on the developed dots, and the ink cannot be applied uniformly, and the ink is white. In order to clean the dots, ultraviolet / ozone irradiation treatment or the like is used. However, the ink repellent agent described in Patent Document 1 is not sufficiently resistant, and the ink repellency of the partition walls is greatly reduced. there were.

The present invention has been made in view of the above circumstances, and can form a partition wall that is excellent in ink repellency, excellent in ink repellency even after being subjected to ultraviolet / ozone irradiation treatment, and having little residue on dots. An object of the present invention is to provide a positive photosensitive resin composition having excellent storage stability.
Another object of the present invention is to provide an optical element having a partition wall that is excellent in ink repellency and excellent in ink repellency even after being subjected to ultraviolet / ozone irradiation treatment.

The present invention provides a positive photosensitive resin composition, partition walls, and optical elements having the following configurations [1] to [15].
[1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B) and an ink repellent agent (C),
Partial hydrolysis of a mixture in which the ink repellent agent (C) includes a hydrolyzable silane compound represented by the following formula (c-1) and a hydrolyzable silane compound represented by the following formula (c-2) A positive photosensitive resin composition comprising a condensate and having a fluorine atom content of 10 to 55 mass% in the ink repellent agent (C).

(The symbols in formulas (c-1) and (c-2) are as follows.
R ^f : a perfluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group having 2 to 40 carbon atoms represented by R ^f1 OR ^f2 — (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms) And R ^f2 is a perfluoroalkylene group which may have an etheric oxygen atom between carbon-carbon atoms).
Q ¹ : a divalent organic group not containing a fluorine atom having 1 to 10 carbon atoms,
R ^H1 : a hydrocarbon group having 1 to 6 carbon atoms,
X ¹ and X ² : hydrolyzable groups,
p: 0, 1 or 2.
However, three X ^{1 s in} the formula (c-1), (4-p) X ^{2 s} in the formula (c-2), and p ^{RH 1 s} may be the same or different from each other. There may be. )

[2] The positive photosensitive resin composition according to the above [1], wherein the content of the alkali-soluble resin (A) in the total solid content in the positive photosensitive resin composition is 10 to 90% by mass.
[3] The positive photosensitive resin as described in [1] or [2] above, wherein the content of the photosensitive agent (B) in the total solid content in the positive photosensitive resin composition is 0.1 to 50% by mass. Resin composition.
[4] The above-mentioned [1] to [3], wherein the content of the ink repellent agent (C) in the total solid content in the positive photosensitive resin composition is 0.01 to 10% by mass. A positive photosensitive resin composition.
[5] The positive photosensitive resin composition according to any one of [1] to [4], wherein the ink repellent agent (C) has a number average molecular weight (Mn) of 500 or more and less than 1,000,000. .

[6] The positive photosensitive resin composition according to any one of the above [1] to [5], wherein the alkali-soluble resin (A) is a novolak type phenol resin.
[7] The positive photosensitive resin composition according to any one of [1] to [6] above, wherein the photosensitive agent (B) is a compound having a quinonediazide group.

[8] The positive photosensitive resin composition according to any one of [1] to [7], wherein the mixture further contains a hydrolyzable silane compound represented by the following formula (c-3).

(The symbols in formula (c-3) are as follows.
Y: a hydrogen atom, a phenyl group optionally 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,
Q ² : single bond or divalent organic group,
R ^H2 : a hydrocarbon group having 1 to 6 carbon atoms,
X ³ : hydrolyzable group,
q: 1 or 2,
r: a number that is 0 or 1 and q + r is 1 or 2.
However, q pieces of Y, ^{Q 2,} and ^{Y-Q 2,} and (4-q-r) pieces of ^{X 3} may each be the same or different from each other. )

[9] The positive photosensitive resin composition according to any one of [1] to [8], further including a solvent (D).
[10] The positive photosensitive resin composition according to any one of [1] to [9], further including a thermosetting agent (E).
[11] The positive photosensitive resin composition according to [10], further including a thermosetting accelerator (F).
[12] The positive photosensitive resin composition according to any one of [1] to [11], further including a colorant (G).

[13] A partition formed in a shape that partitions the substrate surface into a plurality of compartments for pixel formation, the cured film of the positive photosensitive resin composition according to any one of [1] to [12] above Partition wall.
[14] An optical element having a plurality of pixels and a partition located between adjacent pixels on the surface of the substrate, wherein the partition is formed by the partition described in [13].
[15] The optical element according to the above [14], wherein the optical element is a color filter, a TFT (Thin Film Transistor) array, or an organic EL element.

The positive photosensitive resin composition of the present invention is excellent in ink repellency, can form a partition wall excellent in ink repellency even after being subjected to ultraviolet / ozone irradiation treatment, and is excellent in storage stability.
The optical element of the present invention is excellent in ink repellency, and has a partition wall that is excellent in ink repellency even after being subjected to ultraviolet / ozone irradiation treatment.

It is sectional drawing which shows typically the manufacture example of the partition for optical elements using the positive photosensitive resin composition of this invention.

In the present specification, the compound represented by the formula (c-1) is referred to as “compound (c-1)”. The same applies to other compounds.
The “total solid content” in this specification is a partition-forming component among the components contained in the positive photosensitive resin composition, and is a volatile material that volatilizes by heating or the like in the partition-forming process such as the solvent (D). All components other than components are shown. It is measured as a residue obtained by heating the positive photosensitive resin composition at 140 ° C. for 24 hours to remove the solvent. The total solid content can also be calculated from the amount of each component charged.
In the present specification, a film coated with a positive photosensitive resin composition is referred to as a “coating film”, a dried state is referred to as a “film”, and a film obtained by curing the film is referred to as a “cured film”. .

In this specification, the “surface” of the partition wall is used as a term indicating only the upper surface of the partition wall. Therefore, the “surface” of the partition does not include the side surface of the partition.
The “ink” in the present specification is a general term for, for example, liquids having optically and electrically functions after being dried and cured, and is not limited to conventionally used coloring materials. Similarly, “pixels” formed by injecting the ink are also used to indicate sections having optical and electrical functions, which are partitioned by partition walls.
“Ink repellency” in the present specification refers to a property having moderately both water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later.
Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification,% represents the mass%.

[Alkali-soluble resin (A)]
As alkali-soluble resin (A) in the positive photosensitive resin composition of this invention, well-known alkali-soluble resin used for positive photosensitive resin composition is used.
The alkali-soluble resin (A) functions as a positive photosensitive resin composition by being used together with a photosensitizer (B) described later. That is, in the positive photosensitive resin composition, upon exposure such as photolithography, the photosensitive agent (B) is activated in the exposed portion, and the solubility in the developer is increased. The exposed portion is removed by dissolving in a developer (usually an alkali developer) during development. A portion that is not irradiated with light (an unexposed portion) serves as a partition wall. The alkali-soluble resin (A) may be insolubilized in the developer by combining with the photosensitizer (B) before exposure.

Examples of the alkali-soluble resin (A) include phenols and aldehydes, unmodified or modified novolak type phenol resins, polyhydroxystyrene, polyhalogen produced by polycondensation by adding various modifiers as necessary. Hydroxystyrene, N- (4-hydroxyphenyl) methacrylamide copolymer, and hydroquinone monomethacrylate copolymer. In addition, various alkali-soluble polymer compounds such as sulfonylimide polymers, carboxyl group-containing polymers, acrylic resins containing phenolic hydroxyl groups, acrylic resins having sulfonamide groups, urethane resins, etc. may be used. it can.
As the alkali-soluble resin (A) in the positive photosensitive resin composition of the present invention, a novolac type phenol resin is preferable.

Examples of the phenols used for producing the novolak type phenol resin include cresols such as phenol, o-cresol, p-cresol, m-cresol; 3,5-xylenol, 2,5-xylenol, 2, Xylenols such as 3-xylenol and 3,4-xylenol; 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,4,5-trimethylphenol, 3,4,5-trimethylphenol, etc. Trimethylphenols; t-butylphenols such as 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol; 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol 2,5-dimethoxyphenol, 3 Methoxyphenols such as 5-dimethoxyphenol; 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,3-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, 3, Ethylphenols such as 4,5-triethylphenol; chlorophenols such as o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol; resorcinol, 2-methylresorcinol, 4-methylresorcinol Resorcinols such as 5-methylresorcinol; Catechols such as 5-methylcatechol; Pyrogallols such as 5-methylpyrogalol; Bisphenols such as bisphenol A, B, C, D, E, and F; 2,6-dimethylol -P-Crezo Methylolated cresols etc; alpha-naphthol, naphthol such as β- naphthol; and the like. These may be used alone or in combination of two or more.

Examples of aldehydes used for producing novolak type phenol resins include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, Examples thereof include benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. These may be used alone or in combination of two or more.

Among the novolak type phenol resins, novolak type phenol resins using cresols, xylenols and the like are preferable as phenols from the viewpoints of easy availability and few metal impurities, and novolak type using cresols. Phenol resin (hereinafter also referred to as “cresol novolac resin”) is particularly preferable.

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 0.5 × 10 ³ to 20 × 10 ³ , particularly preferably 2 × 10 ³ to 15 × 10 ³ . When the mass average molecular weight (Mw) is in the above range, the solubility in a developer after exposure is excellent.
In addition, in this specification, a mass average molecular weight (Mw) means the mass average molecular weight converted on the basis of standard polystyrene, which is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase. The number average molecular weight (Mn) means the number average molecular weight measured by the same GPC.

The alkali-soluble resin (A) preferably has excellent solubility in an alkali developer. For example, as an alkaline developer of a positive photosensitive resin composition, a dissolution rate (angstrom / second, hereinafter simply referred to as “dissolution rate”) in a general 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution. Is an index of 50 to 400 angstrom / second, particularly preferably 100 to 200 angstrom / second. When the dissolution rate is in the above range, the developability of the positive photosensitive resin composition becomes good.

A commercially available product can be used as the alkali-soluble resin (A). Commercially available products are trade names manufactured by Asahi Organic Materials Co., Ltd., EP4020G (Mw: 9,000 to 14,000, dissolution rate: 160 to 250 angstrom / second), EPR5010G (Mw: 7,000 to 12) 500, dissolution rate: 50 to 150 angstroms / second) (both are cresol novolac resins).

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 in the positive photosensitive resin composition is preferably 10 to 90% by mass, particularly preferably 30 to 80% by mass. When the content is in the above range, the developability of the positive photosensitive resin composition is improved.

[Photosensitive agent (B)]
As the photosensitive agent (B) in the positive photosensitive resin composition of the present invention, a known photosensitive agent used for the positive photosensitive resin composition is used.
As the photosensitive agent (B), a compound having a quinonediazide group is preferable. As the compound having a quinonediazide group, a known compound having a quinonediazide group used in combination with a novolak type phenol resin is used.

Examples of the photosensitive agent (B) include a complete condensate and a partial condensate of a compound α and a compound β having a quinonediazide group, which will be described later, which can be condensed with each other.

Compound α has a functional group capable of condensation reaction. Examples of the functional group capable of condensation reaction include a sulfo group and a chlorosulfo group. Examples of the compound α include sulfonic acids such as benzoquinone diazide sulfonic acid, naphthoquinone diazide sulfonic acid, and anthraquinone diazide sulfonic acid, and sulfonic acid chlorides thereof. Specific examples of the sulfonic acid chloride include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-4-sulfonic acid chloride, and the like. Is mentioned.

The compound β has a functional group that can undergo a condensation reaction with the compound α. Examples of the functional group capable of the condensation reaction include a hydroxyl group and an amino group, and a hydroxyl group is preferred.
As the compound β, a compound having an aromatic ring is preferable in that the obtained partition wall is excellent in heat resistance. The number of aromatic rings in the aromatic compound is preferably 1 to 6 and particularly preferably 2 to 4 in terms of heat resistance and the ability to introduce a large number of hydroxyl groups.
As the 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 preferable. The number of hydroxyl groups in one molecule is preferably 1 to 10 and particularly preferably 2 to 4.

As a specific example of the compound β,
Phenols such as phenol and 4-methylphenol;
Polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone;
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, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethyl) Phenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxy Phenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3) , 5-Dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) 3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenyl Trisphenol type compounds such as methane, 1,3,5-tris (4-hydroxyphenyldimethylbenzyl) benzene;
Linear type 3, such as 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol and 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Nuclear phenolic compounds;
1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) ) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl)- 4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl- 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Roxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy- 5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl-3- ( Linear or cyclic tetranuclear phenolic compounds such as 2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;
2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5 Linear type such as -methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol or Linear or cyclic polyphenol compounds such as cyclic pentanuclear phenol compounds;
Bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- (2,3,4) -Trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2 -(3,4-dihydroxyphenyl) -2- (3 ', 4'-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro -4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4 ' Hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'- Bisphenol type compounds such as hydroxy-3 ', 5'-dimethylphenyl) propane;
1- [1,1-bis (4-hydroxyphenyl) ethyl] -4- [1 ', 1'-bis (4'-hydroxyphenyl) ethyl] benzene, 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl) Polyhydroxy branched compounds such as -4-hydroxyphenyl) ethyl] benzene;
1,1-bis (4-hydroxyphenyl) cyclohexane, 2-bis [1,1-bis (4-hydroxyphenylcyclohexyl)]-2-bis [1 ', 1'-bis (4'-hydroxyphenylcyclohexyl) ] Condensed phenolic compounds such as propane;
1,1'-spirobi [1H-indene] -5,5 ', 6,6'-tetraol, 2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman, pentacyclo ^{[19,3,1,1 3,7,} 1 ^{9, 13, 1 15, 19]} Okutakosa -1,3,5,7,9,11,13,15,17,19,21,23- dodecaene - 4, 6, 10, 12, 16, 18, 22, 24-octaol and the like. These may be used alone or in combination of two or more.

The photosensitizer (B) is more preferably a complete condensate or partial condensate of the following compound α and compound β.
Compound α: 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-4-sulfonic acid chloride, etc.
Compound β: phenol as phenols, 4-methylphenol;
2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone as polyhydroxybenzophenones;
Trisphenol type compounds include 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, 1,3,5-tris (4-hydroxyphenyldimethylbenzyl) benzene;
Bisphenol type compounds include 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- (3,4-dihydroxyphenyl) -2- (3 ', 4'-dihydroxyphenyl) propane, 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 the polynuclear branched compound;
2-bis [1,1-bis (4-hydroxyphenylcyclohexyl)]-2-bis [1 ′, 1′-bis (4′-hydroxyphenylcyclohexyl)] propane as the condensed phenol compound;
1,1'-spirobi [1H-indene] -5,5 ', 6,6'-tetraol, 2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman, pentacyclo ^{[19,3,1,1 3,7,} 1 ^{9, 13, 1 15, 19]} Okutakosa -1,3,5,7,9,11,13,15,17,19,21,23- dodecaene - 4,6,10,12,16,18,22,24-octaol.

As the photosensitive agent (B), condensation of 1,2-naphthoquinonediazide-5-sulfonic acid chloride or 1,2-naphthoquinonediazide-4-sulfonic acid chloride with 2,3,4,4′-tetrahydroxybenzophenone A compound represented by the formula (b-1) which is a reactant is particularly preferred.

(In the formula (b-1), D represents a hydrogen atom or a group represented by the following formula (b-2), provided that at least one of D is a group represented by the formula (b-2). .)

The photosensitive agent (B) in the positive photosensitive resin composition of the present invention may be a mixture of compounds having different numbers of quinonediazide groups in one molecule, and the quinonediazide group as an average value of the entire photosensitive agent (B), Compounds having 1 to 4 per molecule are preferred, and compounds having 2.5 to 3 are particularly preferred.

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

[Ink repellent (C)]
The ink repellent agent (C) in the positive photosensitive resin composition of the present invention is a hydrolyzable silane compound (hereinafter also referred to as compound (c-1)) represented by the following formula (c-1), Partially hydrolyzed condensate of a mixture (hereinafter also referred to as “hydrolyzable silane compound mixture”) containing a hydrolyzable silane compound represented by (c-2) (hereinafter also referred to as compound (c-2)) The fluorine atom content in the ink repellent agent (C) is 10 to 55% by mass.

(The symbols in formulas (c-1) and (c-2) are as follows.
R ^f : a perfluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group having 2 to 40 carbon atoms represented by R ^f1 OR ^f2 — (R ^f1 is a perfluoroalkyl group having 1 to 6 carbon atoms) And R ^f2 is a perfluoroalkylene group which may have an etheric oxygen atom between carbon-carbon atoms).
Q ¹ : a divalent organic group not containing a fluorine atom having 1 to 10 carbon atoms,
R ^H1 : a hydrocarbon group having 1 to 6 carbon atoms,
X ¹ and X ² : hydrolyzable groups,
p: 0, 1 or 2.
However, when a plurality of X ¹ , X ² and R ^H1 are present in the formula (c-1) or the formula (c-2), they may be different from each other or the same. )

By containing the perfluoroalkyl group derived from the compound (c-1), the ink repellent agent (C) can impart excellent ink repellency to the partition formed using the positive photosensitive resin composition. When the positive photosensitive resin composition is applied to the substrate, R ^f derived from the hydrolyzable silane compound (c-1) tends to stay on the side opposite to the substrate (that is, the air side). That is, the ink repellent agent (C) tends to stay on the side opposite to the substrate. Further, since the compound (c-1) has R ^f and a silicon atom, the partition wall is excellent in ink repellency and ultraviolet / ozone resistance.

The ink repellent agent (C) contains a unit derived from the compound (c-2), so that the ink repellent agent (C) is excellent in solubility in a hydrocarbon solvent and film forming property. Further, the fluorine atom content of the ink repellent agent (C) can be adjusted.

The fluorine atom content of the ink repellent agent (C) is from 10 to 55 mass%, preferably from 12 to 40 mass%, particularly preferably from 15 to 30 mass%. When the fluorine atom content is in the above range, the ink repellency resistant to ultraviolet rays or ozone irradiation can be imparted to the partition formed using the positive photosensitive resin assembly.

The ink repellent agent (C) preferably has a silanol group. The number of silanol groups is preferably 0.2 to 3.5, more preferably 0.2 to 2, and particularly preferably 0.5 to 1.5 per silicon atom. When it is at least the lower limit of the above range, it is possible to prevent detachment of the ink repellent agent (C) from the substrate surface when the partition is formed using the positive photosensitive resin composition. When the amount is not more than the upper limit of the above range, the ink repellent agent (C) is excellent in compatibility with the solvent and other components in the positive photosensitive resin composition.
The number of silanol groups in the ink repellent agent (C) is calculated by the ratio of peak areas of Si groups having silanol groups and Si groups having no silanol groups, as measured by ²⁹ Si-NMR.

The hydrolyzable silane compound mixture of the present invention contains compound (c-1) and compound (c-2). Furthermore, one or more hydrolyzable silane compounds other than the compound (c-1) and the compound (c-2) may be contained.

Examples of the hydrolyzable silane compound other than the compound (c-1) and the compound (c-2) include a hydrolyzable silane compound having a phenyl group-containing organic group (the hydrolyzable silane compound (c-1), And (c-2) are excluded). For example, a hydrolyzable silane compound in which an organic group having one or two phenyl groups at the end, 0 or 1 hydrocarbon group, and 1 to 3 hydrolyzable groups are bonded to a silicon atom. The compound (c-3) described later is preferable.

(Hydrolyzable silane compound (c-1))
The hydrolyzable silane compound (c-1) is a silane compound represented by the above formula (c-1).
In formula (c-1), R ^f is preferably a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 4 to 9 carbon atoms containing an etheric oxygen atom, and is a perfluoroalkyl group having 6 carbon atoms. The group is particularly preferred. When R ^f is in the above range, the partition formed using the positive photosensitive resin composition has excellent ink repellency, particularly excellent UV / ozone ink repellency, and a general-purpose solvent. Excellent solubility in
^Examples of the structure of R ^f include a linear structure, a branched structure, a ring structure, or a structure having a partial ring, and a linear structure is preferable.

Specific examples of R ^f include the following groups.
F (CF ₂ ) ₄ —, F (CF ₂ ) ₆ —.
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ —, CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ —, CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ —, CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ —.
CF ₃ CF ₂ CF ₂ OCF _2- , CF ₃ CF ₂ CF ₂ OCF ₂ CF _2- , CF ₃ CF ₂ CF ₂ OCF (CF ₃ )-, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF _2- , CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- , CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ )-, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF _2- , CF ₃ OCF (CF ₃ ) CF ₂ OCF (CF ₃ )-, CF ₃ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ )-.

In formula (c-1), when Q ¹ is represented by the fact that Si is bonded to the right bond and R ^f is bonded to the left bond, specifically, — (CH ₂ ) _i1 — ( i1 is an integer of 1 to 5.), —CH ₂ O (CH ₂ ) _i2 — (i2 is an integer of 1 to 4), —SO ₂ NR ¹ — (CH ₂ ) _i3 — (R ¹ is a hydrogen atom, A methyl group or an ethyl group, i3 is 1 or more, and an integer of 4 or less in total with the number of carbon atoms of R ¹ ), — (C═O) —NR ¹ — (CH ₂ ) _i4 — ( R ¹ is the same as above, i4 is 1 or more, and a group represented by a total of 4 or less in total with the number of carbon atoms of R ¹ is preferable. As Q ¹ , — (CH ₂ ) _i1 — in which i1 is 2 or 3 is more preferable, and — (CH ₂ ) ₂ — is particularly preferable.

When R ^f is a perfluoroalkyl group having 1 to 6 carbon atoms, Q ¹ is preferably a group represented by — (CH ₂ ) _i1 — (wherein i1 is the same as above). i1 is preferably an integer of 2 to 4, particularly preferably — (CH ₂ ) ₂ —.
In the case where R ^f is a C 4-9 perfluoroalkyl group containing an etheric oxygen atom, the above Q ¹ includes — (CH ₂ ) _i1 —, —CH ₂ O (CH ₂ ) _i2 —, —SO A group represented by ₂ NR ¹ — (CH ₂ ) _i3 —, — (C═O) —NR ¹ — (CH ₂ ) _i4 — (i1 to i4 and R ¹ are the same as above) is preferable. Also in this case, — (CH ₂ ) ₂ — is particularly preferable.

In formula (c-1), examples of X ¹ include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, or a group in which a hydrogen atom of an amino group is substituted with an alkyl group. Of these, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferable, and a methoxy group, an ethoxy group, or a chlorine atom is particularly preferable. These groups are converted into hydroxyl groups (silanol groups) by a hydrolysis reaction, and further, a reaction for forming a Si—O—Si bond through a condensation reaction between molecules tends to proceed smoothly.

Specific examples of the compound (c-1) include the following compounds.
F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , F (CF ₂ ) ₄ CH ₂ CH ₂ SiCl ₃ , F _{(CF 2) 6 CH 2 CH} 2 Si (OCH 3) 3, F (CF 2) 6 CH 2 CH 2 Si (OCH 2 CH 3) 3, F (CF 2) 6 CH 2 CH 2 SiCl 3.
CF ₃ OCF ₃ CF ₂ CF ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , CF ₃ OCF (CF ₃ ) CF ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .
F (CF ₂ ) ₂ OCF ₂ CF ₂ OCF ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₂ O (CF ₂ ) ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .
_{F (CF 2) 3 OCF 2} CF 2 CH 2 CH 2 SiCl 3, F (CF 2) 3 OCF (CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3.

Examples of the compound (c-1) include F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , F ( _{CF 2) 6 CH 2 CH 2} SiCl 3, F (CF 2) 3 OCF (CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3 are particularly preferred.
The compound (c-1) contained in the hydrolyzable silane compound mixture may be used alone or in combination of two or more.

(Hydrolyzable silane compound (c-2))
The hydrolyzable silane compound (c-2) is a silane compound represented by the above formula (c-2).
In the formula (c-2), R ^H1 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.
X ² is a hydrolyzable group, and is the same as X ¹ in the above formula (c-1), including preferred embodiments.
p is 0, 1 or 2, but when p is 2, two R ^H1 and (4-p) X ² may be different from each other or the same.
p is preferably 0 or 1.

In the ink repellent agent (C), water repellency is expressed by R ^f1 derived from the compound (c-1) and R ^H1 derived from the compound (c-2), and oil repellency is expressed mainly by R ^f . In order for the cured product of the ink repellent agent (C) to exhibit sufficient oil repellency, the ratio of R ^f is high with respect to the total of R ^f and R ^H1 in the ink repellent agent (C). preferable. When p is 0, the ratio of R ^f in the ink repellent agent (C) is increased, the oil repellency is improved, and the film forming property is excellent. When p is 1 or 2, the presence of a certain amount of R ^H1 makes the ink repellent agent (C) easily dissolved in a hydrocarbon solvent, and a coating of a positive photosensitive resin composition is formed on the surface of the substrate. In forming, a relatively inexpensive solvent can be selected.

As the compound (c-2), the following compounds are preferred. If necessary, a partial hydrolysis-condensation product obtained by partial hydrolysis-condensation of a plurality of them may be used. The same applies to other hydrolyzable silane compounds.
Si (OCH ₃ ) ₄ , Si (OCH ₂ CH ₃ ) ₄ , CH ₃ Si (OCH ₃ ) ₃ ,
CH ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ CH ₂ Si (OCH ₃ ) ₃ ,
CH ₃ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ ,
(CH ₃ ) ₂ Si (OCH ₂ CH ₃ ) ₂ ,
A compound obtained by hydrolytic condensation of Si (OCH ₃ ) ₄ (for example, methyl silicate 51 (trade name) manufactured by Colcoat Co.),
Compounds obtained by hydrolytic condensation of Si (OCH ₂ CH ₃ ) ₄ (for example, ethyl silicate 40 and ethyl silicate 48 (both trade names) manufactured by Colcoat).

The compound (c-2) contained in the hydrolyzable silane compound mixture of the present invention may be used alone or in combination of two or more. When using 2 or more types together, a bifunctional compound can also be used together with a tetrafunctional compound and / or a trifunctional compound.
The content of the compound (c-2) in the hydrolyzable silane compound mixture is preferably 0.1 to 9 mol of the compound (c-2) with respect to 1 mol of the compound (c-1). ˜9 mol is particularly preferred.

(Hydrolyzable silane compound (c-3))
The hydrolyzable silane compound (c-3) is a hydrolyzable silane compound represented by the following formula (c-3) (hereinafter also referred to as “compound (c-3)”).

In the formula (c-3), X ³ representing a hydrolyzable group is the same as X ¹ in the formula (c-1), including preferred embodiments.
^Further, the ^{R H2} is the same, including the preferred embodiments and ^{R H1} in the formula (c-2).
In formula (c-3), Y represents a phenyl group optionally substituted with a hydrogen atom, 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.
Q ² is a group linking a silicon atom and a 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.
In the formula (c-3), when q is 2, two Q ² may be different or the same, and when q + r is 1, three X ³ are different from each other. May be the same, and when q + r is 2, two X ³ may be different or the same.
In formula (c-3), q is preferably 1 and r is 1, or q is 1 and r is preferably 0.

In formula (c-3), Y includes a phenyl group, a fluorophenyl group, a chlorophenyl group, a dichlorophenyl group, and the like, and a phenyl group is particularly preferable. By using such a compound (c-3), it is possible to obtain a partition wall with high resolution and little residue in the dot portion. This is because the phenyl group derived from the compound (c-3) is transferred to the diazide group of the photosensitive agent (B) in the developer after the ink repellent agent (C) has moved to the film surface of the positive photosensitive resin composition. It is presumed that the ink repellent agent (C) is likely to stay on the film surface of the positive photosensitive resin composition by the azo coupling reaction. Thereby, even after developing, post-baking, etc., the surface of the obtained partition wall can be kept ink-repellent and the side surface can be kept ink-philic.

In the formula (c-3), when Q ² is a divalent organic group, — (CH ₂ ) _j — (j is an integer of 1 to 6), —NH—, —NH— (C _k H _2k )-(k is an integer of 1 to 6) and -N (C _g H _{2g + 1} )-(g is an integer of 1 to 6) are electron donating groups, and are preferable from the viewpoint of availability. Q ² is particularly preferably a single bond or —NH—.

Specific examples of compound (c-3) 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 (c-3) contained in the hydrolyzable silane compound mixture of the present invention may be used alone or in combination of two or more.
The compounding amount of the compound (c-3) in the hydrolyzable silane compound mixture of the present invention is 5 mol or less with respect to 1 mol of the total amount of the hydrolyzable silane compounds (c-1) and (c-2). Is preferably 4 mol or less.

The ink repellent agent (C) used in the positive photosensitive resin composition of the present invention is a partial hydrolysis condensate of the above-mentioned raw material hydrolyzable silane compound mixture, and usually a plurality of condensates having different degrees of polymerization. It is a composed composition.
That is, when the ink repellent agent (C) is produced using the hydrolyzable silane compound (c-1) and the compound (c-2) as essential components and optionally using the compound (c-3), It has the structure of the average composition formula represented by the following formula (1). However, since it is actually a product (partially hydrolyzed condensate) in which a hydrolyzable group or silanol group remains, it is difficult to express this product by a chemical formula.
The average composition formula represented by the formula (1) is that the hydrolyzable group or silanol group is completely hydrolyzed and condensed into a siloxane bond in the partially hydrolyzed condensate produced as described above. Is the chemical formula.

In formula (1), the preferred ranges of R ^f , R ^H1 , R ^H2 , Y, Q ¹ , Q ² , p, q, and r are the same as those described above. s, t, and u are the average number of moles of each unit in a plurality of fluorine-containing silane compound mixtures having different degrees of polymerization.

In the partial hydrolysis-condensation product having the structure of the average composition formula represented by the formula (1), the units derived from the compound (c-1), the compound (c-2) and the compound (c-3) are Presumed to be randomly arranged.
The s / t (molar ratio) in the following average composition formula (2) when using the compound (c-1) and the compound (c-2) is the average value of the entire ink repellent agent (C). The content of the compound (c-2) with respect to the compound (c-1) in the decomposable silane compound mixture is preferably in the above-mentioned range, that is, 10/1 to 90 (molar ratio), preferably 10/5 to 90 (molar ratio). Particularly preferred.

In formula (2), the preferred ranges of R ^f , R ^H1 , Q ¹ and p are the same as those described above. s and t are the average number of moles of each unit in a plurality of fluorine-containing silane compound mixtures having different degrees of polymerization.

When the ink repellent agent (C) is produced using the hydrolyzable silane compound (c-1), hydrolyzable silane compound (c-2) and hydrolyzable silane compound (c-3), the formula ( 2) has an average composition formula structure in which the units derived from the compound (c-3) of the formula (1) are further co-condensed.

In the formula (1), as an average value of the entire ink repellent agent (C), u is preferably within the above-mentioned range, that is, 5 or less (molar ratio) with respect to 1 of (s + t), and 4 or less (molar ratio) Particularly preferred.

The ink repellent agent (C) in the positive type photosensitive resin composition of the present invention has excellent ink repellency even when it is exposed to ultraviolet rays / ozone when the contained silanol groups are further condensed in the process of exposure and curing. It is considered to form a partition wall showing

The number average molecular weight (Mn) of the ink repellent agent (C) in the positive photosensitive resin composition of the present invention is preferably 500 or more, preferably less than 1,000,000, and particularly preferably less than 10,000. When the number average molecular weight (Mn) is not less than the lower limit of the above range, detachment from the substrate surface can be prevented when the partition is formed using the positive photosensitive resin composition. When the number average molecular weight (Mn) is less than the upper limit of the above range, the solubility in a solvent is good and the workability is excellent. The number average molecular weight (Mn) of the ink repellent agent (C) can be adjusted by selecting reaction conditions and the like.

(Manufacture of ink repellent agent (C))
The ink repellent agent (C) in the positive photosensitive resin composition of the present invention can be produced by hydrolyzing and partially condensing the hydrolyzable silane compound mixture described above (hereinafter also referred to as “reaction step”). . As described above, hydrolysis and partial condensation are reactions in which a silanol group is generated by a hydrolysis reaction of a hydrolyzable group and a siloxane bond is generated by a dehydration condensation reaction between silanol groups. For the reaction step, the reaction conditions usually used for the reaction of hydrolyzing and condensing a hydrolyzable silane compound can be applied without particular limitation, and for example, water, a catalyst, an organic solvent and the like can be used.

When water is used in the reaction step, the amount is preferably 25 to 9,900 parts by weight, particularly preferably 100 to 1,900 parts by weight, based on 100 parts by weight of the hydrolyzable silane compound mixture. By controlling the amount of water in the above range, the hydrolysis and condensation reaction can be easily controlled.

As the catalyst used in the reaction step, it is preferable to use inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid, oxalic acid and maleic acid. The amount of the catalyst used is preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the hydrolyzable silane compound mixture.

An organic solvent may be used in the reaction step. The organic solvent is an organic solvent that is usually used when hydrolyzing and condensing the hydrolyzable silane compound, specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- Alcohols such as butanol, isobutanol, 2-methyl-2-propanol, ethylene glycol, glycerin and propylene glycol; Ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Cellsolves such as 2-methoxyethanol and 2-ethoxyethanol Carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol; methyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, -Esters such as butyrolactone, butyl acetate and 3-methoxybutyl acetate; monoalkyl ethers of glycols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether And dialkyl ethers of glycols such as dipropylene glycol dimethyl ether. Other examples include benzyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone and the like. An organic solvent may be used individually by 1 type, or may use 2 or more types together.
In the reaction step, the amount of the organic solvent is preferably 25 to 9,900 parts by weight, particularly preferably 100 to 1,900 parts by weight, based on 100 parts by weight of the hydrolyzable silane compound mixture.

The resulting partially hydrolyzed condensate is blended into the positive photosensitive resin composition together with the solvent used in the reaction step. Therefore, it is preferable to use a solvent that stabilizes the silanol group in the ink repellent agent (C) as the solvent used in the reaction step. Examples of the solvent that stabilizes the silanol group include compounds having a hydroxyl group and a relative dielectric constant (ε) at 25 ° C. of 5 to 20, preferably 8 to 15.

Specific examples include glycol monoalkyl ether acetate solvents having 2 to 8 carbon atoms, glycol monoalkyl ether solvents, glyme solvents, hydrocarbon alcohols having 2 to 4 carbon atoms, and the like. .
More specifically, propylene glycol monomethyl ether acetate (ε: 8.3) as a glycol-based monoalkyl ether acetate solvent, propylene glycol monomethyl ether (ε: 12.3) as a glycol-based monoalkyl ether solvent, carbonization Examples of the hydrogen alcohol include 2-propanol (ε: 19.92). Propylene glycol monomethyl ether is particularly preferred because of its high silanol group stabilizing effect.

The reaction step is preferably carried out at a temperature from room temperature to the boiling point of the solvent under suitable stirring conditions.
The reaction time may be about 0.5 to 24 hours, preferably 1 to 10 hours, depending on the amount of raw material components used, reaction temperature, stirring conditions and the like.
After completion of the reaction, the obtained ink repellent agent (C) can be added to the positive photosensitive resin composition of the present invention without removing the organic solvent. After removing the organic solvent by a usual method, the ink repellent agent (C) may be isolated and then added to the positive photosensitive resin composition.

The content of the ink repellent agent (C) in the total solid content in the positive photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 6% by mass, and 2 to 3% by mass is particularly preferred. When the content of the ink repellent agent (C) is in the above range, the storage stability of the positive photosensitive resin composition is excellent, and the partition walls of the optical element formed using the positive photosensitive resin composition are Excellent ink repellency and has a smooth surface.

[Solvent (D)]
The positive photosensitive resin composition of the present invention may contain a solvent (D).
By containing a solvent (D), the coating property to the board | substrate of this composition and the adhesiveness with the substrate surface are more excellent. Moreover, ink repellent agent (C) can be made to exist stably in this composition by containing a solvent (D).
The solvent (D) is an alkali-soluble resin (A), a photosensitive agent (B), an ink repellent agent (C), which is contained as an essential component in the positive photosensitive resin composition, and a thermosetting agent (E) which is contained as an optional component. The thermosetting accelerator (F) and other additives are not particularly limited as long as they are uniformly dissolved or dispersed and do not have reactivity with each component 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; 2-methoxyethanol, 2- Cellsorbs such as 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, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, die Lenglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, butyl lactate, γ -Esters such as butyrolactone, 3-methyl-3-methoxybutyl acetate, glycerol triacetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ester And ether, dibutyl ether, diethylene glycol methyl ethyl ether and the like. Other examples include chain hydrocarbons such as n-butane and n-hexane; cyclic saturated hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene, xylene and benzyl alcohol; These may 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 from 5 to 2,000 mass%, preferably from 100 to 100 mass%, based on 100 mass% of the total solid content of the positive photosensitive resin composition. 500 mass% is more preferable.

[Thermosetting agent (E)]
The positive photosensitive resin composition of the present invention may contain a thermosetting agent (E) as an optional component that promotes thermosetting.
The thermosetting agent (E) is preferably at least one selected from the group consisting of amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, and polycarbodiimide compounds.
As the amino resin, a compound obtained by hydroxymethylating a part or all of an amino group such as a melamine compound, a guanamine compound or a urea compound, or a part or all of the hydroxyl group of the hydroxymethylated compound is methanol, ethanol , A compound etherified with n-butyl alcohol, 2-methyl-1-propanol and the like, for example, hexamethoxymethylmelamine and the like.

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, trisphenol methane type epoxy resin, brominated epoxy resin and the like glycidyl ethers; Cycloaliphatic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether; glycidyl such as diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate Esters; Tetraglycidyldiaminodiphenylmethane, glycidylamines such as triglycidylparaaminophenol; Heterocyclic forms such as triglycidyl isocyanurate Epoxy resin; and the like.

Examples of the oxazoline compound include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl And copolymers of polymerizable monomers such as -4-methyl-2-oxazoline.
These compounds may be used individually by 1 type, or may use 2 or more types together.

As the thermosetting agent (E), a compound having two or more epoxy groups in one molecule is particularly preferable. By including the thermosetting agent (E) in the positive photosensitive resin composition, the positive photosensitive resin composition is more excellent in curability at the time of exposure and forms a stable partition after thermosetting. Can do.

The content of the thermosetting agent (E) in the total solid content in the positive photosensitive resin composition of the present invention is preferably 5 to 20% by mass, particularly preferably 10 to 15% by mass. Within the above range, when a cured film having partition walls is formed using the positive photosensitive resin composition, the wettability of ink other than the partition wall surface (dots) is more excellent.

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

A thermosetting accelerator (F) is a compound which has the effect | action which forms a crosslinked structure in positive type photosensitive resin composition by heating.
As the thermosetting accelerator (F), for example, a compound that itself reacts with the thermosetting agent (E) and crosslinks to form a crosslinked structure, or the thermosetting agent (E) does not crosslink itself. Examples thereof include compounds having a catalytic action.
When using an epoxy compound as the thermosetting agent (E), examples of the thermosetting accelerator (F) that forms a crosslinked structure include polyamines, polythiols, and polycarboxylic acid anhydrides. More specifically, as polyamines, ethylenediamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylenepolyamine, isophoronediamine, mensendiamine, 3,9-bis (3-aminopropyl) ) -2,4,8,10-tetraoxaspiro (5,5) undecane. Examples of polythiols include polyether polythiol and polycarboxylic acid anhydrides such as hydrosuccinic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the like.
Examples of those having a catalytic action include curing catalysts such as tertiary amines, imidazoles, Lewis acids, onium salts, dicyandiamides, organic acid dihydrazides, and phosphines. More specifically, 2-methylimidazole, 2-ethyl-4-methylimidazole, tris (dimethylaminomethyl) phenol, boron trifluoride-amine complex, dicyandiamide, diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate Etc.
A thermosetting accelerator (F) may use these 1 type independently, or may use 2 or more types together.

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

[Colorant (G)]
When the positive photosensitive resin composition of the present invention is used for forming a black matrix that is a grid-like black portion surrounding the three color pixels R, G, and B of a color filter of a liquid crystal display element, (G) is preferably included.
Examples of the colorant (G) include carbon black, aniline black, anthraquinone black pigment, and perylene black pigment. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned. As the colorant (G), a mixture of organic pigments such as red pigments, blue pigments, green pigments, and inorganic pigments can also be used.

When the positive photosensitive resin composition of the present invention contains the colorant (G) and is used for black matrix formation or the like, the content of the colorant (G) in the total solid content in the positive photosensitive resin composition Is preferably 15 to 65% by mass, particularly preferably 20 to 50% by mass. Within the above range, the positive photosensitive resin composition has excellent sensitivity, and the formed partition wall has excellent light shielding properties.

When the positive photosensitive resin composition of the present invention contains a dispersible material such as the colorant (G), in order to improve the dispersibility, a polymer dispersant, a dispersion aid, etc. It may contain. These can be contained in the positive photosensitive resin composition in such a content that does not impair the effects of the present invention.

[Silane coupling agent (H)]
The positive photosensitive resin composition of the present invention may contain a silane coupling agent (H) as necessary. By containing a silane coupling agent (H), the board | substrate adhesiveness of the cured film formed is more excellent.
Examples of the silane coupling agent (H) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane. , 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and the like. These may be used alone or in combination of two or more.

The content of the silane coupling agent (H) in the total solid content in the positive photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass. When it is at least the lower limit of the above range, the substrate adhesion of the cured film formed from the positive photosensitive resin composition is more excellent, and when it is at most the upper limit of the above range, the ink repellency of the cured film is good. is there.

[Fine particles (I)]
The positive photosensitive resin composition of the present invention may contain fine particles (I) as necessary. By containing the fine particles (I), the thermal sag of the partition formed using the positive photosensitive resin composition can be prevented.

The fine particles (I) are not particularly limited, and inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO); polyethylene, polymethyl methacrylate (PMMA) and the like Organic fine particles are exemplified. From the viewpoint of heat resistance, inorganic fine particles are preferable, and from the viewpoint of availability and dispersion stability, silica or zirconia is particularly preferable.
Further, when the positive photosensitive resin composition contains the colorant (G) and the polymer dispersant, the fine particles (I) are negatively charged in consideration of the adsorption ability of the polymer dispersant. It is preferable.
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 at the time of exposure, i-line (365 nm) which is the main emission wavelength of the ultra-high pressure mercury lamp, It is particularly preferable not to absorb h-line (405 nm) and g-line (436 nm).

The average particle diameter of the fine particles (I) is preferably 1 μm or less, and particularly preferably 200 nm or less, from the viewpoint that the surface smoothness of the partition wall is improved. Among these, the average particle diameter is most preferably 5 to 100 nm.
The content of the fine particles (I) in the total solid content in the positive photosensitive resin composition of the present invention is preferably 5 to 35% by mass, particularly preferably 10 to 30% by mass. When the content is not less than the lower limit of the above range, there is an effect of suppressing the decrease in ink repellency, and when it is not more than 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, as other additives, a thickener, a plasticizer, an antifoaming agent, a leveling agent, and a repellency inhibitor are added as necessary, as long as the effects of the present invention are not impaired. And one or more selected from the group consisting of ultraviolet absorbers.

[Method for producing positive photosensitive resin composition]
As a method for producing a positive photosensitive resin composition, an alkali-soluble resin (A), a photosensitive agent (B), an ink repellent agent (C), if necessary, a solvent (D), a thermosetting agent (E), A method of mixing with the thermosetting accelerator (F), the colorant (G), the silane coupling agent (H), the fine particles (I), and other additives is preferable.
The mixing is performed using a stirrer at a temperature of 20 ° C. to 25 ° C. and for a time of 3 hr to 6 hr, and the obtained composition is used as it is.

The positive photosensitive resin composition of the present invention is used as a material such as photolithography in the same manner as an ordinary positive photosensitive resin composition, and the obtained cured film is an ordinary positive photosensitive resin composition. It can be used as a member of an optical element in which a cured film is used.

[Partition and manufacturing method thereof]
The partition of this invention is a partition formed in order to provide a division on a board | substrate, Comprising: The positive photosensitive resin composition of the said this invention is apply | coated, and it consists of a cured film formed by drying and hardening.
The partition of the present invention is suitably used for an optical element. When the positive photosensitive resin composition contains a colorant (G), the resulting partition can be applied as a black matrix. .
The partition of the present invention is applied to a partition for an optical element having, for example, a plurality of pixels and a partition located between adjacent pixels on a substrate.

Examples of a method for producing a partition for an optical element using the positive photosensitive resin composition of the present invention include the following methods.

The positive photosensitive resin composition of the present invention is applied onto a substrate to form a coating film (coating film forming process), and then the coating film is dried to form a film (prebaking process). Only the part which does not become a partition is exposed (exposure process), and then the exposed part of the coating film is removed to form a partition consisting of an unexposed part of the coating film (development process). Next, the partition walls for the optical element of the present invention can be manufactured by further thermally curing the formed partition walls and the like as necessary (post-baking step).

The material of the substrate is not particularly limited, but various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, polymethacrylic resin, acrylic resin, etc. Thermoplastic plastic sheet; Cured sheet of thermosetting resin such as epoxy resin and unsaturated polyester; etc. can be used. In particular, a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance. Moreover, it is preferable that it is a transparent substrate.

The shape of the substrate and the surface on which the partition walls are formed are not particularly limited and are appropriately selected depending on the application. When the substrate is plate-shaped, it may be a flat plate, or the entire surface or a part thereof may have a curvature. The thickness of the substrate can be appropriately selected depending on the use of the partition wall, but is generally preferably 0.5 to 10 mm.

In the substrate used in the present invention, it is preferable that the surface on which the positive photosensitive resin composition is applied is previously cleaned by alcohol cleaning, ultraviolet / ozone cleaning, or the like.

FIG. 1 is a cross-sectional view schematically showing a production example of an optical element partition using the positive photosensitive resin composition of the present invention.
FIG. 1I is a view showing a cross section in a state where a coating film 2 made of the positive photosensitive resin composition of the present invention is formed on a substrate 1.
FIG. 1 (II) schematically shows the exposure process.
FIG. 1 (III) is a cross-sectional view showing the substrate 1 after the development process and the partition wall 6 formed on the substrate.
Hereinafter, the manufacturing method of the partition for optical elements using the positive photosensitive resin composition of this invention is demonstrated concretely using FIG.

(Coating film formation process)
As shown in FIG. 1 (I), the positive photosensitive resin composition of the present invention is applied onto a substrate 1 to form a coating film 2 made of the positive photosensitive resin composition.

The coating method of the positive photosensitive resin composition is not particularly limited as long as a coating film having a uniform film thickness is formed. Spin coating, spraying, slit coating, roll coating, spin coating The method used for normal coating-film formation, such as a method and a bar coating method, is mentioned.
The film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained. The film thickness of the coating film 2 is preferably 100 to 200%, particularly preferably 100 to 130% of the height of the partition wall finally obtained. The thickness of the coating film 2 is preferably from 0.3 to 325 μm, particularly preferably from 1.3 to 65 μm.

(Pre-baking process)
The coating film 2 formed on the substrate 1 in the 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-sticky film is obtained. Further, the ink repellent agent (C) moves to the vicinity of the film surface.
As a heating method, the coating film 2 together with the substrate 1 is heated at 50 to 120 ° C., preferably 70 to 110 ° C. for 10 to 2,000 seconds, preferably about 30 to 180 seconds by a heating device such as a hot plate or oven. The method of heat-processing is mentioned.

In order to remove volatile components such as a solvent, a drying process such as vacuum drying other than heating (drying) may be separately provided before the pre-baking process. Further, in order to efficiently dry the coating film without causing unevenness in the appearance of the coating film, it is more preferable to use heating combined with drying by the pre-baking step and vacuum drying in combination. The conditions for vacuum drying vary depending on the type of each component, the blending ratio, and the like, but can be performed at 500 to 10 Pa in a wide range of about 10 to 300 seconds.

(Exposure process)
As shown in FIG. 1 (II), the film 2 is irradiated with light 5 through a mask 4 having a predetermined pattern. Only the predetermined pattern portion cut by the mask 4 transmits the light 5 and reaches the film 2 on the substrate 1. Since only the exposed portion is alkali-solubilized, the predetermined pattern is provided in a shape that matches the shape of the partition. The average width of the partition walls after the post-baking step is preferably 100 μm or less, and particularly preferably 20 μm or less. Moreover, it is preferable that the average of the distance between adjacent partition walls will be 300 micrometers or less, and 100 micrometers or less are especially preferable. As the mask 4, it is preferable to use a mask in which a pattern is formed so as to be in this range.

In FIG. 1 (II), the exposed portion of the film irradiated with light becomes a solubilized portion of the positive photosensitive resin composition, while the unexposed portion 3 is the film 2 itself of the positive photosensitive resin composition. It is a state.

The irradiation light 5 is visible light; ultraviolet light; far ultraviolet light; excimer laser such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser; X-ray; Examples include lines. The irradiation light 5 is preferably an electromagnetic wave having a wavelength of 100 to 600 nm, more preferably a light ray having a distribution in the range of 300 to 500 nm, particularly i-line (365 nm), h-line (405 nm) and g-line (436 nm). preferable.

As the irradiation device (not shown), a known ultra-high pressure mercury lamp, deep UV lamp, or the like can be used. Exposure is preferably 5 ~ 1,000mJ / cm ^2, particularly preferably 50 ~ 400mJ / cm ^2. When the exposure amount is at least the lower limit of the above range, the solubility of the solubilized portion of the positive photosensitive resin composition in the developer becomes sufficient, and development residues are eliminated. A high resolution is obtained when it is not more than the upper limit of the above range.
The exposure time 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 process)
Development is performed using a developer, and the exposed portion on the substrate 1 shown in FIG. 1 (II) is removed. Thereby, the structure of the partition 6 formed by the film | membrane of the positive photosensitive resin composition on the board | substrate 1 and the said board | substrate as FIG. 1 (III) shows sectional drawing is obtained. A portion surrounded by the partition wall 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 an optical element in an ink jet system through a post-bake process described later.

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

The development time (time for contact with the developer) is preferably 5 to 180 seconds, and more preferably 10 to 60 seconds.
Examples of the developing method include a liquid piling method, a dipping method, and a shower method. After the development, water on the substrate 1 and the partition wall 6 can be removed by performing high-pressure water washing or running water washing and air-drying with compressed air or compressed nitrogen.

(Post bake process)
As a post-bake process, the partition 6 on the substrate 1 is heated. Examples of the heating method include a method in which the partition wall 6 together with the substrate 1 is heated at 150 to 250 ° C. for 5 to 90 minutes by a heating device such as a hot plate or an oven.
By heating, the partition walls 6 made of a cured film of the positive photosensitive resin composition on the substrate 1 are further cured, and the shape of the dots 7 surrounded by the partition walls 6 and the substrate 1 is further fixed. The heating temperature is particularly preferably 180 ° C. or higher. If the heating temperature is too low, the partition wall 6 is not sufficiently cured and sufficient chemical resistance cannot be obtained. When ink is injected into the dots 7 in an ink injection process described later, the partition wall 6 may swell or the ink may ooze depending on the solvent contained in the ink. On the other hand, if the heating temperature is too high, thermal decomposition of the partition wall 6 may occur.

The average width of the partition walls to be formed is preferably 100 μm or less, particularly preferably 20 μm or less. Of these, 5 to 20 μm is most preferable.
In addition, the average distance between adjacent barrier ribs (dot width) is preferably 300 μm or less, and particularly preferably 100 μm or less. Of these, 30 to 80 μm is most preferable.
Further, the average height of the partition walls is preferably 0.05 to 50 μm, particularly preferably 0.2 to 10 μm.

[Method for Manufacturing Optical Element]
In the optical element of the present invention, after the partition wall is formed on the substrate by the above-described manufacturing method, for example, the exposed substrate surface in the region surrounded by the substrate and the partition wall is subjected to an ink affinity treatment (ink affinity treatment). Processing step), and then the ink is injected into the region by an ink jet method to form the pixel (ink injection step).

(Ink affinity process)
Examples of the lyophilic process include a cleaning process using an alkaline aqueous solution, an ultraviolet cleaning process, an ultraviolet / ozone cleaning process, an excimer cleaning process, a corona discharge process, and an oxygen plasma process.
The cleaning process with an alkaline aqueous solution is a wet process in which the substrate surface is cleaned with an alkaline aqueous solution (potassium hydroxide, tetramethyl ammonium hydroxide aqueous solution, or the like).
The ultraviolet cleaning process is a dry process for cleaning the substrate surface using ultraviolet rays.
The ultraviolet / ozone cleaning process is a dry process that cleans the substrate surface using a low-pressure mercury lamp that emits light of 185 nm and 254 nm.
The excimer cleaning process is a dry process that cleans the substrate surface using a xenon excimer lamp that emits light of 172 nm.
The corona discharge treatment is a dry treatment that uses a high-frequency high voltage to generate corona discharge in the air and cleans the substrate surface.
The oxygen plasma treatment is a dry treatment in which the surface of the substrate is cleaned using a highly reactive “plasma state” in which oxygen is excited by using a high frequency power source or the like as a trigger in vacuum.

As a method for the ink-philic treatment, a dry treatment method such as an ultraviolet / ozone cleaning treatment is preferable because it is simple. UV / ozone can be generated using commercially available equipment.
The ink-repellent treatment is performed by installing a substrate with partition walls inside the ultraviolet / ozone device and performing treatment in air and at room temperature for about 1 to 10 minutes within a range that does not impair the oil repellency of the partition walls. Can do. In addition, what is necessary is just to adjust processing time so that it may become the range which does not impair the ink repellency of a partition according to each ultraviolet-ray / ozone apparatus.

A color display device using an optical element that can sufficiently measure the ink-inking of the dots by sufficiently removing the development residue remaining on the dots after the partition is formed by the ink-inking treatment. It is possible to prevent white spots such as the above. In addition, if the partition formed using the positive photosensitive resin composition of the present invention is used, it is possible to make the ink affinity by the ultraviolet cleaning treatment or the like without reducing the ink repellency of the partition. is there.

Here, the ink repellency (water / oil repellency) of the cured film formed from the positive photosensitive resin composition is water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent often used as a solvent for the ink. ) And the contact angle can be estimated.
When an optical element is produced using a substrate having partition walls formed using the positive photosensitive resin composition of the present invention, the partition walls are required to have sufficient ink repellency even after the above-mentioned ink-philic treatment. It is done. The water contact angle of the partition walls is preferably 90 ° or more, and particularly preferably 95 ° or more. Further, the contact angle of PGMEA of the partition wall is preferably 30 degrees or more, and particularly preferably 35 degrees or more.
On the other hand, when manufacturing an optical element using a substrate having a partition formed using the positive photosensitive resin composition of the present invention, the dots are required to be ink-philic, and contact with water. The angle is preferably 20 degrees or less, particularly preferably 10 degrees or less.

(Ink injection process)
This is a step of forming pixels by injecting ink into the dots after the ink-philic processing step by an ink jet method.
This step can be performed in the same manner as a normal method using an ink jet apparatus generally used in the ink jet method. The ink jet device used for forming such pixels is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, and ink is ejected intermittently using a piezoelectric element. An ink jet apparatus using various methods such as a method, a method of heating ink, and a method of intermittently ejecting the ink using the bubbling can be used.

Examples of optical elements produced using the positive photosensitive resin composition of the present invention include color filters, organic EL elements, and organic TFT arrays.

[Manufacture of color filters]
The formation of the partition walls, the process of making dots ink-philic, and the ink injection by the ink jet method are as described above.
In the color filter, the shape of the pixel to be formed can be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.

The ink used for forming the pixel mainly includes a coloring component, a binder resin component, and a solvent.
As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin.
The water-based ink contains water and optionally a water-soluble organic solvent as a solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary.
The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
After the ink is injected by the ink jet method, it is preferable to perform drying, heat curing, and / or ultraviolet curing as necessary.

After the pixels are formed, a protective film layer is formed using an overcoat coating solution as necessary.
The protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer.
When forming the protective film layer, it is preferable to remove the ink repellency of the partition wall in advance. If the ink repellency is not removed, the overcoat coating solution is repelled, and a uniform film thickness cannot be obtained.
Examples of the method for removing the ink repellency of the partition include plasma ashing and light ashing.
Further, if necessary, it is preferable to form a photo spacer on a black matrix composed of partition walls in order to improve the quality of a liquid crystal panel manufactured using a color filter.

[Manufacture of organic EL elements]
Before forming the partition 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 a sputtering method or the like. The transparent electrode is etched into a desired pattern. Next, a partition is formed using the positive photosensitive resin composition of the present invention, the ink is made into an ink, and then a hole transport material and a light emitting material solution are sequentially applied to the dots using an inkjet method. And dried to form a hole transport layer and a light emitting layer. Then, the pixel of an organic EL element is obtained by forming electrodes, such as aluminum, by a vapor deposition method etc.

[Manufacture of organic TFT array]
An organic TFT array can be manufactured through the following steps (1) to (3).
(1) A partition wall is formed on a transparent substrate such as glass using the positive photosensitive resin composition of the present invention. Next, after the dot is made ink-insensitive, a solution of a gate electrode material is applied to the dots using an inkjet method to form a gate electrode.
(2) After forming the gate electrode, a gate insulating film is formed thereon. Next, a partition is formed on the gate insulating film using the positive photosensitive resin composition of the present invention, and after the dot is made to be an ink-inking solution, a solution of the source / drain electrode material is formed on the dot using an inkjet method. Is applied to form source / drain electrodes.
(3) After the source / drain electrodes are formed, partition walls are formed using the positive photosensitive resin composition of the present invention so as to surround a region including the pair of source / drain electrodes. Next, after the dot is made into an ink-inking process, an organic semiconductor solution is applied to the dots using an inkjet method, and an organic semiconductor layer is formed between the source and drain electrodes.
In the steps (1) to (3), the partition using the positive photosensitive resin composition of the present invention may be formed and used in only one step, or in two or more steps. A partition using the positive photosensitive resin composition of the present invention may be formed and used.

The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited to these examples.
Examples 1 to 4 are examples, and example 5 is a comparative example.

Each measurement was performed by the following method.
[Number average molecular weight (Mn)]
Gel permeation chromatography (GPC) of several types of monodisperse polystyrene polymers with different degrees of polymerization, which are commercially available as standard samples for molecular weight measurement, were prepared using a commercially available GPC measuring device (manufactured by Tosoh Corporation, device name: HLC-8320GPC). ), And a calibration curve was created based on the relationship between the molecular weight of polystyrene and the retention time (retention time).
The sample was diluted to 1.0% by mass with tetrahydrofuran and passed through a 0.5 μm filter, and then GPC of the sample was measured using the GPC measurement apparatus.
The number average molecular weight (Mn) of the sample was determined by computer analysis of the GPC spectrum of the sample using the calibration curve.

[Water contact angle]
In accordance with JIS R3257 “Testing method for wettability of substrate glass surface”, water droplets were placed on three measurement surfaces on the substrate by a sessile drop method, and each water droplet was measured. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. The contact angle is indicated by an average value of three measured values (n = 3).

[PGMEA contact angle]
According to JIS R3257 “Test method for wettability of substrate glass surface”, PGMEA droplets were placed at three locations on the measurement surface on the substrate, and each PGMEA droplet was measured. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. The contact angle is indicated by an average value of three measured values (n = 3).

Abbreviations of the compounds used in Synthesis Examples 1 to 5 and Examples 1 to 5 are as follows.
(Alkali-soluble resin (A))
EP4020G (trade name; EP4020G, manufactured by Asahi Organic Materials Co., Ltd., cresol novolak resin (mass average molecular weight (Mw): 11,600, dissolution rate: 164 (angstrom / second)).

(Photosensitive agent (B))
4NT-250 (trade name; 4NT-250, manufactured by Toyo Gosei Co., Ltd. (2,3,4,4′-tetrahydroxybenzophenone and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid) (Mono-tetra) esters)).

(Hydrolyzable silane compound as a raw material for the ink repellent agent (C))
Compound (c-11) corresponding to the hydrolyzable silane compound (c-1): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (manufactured by Asahi Glass Co., Ltd.).
Compound (c-21) corresponding to the hydrolyzable silane compound (c-2): Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat).
Compound (c-31) corresponding to the hydrolyzable silane compound (c-3): C ₆ H ₅ Si (OC ₂ H ₅ ) ₃ (manufactured by Shin-Etsu Chemical Co., Ltd.).
Compound (c-32) corresponding to the hydrolyzable silane compound (c-3): C ₆ H ₅ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (manufactured by Shin-Etsu Chemical Co., Ltd.).
_{C6FMA: CH 2 = C (CH} 3) COOCH 2 CH 2 (CF 2) 6 F.
MEK: methyl ethyl ketone.
MAA: methacrylic acid.
GMA: glycidyl methacrylate.
MMA: methyl methacrylate.
V-65: (trade name, manufactured by Wako Chemical Industries, Ltd. (2,2′-azobis (2.4dimethylvaleronitrile) (polymerization initiator)).

(Solvent (D))
PGMEA: Propylene glycol monomethyl ether acetate.
PGME: Propylene glycol monomethyl ether (manufactured by Toho Chemical Co., Ltd.).
(Thermosetting agent (E))
TEP-G (trade name; TEP-G, manufactured by Asahi Organic Materials Co., Ltd., epoxy resin).
(Thermosetting accelerator (F))
2-MI (trade name, manufactured by Tokyo Chemical Industry Co., Ltd. (2-methylimidazole)).

[Synthesis Examples 1 to 3: Synthesis of ink repellent agents (CA1) to (CA3) and preparation of (CA1-1) to (CA3-1) solutions]
In a 50 cm ³ three-necked flask equipped with a stirrer, 0.57 g of the compound (c-11), 1.27 g of the compound (c-21), and 0.74 g of the compound (c-31) were placed. Thus, a raw material mixture of the ink repellent agent (C1) was obtained. Next, 9.85 g of PGME was added to the raw material mixture to prepare a solution (raw material solution).
To the obtained raw material solution, 1.33 g of 1.0 mass% phosphoric acid aqueous solution was dropped as a catalyst while stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 5 hours to conduct hydrolysis and partial condensation reaction to obtain a (CA1-1) solution that was a PGME solution containing 10% by mass of the ink repellent agent (CA1).
The same procedure as in Synthesis Example 1 was performed except that 1.33 g of the catalyst shown in Table 1 was used instead of the 1.0 mass% phosphoric acid aqueous solution as the catalyst, and the ink repellent agents (CA2) to (CA3) were added at 10 mass%. The (CA2-1) to (CA3-1) solutions that are PGME solutions contained were obtained.

[Synthesis Example 4: Synthesis of ink repellent agent (CA4) and preparation of (CA4-1) solution]
A raw material solution of an ink repellent agent (CA4) was prepared in the same manner as in Synthesis Example 1 except that the compound (c-32) was used in place of the compound (c-31).
0.93g of 1.0 mass% nitric acid aqueous solution was dripped at the obtained raw material solution, stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 5 hours to conduct hydrolysis and partial condensation reaction, thereby obtaining a (CA4-1) solution that was a PGME solution containing 10% by mass of the ink repellent agent (CA4).

[Synthesis Example 5: Preparation of ink repellent (CA5) and (CA5-1) solutions]
In an autoclave with an internal volume of 1000 cm ³ equipped with a stirrer, 420.0 g of MEK, 86.4 g of C6FMA, 18.0 g of MAA, 21.6 g of GMA, 54.0 g of MMA and 0.8 g of V-65 And a polymerization reaction was carried out at 50 ° C. for 24 hours while stirring under a nitrogen atmosphere to synthesize a crude copolymer. Hexane was added to the resulting crude copolymer solution for reprecipitation, purification, and vacuum drying. To the obtained solid, 14,643 g of PGMEA was added and stirred to obtain a (CA5-1) solution that was a PGMEA solution containing 10% by mass of the ink repellent agent (CA5).

Compositions prepared by the synthesis examples 1 to 5 except for the solvents (CA1-1) to (CA5-1) containing the ink repellent agent at 10% by mass, that is, the ink repellent agent (CA1). Table 1 shows the fluorine-containing content (mass% of fluorine atoms) and number average molecular weight (Mn) of (CA5).
In addition, Table 1 shows the charged amount compositions (mol%) of the ink repellent agents (CA1) to (CA5).

[Example 1]
(Manufacture of positive photosensitive resin composition 1)
1 g of (CA1-1) solution (solid content is 0.1 g, the rest is PGME (solvent)), 15.6 g of EP4020G, 5.4 g of 4NT-250, 3.1 g of TEP-G, 2-MI 0.8 g and 74.1 g of PGMEA were put in a 500 cm ³ stirring container and stirred for 30 minutes to prepare a positive photosensitive resin composition 1.

(Manufacture of cured film)
A 10 cm square glass substrate was ultrasonically cleaned with ethanol for 30 seconds, and then subjected to ultraviolet / ozone cleaning for 5 minutes. For UV / ozone cleaning, PL7-200 (manufactured by Sen Engineering) was used as an UV / ozone generator. In addition, this apparatus was used as an ultraviolet / ozone generator for all the following ultraviolet / ozone treatments.

The positive photosensitive resin composition 1 was applied to the cleaned glass substrate surface using a spinner and then dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1.3 μm. On the surface of the obtained film, a gap of 50 μm is opened from the film side through a photomask having a hole pattern (2.5 cm × 5 cm) (a photomask in which light is irradiated to the area of the pattern portion), Ultraviolet light from a high-pressure mercury lamp was irradiated at 25 mW / cm ² for 10 seconds.

Then, the exposed glass substrate was developed by immersing in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 40 seconds, and the exposed film was washed with water and dried. Next, this was heated on a hot plate at 230 ° C. for 20 minutes to obtain a glass substrate 1 in which a cured film of the positive photosensitive resin composition 1 was formed in a region excluding the hole pattern portion.

(Evaluation)
The following evaluation was performed about the glass substrate 1 in which the positive photosensitive resin composition 1 obtained above and the cured film (partition) were formed.
<Ink repellency (partition wall), ink affinity (dot), and development residue>
The contact angle with respect to PGMEA of the cured film of the obtained glass substrate 1, that is, the partition wall surface (unexposed part), and the contact angle with respect to water of the part where the film was removed by development, that is, the dot part (glass substrate surface) were measured. . At this time, the development residue was evaluated based on the contact angle of the dot portion with water. Evaluation was performed as follows.
○ (Good): Water contact angle is less than 30 degrees.
X (defect): The contact angle of water is 30 degrees or more.
Thereafter, the entire surface of the glass substrate 1 on which the cured film was formed was irradiated with ultraviolet rays / ozone for 1 minute. The contact angle with PGMEA on the surface of the cured film after irradiation for 1 minute and the contact angle with water on the surface of the glass substrate were measured. The measurement method is as described above. The evaluation results are shown in Table 2.

<Storage stability>
The positive photosensitive composition was stored in a glass screw bottle at 23 ° C. (room temperature) for one month. After storage for one month, a positive photosensitive composition was applied to the surface of a 10 cm × 10 cm glass substrate washed in the same manner as in Example 1 using a spinner to form a coating film. Subsequently, it was dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1 μm. The appearance of the film was visually observed and evaluated as follows.
○ (good): The number of foreign matters on the film is 5 or less.
X (defect): There were 6 or more foreign matters on the film, and radial streaks were observed from the center of the glass substrate.

[Examples 2 to 5]
In the same manner as in Example 1 except that the (CA2-1) to (CA5-1) liquids shown in the table were used instead of the (CA1-1) liquid, positive type photosensitive resin compositions 2 to 5 and positive type were used. Glass substrates 2 to 5 on which cured films of the photosensitive resin compositions 2 to 5 were formed were prepared and evaluated in the same manner as in Example 1.
The results are summarized in Table 2. The compositions of the compositions obtained in Examples 1 to 5 are also shown in Table 2.

As can be seen from Table 2, the positive photosensitive resin compositions obtained in Examples 1 to 4 are excellent in storage stability. By using the composition, it is possible to obtain a partition wall having no development residue. The cured films obtained in Examples 1 to 4 were excellent in ink repellency because of using the ink repellent agent of the present invention, excellent in ink repellency even after UV / ozone irradiation, and excellent in dot (glass substrate surface). It can be seen that it has ink affinity.
On the other hand, the cured film obtained in Example 5 using an ink repellent agent not according to the present invention had insufficient ink repellency after ultraviolet / ozone irradiation.

The positive photosensitive resin composition of the present invention is excellent in ink repellency, has excellent ink repellency even after being irradiated with ultraviolet rays / ozone, and can produce a partition wall with little residue in dots. It can be suitably used for the formation of partition walls in the production of color filters using the recording technique, the production of organic EL elements, and the production of organic TFT arrays, and is particularly suitable for the formation of partition walls on large-area substrates.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2012-053448 filed on March 9, 2012 are cited herein as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Coating film of positive type photosensitive resin composition, 3 ... Unexposed part of coating film, 4 ... Mask, 5 ... Light, 6 ... Partition, 7 ... Dot, 10 ... Optical element used for inkjet system Substrate

Claims (15)

1. A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B) and an ink repellent agent (C),
   Partial hydrolysis of a mixture in which the ink repellent agent (C) includes a hydrolyzable silane compound represented by the following formula (c-1) and a hydrolyzable silane compound represented by the following formula (c-2) A positive photosensitive resin composition comprising a condensate and having a fluorine atom content of 10 to 55% by mass in the ink repellent agent (C).
   

   

   
   (The symbols in formulas (c-1) and (c-2) are as follows.
   R ^f : a perfluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group having 2 to 40 carbon atoms represented by R ^f1 OR ^f2 — (wherein R ^f1 is a perfluorocarbon having 1 to 6 carbon atoms) An alkyl group, and R ^f2 is a perfluoroalkylene group which may have an etheric oxygen atom between carbon-carbon atoms).
   Q ¹ : a divalent organic group not containing a fluorine atom having 1 to 10 carbon atoms,
   R ^H1 : a monovalent hydrocarbon group having 1 to 6 carbon atoms,
   X ¹ and X ² : hydrolyzable groups,
   p: 0, 1 or 2.
   However, three X ^{1 s in} the formula (c-1), (4-p) X ^{2 s} in the formula (c-2), and p ^{RH 1 s} may be the same or different from each other. There may be. )
2. The positive photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble resin (A) in the total solid content in the positive photosensitive resin composition is 10 to 90% by mass.
3. The positive photosensitive resin composition according to claim 1 or 2, wherein the content of the photosensitive agent (B) in the total solid content of the positive photosensitive resin composition is 0.1 to 50% by mass.
4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the ink repellent agent (C) in the total solid content of the positive photosensitive resin composition is 0.01 to 10% by mass. Resin composition.
5. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the number average molecular weight (Mn) of the ink repellent agent (C) is 500 or more and less than 1,000,000.
6. The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (A) is a novolac type phenol resin.
7. The positive photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) is a compound having a quinonediazide group.
8. The positive photosensitive resin composition according to any one of claims 1 to 7, wherein the mixture further contains a hydrolyzable silane compound represented by the following formula (c-3).
   

   

   
   (The symbols in formula (c-3) are as follows.
   Y: a hydrogen atom, a phenyl group optionally 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,
   Q ² : single bond or divalent organic group,
   R ^H2 : monovalent hydrocarbon group having 1 to 6 carbon atoms,
   X ³ : hydrolyzable group,
   q: 1 or 2,
   r: a number that is 0 or 1 and q + r is 1 or 2.
   However, q pieces of Y, ^{Q 2,} and ^{Y-Q 2,} and (4-q-r) pieces of ^{X 3} may each be the same or different from each other. )
9. The positive photosensitive resin composition according to any one of claims 1 to 8, further comprising a solvent (D).
10. The positive photosensitive resin composition according to any one of claims 1 to 9, further comprising a thermosetting agent (E).
11. The positive photosensitive resin composition according to claim 10, further comprising a thermosetting accelerator (F).
12. The positive photosensitive resin composition according to any one of claims 1 to 11, further comprising a colorant (G).
13. A partition formed in a shape that partitions the substrate surface into a plurality of sections for pixel formation,
    A partition comprising a cured film of the positive photosensitive resin composition according to any one of claims 1 to 12.
14. An optical element having a plurality of pixels and a partition located between adjacent pixels on the substrate surface, wherein the partition is formed by the partition according to claim 13.
15. The optical element according to claim 14, wherein the optical element is a color filter, a TFT array, or an organic EL element.

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