KR101998447B1

KR101998447B1 - Positive photosensitive resin composition, partition wall and optical element

Info

Publication number: KR101998447B1
Application number: KR1020147024842A
Authority: KR
Inventors: 마사유키 가와시마; 히데유키 다카하시; 유타카 후루카와
Original assignee: 에이지씨 가부시키가이샤
Priority date: 2012-03-09
Filing date: 2013-03-07
Publication date: 2019-07-09
Also published as: WO2013133392A1; TW201344366A; JP6098635B2; KR20140134662A; CN104160336B; TWI575320B; CN104160336A; JPWO2013133392A1

Abstract

A positive photosensitive resin composition which is excellent in ink-repellency, excellent in ink property even after being subjected to ultraviolet / ozone irradiation treatment, and capable of producing a partition wall having few residues in dots, is a positive type photosensitive resin composition having sufficient storage stability Providing a photosensitive resin composition, a partition wall formed by using the resin composition, and an optical element. 1. A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitizer (B) and a repellent agent (C), wherein the repellent agent (C) is a partial photopolymerizable compound of a mixture containing a fluorinated hydrolyzable silane compound Wherein the content of fluorine atoms in the hydrolyzable silane compound is 10 to 55% by mass, the partition wall and the optical element formed by using the resin composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a positive photosensitive resin composition, a partition wall and an optical element,

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

[0003] It is known that a partition wall used for a pixel portion of a color filter or an organic EL (Electro-Luminescence) element which is an optical element is formed by coating a photosensitive resin composition on a substrate and forming it by photolithography.

In recent years, as a manufacturing method of a pixel portion of a color filter or an organic EL element, a low-cost process using an ink-jet method has been proposed.

For example, in the manufacture of a color filter, after a partition is formed by photolithography, ink of R (red), G (green) and B (blue) is applied to an opening (dot) And forms a pixel.

In the ink-jet method, it is necessary to prevent mixing of ink between adjacent pixels. Therefore, it is required that the partition wall has a property of bouncing ink including water or an organic solvent, which is a jetting liquid of an ink jet, so-called ink property. On the other hand, an ink layer formed on a pixel by an ink-jet method requires good film thickness uniformity. Therefore, dots surrounded by the partition walls are required to have good wettability with respect to the ejection liquid, that is, so-called ink affinity.

In order to make the surface of the partition wall ink-repellent, a technique of adding a repellent agent to the photosensitive resin composition used for forming barrier ribs has been developed.

The positive photosensitive resin is superior to the negative photosensitive resin in that it has fewer residues after development (hereinafter, also referred to as " developing residue ") and may be preferably used. For example, Patent Document 1 discloses a technique of imparting ink repellency to the surface of a partition wall by using a positive photosensitive resin composition containing a reducing agent having a small surface free energy.

JP-A-2009-251327

However, in the positive-working photosensitive resin composition described in Patent Document 1, there is a problem that the surface transfer property of the ink for ink is insufficient and the ink for ink remains in the inside of the partition, resulting in poor ink affinity on the side of the partition. There has been a problem that the ink remains on the developed dot, the ink can not be applied uniformly, and the discoloration of the ink occurs. In order to clean the dots, ultraviolet / ozone irradiation treatment or the like is used. However, the ink described in Patent Document 1 has insufficient resistance and there is a problem that the ink repellency of the partition walls is considerably lowered.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a dye-sensitized solar cell which is excellent in ink-repellency and excellent in ink- And also to provide a positive-working photosensitive resin composition having excellent properties.

It is another object of the present invention to provide an optical element having excellent ink repellency and having partition walls excellent in ink-repellency even after ultraviolet / ozone irradiation treatment.

The present invention provides a positive photosensitive resin composition, a partition, and an optical element having the following structures [1] to [15].

[1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitizer (B), and a repellent agent (C)

(C) comprises a partial hydrolyzed condensate of a mixture comprising a hydrolyzable silane compound represented by the following formula (c-1) and a hydrolyzable silane compound represented by the following formula (c-2) Wherein the fluorine atom content in the repellent agent (C) is 10 to 55 mass%.

[Chemical Formula 1]

(The symbols in the formulas (c-1) and (c-2) are as follows.

R ^{f is 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 perfluoroalkyl group having 1 to 6 carbon atoms , R ^f2 is a perfluoroalkylene group which may have an etheric oxygen atom between carbon-carbon atoms),

Q ¹ : a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom,

R ^{H1 represents} a hydrocarbon group having 1 to 6 carbon atoms,

X ¹ and X ² : a hydrolyzable group,

p: 0, 1 or 2.

3 X ¹ in formula (c-1), (4-p) X ² in formula (c-2), and p R ^H1 may be the same or different from each other.

[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-working photosensitive resin composition is 10 to 90% by mass.

[3] The positive photosensitive resin composition according to [1] or [2], wherein the content of the photosensitive agent (B) in the total solid content in the positive photosensitive resin composition is 0.1 to 50 mass%.

[4] The positive photosensitive resin composition according to any one of [1] to [3], wherein the content of the repelling ink (C) in the total solid content in the positive photosensitive resin composition is 0.01 to 10% by mass.

[5] The positive photosensitive resin composition according to any one of [1] to [4], wherein the number average molecular weight (Mn) of the repellent agent (C) is 500 or more and less than 1,000,000.

[6] The positive photosensitive resin composition according to any one of [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], 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)

(2)

(The symbols in the formula (c-3) are as follows.

Y is 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 phenyl group optionally substituted with a nitro group,

Q ² : a single bond or a divalent organic group,

R ^H2 : hydrocarbon group having 1 to 6 carbon atoms,

X ³ : hydrolyzable group,

q is 1 or 2,

r is 0 or 1, and q + r is 1 or 2;

Q, Y, Q ² , and YQ ² , and (4 - q - r) X ³ may be mutually different or the same.

[9] The positive photosensitive resin composition according to any one of [1] to [8], further comprising a solvent (D).

[10] The positive photosensitive resin composition according to any one of [1] to [9], further comprising a heat curing agent (E).

[11] The positive photosensitive resin composition according to [10], further comprising a thermal curing accelerator (F).

[12] The positive photosensitive resin composition according to any one of [1] to [11], further comprising a colorant (G).

[13] A barrier rib formed of a cured film of a positive photosensitive resin composition according to any one of [1] to [12], the barrier rib formed in such a manner that the substrate surface is divided into a plurality of sections for pixel formation.

[14] An optical element having a partition wall positioned between a plurality of pixels and adjacent pixels on a surface of a substrate, wherein the partition is formed of the partition described in [13] above.

[15] The optical element according to the above-mentioned [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 and can form barrier ribs having excellent ink-repellency even after ultraviolet / ozone irradiation treatment, and has excellent storage stability.

The optical element of the present invention has excellent ink repellency and has a partition wall excellent in ink repellency even after subjected to an ultraviolet / ozone irradiation treatment, thereby suppressing the occurrence of discoloration and the like, and having good appearance.

1 is a cross-sectional view schematically showing an example of production of a partition for an optical element using the positive photosensitive resin composition of the present invention.

In the present specification, the compound represented by formula (c-1) is referred to as "compound (c-1)". Other compounds are also the same.

The term " total solid content " in the present specification refers to a total of the components other than the volatile components volatilized by heating or the like in the process of forming the partition wall such as the solvent (D) among the components contained in the positive photosensitive resin composition, Lt; / RTI > The positive photosensitive resin composition was heated at 140 占 폚 for 24 hours to remove the solvent and measured as a remnant. Further, the total solid content can also be calculated from the injection amount of each component.

In the present specification, a film coated with a positive photosensitive resin composition is referred to as a " coating film ", a state in which the film is dried, 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. Therefore, the " surface " of the partition does not include the side surface of the partition.

In the present specification, the term " ink " refers generally to liquids having optical and electrical functions, for example, after drying and curing, and is not limited to conventionally used coloring materials. The "pixel" formed by injecting the ink is also used as a partition having optical and electrical functions divided into barrier ribs.

The term " ink repellency " in the present specification refers to a property having appropriate water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later.

Hereinafter, embodiments of the present invention will be described. In the present specification, unless otherwise specified,% represents mass%.

[Alkali-soluble resin (A)]

As the alkali-soluble resin (A) in the positive-working photosensitive resin composition of the present invention, a known alkali-soluble resin used in the positive-working photosensitive resin composition is used.

The alkali-soluble resin (A) functions as a positive photosensitive resin composition when used in combination with a photosensitizer (B) to be described later. That is, in the positive photosensitive resin composition, the photosensitizer (B) is activated in the exposure portion in exposure such as photolithography, and the solubility in a developing solution is increased. The exposed portion is dissolved and removed in a developer (usually an alkaline developer) at the time of development. The portion not irradiated with light (unexposed portion) becomes a partition wall. The alkali-soluble resin (A) is also insoluble in a developer by combining with the photosensitizer (B) before exposure.

Examples of the alkali-soluble resin (A) include non-modified or modified novolac phenol resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, N (N-vinylpyrrolidone), and the like, which are prepared by polycondensation of phenols and aldehydes, - (4-hydroxyphenyl) methacrylamide, and hydroquinone monomethacrylate copolymer. Further, various alkali-soluble polymer compounds such as a sulfonylimide-based polymer, a carboxyl group-containing polymer, an acrylic resin containing a phenolic hydroxyl group, an acrylic resin having a sulfonamide group, and a urethane resin can also be used.

As the alkali-soluble resin (A) in the positive photosensitive resin composition of the present invention, a novolac phenolic resin is preferable.

Examples of the phenol used for producing the novolak-type phenol resin include cresols such as phenol, o-cresol, p-cresol, m-cresol and the like; Xylylenols such as 3,5-xylenol, 2,5-xylenol, 2,3-xylenol, and 3,4-xylenol; Trimethylphenols such as 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,4,5-trimethylphenol and 3,4,5-trimethylphenol; T-butylphenols such as 2-t-butylphenol, 3-t-butylphenol and 4-t-butylphenol; Methoxyphenols such as 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol and 3,5-dimethoxyphenol; Ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,3-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, 3,4,5-triethylphenol Ethylphenol; chlorophenols such as o-chlorophenol, m-chlorophenol, p-chlorophenol, and 2,3-dichlorophenol; Resorcinols such as resorcinol, 2-methyl resorcinol, 4-methyl resorcinol and 5-methyl resorcinol; Catecholates such as 5-methylcatechol; Pyrogallol, such as 5-methyl pyrogallol; Bisphenols such as bisphenol A, B, C, D, E and F; Methylol cresols such as 2,6-dimethylol-p-cresol; naphthols such as? -naphthol and? -naphthol; And the like. These may be used singly or in combination of two or more.

The aldehydes used to prepare the novolac phenolic resin include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, furfural, glyoxal, n- Caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. These may be used singly or in combination of two or more.

Of the novolak type phenolic resins, novolak type phenolic resins using cresols, xylenols, and the like are preferably used as the phenols from the viewpoints of availability and less metal impurities, and novolak type phenol resins (Hereinafter also referred to as " cresol novolak resin ") is particularly preferable.

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 0.5 x 10 ³ to 20 x 10 ³ , and particularly preferably 2 x 10 ³ to 15 x 10 ³ . When the mass average molecular weight (Mw) is within the above range, the solubility in a developer after exposure is excellent.

In this specification, the mass average molecular weight (Mw) means the mass average molecular weight of a standard polystyrene 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) is preferably excellent in solubility in an alkali developing solution. For example, when the dissolution rate (angstrom / second, hereinafter simply referred to as " dissolution rate ") of an aqueous solution of a 2.38% by mass TMAH (tetramethylammonium hydroxide) solution is used as an index for an alkali developer of a positive- 50 to 400 angstroms / second is preferable, and 100 to 200 angstroms / second is particularly preferable. When the dissolution rate is in the above range, the developability of the positive-working photosensitive resin composition is improved.

Commercially available products of the alkali-soluble resin (A) may also be used. (Mw: 9,000 to 14,000, dissolution rate: 160 to 250 angstroms / sec.), EPR5010G (Mw: 7,000 to 12,500, dissolution rate: 50 to 150 angstroms / sec) as a commercial product, all manufactured by Asahi Organic Materials Industry Co., (All cresol novolac resins) and the like.

The alkali-soluble resin (A) in the positive-working photosensitive resin composition of the present invention may be used singly or in combination of two or more.

The content of the alkali-soluble resin (A) in the total solid content in the positive-type photosensitive resin composition is preferably 10 to 90% by mass, and particularly preferably 30 to 80% by mass. When the content is in the above range, the developability of the positive-working photosensitive resin composition is improved.

[Photosensitive Agent (B)]

As the photosensitizer (B) in the positive photosensitive resin composition of the present invention, a known photosensitizer used in the positive photosensitive resin composition is used.

As the photosensitizer (B), a compound having a quinonediazide group is preferable. As the compound having a quinonediazide group, a compound having a known quinonediazide group, which is used in combination with a novolac phenolic resin, is used.

Examples of the photosensitizer (B) include complete condensates and partial condensates of a compound (a) having a quinone diazide group and which can be condensed with each other and which will be described later.

The compound? Has a functional group capable of condensation reaction. Examples of the functional group capable of the condensation reaction include a sulfo group, a chlorosulfo group and the like. Examples of the compound? Include sulfonic acids such as benzoquinone diazidesulfonic acid, naphthoquinone diazidesulfonic acid and anthraquinone diazidesulfonic 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- Sulfonic acid chloride, and the like.

The compound [beta] has a functional group capable of condensation with the compound [alpha]. Examples of the functional group capable of the condensation reaction include a hydroxyl group and an amino group, and a hydroxyl group is preferable.

As the compound [beta], a compound having an aromatic ring is preferable because the resulting partition wall is excellent in heat resistance. The number of aromatic rings in the aromatic compound is preferably from 1 to 6, and particularly preferably from 2 to 4, since heat resistance and a large number of hydroxyl groups can be introduced.

As the compound [beta], 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 from 1 to 10, and particularly preferably from 2 to 4.

Specific examples of the compound [beta]

Phenols such as phenol and 4-methylphenol;

Polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone;

Tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1- (4-hydroxyphenyl) benzyl] ethane, bis (4-hydroxy-3-methylphenyl) Hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy- 2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2- hydroxyphenylmethane, bis Dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis Methylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl- Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, 1,3,5-tris (4-hydroxyphenyldimethylbenzyl) And the like;

(2,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis Linear type 3-core phenol compounds;

Bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5- Hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5- Hydroxyphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Hydroxyphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-3- Methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane and the like Morphological or cyclic phenol compound nuclei 4;

Bis [4-hydroxy-3- (4-hydroxvbenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4- 5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy- Linear or cyclic pentene compounds such as linear or cyclic pentene compounds such as methylphenol;

Bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- ( (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- Dihydroxyphenyl) propane, 2- (3,4-dihydroxyphenyl) -2- (3 ', 4'-dihydroxyphenyl) 2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (3'- (Dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- , 3,4-trihydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) propane;

(4'-hydroxyphenyl) ethyl] benzene, 1- [1- (4-hydroxyphenyl) ethyl] Phenyl] isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [ Polynuclear branched compounds such as 1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;

Bis [4'-hydroxyphenylcyclohexyl] -2-bis [1 ', 1'-bis (4'- Hydroxyphenylcyclohexyl)] propane;

1,1'-spiro [1 H-indene] -5,5 ', 6,6'-tetraol, 2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) hydroxy chroman, penta-cyclo [19,3,1,1 ^3,7, 1 ^9,13, 1 ^15,19] octa Kosa -1,3,5,7,9,11,13,15,17,19 , 21,23-dodeca-4,6,10,12,16,18,22,24-octanol, and the like. These may be used singly or in combination of two or more.

As the photosensitizer (B), a complete condensate or a partial condensate of the following compounds a and b is more preferable.

The compounds α: 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-

Compound beta: phenols such as phenol and 4-methylphenol; 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone as polyhydroxybenzophenones; Tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- [?,? -Dimethyl-? - (4'-hydroxyphenyl) benzyl] ethane, 1,3,5-tris (4-hydroxyphenyldimethylbenzyl) benzene;

As the bisphenol compound, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- (3,4-dihydroxyphenyl) -2- (3 ', 4'-dihydroxyphenyl) Propane, 2- (2,4,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) '-Hydroxyphenyl) propane;

1- [1,1-bis (4-hydroxyphenyl) ethyl] -4- [1 ', 1'-bis (4'-hydroxyphenyl) ethyl] benzene as polynuclear branched compound;

Bis [1,1-bis (4-hydroxyphenylcyclohexyl)] - 2-bis [1 ', 1'-bis (4'-hydroxyphenylcyclohexyl)] propane as the condensed phenol compound;

1,1'-spiro [1 H-indene] -5,5 ', 6,6'-tetraol, 2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) hydroxy chroman, penta-cyclo [19,3,1,1 ^3,7, 1 ^9,13, 1 ^15,19] octa Kosa -1,3,5,7,9,11,13,15,17,19 , 21,23-dodeca-4,6,10,12,16,18,22,24-octanol.

As the photosensitizer (B), 1,2-naphthoquinonediazide-5-sulfonic acid chloride or 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 2,3,4,4'-tetrahydroxybenzo Particularly preferred are the compounds represented by formula (b-1) which are phenone condensation reactants.

(3)

(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)

[Chemical Formula 4]

The photosensitizer (B) in the positive photosensitive resin composition of the present invention may be a mixture of compounds having different quinone diazide groups in one molecule, and the quinone diazide group may be used in an amount of 1 to 100, 4 compounds are preferable, and compounds having 2.5 to 3 compounds are particularly preferable.

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

[Foot ink composition (C)]

The ink-repellent agent (C) in the positive-working photosensitive resin composition of the present invention is preferably a hydrolyzable silane compound represented by the following formula (c-1) (hereinafter also referred to as a compound (c- (Hereinafter also referred to as a " hydrolyzable silane compound mixture ") comprising a hydrolyzable silane compound (hereinafter also referred to as a compound (c-2)) represented by the formula The content of fluorine atoms in (C) is 10 to 55 mass%.

[Chemical Formula 5]

(The symbols in the formulas (c-1) and (c-2) are as follows.

R ^{H1 represents} a hydrocarbon group having 1 to 6 carbon atoms,

X ¹ and X ² : a hydrolyzable group,

p: 0, 1 or 2.

Provided that when a plurality of X ¹ , X ² , and R ^H1 exist in the formula (c-1) or the formula (c-2), they may be the same or different.

The repellent agent (C) contains a perfluoroalkyl group derived from the compound (c-1), whereby excellent ink repellency can be imparted to the partition wall formed by using the positive photosensitive resin composition. When the positive photosensitive resin composition is applied to a substrate, the R ^f derived from the hydrolyzable silane compound (c-1) tends to remain on the side opposite to the substrate (that is, on the air side). In other words, the repelling agent (C) tends to remain on the side opposite to the substrate. Since the compound (c-1) has R ^f and a silicon atom, the partition walls are excellent in ink-resistant intrinsic ultraviolet / ozone.

The repellent agent (C) contains a unit derived from the compound (c-2), so that the repellent agent (C) has excellent solubility in a hydrocarbon-based solvent and film-forming property. Further, it is possible to adjust the fluorine atom content of the repellent agent (C).

The fluorine atom content of the repellent agent (C) is 10 to 55% by mass, preferably 12 to 40% by mass, and particularly preferably 15 to 30% by mass. When the content of fluorine atoms is within the above range, ink-repellent properties resistant to ultraviolet rays or ozone irradiation can be imparted to the partition walls formed using the positive photosensitive resin composition.

The repellent agent (C) preferably has a silanol group. The number of silanol groups is preferably from 0.2 to 3.5, more preferably from 0.2 to 2, and particularly preferably from 0.5 to 1.5, per silicon atom. If the lower limit of the above range is exceeded, it is possible to prevent the releasing of the repellent agent (C) from the substrate surface when the partition wall is formed using the positive photosensitive resin composition. When the upper limit of the above range is exceeded, the ink-repellent agent (C) is excellent in compatibility with solvents and other components in the positive photosensitive resin composition.

The number of silanol groups in the repellent agent (C) is calculated by the ratio of the peak area of the Si group having no silanol group to the peak of the Si group having the silanol group, which is measured by ²⁹ Si-NMR.

The hydrolyzable silane compound mixture of the present invention includes the compound (c-1) and the compound (c-2). Further, 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 the phenyl group (the hydrolyzable silane compound (c- ) Are excluded). For example, the compound (c-3) to be described later may be used in combination with an organic group having one or two phenyl groups at the end and 0 or 1 hydrocarbon group and a hydrolyzable silane compound having 1 to 3 hydrolyzable groups bonded to silicon atoms, desirable.

(Hydrolyzable silane compound (c-1))

The hydrolyzable silane compound (c-1) is a silane compound represented by the above formula (c-1).

In the 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 and containing an etheric oxygen atom, A perfluoroalkyl group of 6 is particularly preferred. When R ^f is in the above range, the barrier ribs formed using the positive photosensitive resin composition are excellent in ink-repellency, in particular, excellent in ink resistance with ultraviolet / ozone property, and excellent in solubility in a general-purpose solvent Do.

The structure of R ^f may be a linear chain structure, a branched chain structure, a cyclic structure, or a structure having a partially cyclic structure, but a linear chain structure is preferable.

Specific examples of R ^{f include} the following groups.

In the formula (c-1), Q ¹ represents, when Si is bonded to the right hand and R ^f is bonded to the left hand, concretely, - (CH ₂ ) _{i 1} - (i 1 is an integer of _{1 ~ 5), -CH 2 O} (CH 2) i2 - (i2 is an integer of _{1 ~ 4), -SO 2 NR} 1 - (CH 2) i3 - (R 1 represents a hydrogen atom, a methyl group, or ethyl group, i3 is at least 1, and an integer of 4 or less as the sum of the number of carbon atoms of ^{R 1), - (C =} O) -NR 1 - (CH 2) i4 - (R 1 are the same as above, i4 is preferably a group represented by one or more, and an integer of 4 or less as the sum of the number of carbon atoms of R ^1). As Q ¹ , - (CH ₂ ) _{i 1} -, in which i ¹ 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 ) _{i 1} - (i 1 is as defined above). i1 is preferably an integer of 2 to 4, and particularly preferably - (CH ₂ ) ₂ -.

When R ^f is the number of carbon atoms containing an ether oxygen atom of a castle perfluoroalkyl group of 4-9, roneun wherein ^{_{Q 1, - (CH 2)}} i1 -, -CH 2 O (CH 2) i2 -, -SO _{^{_{2 NR 1 - (CH 2)}}} i3 -, - (C = O) -NR 1 - (CH 2) i4 - group represented by (i1 ~ i4 and R ¹ is the same as the aforementioned.) are preferred. Also in this case, - (CH ₂ ) ₂ - is particularly preferable.

Examples of X ^{1 in the} formula (c-1) include groups in which a hydrogen atom of an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group or an amino group is substituted with an alkyl group. Among them, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferable, and a methoxy group, an ethoxy group and a chlorine atom are particularly preferable. These groups become a hydroxyl group (silanol group) by a hydrolysis reaction, and a condensation reaction between molecules is likely to proceed smoothly to form a Si-O-Si bond.

Specific examples of the compound (c-1) include the following compounds.

Roneun compound (c-1), among _{them, 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 and the like are particularly preferable.

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 hydrolysable group and is the same as X ¹ in the formula (c-1) above, including preferred embodiments.

p is 0, 1 or 2, and when p is 2, two R ^H1 and (4 - p) X ² may be mutually different or the same.

p is preferably 0 or 1.

In the repellent agent (C), water repellency is expressed by R ^f1 derived from compound (c-1) and R ^H1 derived from compound (c-2), and oil repellency is mainly expressed by R ^f . Further, it is preferable that the ratio of R ^f is high relative to the total of R ^f and R ^{H1 in} the repellent agent (C) so that the cured product of the repellent agent (C) exhibits sufficient oil repellency. When p is 0, the proportion of R ^{f in} the repellent agent (C) is increased to improve the oil repellency and the film composition is excellent. When p is 1 or 2, there is a certain degree of R ^H1 , so that the repellent agent (C) is easily dissolved in a hydrocarbon-based solvent, and when a coating film of the positive photosensitive resin composition is formed on the surface of the substrate, Low-cost solvent can be selected.

As the compound (c-2), the following compounds are preferable. If necessary, a partially hydrolyzed condensate obtained by partial hydrolysis and condensation of a plurality of the above may be used. The same applies to other hydrolyzable silane compounds.

A compound obtained by hydrolysis and condensation of Si (OCH ₃ ) ₄ (for example, methyl silicate 51 (trade name) manufactured by Colcoat Co., Ltd.)

A compound obtained by hydrolyzing and condensing Si (OCH ₂ CH ₃ ) ₄ (for example, ethyl silicate 40 and ethyl silicate 48 (all trade names) manufactured by Colcoat Co.).

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 two or more compounds are used in combination, a bifunctional compound may 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 moles, more preferably 0.5 to 9 moles, of the compound (c-2) per 1 mole of the compound (c-1).

(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)").

[Chemical Formula 6]

In the formula (c-3), X ³ representing the hydrolyzable group is the same as X ¹ in the formula (c-1) above, including preferred embodiments.

Also, R ^H2 is the same including R ^H1 in the above formula (c-2) and preferred embodiments.

In formula (c-3), Y represents a phenyl group in which the hydrogen atom may be substituted with 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 connecting 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 s} may be different from or the same as each other, and when q + r is 1, three X ^{3 s} may be the same or different from each other , and when q + r is 2, two X < ³ > s may be different from or the same as each other.

In the formula (c-3), it is preferable that q is 1, r is 1, or q is 1 and r is 0.

Examples of Y in the formula (c-3) include a phenyl group, a fluorophenyl group, a chlorophenyl group, and a dichlorophenyl group, and a phenyl group is particularly preferable. By using such a compound (c-3), a partition having a high resolution and few residues in the dot portion can be obtained. This is because the phenyl group derived from the compound (c-3) reacts with the diazide group of the photosensitizer (B) in the developer after the repellent agent (C) migrates to the film surface of the positive photosensitive resin composition, It is presumed that the repellent agent (C) easily remains on the surface of the film of the positive photosensitive resin composition. This makes it possible to keep the surface of the obtained partition wall ink-repellent and the side surface ink-philic, even after development, post-baking and the like.

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 from 1 to 6), -N (C _g H _2g ₊₁₎ - (g is an integer from 1 to 6) are electron-donating group, it is also preferable in view of easy availability. As Q ² , a single bond or -NH- is particularly preferable.

Specific examples of the 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 preferably 5 moles or less, more preferably 4 moles or less per mole of the total amount of the hydrolyzable silane compounds (c-1) and (c- Or less is particularly preferable.

The repellent agent (C) used in the positive photosensitive resin composition of the present invention is a partially hydrolyzed condensation product of the hydrolyzable silane compound mixture of the raw materials, and usually a mixture composed of a plurality of condensates having different degrees of polymerization or the like to be.

That is, the ink-repellent agent (C) can be produced by using the hydrolyzable silane compound (c-1) and the compound (c-2) Has a structure of an average composition formula represented by the following formula (1). However, since the product is actually a product (partial hydrolyzed condensate) in which a hydrolyzable group or a silanol group remains, it is difficult to express this product in a chemical formula.

The average composition formula represented by the formula (1) is a formula when the hydrolyzable group or the silanol group is completely hydrolyzed and condensed to form a siloxane bond in the partially hydrolyzed condensate prepared as described above.

(7)

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

In the partial hydrolyzed condensate having the structure of the average composition formula represented by the formula (1), the units derived from the respective compounds (c-1), (c-2) and (c-3) .

The s / t (molar ratio) in the following average composition formula (2) when the compound (c-1) and the compound (c-2) are used is an average value of the total of the ink- The content of the compound (c-2) relative to the compound (c-1) in the compound mixture is preferably in the range described above, that is, 10/1 to 90 (molar ratio), more preferably 10/5 to 90 desirable.

[Chemical Formula 8]

In the formula (2), preferable 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 present in the plurality of fluorine-containing silane compound mixtures having different degrees of polymerization.

When the repellent ink (C) is produced by using the hydrolyzable silane compound (c-1), the hydrolyzable silane compound (c-2) and the hydrolyzable silane compound (c-3) And the unit derived from the compound (c-3) of the compound (1) is further cocondensed.

In the formula (1), u is preferably in the above-described range, that is, 5 or less (molar ratio), preferably 4 or less (molar ratio), to 1 of (s + t) Particularly preferred.

The ink composition (C) in the positive photosensitive resin composition of the present invention is such that, in the course of exposure and curing, the silanol groups contained therein are further condensed to exhibit excellent ink repellency even when irradiated with ultraviolet rays / ozone Thereby forming a barrier rib.

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

(Production of repellent ink (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 above-described hydrolyzable silane compound mixture (hereinafter also referred to as " reaction step ") . Hydrolysis and partial condensation are reactions in which a silanol group is formed by a hydrolysis reaction of a hydrolyzable group and a siloxane bond is formed by a dehydration condensation reaction between silanol groups as described above. In the reaction step, there can be used, without particular limitation, the reaction conditions usually used in the reaction for hydrolyzing and condensing the hydrolyzable silane compound. 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 mass, particularly preferably 100 to 1,900 parts by mass, per 100 parts by mass of the hydrolyzable silane compound mixture. When the amount of water is in the above range, control of the hydrolysis and condensation reaction becomes easy.

As the catalyst to be 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 to be used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the hydrolyzable silane compound mixture.

An organic solvent may be used for the reaction step. As the organic solvent, when the hydrolyzable silane compound is subjected to the hydrolysis and condensation reaction, the organic solvent used is usually an organic solvent to be used, such as methanol, ethanol, 1-propanol, 2-propanol, , Isobutanol, 2-methyl-2-propanol, ethylene glycol, glycerin, propylene glycol and the like; Ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; Cellosolves such as 2-methoxyethanol and 2-ethoxyethanol; Carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; Esters such as methyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, 4-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, dipropylene And dialkyl ethers of glycols such as glycol dimethyl ether. Other examples include benzyl alcohol, N, N-dimethylformamide, dimethylsulfoxide, dimethylacetamide and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

In the reaction step, the amount of the organic solvent is preferably 25 to 9,900 parts by mass, particularly preferably 100 to 1,900 parts by mass, per 100 parts by mass of the hydrolyzable silane compound mixture.

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

Specifically, there may be mentioned a glycol monoalkyl ether acetate solvent having 2 to 8 carbon atoms, a glycol monoalkyl ether solvent, a grit solvent, and a hydrocarbon-based alcohol having 2 to 4 carbon atoms.

More specifically, propylene glycol monomethyl ether acetate (?: 8.3) as a glycol monoalkyl ether acetate solvent, propylene glycol monomethyl ether (?: 12.3) as a glycol monoalkyl ether solvent, and 2-propanol (?: 19.92) and the like. Propylene glycol monomethyl ether is particularly preferable in that the effect of stabilizing the silanol group is high.

The reaction is preferably carried out at a temperature from room temperature to the boiling point of the solvent under a suitable stirring condition.

The reaction time may vary depending on the amount of the raw material component to be used, the reaction temperature, the stirring conditions, and the like, but is generally 0.5 to 24 hours, preferably 1 to 10 hours.

After completion of the reaction, the obtained repellent ink (C) may be added to the positive photosensitive resin composition of the present invention without removing the organic solvent. The organic solvent may be removed by a conventional method, and then the repellent agent (C) may be isolated and added to the positive photosensitive resin composition.

The content of the ink composition (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, particularly preferably 0.2 to 3% desirable. When the content of the ink composition (C) is within 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 in ink- It has a smooth surface.

[Solvent (D)]

The positive photosensitive resin composition of the present invention may contain a solvent (D).

By containing the solvent (D), the composition of the composition is more excellent in coatability to the substrate and adhesion to the substrate surface. Also, by containing the solvent (D), the ink (C) can be stably contained in the composition.

The solvent (D) is an alkali-soluble resin (A), a photosensitizer (B), a repellant (C), a thermal curing agent (E) (F) and other additives are uniformly dissolved or dispersed so as not to 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; Cellosolves such as 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; Carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; Methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, ,? -butyrolactone, 3-methyl-3-methoxybutyl acetate, and glycerin triacetate; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dibutyl ether, and diethylene glycol methyl ethyl ether. . Other than this, chain type hydrocarbons such as n-butane and n-hexane; Cyclic saturated hydrocarbons such as cyclohexane; Aromatic hydrocarbons such as toluene, xylene and benzyl alcohol; And the like. These may be used singly or in combination of two or more.

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

[Thermal curing agent (E)]

The positive photosensitive resin composition of the present invention may contain a thermosetting agent (E) as an optional component for promoting thermosetting.

As the heat curing agent (E), at least one member selected from the group consisting of an amino resin, an epoxy compound, an oxazoline compound, a polyisocyanate compound, and a polycarbodiimide compound is preferable.

Examples of the amino resin include a compound obtained by hydroxymethylation of a part or all of amino groups such as a melamine compound, a guanamine compound and a urea compound, or a compound obtained by hydroxymethylating a part or all of the hydroxyl groups of a compound obtained by hydroxymethylation of the amino group with methanol, -Butyl alcohol, 2-methyl-1-propanol and the like, for example, hexamethoxymethylmelamine, and the like.

Examples of the epoxy compound include glycidyl ethers such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol / novolak type epoxy resin, cresol / novolak type epoxy resin, trisphenol methane type epoxy resin and brominated epoxy resin ; Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis (2,3-epoxycyclopentyl) ether; Glycidyl esters such as diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate and diglycidyl phthalate; Glycidyl amines such as tetraglycidyldiaminodiphenylmethane and triglycidylparaaminophenol; Heterocyclic epoxy resins such as triglycidyl isocyanurate; And the like.

Examples of the oxazoline compound include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2- 2-isopropenyl-4-methyl-2-oxazoline, and other polymerizable monomers.

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

As the thermosetting agent (E), a compound having two or more epoxy groups in one molecule is particularly preferable. By including the heat curing agent (E) in the positive photosensitive resin composition, the positive photosensitive resin composition at the time of exposure is more excellent in curability, and the partition after the heat curing is stabilized can be formed.

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, and particularly preferably 10 to 15% by mass. When the positive photosensitive resin composition is used in the above range, the wettability of the ink other than the partition wall surface (dot) is better when the cured film having the partition wall is formed.

[Thermal curing accelerator (F)]

The positive photosensitive resin composition of the present invention may contain a thermosetting accelerator (F) as an optional component for promoting thermosetting.

The heat curing accelerator (F) is a compound having an action of forming a crosslinked structure in the positive photosensitive resin composition by heating.

Examples of the thermosetting accelerator (F) include a compound which itself reacts with the thermosetting agent (E) and forms a crosslinked structure by crosslinking, or a compound which itself forms a catalytic function with respect to the thermosetting agent (E) . &Lt; / RTI >

When an epoxy compound is used as the thermosetting agent (E), examples of the thermosetting promoter (F) that forms a crosslinked structure include polyamines, polythiols and polycarboxylic anhydrides. More specifically, examples of the polyamines include polyamines such as ethylenediamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylene polyamine, isophoronediamine, mensenediamine, 3,9-bis -Aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane. Examples of the polythiol include polyether polythiol and polycarboxylic acid anhydride such as succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride.

Examples of the catalyst having a catalytic action include curing catalysts such as tertiary amines, imidazoles, Lewis acids, onium salts, dicyandiamides, organic acid dihydrazides, and phosphines. More specifically, there can be mentioned 2-methylimidazole, 2-ethyl-4-methylimidazole, tris (dimethylaminomethyl) phenol, boron trifluoride-amine complex, dicyandiamide, diphenyliodonium hexafluorophosphate , Triphenylsulfonium hexafluorophosphate, and the like.

These thermosetting accelerators (F) may be used alone or in combination of two or more.

When the thermosetting agent (E) is a compound having two or more epoxy groups in one molecule, 2-methylimidazole and 4-methyl-2-phenylimidazole are particularly preferable as the thermosetting accelerator (F).

The content of the thermosetting accelerator (F) in the total solid content in the photosensitive resin composition of the present invention is preferably 0.1 to 10 mass%, particularly preferably 0.5 to 3 mass%.

[Colorant (G)]

When the positive photosensitive resin composition of the present invention is used for forming a black matrix which is a lattice black portion surrounding the three color pixels of R, G and B of the color filter of the liquid crystal display element, the colorant (G) .

The colorant (G) includes, for example, carbon black, aniline black, anthraquinone black pigment, and perylene black pigment, specifically C.I. Pigment Black 1, 6, 7, 12, 20, 31, and the like. As the colorant (G), a mixture of an organic pigment such as a red pigment, a blue pigment, a green pigment and the like or an inorganic pigment may be used.

When the positive photosensitive resin composition of the present invention contains the colorant (G) and is used for forming a black matrix or the like, the content of the colorant (G) in the total solid content in the positive photosensitive resin composition is preferably from 15 to 65% By mass, and particularly preferably from 20 to 50% by mass. Within this range, the positive photosensitive resin composition is excellent in sensitivity, and the formed barrier ribs are excellent in light shielding property.

When the positive photosensitive resin composition of the present invention contains a dispersible material such as the colorant (G), a polymer dispersant, a dispersion aid, and the like may be further added to improve the dispersibility. These may be contained in the positive photosensitive resin composition in such a content as not to impair the effect of the present invention.

[Silane coupling agent (H)]

The positive photosensitive resin composition of the present invention may optionally contain a silane coupling agent (H). By containing the silane coupling agent (H), the substrate adhesion of the formed cured film is more excellent.

Examples of the silane coupling agent (H) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and the like can be used. . These may be used singly 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 mass%, particularly preferably 1 to 10 mass%. When the lower limit of the above range is exceeded, the substrate adhesion of the cured film formed from the positive photosensitive resin composition is more excellent, and if it is less than the upper limit of the above range, the cured film has good ink repellency.

[Particle (I)]

The positive photosensitive resin composition of the present invention may contain fine particles (I), if necessary. By containing the fine particles (I), sagging due to heat of the partition walls formed by 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, indium tin oxide (ITO), and antimony doped tin oxide (ATO); And organic fine particles such as polyethylene and polymethylmethacrylate (PMMA). From the viewpoint of heat resistance, inorganic fine particles are preferable, and silica or zirconia is particularly preferable from the viewpoints of availability and dispersion stability.

When the positive photosensitive resin composition contains the colorant (G) and the polymer dispersant, it is preferable that the fine particles (I) are negatively charged in consideration of the adsorbing ability of the polymer dispersant.

Considering the exposure sensitivity of the positive photosensitive resin composition, it is preferable that the fine particles (I) do not absorb the light to be irradiated upon exposure, and the i-line (365 nm), the h- (405 nm), and g-line (436 nm).

The average particle size of the fine particles (I) is preferably 1 占 퐉 or less, and particularly preferably 200 nm or less, in that the surface smoothness of the partition walls becomes good. Among them, 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 mass%, particularly preferably 10 to 30 mass%. When the content is lower than the lower limit of the above range, the ink repellency is suppressed. When the content is lower than the upper limit of the above range, the storage stability of the positive photosensitive resin composition is excellent.

[Other additives]

The positive-working photosensitive resin composition of the present invention may further contain other additives as needed, such as a thickener, a plasticizer, a defoaming agent, a leveling agent, a crytallation inhibitor, and an ultraviolet absorber, as long as the effect of the present invention is not impaired One or more of them may be blended.

[Method of producing positive-type photosensitive resin composition]

(A), a photosensitive agent (B), a releasing agent (C), and if necessary, a solvent (D), a thermosetting agent (E), a thermosetting accelerator ), The colorant (G), the silane coupling agent (H), the fine particles (I), and other additives.

The mixing is carried out using a stirrer at a temperature of 20 ° C to 25 ° C for 3 hours to 6 hours, 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 a conventional positive photosensitive resin composition and the obtained cured film is a member of an optical element in which a cured film of a conventional positive photosensitive resin composition is used Can be used.

[Bulkhead and method for manufacturing the same]

A barrier rib of the present invention is a barrier rib formed to form a partition on a substrate, which is composed of a cured film formed by coating, drying and curing the positive photosensitive resin composition of the present invention.

The barrier rib of the present invention is preferably used for the use of an optical element, and when the positive photosensitive resin composition contains a colorant (G), the obtained barrier rib can be applied as a black matrix.

The barrier rib of the present invention is applied to, for example, a barrier rib for an optical element having a plurality of pixels and barrier ribs located between adjacent pixels on the substrate.

Examples of the method for producing the 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 on a substrate to form a coating film (coating film forming step), and then the coating film is dried to form a film (prebaking step). Subsequently, (Exposure step), and thereafter, the coated film of the exposed part is removed to form a partition made of the unexposed part of the coated film (developing step). Then, if necessary, the barrier ribs and the like formed above can be thermally cured (post-baking step) to produce barrier ribs for optical elements of the present invention.

The material of the substrate is not particularly limited, but various glass plates; Thermoplastic plastic sheets such as polyester (polyethylene terephthalate and the like), polyolefin (polyethylene, polypropylene and the like), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, polymethacrylic resin and acrylic resin; A cured sheet of a thermosetting resin such as an epoxy resin or an unsaturated polyester; Etc. may be used. Particularly, a heat-resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance. Further, a transparent substrate is preferable.

The shape of the substrate and the surface on which the barrier ribs 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 from 0.5 to 10 mm.

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

Fig. 1 (I) is a view showing a section of a state in which a coating film 2 made of the positive photosensitive resin composition of the present invention is formed on a substrate 1. Fig.

Fig. 1 (II) is a diagram schematically showing an exposure process.

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, with reference to Fig. 1, a method for producing an optical element barrier rib using the positive photosensitive resin composition of the present invention will be described in detail.

(Coating film forming step)

1 (I), the positive photosensitive resin composition of the present invention is applied onto the substrate 1 to form a coating film 2 made of a positive photosensitive resin composition.

The method of applying the positive photosensitive resin composition is not particularly limited as long as a method of forming a coating film having a uniform film thickness is applicable. Examples of the method include a spin coating method, a spraying method, a slit coating method, a roll coating method, , And a method used for forming a common coating film.

The film thickness of the coating film 2 is determined in consideration of the finally obtained height of the partition wall. The film thickness of the coating film 2 is preferably 100 to 200%, more preferably 100 to 130% of the height of the finally obtained barrier ribs. The film thickness of the coating film 2 is preferably 0.3 to 325 mu m, particularly preferably 1.3 to 65 mu m.

(Pre-bake process)

The coating film 2 formed on the substrate 1 is heated in the coating film forming step to obtain the film 2. By heating, a volatile component including a solvent contained in the positive photosensitive resin composition constituting the coating film is volatilized and removed, and a film having no stickiness is obtained. Further, the ink for ink-repelling agent C shifts to the vicinity of the film surface.

As the heating method, the coating film 2 together with the substrate 1 is heated at a temperature of 50 to 120 ° C, preferably 70 to 110 ° C, for 10 to 2,000 seconds by a heating device such as a hot plate or an oven For 30 to 180 seconds.

In order to remove volatile components such as a solvent, a drying step such as vacuum drying other than heating (drying) may be separately formed before the pre-baking step. 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 and vacuum drying in combination with drying by the prebaking step. Vacuum drying conditions vary depending on the kind of each component, blending ratio, etc., but can be carried out in a wide range of about 10 to 300 seconds at 500 to 10 Pa.

(Exposure step)

As shown in Fig. 1 (II), light 5 is irradiated to the film 2 via a mask 4 having a predetermined pattern. The light 5 passes through only the predetermined pattern portion cut by the mask 4 and reaches the film 2 on the substrate 1. Since only the exposed portion is alkali-soluble, the predetermined pattern is formed in a shape suitable for the shape of the partition wall. The average width of the partition walls after the post-baking process is preferably 100 占 퐉 or less, and particularly preferably 20 占 퐉 or less. Further, it is preferable that the average distance between adjacent barrier ribs is 300 탆 or less, and particularly preferably 100 탆 or less. As the mask 4, it is preferable to use a mask 4 having a pattern formed thereon.

1 (II), the exposed portion of the film irradiated with light becomes the solubilization portion of the positive photosensitive resin composition, while the unexposed portion 3 is the portion of the positive photosensitive resin composition film 2 itself .

As the light 5 to be irradiated, visible light; UV-rays ; Deep ultraviolet light; An excimer laser such as a KrF excimer laser, an ArF excimer laser, an F ₂ excimer laser, a Kr ₂ excimer laser, a KrAr excimer laser, or an Ar ₂ excimer laser; X-rays; Electron beam and the like. The irradiation light 5 is preferably an electromagnetic wave having a wavelength of 100 to 600 nm and more preferably a light ray having a distribution in a range of 300 to 500 nm and an i-ray (365 nm), h-ray (405 nm) And g-line (436 nm) are particularly preferable.

As the irradiation device (not shown), known ultrahigh pressure mercury lamps or deep UV lamps can be used. The exposure dose is preferably 5 to 1,000 mJ / cm2, and particularly preferably 50 to 400 mJ / cm2. When the exposure amount is not less than the lower limit of the above range, the solubility of the portion to be solubilized in the positive photosensitive resin composition to the developer becomes sufficient, and the developed residue disappears. If it is below the upper limit of the above range, high resolution is obtained.

The exposure time may vary depending on the exposure amount, the composition of the photosensitive composition, the thickness of the coating film, and the like, but is preferably 1 to 60 seconds, particularly preferably 5 to 20 seconds.

(Developing step)

Development is carried out using a developing solution to remove an exposed portion on the substrate 1 shown in Fig. 1 (II). As a result, the structure of the partition 1 formed by the film of the positive photosensitive resin composition on the substrate 1 and the substrate as shown in the sectional view in Fig. 1 (III) is obtained. The portion surrounded by the partition 6 and the substrate 1 is a portion called a dot 7 on which pixels are formed by ink injection or the like. The obtained substrate 10 can be used for an optical element in an ink-jet method through a post-baking step to be described later.

As the developing solution, there can be used an aqueous alkaline solution containing an alkaline such as an inorganic alkaline, an amine, an alcohol amine or a quaternary ammonium salt, preferably an alkaline aqueous solution containing an alkaline such as tetramethylammonium hydroxide .

In order to improve solubility and remove residues, a surfactant or an organic solvent such as an alcohol may be added to the developer.

The development time (time for bringing the developer into contact with the developer) is preferably 5 to 180 seconds, more preferably 10 to 60 seconds.

The developing method includes a liquid mounting method, a dipping method, a shower method, and the like. After the development, the water on the substrate 1 and the partition walls 6 can be removed by carrying out high pressure water washing or water washing and air drying with compressed air or compressed nitrogen.

(Post-bake process)

As the post-baking step, the partition walls 6 on the substrate 1 are heated. As a heating method, there is a method in which the partition wall 6 together with the substrate 1 is subjected to heat treatment at 150 to 250 DEG C for 5 to 90 minutes by a heating apparatus such as a hot plate or an oven.

The partition 6 made of the cured film of the positive photosensitive resin composition on the substrate 1 is further cured by heating and the shape of the dot 7 surrounded by the partition 6 and the substrate 1 is further fixed . It is particularly preferable that the heating temperature is 180 DEG C or higher. If the heating temperature is too low, hardening of the partition walls 6 is insufficient, and sufficient chemical resistance can not be obtained. When the ink is injected into the dot 7 by an ink injection process to be described later, depending on the solvent contained in the ink, the partition 6 may swell or the ink may be smudged. On the other hand, if the heating temperature is excessively high, there is a fear that thermal decomposition of the partition wall 6 may occur.

The average of the widths of the partition walls to be formed is preferably 100 占 퐉 or less, and particularly preferably 20 占 퐉 or less. Among them, 5 to 20 mu m is most preferable.

The average of the distance between adjacent partition walls (dot width) is preferably 300 占 퐉 or less, and particularly preferably 100 占 퐉 or less. Among them, 30 to 80 mu m is most preferable.

The average height of the barrier ribs is preferably 0.05 to 50 탆, particularly preferably 0.2 to 10 탆.

[Manufacturing method of 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 substrate surface exposed in the region surrounded by the substrate and the partition wall is subjected to an ink- And then the ink is injected into the region by the ink jet method to form the pixel (ink injection step).

(An ink-lacquering step)

Examples of the method of the ink-affinity treatment include a cleaning treatment with an alkaline aqueous solution, an ultraviolet cleaning treatment, an ultraviolet / ozone cleaning treatment, an excimer cleaning treatment, a corona discharge treatment, and an oxygen plasma treatment.

The cleaning treatment with the alkaline aqueous solution is a wet treatment in which the surface of the substrate is cleaned using an aqueous alkali solution (potassium hydroxide, tetramethylammonium hydroxide aqueous solution, or the like).

The ultraviolet ray cleaning process is a dry process for cleaning the surface of a substrate using ultraviolet rays.

The ultraviolet / ozone cleaning process is a dry process for cleaning 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 for cleaning the substrate surface using a xenon excimer lamp that emits light of 172 nm.

The corona discharge treatment is a dry treatment in which corona discharge is generated in the air using a high frequency high voltage to clean the surface of the substrate.

The oxygen plasma treatment is a dry treatment that cleans the surface of a substrate by using oxygen which is excited by a high-frequency power source or the like in a vacuum mainly in a "plasma state" having high reactivity.

As a method of the ink-affinity treatment, a dry treatment method such as an ultraviolet / ozone cleaning treatment is preferable from the viewpoint of convenience. UV / ozone can be generated using commercially available equipment.

It is possible to carry out the ink-lining treatment by providing a substrate having a partition wall formed in the ultraviolet / ozone device and performing treatment in air or at room temperature for about 1 to 10 minutes or so as not to impair the oil repellency of the partition . The treatment time may be adjusted in accordance with the individual ultraviolet / ozone apparatus so as to be within a range that does not inhibit ink repellency of the partition wall.

After the formation of the barrier ribs, the removal of the remaining developing material remaining in the dots is sufficiently carried out by the ink fusing treatment, so that the dyeing of the dots can be sufficiently achieved, and the color fading phenomenon Can be prevented. In addition, when the barrier ribs formed using the positive photosensitive resin composition of the present invention are used, it is possible to perform the ink-lubrication without lowering the ink repellency of the barrier ribs by the ultraviolet ray cleaning treatment or the like.

Here, the ink repellency (water repellency and oil repellency) of the cured film formed from the positive photosensitive resin composition can be estimated by the contact angle of water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent widely used as a solvent for the ink) .

In the case of producing an optical element using a substrate having a barrier rib formed by using the positive photosensitive resin composition of the present invention, the barrier rib is required to have sufficient ink repellency even after the above-described ink fusing treatment. The contact angle of water on the partition wall is preferably 90 degrees or more, and particularly preferably 95 degrees or more. The contact angle of the PGMEA of the partition wall is preferably 30 degrees or more, more preferably 35 degrees or more.

On the other hand, when an optical element is manufactured using a substrate having a partition formed using the positive photosensitive resin composition of the present invention, the dot is required to be ink-philic and the contact angle of the water is preferably 20 degrees or less, 10 DEG C or less is particularly preferable.

(Ink injection process)

And ink is injected into the dots after the ink-affinity treatment step by the ink-jet method to form pixels.

This step can be carried out in the same manner as usual by using an ink jet apparatus generally used in the ink jet method. The inkjet apparatus used for forming such a pixel is not particularly limited, but a method of continuously injecting charged ink and controlling it by a magnetic field, a method of jetting ink intermittently using a piezoelectric element, , And a method of intermittently spraying using the foaming, may be used.

Examples of the optical element manufactured using the positive photosensitive resin composition of the present invention include a color filter, an organic EL element, and an organic TFT array.

[Production of color filter]

The formation of barrier ribs, the ink-philic treatment of dots, and the ink injection by the ink-jet method are as described above.

In the color filter, the shape of a pixel to be formed can be any known arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type.

The ink used for the formation of the pixel mainly contains 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 transparent and heat-resistant resin is preferable, and acrylic resin, melamine resin, urethane resin and the like can be given.

The aqueous ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin or a water-dispersible resin as a binder resin component, and includes various auxiliaries as necessary.

The oily ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliaries as necessary.

After the ink is injected by the ink-jet method, it is preferable to perform drying, heat curing, and / or ultraviolet curing, if necessary.

After forming a pixel, a protective film layer is formed by using a coating liquid for overcoating, if necessary.

It is preferable that the protective film layer is formed for the purpose of increasing the surface flatness and for preventing the elution of ink from the partition wall or the ink in the pixel portion from reaching the liquid crystal layer.

In the case of forming the protective film layer, it is preferable to remove the ink repellency of the partition wall in advance. If the ink-repelling property is not removed, the coating liquid for overcoat is cratered and a uniform film thickness can not be obtained, which is not preferable.

Plasma ashing, light ashing, and the like can be given as a method for removing the ink repellency of the barrier ribs.

Further, if necessary, in order to improve the quality of the liquid crystal panel manufactured using the color filter, it is preferable that the photo spacers are formed on the black matrix constituted by the partition walls.

[Production of organic EL device]

Prior to forming the barrier ribs using the positive photosensitive resin composition of the present invention, a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like, The transparent electrode is etched. Next, a partition wall is formed by using the positive photosensitive resin composition of the present invention, an ink-jetting treatment is performed on the dots, a solution of the hole transporting material and the light emitting material is sequentially applied to the dots using the inkjet method, And dried to form a hole transporting layer and a light emitting layer. Thereafter, electrodes of aluminum or the like are formed by vapor deposition or the like to obtain pixels of the organic EL element.

[Production of Organic TFT Array]

The organic TFT array can be manufactured through the following steps (1) to (3).

(1) A barrier rib is formed on a transparent substrate such as glass using the positive photosensitive resin composition of the present invention. Subsequently, after the ink is subjected to the ink-philic treatment, a solution of the gate electrode material is applied to the dots using the ink-jet method to form the gate electrode.

(2) After a gate electrode is formed, a gate insulating film is formed thereon. Subsequently, a barrier rib is formed on the gate insulating film using the positive photosensitive resin composition of the present invention, and the solution of the source / drain electrode material is applied to the dot using the inkjet method , And source and drain electrodes are formed.

(3) After forming the source / drain electrodes, the barrier ribs are formed using the positive photosensitive resin composition of the present invention so as to surround the region including the pair of source / drain electrodes. Subsequently, after the ink is subjected to the ink-philic treatment, a solution of the organic semiconductor is applied to the dots using the ink-jet method, and the organic semiconductor layer is formed between the source and drain electrodes.

The steps (1) to (3) may be performed by forming the barrier ribs using the positive photosensitive resin composition of the present invention only in each step, A partition wall using a photosensitive resin composition may be formed and used.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not construed as being limited to these Examples.

Examples 1 to 4 are examples, and Example 5 is a comparative example.

Each measurement was carried out in the following manner.

[Number average molecular weight (Mn)]

Gel permeation chromatography (GPC) of various types of monodispersed polystyrene polymers having different commercially available degree of polymerization as standard samples for measuring molecular weights was carried out by using a commercially available GPC measuring apparatus (manufactured by Tosoh Corporation, HLC-8320GPC) And a calibration curve was prepared based on the relationship between the molecular weight of the polystyrene and the retention time (retention time).

The sample was diluted with tetrahydrofuran to 1.0% by mass and passed through a 0.5 탆 filter, and the GPC of the sample was measured using the above GPC measuring device.

Using the calibration curve, the GPC spectrum of the sample was subjected to computer analysis to determine the number average molecular weight (Mn) of the sample.

[Water contact angle]

According to JIS R3257 " Test method for wettability of substrate glass surface " by static method, water droplets were placed at three points of the measurement surface on the substrate, and measurement was made for each water droplet. The droplet was 2 占 퐇 / drop, and the measurement was carried out at 20 占 폚. The contact angle is represented by the average of three measurements (n = 3).

[PGMEA contact angle]

According to JIS R3257 " Test Method for Wettability of Substrate Glass Surface " by static method, PGMEA droplets were placed at three points of the measurement surface on the substrate and measured for each PGMEA droplet. The droplet was 2 占 퐇 / drop, and the measurement was carried out at 20 占 폚. The contact angle is expressed as the average of three measurements (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))

Cresol novolak resin (mass average molecular weight (Mw): 11,600, dissolution rate: 164 (angstrom / sec) manufactured by Asahi Organic Materials Industry Co., Ltd.).

(Photosensitive agent (B))

4NT-250 (trade name: 4NT-250, manufactured by Toyobo Co., Ltd. (2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydro-5-oxo-naphthalene- (Mono-tetra) ester)).

(A hydrolyzable silane compound as a raw material of the ink-repellent agent (C)),

Corresponding to the hydrolyzable silane compound (c-1), Compound _{(c-11): CF 3} (CF 2) 5 CH 2 CH 2 Si (OCH 3) 3 ( manufactured by Asahi Glass Co., Ltd.).

(C-21): Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat Co., Ltd.) corresponding to the hydrolyzable silane compound (c-2).

(C-31): C ₆ H ₅ Si (OC ₂ H ₅ ) ₃ (manufactured by Shin-Etsu Chemical Co., Ltd.) corresponding to the hydrolyzable silane compound (c-3).

(C-32): C ₆ H ₅ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (manufactured by Shin-Etsu Chemical Co., Ltd.) corresponding to the hydrolyzable silane compound (c-3).

_{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 Pure Chemical Industries, Ltd. (2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator)).

(Solvent (D))

PGMEA: Propylene glycol monomethyl ether acetate.

PGME: propylene glycol monomethyl ether (manufactured by Toho Chemical Industry Co., Ltd.).

(Heat curing agent (E))

TEP-G (trade name: TEP-G, manufactured by Asahi Organic Materials Industry Co., Ltd., epoxy resin).

(Thermal curing 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)

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 in a 50 cm 3 three-necked flask equipped with a stirrer, To obtain a raw material mixture of the (C1). Then, 9.85 g of PGME was added to the raw material mixture to obtain a solution (raw material solution).

1.33 g of a 1.0 mass% phosphoric acid aqueous solution as a catalyst was added dropwise to the obtained raw material solution while stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 5 hours to carry out a hydrolysis and partial condensation reaction to obtain a (CA1-1) solution which was a PGME solution containing 10% by mass of a repellent agent (CA1).

Except that 1.33 g of the compound shown in Table 1 was used in place of the 1.0 mass% phosphoric acid aqueous solution as the catalyst, and the same procedure as in Synthesis Example 1 was carried out except that the PGME solution containing 10 mass% of the ink repellent agents (CA2) to (CA2-1) to (CA3-1).

[Synthesis Example 4: Synthesis of ink-repellent (CA4) and preparation of (CA4-1) liquid]

(CA-4) 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).

To the obtained raw material solution, 0.93 g of a 1.0 mass% nitric acid aqueous solution was added dropwise at room temperature with stirring. After completion of the dropwise addition, the mixture was further stirred for 5 hours to carry out a hydrolysis and partial condensation reaction to obtain a (CA4-1) solution which was a PGME solution containing 10% by mass of a repellent agent (CA4).

[Synthesis Example 5: Preparation of liquid for ink-repellent (CA5) and liquid for CA5-1]

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 M-65 were poured into an autoclave having an inner volume of 1000 cm 3 equipped with a stirrer, Under stirring at 50 캜 for 24 hours to synthesize a crude copolymer. To the solution of the obtained crude copolymer was added hexane to reprecipitate, purify and then vacuum dried. To the solid obtained, 14,643 g of PGMEA was added and stirred to obtain a solution of (CA5-1) which was a PGMEA solution containing 10% by mass of a releasing agent (CA5).

(CA1-1) to (CA5-1) which were prepared in Synthesis Examples 1 to 5 and in which the solvents (CA1-1) to (CA5-1) containing 10 mass% (% By mass of fluorine atoms) and the number average molecular weight (Mn) are shown in Table 1. [Table 1]

Table 1 also shows the injection amount composition (mol%) of the ink repellents (CA1) to (CA5).

[Example 1]

(Preparation of positive-type photosensitive resin composition 1)

15 g of EP4020G, 5.4 g of 4NT-250, 3.1 g of TEP-G, 0.8 g of 2-MI, and 1 g of water (CA1-1) 74.1 g of PGMEA was placed in a 500 cm 3 stirring container and stirred for 30 minutes to prepare a positive photosensitive resin composition 1.

(Preparation of cured film)

A glass substrate having a width of 10 cm was ultrasonically cleaned with ethanol for 30 seconds and then subjected to ultraviolet / ozone cleaning for 5 minutes. For ultraviolet / ozone cleaning, PL7-200 (Sen Engineering) was used as an ultraviolet / ozone generator. Also, with respect to all of the following ultraviolet / ozone treatment, this apparatus was used as an ultraviolet / ozone generator.

The positive photosensitive resin composition 1 was coated on the cleaned glass substrate surface using a spinner and dried on a hot plate at 100 캜 for 2 minutes to form a film having a thickness of 1.3 탆. On the surface of the obtained film, a 50 占 퐉 gap was provided via a photomask (photomask with light irradiation to the region of the pattern portion) having an opening pattern (2.5 cm 占 5 cm) from the film side, And ultraviolet rays of the lamp were irradiated at 25 mW / cm 2 for 10 seconds.

Subsequently, the glass substrate subjected to the exposure treatment was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 40 seconds and developed, and the film of the exposed portion was washed with water, washed and dried. Then, this was heated on a hot plate at 230 占 폚 for 20 minutes to obtain a glass substrate 1 on which a cured film of the positive photosensitive resin composition 1 was formed in the region except for the above-mentioned opening pattern portion.

(evaluation)

The following evaluations were performed on the positive photosensitive resin composition 1 and the glass substrate 1 on which the cured films (partitions) were formed.

&Lt; ink-repellent (partition wall), inkphilic property (dot), and development residue >

The contact angle of the obtained cured film of the glass substrate 1, that is, the contact angle with respect to the PGMEA of the partition wall surface (unexposed portion) and the portion where the film was removed by development, that is, the dot portion (glass substrate surface) with respect to water was measured. At this time, the developed residue was evaluated by the contact angle of the dot portion with respect to water. The evaluation was carried out as follows.

○ (Good): The contact angle of water is less than 30 degrees.

× (poor): The contact angle of water is 30 degrees or more.

Thereafter, ultraviolet / ozone irradiation was performed for one minute on the entire surface of the glass substrate 1 on which the cured film was formed. The contact angle of the surface of the cured film with respect to PGMEA and the contact angle of water on the surface of the glass substrate after 1 minute irradiation were measured. The measurement method is as described above. The evaluation results are shown in Table 2.

The positive photosensitive composition was stored in a glass screw bottle at 23 占 폚 (room temperature) for 1 month. After preserving for one month, a photosensitive film was formed on the surface of a 10 cm x 10 cm glass substrate cleaned in the same manner as in Example 1, using a spinner, by applying a photosensitive composition for a positive type. Then, it was dried on a hot plate at 100 DEG C for 2 minutes to form a film having a thickness of 1 mu m. The appearance of the membrane was visually observed and evaluated as follows.

○ (Good): There are no more than 5 foreign substances on the film.

X (defective): 6 or more foreign substances on the film were observed, and a radial streak shape was observed from the center of the glass substrate.

[Examples 2 to 5]

Positive photosensitive resin compositions 2 to 5 and positive photosensitive resin composition 2 (CA2-1) were prepared in the same manner as in Example 1, except that the (CA2-1) to (CA5-1) To 5 glass substrates 2 to 5 on which a cured film was 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, barrier ribs free from development residue can be obtained. The cured films obtained in Examples 1 to 4 were excellent in ink repellency and excellent in ink repellency even after irradiation with ultraviolet rays / ozone because the repelling ink of the present invention was used, and dots (glass substrate surface) It can be seen that there is a property. On the other hand, the cured film obtained in Example 5 using the ink-repellent agent not according to the present invention had insufficient ink repellency after irradiation with ultraviolet rays / ozone.

Industrial availability

The positive photosensitive resin composition of the present invention is excellent in ink repellency and excellent in ink repellency even after irradiation with ultraviolet rays and ozone, and is capable of producing a partition wall having few residues in dots, Can be suitably used for the production of color filters using organic EL devices, the production of organic EL devices, and the formation of barrier ribs in the production of organic TFT arrays.

The entire contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2012-053448 filed on March 9, 2012 are hereby incorporated herein by reference and the disclosure of the specification of the present invention.

One ; Board
2 ; The coating film of the positive photosensitive resin composition
3; The unexposed portion of the coating film
4 ; Mask
5; ore
6; septum
7; dot
10; A substrate for an optical element used in an inkjet method

Claims

A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitizer (B), and a repellent agent (C)
Wherein the alkali-soluble resin (A) is a novolak type phenolic resin,
(C) comprises a partial hydrolyzed condensate of a mixture comprising a hydrolyzable silane compound represented by the following formula (c-1) and a hydrolyzable silane compound represented by the following formula (c-2) Wherein the fluorine atom content in the repellent agent (C) is 10 to 55 mass%.
[Chemical Formula 1]

(The symbols in the formulas (c-1) and (c-2) are as follows.
R ^{f is 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 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 having 1 to 10 carbon atoms and not containing a fluorine atom,
R ^{H1 represents a} monovalent hydrocarbon group of 1 to 6 carbon atoms,
X ¹ and X ² : a hydrolyzable group,
p: 0, 1 or 2.
3 X ¹ in the formula (c-1), (4-p) X ² in the formula (c-2) and p R ^H1 may be mutually different or the same.

The method according to claim 1,
Wherein the content of the alkali-soluble resin (A) in the total solid content in the positive-working photosensitive resin composition is 10 to 90% by mass.

The method according to claim 1,
Wherein the content of the photosensitive agent (B) in the total solid content in the positive photosensitive resin composition is 0.1 to 50 mass%.

The method according to claim 1,
Wherein the content of the ink-repelling agent (C) in the total solid content in the positive-type photosensitive resin composition is 0.01 to 10 mass%.

The method according to claim 1,
Wherein the number average molecular weight (Mn) of the repellent agent (C) is 500 or more and less than 1,000,000.

delete

The method according to claim 1,
Wherein the photosensitive agent (B) is a compound having a quinonediazide group.

The method according to claim 1,
Wherein the mixture further comprises a hydrolyzable silane compound represented by the following formula (c-3).
(2)

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

The method according to claim 1,
A positive photosensitive resin composition further comprising a solvent (D).

The method according to claim 1,
A positive photosensitive resin composition further comprising a thermal curing agent (E).

11. The method of claim 10,
A positive photosensitive resin composition further comprising a thermosetting accelerator (F).

The method according to claim 1,
A positive photosensitive resin composition further comprising a colorant (G).

1. A barrier rib formed in such a manner that a surface of a substrate is divided into a plurality of sections for pixel formation,
A barrier rib comprising the cured film of the positive photosensitive resin composition according to any one of claims 1 to 5 and 7 to 12.

An optical element having a partition wall positioned between a plurality of pixels and adjacent pixels on a surface of a substrate, wherein the partition wall is formed of the partition described in claim 13.

15. The method of claim 14,
Wherein the optical element is a color filter, a TFT array, or an organic EL element.