KR20200049618A - Photosensitive resin composition for partition wall, cured product thereof, and production method thereof - Google Patents

Abstract

The present invention relates to a resin composition for a partition, which does not cause desired optical density, a desired cross-sectional shape, and a shrinkage difference when cured, and to a cured product thereof. The photosensitive resin composition for a partition comprises: (A) an unsaturated group-containing photosensitive resin; (B) a dendritic polymer having two or more ethylenically polymerizable groups at ends; and (C) a photopolymerization initiator. The partition of the present invention is a cured product obtained by curing the photosensitive resin composition for a partition.

Description

Photosensitive resin composition for bulkhead and its cured product and its manufacturing method {PHOTOSENSITIVE RESIN COMPOSITION FOR PARTITION WALL, CURED PRODUCT THEREOF, AND PRODUCTION METHOD THEREOF}

The present invention relates to a photosensitive resin composition for bulkheads, a cured product obtained by curing the resin composition, and a method for manufacturing the same.

In recent years, in the manufacture of color filters including organic EL elements, quantum dot displays, TFT arrays, and wavelength conversion elements, exposure is unnecessary, and organic layers such as pixels are formed by an inkjet method capable of applying a coloring material only to necessary portions. The inkjet method for pattern printing is employed. Here, the inkjet method is a method of forming a partition on a transparent substrate such as a glass or plastic sheet, and then injecting ink containing a predetermined amount of an organic layer material into an area surrounded by the formed partition.

In the case of the inkjet method, when ink is injected into an area surrounded by the partition wall, it is necessary to impart ink repellency to the partition wall in order to suppress the introduction of ink into the adjacent area and the adhesion of ink to the partition wall. Do. In addition, in order to retain ink in the partition wall, it is required that the partition wall is a thick film. However, since the difference in crosslinking density with respect to the film thickness direction in the exposed portion is enlarged as the partition wall is thickened, it is difficult to obtain a membrane having no wrinkles and a good shape.

Patent Document 1 discloses that a black resist to which an acrylic copolymer is added as an alkali-soluble resin suppresses the occurrence of wrinkles in a thick film having a thickness of 1 µm or more.

Patent Document 2 discloses a dendritic polymer in which a small amount of a polyhydric mercapto compound is added to the polyfunctional acrylate with respect to the ethylenic double bond of the polyfunctional acrylate. Accordingly, it is said that it is possible to provide a resin composition comprising a multi-branched polymer having flexibility and scratch resistance against bending. Here, the dendritic polymer is also referred to as a dendrimer or a multi-branched polymer.

Japanese Patent Publication 2007-286478 International Publication No. 2008/47620

In Patent Document 1, it is said that a resin composition capable of suppressing wrinkles even with a thick film, and Patent Document 2 can provide a resin composition excellent in flexibility and scratch resistance. However, according to the examination of the present inventors, when the partition wall is formed of the resin composition described in Patent Documents 1 and 2, the partition wall that satisfies all the conditions that a desired optical density, a desired cross-sectional shape, and no shrinkage difference when cured does not occur Was not obtained.

The object of the present invention has been achieved in view of these points, and it is to provide a resin composition for a barrier rib and a cured product thereof that do not cause a difference in shrinkage when cured and a desired optical density and desired cross-sectional shape. In addition, an object of the present invention is to provide a method for producing a partition wall using the resin composition.

The photosensitive resin composition for bulkheads according to the present invention comprises: (A) an unsaturated group-containing photosensitive resin, (B) a dendritic polymer having two or more ethylenically polymerizable groups at the ends, and (C) a photopolymerization initiator for a bulkhead comprising a photopolymerization initiator. It is a composition.

The cured product according to the present invention is a cured product obtained by curing the photosensitive resin composition for partition walls.

The method for manufacturing a partition wall according to the present invention comprises the step of forming a coating film by applying the photosensitive resin composition for the partition wall, wherein the component (E) is a black pigment or a mixed organic pigment, on a substrate, and drying the coating film, and exposing the coating film to ultraviolet light. It has a process of exposing with a device and a process of developing and thermally baking the coating film with an aqueous alkali solution. The optical density (OD) of the partition wall is 0.2 to 4.0 / µm.

In addition, the method for manufacturing a partition wall according to the present invention comprises the step of forming a coating film by coating the photosensitive resin composition for the partition wall, wherein the component (E) is a white pigment, on a substrate, and drying the coating film, and the coating film is exposed to a UV light exposure device. It has a process of exposing to, and a process of developing the coating film with an aqueous alkali solution and thermally calcining it. The partition wall has an optical density (OD) of 0.1 to 0.3 / µm.

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the resin composition for partition walls and its hardened | cured material which are excellent in light-shielding property, favorable surface appearance and pattern shape, and excellent surface ink repellency can be provided. In addition, an object of the present invention can provide a method for producing a partition wall using the resin composition.

Hereinafter, the present invention will be described in detail. The photosensitive resin composition for partition walls of the present invention (hereinafter may be abbreviated as a photosensitive resin composition) contains components (A) to (E). The components (A) to (E) will be described below.

(Component (A))

(A) It is preferable that the photosensitive resin containing an unsaturated group which is a component has a polymerizable unsaturated group in one molecule, and an acidic group for expressing alkali solubility, and more preferably contains both a polymerizable unsaturated group and a carboxyl group. The resin is not particularly limited and can be widely used.

Examples of the photosensitive resin containing an unsaturated group include a compound having a hydroxyl group obtained by reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols (hereinafter referred to as "bisphenol type epoxy compound"). There are epoxy (meth) acrylate acid adducts obtained by reacting polybasic carboxylic acids or anhydrides thereof. The epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin or an equivalent thereof. (A) The photosensitive resin containing an unsaturated group as a component, in order to have an ethylenically unsaturated double bond and a carboxyl group, may provide excellent photocurability, good developability, and patterning properties as a photosensitive resin composition, resulting in improvement in physical properties of the light-shielding film. Particularly, the patterning property using the resin is not only a pixel pattern of a thick line formed when, for example, a negative photomask with a 20 μm aperture is used, but also a thin line pixel formed when a negative photomask with a 5 μm aperture is used. Patterns can also have good patterning properties. In addition, "(meth) acrylic acid" is a generic term for acrylic acid and methacrylic acid, and means one or both of them.

It is preferable that the photosensitive resin containing the unsaturated group which is (A) component is a bisphenol type epoxy compound represented by general formula (1).

In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9 represented by formula (2) -Represents a diyl group or a single bond, and l is an integer from 0 to 10.

The bisphenol-type epoxy compound represented by the general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. Since the reaction generally involves oligomerization of the diglycidyl ether compound, an epoxy compound containing two or more bisphenol skeletons is included.

Examples of bisphenols used in this reaction include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and bis (4-hydroxy-3,5-dichlorophenyl). Ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxy Phenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxy Hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, Bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) prop , 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4- Hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4 -Hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy -3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromo Phenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol, and the like. Among these, bisphenols having a fluorene-9,9-diyl group are preferable.

Further, examples of the acid anhydride of (a) dicarboxylic acid or tricarboxylic acid reacting with a hydroxyl group in an epoxy (meth) acrylate molecule obtained by reacting such an epoxy compound with (meth) acrylic acid is a chain hydrocarbon dicarboxyl. Acid anhydrides of acids or tricarboxylic acids, alicyclic dicarboxylic acids or acid monohydrates of tricarboxylic acids, acid dihydrates of aromatic dicarboxylic acids or tricarboxylic acids, and the like. Here, examples of the acid anhydride of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid are succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, Acid anhydrides such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. In addition, acid anhydrides of dicarboxylic acid or tricarboxylic acid in which an optional substituent is introduced, and the like are included. Further, examples of the acid anhydride of an alicyclic dicarboxylic acid or tricarboxylic acid include cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornane dicarboxylic acid, etc. Contains acid anhydride of. Moreover, the acid anhydride of dicarboxylic acid or tricarboxylic acid in which the arbitrary substituent was introduced, etc. are also included. Further, examples of the acid monohydride of the aromatic dicarboxylic acid or tricarboxylic acid include acid monohydrides such as phthalic acid, isophthalic acid, trimellitic acid. Also included are acid dianhydrides of dicarboxylic acids or tricarboxylic acids in which optional substituents have been introduced.

Further, examples of the acid dianhydride of (b) tetracarboxylic acid to react with a hydroxyl group in the epoxy (meth) acrylate molecule obtained by reacting such an epoxy compound with (meth) acrylic acid, acid dianhydride of chain hydrocarbon tetracarboxylic acid, Acid dianhydrides of alicyclic tetracarboxylic acids or acid dianhydrides of aromatic tetracarboxylic acids. Here, examples of the acid dianhydride of the chain hydrocarbon tetracarboxylic acid include acid dianhydrides such as butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid, and tetracar in which an optional substituent is introduced Acid dianhydrides of carboxylic acids are included. Further, examples of the acid dianhydride of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, etc. The acid dianhydride of is included, and also the acid dianhydride of the introduced tetracarboxylic acid of any substituent is included. Further, examples of the acid dianhydride of the aromatic tetracarboxylic acid include acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and biphenyl ether tetracarboxylic acid, and any Acid dianhydrides of the introduced tetracarboxylic acids of the substituents are included.

The molar ratio of (a) dicarboxylic acid or tricarboxylic acid anhydride reacted with epoxy (meth) acrylate to (b) tetracarboxylic acid dianhydride (a) / (b) is 0.01 to 10.0 It is preferable, and it is more preferable that it is 0.02 or more and less than 3.0. When the molar ratio (a) / (b) deviates from the above range, it is not preferable because the optimum molecular weight for obtaining a photosensitive resin composition having good light patterning properties cannot be obtained. In addition, the smaller the molar ratio (a) / (b), the larger the molecular weight, and the alkali solubility tends to decrease.

Moreover, reaction of an epoxy compound and (meth) acrylic acid, and the reaction of the epoxy (meth) acrylate obtained by this reaction with polybasic acid, or its acid anhydride are not specifically limited, A well-known method can be employ | adopted. In addition, the weight average molecular weight (Mw) of the unsaturated group-containing photosensitive resin synthesized in the above reaction is preferably 2000 to 10000, and the acid value is preferably 30 to 200 mg / KOH.

(A) As another example of the resin preferable as a photosensitive resin containing an unsaturated group which is a component, copolymers, such as (meth) acrylic acid and (meth) acrylic acid ester, include resins having (meth) acrylic groups and carboxyl groups. As an example of the resin, (meth) acrylic acid is reacted with a copolymer obtained by copolymerizing (meth) acrylic acid esters containing glycidyl (meth) acrylate in a solvent, and dicarboxylic acid or tricarboxylic acid is finally reacted. A polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting an anhydride of the above is included. The copolymer is 20 to 90 mol% of a repeating unit derived from a diester glycerol esterified with (meth) acrylic acid with hydroxyl groups at both ends, as shown in Japanese Patent Laid-Open No. 2014-111722, and at least one copolymerizable therewith. A copolymer composed of 10 to 80 mol% of repeating units derived from a polymerizable unsaturated compound, and having a number average molecular weight of 2000 to 20,000 and an acid value of 35 to 120 mgKOH / g, and Japanese Patent Publication No. 2018-141968 Weight average molecular weight (Mw) 3000-50000, acid value 30-200 mg including the unit derived from the (meth) acrylic acid ester compound, and the unit having a (meth) acryloyl group and a di or tricarboxylic acid residue. Reference may be made to alkali-soluble resins containing a polymerizable unsaturated group, which is a polymer of / KOH.

About the photosensitive resin containing the unsaturated group of the component (A), only 1 type may be used individually and 2 or more types may be used together.

(Component (B))

The dendritic polymer as component (B) is a multi-branched polymer having two or more ethylenically polymerizable groups at the ends. It is preferable that the ethylenic polymerizable group is derived from (meth) acrylate. Here, the ethylenically polymerizable group is a group having a carbon-carbon double bond, and a nucleating agent such as a mercapto compound in a conjugated compound such as an α, β-unsaturated carbonyl compound having a carbonyl group bonded to the carbon-carbon double bond. It is known that Michael addition reaction occurs with the vinyl group having the strongest interaction with. Therefore, by reacting a compound having a plurality of ethylenically polymerizable groups, such as an α, β-unsaturated carbonyl compound, and a compound having a plurality of nucleophilic groups, such as a polyvalent mercapto compound, an addition reaction to the carbon at the β position with respect to the carbonyl group is performed. Occurs. Here, when there are a plurality of groups in which an addition reaction occurs, many branches are formed to become a dendritic polymer. Such dendritic polymers are known from Patent Literature 2 and the like, and can be obtained by the methods described in these documents.

(B) As an example of the dendritic polymer which is a component, the polyfunctional (meth) acrylate represented by general formula (3) and the polyhydric mercapto compound represented by general formula (4) are added by Michael (carbon at the β-position with respect to the carbonyl group- Polymerized by addition to a carbon double bond).

Here, the Michael addition of the polyvalent mercapto compound represented by the general formula (4) to the polyfunctional (meth) acrylate represented by the general formula (3) is based on the carbon-carbon double bond even after the resulting dendritic polymer is obtained. When the total amount of carbon-carbon double bonds of the compound represented by the general formula (3) is 100 mol%, the carbon-carbon double bonds remain in the range of 0.1 to 50 mol% so that radiation polymerization can be performed. It is preferred.

For example, the mercapto group of the polyvalent mercapto compound represented by the general formula (4) and the carbon-carbon double bond of the polyfunctional (meth) acrylate represented by the general formula (3) (to the general formula (3)) In addition, the ratio of addition with CH ₂ = C (R ₅ )-is double bond, and in the case of calculation of the molar ratio, the ratio of mercapto group / double bond molar ratio is 1/100 to 1 It is preferably / 3, more preferably 1/50 to 1/5, and particularly preferably 1/20 to 1/8.

Further, it is preferable that the dendritic polymer has a sufficient amount of functional groups for radiation polymerization. For this reason, in the molecular weight of the dendritic polymer, the molecular weight per 1 mol of carbon-carbon double bond is preferably in the range of 100 to 10000. Further, the weight average molecular weight (Mw) of the dendritic polymer is preferably in the range of 1000 to 20,000, more preferably in the range of 8000 to 15000.

In the general formula (3), R ₅ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₆ is n hydroxyl group among m hydroxyl groups of the polyhydric alcohol R ₇ (OH) _m . ). R ₇ (OH) _m is a polyhydric alcohol based on a non-aromatic straight-chain or branched-chain hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyhydric alcohol formed by linking multiple molecules of polyhydric alcohols through ether bonding by dehydration condensation of the alcohol Ethers, or their polyhydric alcohols or esters of polyhydric alcohol ethers and hydroxy acids. In general formula (3), m represents the integer of 2-20, n represents the integer of 2-20, but m≥n.

Examples of the polyfunctional (meth) acrylate represented by the general formula (3) are ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) Acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate Tri, pentaerythritol hepta (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, epi Chlorohydrin-modified hexahydrophthalic acid di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate , Propylene oxide-modified neopentyl glycol di (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolpropane benzoate (meth) acrylate , Tris ((meth) acryloxyethyl) isocyanure (Meth) such as yttrium, alkoxy-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, and dimethylolpropane tetra (meth) acrylate Acrylic esters. These compounds may be used alone or in combination of two or more.

Wherein in the formula (4), R ₈ is a single bond or a 2 to 6-valent group having 1 to 6 carbon atoms of a hydrocarbon group-containing group, p is unity when R ₈ is unity 2, R ₈ is 2 to 6 valent when date It represents the integer of 2-6. Here, R ₈ may have a single bond or a substituent, and may further contain an oxygen atom in the skeleton of a hydrocarbon group having 1 to 6 carbon atoms or a hydrocarbon group. These hydrocarbon groups may be straight chain or branched chain. In addition, these hydrocarbon group-containing groups may also have a carbonyloxy group bonded to a part of the thiomethyl group (HSCH _2- ) represented in the general formula (4). Moreover, when an oxygen atom is contained in the skeleton of a hydrocarbon group, it is preferable that both ends are a hydrocarbon group. Here, p represents an integer of 2 to 6, and corresponds to the valence of R _8. Therefore, when R ₈ is a single bond, p is 2, when R ₈ has 1 carbon, p is 2 to 4, and when R ₈ has 2 to 6 carbons, p is 2 to 6.

Examples of the polyvalent mercapto compound represented by the general formula (4) are 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, and trimethyl Allpropane tri (mercaptoacetate), trimethylolpropane tri (mercaptopropionate), pentaerythritol tetra (mercaptoacetate), pentaerythritol tree (mercaptoacetate), pentaerythritol tetra (mercaptopropionate), Dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (mercaptopropionate), and the like.

When synthesize | combining the dendritic polymer which is said (B) component, you may add a polymerization inhibitor as needed. Examples of the polymerization inhibitor include hydroquinone-based compounds and phenol-based compounds. Specific examples of these include hydroquinone, methoxyhydroquinone, catechol, p-tert-butyl catechol, cresol, dibutylhydroxytoluene, 2,4,6-tri-tert-butylphenol (BHT), and the like. Is included.

(B) Confirmation of the completion of synthesis of the component dendritic polymer can be confirmed by liquid chromatography, gel filtration chromatography, or other general analyzer.

(B) When synthesizing a dendritic polymer as a component, the Michael addition reaction in which the polyvalent mercapto compound represented by the general formula (4) is added to the double bond of the polyfunctional (meth) acrylate represented by the general formula (3) Occurs. This reaction can be performed by mixing a polyfunctional (meth) acrylate and a polyvalent mercapto compound and adding a basic catalyst at room temperature to 100 ° C. The reaction time is usually 30 minutes to 20 hours, and more preferably 6 to 12 hours.

The detailed mechanism of that the component (B) dendritic polymer having excellent properties as a photosensitive resin composition is not certain. However, in general, the dendritic polymer using thiol and acrylate has a unique structure, which is less susceptible to reaction inhibition by oxygen or solvent in radical polymerization, cures at low energy, has little curing shrinkage, and deteriorates the surface roughness of the coating film. From the viewpoint of being suppressed, it is considered to have particularly excellent properties, for example, in the case of a light shielding film.

In addition, the ratio of the content of the components (A) and (B) is preferably 95/5 to 40/60, more preferably 60/40 to 50/50. By setting the ratio of the content of the components (A) and (B) within a preferred range, it is possible to suppress peeling reduction and to perform appropriate patterning to suppress surface wrinkles. Further, by setting it within a more preferable range, it is possible to obtain a cured film pattern excellent in pattern shape and pattern surface properties with appropriate development time by patterning a thick film having a thickness of 5 to 25 μm required for the partition wall.

When the proportion of the component (A) is less than the above range, the cured product after the photocuring reaction tends to be fragile. Conversely, when the mixing ratio of the component (A) is more than the above range, it is difficult to increase the dissolution rate in the alkali developing solution of the unexposed portion. Therefore, when the blending component of the component (A) is more than the above range, it is possible to control at an appropriate developing speed when patterning a film thickness of 2 µm or less, which is usually formed for color filters, but it is possible to control the film thickness to 5 µm or more. When it is patterned, it becomes difficult to control an appropriate developing speed and pattern shape.

(Other photopolymerizable monomers)

In order to control the photocurability, in addition to the component (A) and the component (B), a photopolymerizable monomer having at least two ethylenically unsaturated bonds (component B ') can be used in combination. Examples of the photopolymerizable monomer are ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (Meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylic Late, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene, alkylene oxa And (meth) acrylic acid esters such as id-modified hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These photopolymerizable monomers may be used alone or in combination of two or more.

(Component (C))

(C) Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone Benzophenones such as acetophenones, benzophenone, 2-chlorobenzophenone, and p, p'-bisdimethylaminobenzophenone; Benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluoro Biimidazole type such as phenyl) -4,5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenyl biimidazole, 2,4,5-triarylbiimidazole Compounds; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-triclo Halomethylthiazole compounds such as romethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole; 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl-1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-tri Methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1, Halomethyl-S-triazine compounds such as 3,5-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- ( 4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butan-1-one-oxime-O-acetate, etc. O-acyloxime-based compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Sulfur compounds; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, etc. Organic peroxides of; thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, tertiary amines such as triethanolamine and triethylamine, and the like. The photopolymerization initiator may be used alone or in combination of two or more.

In particular, when using a photosensitive resin composition containing a colorant, it is preferable to use O-acyloxime compounds (including ketooxime). In addition, when a coloring agent is used at a high concentration of a paint and when forming a light-shielding film pattern, it is preferable to use an O-acyloxime-based photopolymerization initiator having a molar extinction coefficient at 365 nm of 10000 or more. As the specific compound group, there is an O-acyloxime-based photopolymerization initiator represented by the general formula (5). In addition, the term "photopolymerization initiator" used in the present invention is used to mean a sensitizer.

(In formula (5), R ₉ and R ₁₀ each independently represent a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group, or a C4 to C12 heterocyclic group, and R ₁₁ is C1 to C1 to It represents an alkyl group of C15, an aryl group of C6 to C18, an arylalkyl group of C7 to C20, wherein the alkyl group and the aryl group are C1 to C10 alkyl group, C1 to C10 alkoxy group, C1 to C10 alkanoyl group, halogen It may be substituted, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and the alkyl group may be a straight chain, branched or cyclic alkyl group.

The amount of the photopolymerization initiator used in the component (C) is preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of each component in the components (A) and (B). When the compounding ratio of the component (C) is less than 3 parts by weight, the sensitivity decreases, and the rate of photopolymerization becomes slow. On the other hand, when the compounding ratio of component (C) exceeds 30 parts by weight, the sensitivity is too strong, and there is a fear that a desired pattern line width and a desired pattern edge cannot be obtained.

(Component (D))

The ink repellent agent of component (D) imparts ink repellency to the ink on the partition wall. When injecting ink containing a predetermined amount of the organic layer material into the region surrounded by the partition wall, it is preferable to contain an ink repellent agent. This is because the introduction of ink into adjacent partition walls and the adhesion of ink to the partition walls can be suppressed.

Examples of the ink repellent agent of component (D) include silicone-containing compounds and fluorine-based compounds. In the present invention, the ink repellent agent of component (D) is preferably a fluorine-based compound, and more preferably a fluorine-based compound containing a crosslinking group. This is because when a fluorine-based compound is used as the ink repellent, the group having the fluorine atom is oriented on the surface of the partition wall, thereby suppressing ink bleeding and color mixing. In addition, it is because it is possible to suppress the group from entering the region of the adjacent partition wall by repelling the ink. In addition, by using a fluorine-based compound containing a crosslinking group, the crosslinking reaction on the surface can be accelerated when exposing the formed coating film. This makes it difficult for the ink repellent agent to flow out of the coating film in the development process, so that a partition wall having high ink repellency can be obtained.

An epoxy group or an ethylenically unsaturated group is preferable as the crosslinking group, and an ethylenically unsaturated group is preferred from the viewpoint of suppressing spillage of the ink repellent agent from the partition wall. Here, examples of the fluorine-based compound having an ethylenically unsaturated group include perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt, and perfluoroalkyl group Oligomers containing hydrophilic groups, oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups and hydrophilic groups and new organic groups, urethanes containing perfluoroalkyl and hydrophilic groups, perfluoroalkyl esters, perfluoro And fluorine-containing organic compounds such as alkyl phosphate esters.

The molecular weight of the ink repellent agent of the component (D) used in the present invention is not particularly limited, and may be small or large. Here, the use of an ink repellent having a large molecular weight is preferable because the fluidity of the ink repellent by firing can be suppressed and the flow of the ink repellent from the partition can be suppressed. In addition, the weight average molecular weight (Mw) of the ink repellent agent is preferably in the range of 100 to 200,000, more preferably in the range of 1,000 to 150,000, and particularly preferably in the range of 10,000 to 130,000. When the mass average molecular weight (Mw) is at least the lower limit value (Mw: 100), the ink repellent agent tends to migrate to the upper surface when forming a cured film using a negative photosensitive resin composition. Moreover, since it is less than the upper limit (Mw: 200,000), the opening residue is less, which is preferable.

The content of the ink repellent agent of the component (D) in the photosensitive resin composition of the present invention is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 8% by mass or less, and more preferably 0.1% by mass, based on the total solid content. It is especially preferable that it is 6 mass% or more. Here, by making the content of the ink repellent agent 0.01% by mass or more, it has high ink repellency, and by setting the content of the ink repellent agent to 10% by mass or less, leakage to the pixel portion can be suppressed.

Examples of the ink repellent agent include a ink repellent agent composed of a compound whose main chain is a hydrocarbon chain and a fluorine atom in the side chain. In addition, an ink repellent composed of a partially hydrolyzed condensate of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine atom may be used as the ink repellent agent. The ink repellent agent may be used alone or in combination of two or more.

((E) component)

The colorant of the black pigment, mixed color organic pigment, and white pigment of the component (E) that can be used in the present invention has an average particle diameter of 1 to 1000 nm (laser diffraction / scattering method particle size distribution system or dynamic light scattering method particle size distribution system). ), A known colorant can be used without particular limitation.

Here, examples of the black pigment include perylene black, cyanine black, aniline black, carbon black, titanium black, and the like. Examples of mixed organic pigments include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, styrene pigments, perylene pigments, and perinone pigments , A pigment mixed with at least two colors selected from organic pigments such as quinophthalone pigment, diketopyrrolopyrrole pigment, and thioindigo pigment. Examples of white pigments include titanium oxide pigments and composite oxide pigments; And inorganic fillers such as calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, and barium sulfate. These (E) components may be used alone or in combination of two or more depending on the function of the target photosensitive resin composition.

Moreover, as an example of the organic pigment which can be used as a component (E), the thing of the following numbers is included in the color index name, but it is not limited to this.

Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc.

Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.

Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.

Pigment Green 7, 36, 58, etc.

Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, 80, etc.

Pigment Violet 19, 23, 37, etc.

Although the mixing ratio of the colorant of the component (E) can be arbitrarily determined by a desired light-shielding degree, it is preferably 1 to 80% by mass relative to the solid component in the photosensitive resin composition. Here, when forming a black partition, it is more preferably 3 to 50% by mass, and when forming a white partition, it is more preferably 10 to 80% by mass.

The component (E) is a colorant dispersion dispersed in a solvent, and is usually mixed with other compounding components. At this time, a dispersant (component E ') can be added. The dispersant may be a known compound (dispersant, dispersant wetting agent, compound sold under the names of dispersing accelerators, etc.) used for dispersing pigments (colorants), etc., without particular limitation. Examples of the dispersant include cationic polymer-based dispersants, anionic polymer-based dispersants, nonionic polymer-based dispersants, and pigment derivative-type dispersants (dispersing aids). In particular, the dispersant has cationic functional groups such as imidazolyl groups, pyrrolyl groups, pyridyl groups, primary, secondary or tertiary amino groups as adsorption points to colorants, and has an amine value of 1 to 100 mgKOH / g, water. It is preferable that the average molecular weight is a cationic polymer-based dispersant in the range of 10 to 100,000. It is preferable that the compounding quantity of this dispersing agent is 1 to 35 mass% with respect to a coloring agent, and it is more preferable that it is 2 to 25 mass%. In addition, high-viscosity materials such as resins generally have a function of stabilizing dispersion, but those that do not have a dispersion promoting ability are not treated as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion.

The photosensitive resin composition of this invention can be prepared by mixing and dispersing the said (A)-(E) component by an appropriate method.

(solvent)

It is preferable to use the solvent which is a component (F) other than the components of (A)-(E) for the photosensitive resin composition of this invention. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Glycol ethers such as monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, cellosolve acetate, ethylcellosolve acetate, butylcellosolve acetate, carbitol acetate, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. The acetic acid esters of are included. These can be used alone or in combination of two or more of them to dissolve and mix to obtain a uniform solution phase composition.

Further, in the photosensitive resin composition of the present invention, if necessary, resins other than (A) components such as epoxy resins, curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, antifoaming agents, surfactants, coupling agents Additives, such as, can be blended. Here, examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, phenothiazine, and a hindered phenol compound. Examples of plasticizers include dibutylphthalate, dioctylphthalate, tricresyl phosphate, and the like. Examples of fillers include glass fibers, silica, mica, alumina, and the like. Examples of the antifoaming agent or leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like. Examples of the coupling agent include 3- (glycidyloxy) propyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-ureidopropyl triethoxysilane, etc. This is included.

The photosensitive resin composition of the present invention includes (A) an unsaturated group-containing photosensitive resin as component (A), a dendritic polymer as component (B), and (C) component as a solid component (a solid component includes a monomer that becomes a solid component after curing) excluding a solvent. It is preferable that the phosphorus photopolymerization initiator, the ink repellent agent (D), and the coloring agent (E) in total are 80% by mass or more, preferably 90% by mass or more. The amount of the solvent varies depending on the target viscosity, but is preferably 40 to 90% by mass relative to the total amount.

In addition, the cured product (bulk wall) obtained by curing the photosensitive resin composition of the present invention is cured by, for example, applying a solution of the photosensitive resin composition to a substrate, drying the solvent, and irradiating light (including ultraviolet rays, radiation, etc.). It is obtained by. A photomask or the like is used to form a portion that does not and does not touch the light, and only the portion that the light touches is cured to dissolve the other portion with an alkali solution, whereby a desired pattern of barrier ribs is obtained.

Each process of the film-forming method by application | coating and drying of a photosensitive resin composition is illustrated concretely.

As a method of applying the photosensitive resin composition to the substrate, any method such as a known solution immersion method, a spray method, a roller coater, a land coater, a slit coater or a spinner can be used. By these methods, a film is formed by applying a desired thickness and then removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, or the like, vacuum drying, or a combination thereof. The heating temperature and the heating time in pre-baking can be appropriately selected depending on the solvent used, but is preferably performed at 80 to 120 ° C for 1 to 10 minutes, for example.

As the radiation used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like can be used, but the wavelength range of the radiation is preferably 250 to 450 nm. Moreover, as a developing solution suitable for this alkali development, aqueous solutions, such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide, can be used, for example. These developer solutions can be appropriately selected in accordance with the properties of the resin layer, but it is also effective to add a surfactant if necessary. The developing temperature is preferably 20 to 35 ° C, and a fine image can be precisely formed using a commercially available developer or ultrasonic cleaner. Moreover, after alkali development, it is washed with water normally. As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid growth) developing method, or the like can be applied.

After developing in this way, heat treatment (post baking) is performed at 180 to 250 ° C for 20 to 100 minutes. However, when the heat resistance of the substrate to be formed is low, the composition may be designed so that the post-baking conditions at 80 to 180 ° C for 30 to 100 minutes can be performed. This post-baking is performed for the purpose of increasing the adhesion between the patterned coating film and the substrate. This is done by heating with an oven, hot plate or the like, similar to prebaking.

From the above, in the present invention, in the present invention, the optical density (OD) is 0.2 to 4.0 / µm, the black partition wall with a taper angle of 21 ° or more, and the optical density (OD) is 0.1 to 0.3 / µm, and the taper angle of white is 21 ° or more. Bulkhead can be obtained. Further, a black partition wall with an optical density (OD) of 0.2 to 4.0 / µm, a taper angle of 51 ° or more, and a white partition wall with an optical density (OD) of 0.1 to 0.3 / µm and a taper angle of 51 ° or more can be obtained. .

The photosensitive resin composition of the present invention can be used for the production of color filters including organic EL elements, quantum dot displays, TFT arrays and wavelength conversion elements.

(Example)

Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited to these. Moreover, the synthesis example of the photosensitive resin containing the unsaturated group which is (A) component, and the dendritic polymer which is (B) component is shown. In addition, the scope of the present invention is not limited by these examples.

The symbols used in Synthesis Examples 1 to 3 are as follows.

BPFE: Bisphenol fluorene-type epoxy compound (9,9-bis (4-hydroxyphenyl) fluorene reacted with chloromethyloxyran (epoxy equivalent: 250 g / eq).

AA: acrylic acid

PGMEA: Propylene glycol monomethyl ether acetate

TEAB: tetraethylammonium bromide

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride

THPA: Tetrahydrophthalic anhydride

MAA: methacrylic acid

MMA: methyl methacrylate

CHMA: cyclohexyl methacrylate

AIBN: Azobisisobutylonitrile

GMA: glycidyl methacrylate

TPP: triphenylphosphine

TBPC: 2,6-di-tert-butyl-p-cresol

PTMA: pentaerythritol tetra (mercaptoacetate)

DPHA: mixture of dipentaerythritol pentaacrylate and hexaacrylate

HQ: Hydroquinone

BzDMA: benzyldimethylamine

[Synthesis Example 1]

In a 500 ml four-neck flask with a reflux cooler, BPFE (114.4 g (0.23 mol), AA (33.2 g (0.46 mol)), PGMEA (157 g) and TEAB (0.48 g)) were added and stirred at 100 to 105 ° C. for 20 hours. Subsequently, BPDA (35.3 g (0.12 mol)) and THPA (18.3 g (0.12 mol)) were added into the flask, and stirred at 120 to 125 ° C for 6 hours to prepare an unsaturated group-containing photosensitive resin (A) -1. The obtained resin solution had a solid content concentration of 56.1 mass%, an acid value (in terms of solid content) of 103 mgKOH / g, and Mw of 3600 by GPC analysis.

[Synthesis Example 2]

In a 1000 ml four-necked flask with nitrogen inlet and reflux tubes, MAA (51.65 g (0.60 mol)), MMA (36.04 g (0.36 mol)), CHMA (40.38 g (0.24 mol)), AIBN (5.91 g), and PGMEA (360 g) was added, and the mixture was polymerized by stirring for 8 hours at 80 to 85 ° C under a nitrogen stream. Further, GMA (61.41 g (0.43 mol)), TPP (2.27 g) and TBPC (0.086 g) were added into the flask, and stirred at 80 to 85 ° C. for 16 hours to obtain an unsaturated group-containing photosensitive resin (A) -2. . The obtained resin solution had a solid content concentration of 35.7 mass%, an acid value (in terms of solid content) of 50 mgKOH / g, and Mw of GPC analysis of 19600.

[Synthesis Example 3]

In a 1 L 4-neck flask, PTMA (20 g (mercapto group: 0.19 mol)), DPHA (212 g (acrylic group: 2.12 mol)), PGMEA (58 g), HQ (0.1 g), and BzDMA (0.01 g) It injected | threw-in and stirred at 60 degreeC for 12 hours, and superposed | polymerized, and the dendritic polymer (B) was obtained. The concentration of solid content of the obtained dendritic polymer was 80% by mass, and Mw by GPC analysis was 10000. In the dendritic polymer, disappearance of mercapto groups was confirmed by the iodine titration method.

The solid content concentration, acid value and molecular weight of the unsaturated group-containing photosensitive resin and the dendritic polymer obtained in Synthesis Examples 1 to 3 were determined by the following method.

[Solid content concentration]

1 g of the resin solution obtained in the Synthesis Example was impregnated into a glass filter [weight: W0 (g)], weighed [W1 (g)], and heated at 160 ° C for 2 hours from the weight [W2 (g)] by the following equation. I got it.

Solid content concentration (% by weight) = 100 × (W2-W0) / (W1-W0)

[Acid value]

The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus (Hiranuma Inc., trade name COM-1600).

[Molecular Weight]

Gel permeation chromatography (GPC) [manufactured by Tosoh Corporation, trade name: HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgelSuper-H-2000 (2 pcs.) + TSKgelSuperH-3000 (1 pc.) + TSKgelSuperH-4000 (1 pc.) ) + TSKgelSuper-H5000 (1 pc.) [Tosoh Corporation], temperature: 40 ° C., rate: 0.6 ml / min], and measured as standard polystyrene [Tosoh Corporation, PS-Oligomer Kit] weight average molecular weight (in terms of conversion) Mw).

Tables 1 and 2 show the respective components of the photosensitive resin composition for partition walls of Examples 1 to 17 and Comparative Example 1 and their blending amounts. In addition, each component of (A)-(E) in Tables 1 and 2 is a quantity of solid content other than a solvent, and the amount of the solvent of a resin solution and a colored dispersion liquid is shown by adding to the solvent (F). In addition, the components represented by (A)-(F) were described below.

Symbols used in Examples and Comparative Examples shown in Tables 1 and 2 are as follows.

(A) Photosensitive resin containing an unsaturated group

(A) -1: Resin obtained in Synthesis Example 1

(A) -2: Resin obtained in Synthesis Example 2

(B) dendritic polymer: dendritic polymer obtained in Synthesis Example 3

(B ') Photopolymerizable monomer: a mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(C) Photopolymerization initiator: oxime ester-based photopolymerization initiator (ADEKA ARKLS NCI-831, manufactured by ADEKA Corporation, "Adeka Acrouz" is a registered trademark of the company)

(D) Ink ink: (MAGAFACE RS-72-K, DIC Corporation, `` Megapack '' is a registered trademark of the company)

(E) Coloring agent

(E) -1: Carbon black

(E) -2: lactam black

(E) -3: titanium oxide

(E ') Dispersant

(F) Solvent: PGMEA

[Example 1]

Each component from (A) to (F) was blended at the ratios shown in Table 1, and uniformly mixed to obtain a photosensitive resin composition for partition walls according to Example 1.

The following evaluation was performed using the photosensitive resin composition for partition walls obtained in Example 1.

[Optical concentration (OD)]

The photosensitive resin composition for bulkheads was coated on a 125 mm × 125 mm glass plate using a spin coater (EAGLE XG, manufactured by Corning Incorporated, “EAGLE XG” is a registered trademark of the company) so that the film thickness after post-baking is 1 μm. It was applied and prebaked at 90 ° C for 1 minute. After heat post-baking at 230 ° C for 30 minutes using a hot air dryer, measurement was performed using a Macbeth transmission densitometer, and optical density (OD) was evaluated.

The optical density (OD) was calculated by the following equation (1).

Optical density (OD) =-log ₁₀ T (1)

(T represents transmittance)

[Development time (film thickness: 10 µm)]

The photosensitive resin composition for partition walls was coated on a 125 mm × 125 mm glass plate (EAGLE XG, manufactured by Corning Incorporated) using a spin coater so that the film thickness after post-baking was 10 μm and pre-baked at 90 ° C. for 1 minute. . On the dry coating film, a negative photomask with a 20 µm opening was covered with an exposure gap of 100 µm, and an ultraviolet ray of 80 mJ / cm 2 was irradiated with an ultra-high pressure mercury lamp having an i-line illumination of 30 mW / cm 2 to perform a photocuring reaction of the photosensitive portion. . Subsequently, the development time at which the pattern began to appear at a shower developing pressure of 1 kgf / cm 2 was evaluated for this exposed plate using 25 ° C. and a 0.05% potassium hydroxide aqueous solution.

The development time when the film thickness was 10 µm was evaluated as follows.

(evaluation)

○: The development time that the pattern starts to appear is less than 2 minutes.

△: The development time at which the pattern starts to appear is 2 minutes or more and less than 3 minutes.

×: The development time at which the pattern starts to appear is 3 minutes or more

[Development time (film thickness: 2 μm)]

Evaluation was performed in the same manner as the operation of the development time of the film thickness (10 μm) except that the film thickness after post-baking was 2 μm.

The development time when the film thickness was 2 µm was evaluated as follows.

(evaluation)

○: The development time at which the pattern starts to appear is 20 seconds or more.

△: Development time at which the pattern starts to appear is less than 20 seconds.

×: development time at which the pattern starts to appear is less than 5 seconds

[Patternability of thin wire (film thickness: 5 µm)]

The photosensitive resin composition for partition walls was coated on a 125 mm × 125 mm glass plate (EAGLE XG, manufactured by Corning Incorporated) using a spin coater so that the film thickness after post-baking was 10 μm and pre-baked at 90 ° C. for 1 minute. . On a dry coating film, a negative photomask with a 5 µm opening was covered with an exposure gap of 100 µm, and an ultraviolet ray of 80 mJ / cm 2 was irradiated with an ultra-high pressure mercury lamp with an i-line illumination of 30 mW / cm 2 to perform a photocuring reaction of the photosensitive portion. . Subsequently, this exposure-finished plate was 5 kgf / cm 2 pressure after development after 10 seconds elapsed from the development time at which the pattern began to appear at a developing pressure of 1 kgf / cm 2 using a 25 ° C., 0.05% aqueous potassium hydroxide solution. By spray washing with water, the unexposed portion of the coating film was removed, and it was confirmed whether or not a pixel pattern was formed on the glass substrate.

[Patternability of thick line (film thickness: 20㎛)]

It was confirmed whether or not a pixel pattern was formed on the glass substrate as in the patterning property of the thin wire except that the opening of the negative photomask was changed from 5 µm to 20 µm.

The evaluation of the patterning characteristics of thin and thick lines was evaluated as follows.

(evaluation)

○: pattern is formed

(Triangle | delta): Although a pattern is formed, peeling is seen in part

×: No pattern is formed

[Taper angle]

The photosensitive resin composition for partition walls was coated on a 125 mm × 125 mm glass plate (EAGLE XG, manufactured by Corning Incorporated) using a spin coater so that the film thickness after post-baking was 10 μm and pre-baked at 90 ° C. for 1 minute. . On the dry coating film, a negative photomask with a 20 µm opening was covered with an exposure gap of 100 µm, and an ultraviolet ray of 80 mJ / cm 2 was irradiated with an ultra-high pressure mercury lamp having an i-line illumination of 30 mW / cm 2 to perform a photocuring reaction of the photosensitive portion. . Subsequently, this exposure-finished plate was 5 kgf / cm 2 pressure after development after 10 seconds elapsed from the development time at which the pattern began to appear at a developing pressure of 1 kgf / cm 2 using a 25 ° C., 0.05% aqueous potassium hydroxide solution. By spray washing with water, the unexposed portion of the coating film was removed, and a pixel pattern was formed on the glass substrate. The formed pixel pattern (lattice-shaped partition wall) was cut to prepare a sample for cross-section observation, and the cross-sectional shape of the partition wall was observed using a scanning electron microscope (manufactured by Keyence Corporation) to measure the taper angle.

The evaluation of the taper angle was evaluated as follows.

(evaluation)

◎: taper angle is 51 to 90 °

○: taper angle is 21-50 °

×: taper angle is 5 to 20 °

(Evaluation of surface wrinkles)

For the taper angle evaluation sample, the surface of the formed pixel pattern was observed with an optical microscope to evaluate the presence or absence of wrinkles.

Evaluation of surface wrinkles was evaluated as follows.

(evaluation)

○: No wrinkles on the surface

△: There are wrinkles that do not affect the next process.

×: surface has wrinkles

[Examples 2 to 17 and Comparative Example 1]

Similarly to Example 1, Examples 2 to 17 and Comparative Examples 1 were also blended with the components from (A) to (F) at the ratios shown in Table 1, and uniformly mixed to obtain Examples 2 to 17 and Comparative Examples. The photosensitive resin composition for partition walls according to 1 was obtained. Each evaluation of the photosensitive resin composition for partition walls affecting Examples 2 to 17 and Comparative Example 1 was performed in the same manner as in Example 1.

The evaluation results of Examples 1 to 17 and Comparative Example 1 are shown in Tables 3 and 4.

From the evaluation results shown in Tables 3 and 4, it was confirmed that wrinkles were not formed on the surface of the pixel pattern after curing by using the unsaturated group-containing photosensitive resin (A) and the dendritic polymer (B) together. Therefore, the dendritic polymer (B) is effective in suppressing the shrinkage difference when the photosensitive resin composition for partition walls is cured.

In addition, by adjusting the compounding amount of the unsaturated group-containing photosensitive resin (A) and the blending amount of the dendritic polymer (B), it is possible to provide a photosensitive resin composition for partition walls that can be applied from a thin film such as 2 μm to a thick film such as 10 μm.

Further, by using an epoxy acrylate acid adduct derived from a bisphenol-type epoxy compound (for example, (A) -1) as an unsaturated group-containing photosensitive resin, good patterning property can be obtained not only in the thick line but also in the fine line. I knew that.

The photosensitive resin composition of the present invention is very useful for the production of color filters including organic EL elements, quantum dot displays, TFT arrays and wavelength conversion elements. In addition, since it is also a composition specialized for thick film partition walls, it is considered to be useful as a color mixing preventing material for strong light source bodies such as mini LED and micro LED partition walls.

Claims (8)

(A) a photosensitive resin containing an unsaturated group,
(B) a dendritic polymer having two or more ethylenically polymerizable groups at the ends,
(C) Photosensitive resin composition for partition walls containing photopolymerization initiator. In accordance with paragraph 1,
The component (A) is obtained by further reacting a reactant of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the general formula (1) with (meth) acrylic acid with a polybasic carboxylic acid or anhydride thereof. A photosensitive resin composition for bulkheads, characterized in that it is an unsaturated group-containing photosensitive resin.

[In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9 represented by the general formula (2) -Represents a diyl group or a single bond, and l is an integer from 0 to 10]

The method of claim 1 or 2,
The component (B) is a polyvalent mercapto compound represented by the general formula (4), to a part of the carbon-carbon double bond in the (meth) acryloyl group of the polyfunctional (meth) acrylate represented by the general formula (3) It is a dendritic polymer obtained by adding a photosensitive resin composition for a partition wall.

[In formula (3), R ₅ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₆ represents n hydroxyl groups among m hydroxyl groups of the polyhydric alcohol R ₇ (OH) _m . Represents the rest of the donation to the ester bond in the m, m represents an integer from 2 to 20, n represents an integer from 2 to 20, but m≥n]

[Equation (4) of, R ₈ is a single bond or a group containing 2 to 6-valent group having 1 to 6 carbon atoms of a hydrocarbon, p is unity when R ₈ is unity 2, R ₈ is 2 to 6 valent when 2 to date Represents an integer of 6] The method according to any one of claims 1 to 3,
The photosensitive resin composition for bulkheads comprises a ink repellent as a component (D), the photosensitive resin composition for bulkheads. The method according to any one of claims 1 to 4,
The photosensitive resin composition for bulkheads comprises at least one colorant selected from black pigments, mixed organic pigments, and white pigments as component (E), and the photosensitive resin composition for bulkheads. Hardened | cured material formed by hardening the photosensitive resin composition for partition walls in any one of Claims 1-5. (E) The step of forming a coating film by applying the photosensitive resin composition for partitions according to any one of claims 1 to 4, wherein the component is a black pigment or a mixed organic pigment on a substrate, and drying the coating film.
A step of exposing the coating film with an ultraviolet exposure apparatus,
A method for producing a barrier rib having a step of developing and thermally firing the coating film with an aqueous alkali solution,
The method of manufacturing a partition wall, characterized in that the optical density (OD) of the partition wall is 0.2 to 4.0 / ㎛. (E) The step of applying a photosensitive resin composition for a barrier rib according to any one of claims 1 to 4, wherein the component is a white pigment, onto a substrate to form a coating film, and drying the coating film.
A step of exposing the coating film with an ultraviolet exposure apparatus,
A method for producing a barrier rib having a step of developing and thermally firing the coating film with an aqueous alkali solution,
The method of manufacturing a partition wall, characterized in that the optical density (OD) of the partition wall is 0.1 to 0.3 / ㎛.