TW201314366A - Negative photosensitive resin composition, partition wall, black matrix and optical element - Google Patents

Abstract

Provided are: a negative photosensitive resin composition, which contains a pigment at high concentration and is capable of producing a black matrix that has high light shielding properties, which has high re-solubility, which is capable of providing a coating film by a slit coating method, said coating film being free from defects, and which has such a viscosity that enables coating by a slit coating method; a partition wall which is formed by curing the photosensitive resin composition and has high light shielding properties; and an optical element which has the partition wall. A negative photosensitive resin composition, which contains an alkali-soluble resin, a photopolymerization initiator, a black coloring agent and a solvent, and wherein the black coloring agent is contained in an amount of more than 20% by mass relative to the total solid content of the composition and the solvent contains a compound represented by R1O(C2H4O)2R2 (wherein R1 represents a methyl group and R2 represents an alkyl group having 2 or 3 carbon atoms) in an amount of 20-100% by mass relative to the total mass of the solvent; and a partition wall which is formed of a cured film of the negative photosensitive resin composition and which is formed to have such a shape that divides the surface of a substrate into a plurality of compartments for pixel formation.

Description

Negative photosensitive resin composition, partition, black matrix, and optical element Field of invention

The present invention relates to a negative photosensitive resin composition, a partition wall using the same, a black matrix, and an optical element having the partition.

Background of the invention

There is a known method in which a photosensitive resin composition is applied onto a substrate by a photolithography technique to form a partition wall for use in a pixel portion of a color filter or an organic EL (Electro-Luminescence) device. Conventionally, the coating of the photosensitive resin composition is carried out by a spin coating method. As the size of the substrate increases, it becomes difficult to apply the spin coating method. Therefore, a coating method using a slit coating method has been proposed.

When the photosensitive composition is applied to the surface of the substrate by the slit coating method, the coating speed varies depending on the coating speed. However, in order to obtain good film thickness uniformity, the viscosity of the photosensitive resin composition should be less than 3.5 mPa. s. When the viscosity of the photosensitive resin composition is high, the photosensitive resin composition supplied from the slit nozzle interrupts the supply of the liquid and generates an uncoated portion on the surface of the substrate.

Further, when the photosensitive resin composition is applied by the slit coating method, it is necessary to wash the dried cured product adhered to the photosensitive resin composition of the slit nozzle during repeated use before application. When the re-solubility of the dried cured product to the photosensitive resin composition is low, there is a problem that the dried solidified matter remaining in the nozzle portion becomes a protrusion remaining, and when the photosensitive resin composition is coated on the substrate, Produced in the direction of the nozzle The ribs or the dried cured product of the photosensitive resin composition falls and adheres to the substrate to become a defect, and the yield is lowered. Therefore, it is quite important to have resolubility in the photosensitive resin composition in terms of productivity. In order to improve the re-solubility of the photosensitive resin composition, a photosensitive resin composition using a specific solvent has been proposed (for example, Patent Document 1, Patent Document 2, and Patent Document 3).

One of the required characteristics of the color filter is high contrast. Further, it is required to produce a photosensitive resin composition having a black matrix having a high light-shielding property. In order to produce a black matrix having a high light-shielding property, a photosensitive resin composition containing a pigment at a high concentration has been proposed (for example, Patent Document 4).

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2008-58551

Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-89743

Patent Document 3: Japanese Laid-Open Patent Publication No. 2008-89744

Patent Document 4: International Publication No. 2008/133312

Invention

As proposed in Patent Document 4, it is necessary to form a photosensitive resin composition capable of producing a black matrix having a high light-shielding property to contain a pigment at a high concentration. However, as the pigment concentration increases, the resolubility of the photosensitive resin composition deteriorates.

According to the findings of the present inventors, in the photosensitive resin composition containing a pigment at a high concentration for high contrast, even if it is mentioned in the prior literature In the coating film of the photosensitive resin composition described in Patent Document 4, the coating film of the photosensitive resin composition described in Patent Document 4 is applied by the slit coating method, and the defects due to the dried cured product are likely to occur.

An object of the present invention is to provide a negative-type photosensitive resin composition and a partition wall and a black matrix using the same, and the negative-type photosensitive resin composition can produce a black matrix containing a pigment at a high concentration and having high light-shielding properties, and is itself The redissolution of the dissolved and dried cured product is high, and the coating film obtained by the slit coating method does not cause defects, and has a viscosity which can be applied by the slit coating method. Moreover, an object of the present invention is to provide an optical element having a partition which is formed by curing the photosensitive resin composition and has high light-shielding property.

The present invention provides a negative photosensitive resin composition having the following constitutions [1] to [12], a partition wall, a black matrix, and an optical element.

[1] A negative photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerization initiator (B), a black colorant (C), and a solvent (D), wherein the composition is relative to the above composition The content of the black solid coloring agent (C) is more than 20% by mass, and the solvent (D) contains a solvent (D1) in a ratio of 20 to 100% by mass based on the total amount of the solvent (D). The solvent (D1) is a compound represented by the following formula (1): R ¹ O(C ₂ H ₄ O) ₂ R ² (1)

In the formula (1), R ¹ represents a methyl group, and R ² represents an alkyl group having 2 or 3 carbon atoms.

[2] The negative photosensitive resin composition according to [1], wherein the solvent (D1) is diethylene glycol ethyl methyl ether.

[3] The negative photosensitive resin composition of [1] or [2], wherein the solvent (D) further contains a solvent (D2) in a ratio of 10 to 40% by mass based on the total amount of the solvent (D). The solvent (D2) is an aliphatic cyclic compound containing one or more carbon atoms bonded to an oxygen atom by a double bond as a ring-constituting atom, and may also contain an etheric oxygen atom.

[4] The negative photosensitive resin composition according to [3], wherein the aliphatic cyclic compound is a cyclic ester or a cyclic ketone.

[5] The negative photosensitive resin composition according to any one of [1] to [4] wherein the alkali-soluble resin (A) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule.

[6] The negative photosensitive resin composition according to any one of [1] to [5] wherein the alkali-soluble resin (A) is an epoxy (meth) acrylate resin having an acidic group introduced therein.

[7] The negative photosensitive resin composition according to any one of [1] to [6] wherein the photopolymerization initiator (B) is an O-antimony compound.

[8] The negative photosensitive resin composition according to any one of [1], wherein the photopolymerization initiator (B) is an O-quinone compound represented by the following formula (3):

In the formula (3), R ³ represents a hydrogen atom, R ⁶¹ or OR ⁶² , and R ⁶¹ and R ⁶² each independently represent an alkyl group having 1 to 20 carbon atoms, and a hydrogen atom in the cycloalkyl ring may be substituted by an alkyl group. a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a hydrogen atom in the benzene ring, or a phenyl group having 6 to 30 carbon atoms or a benzene ring substituted by an alkyl group A phenylalkyl group having 7 to 30 carbon atoms which may be substituted by an alkyl group.

R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted by an alkyl group. The hydrogen atom in the benzene ring may be substituted by an alkyl group, the phenylalkyl group having 7 to 30 carbon atoms, the alkanoyl group having 2 to 20 carbon atoms, or the hydrogen atom in the benzene ring may be substituted by an alkyl group. The benzoylcarbonyl group having 7 to 20 benzylidene groups, the alkoxycarbonyl group having 2 to 12 carbon atoms or the hydrogen atom in the benzene ring may be substituted with an alkyl group and having 7 to 20 carbon atoms or a cyano group.

R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom in the benzene ring may be substituted by an alkyl group, a phenyl group having 6 to 30 carbon atoms, or a hydrogen atom in a benzene ring may be substituted by an alkyl group. A phenylalkyl group having an atomic number of 7 to 30.

R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a cyano group, a halogen atom, a nitro group, R ⁶¹ , OR ⁶² , an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring. a benzylidene group having 7 to 20 carbon atoms which may be substituted by an alkyl group, a benzocarbonyl group having 7 to 20 carbon atoms and an alkyl group having 2 to 12 carbon atoms which may be substituted by an alkyl group. The oxycarbonyl group or the hydrogen atom in the benzene ring may be substituted with an alkyl group and have a phenoxycarbonyl group having 7 to 20 carbon atoms and a decylamino group having 1 to 20 carbon atoms.

R ⁰ represents R ⁶¹ , OR ⁶² , a cyano group or a halogen atom. a is 0 or an integer from 1 to 3.

[9] A negative photosensitive resin composition according to any one of [1] to [8] And the aforementioned black colorant (C) is a carbon black or an organic pigment.

[10] A partition wall formed by dividing a surface of a substrate into a plurality of divided regions for forming a pixel, wherein the partition wall is negative photosensitive according to any one of [1] to [9]. It is composed of a cured film of a resin composition.

[11] A black matrix characterized in that a surface of a substrate composed of a partition wall such as [10] is divided into a plurality of divided regions.

[12] An optical element comprising a plurality of pixels on a surface of a substrate and a partition wall between adjacent pixels, wherein the partition wall is formed by a partition wall of [10].

According to the present invention, it is possible to provide a negative-type photosensitive resin composition and a partition wall and a black matrix using the same, and the negative-type photosensitive resin composition can produce a black matrix containing a pigment at a high concentration and having a high light-shielding property and dissolve itself The dried cured product has high resolubility, and has a viscosity that does not cause defects in the coating film produced by the slit coating method, and can be applied by a slit coating method. According to the present invention, an optical element using the negative photosensitive resin composition of the present invention described above can be obtained.

Form for implementing the invention

In the present specification, "(meth)acryloyl group..." is a generic term for "methacryloyl fluorenyl..." and "acrylic fluorenyl...". (meth)acrylic acid, (meth) acrylate, (meth) acrylamide, and (meth)acrylic resin are also the same.

The compound represented by the formula (1) in the present specification is referred to as a compound. (1). Other compounds are also the same.

The "total solid content" in the present specification is a partition forming component in the component contained in the negative photosensitive resin composition, and the negative photosensitive resin composition is heated at 140 ° C for 24 hours to remove the solvent residue. Specifically, it is a total component other than the volatile component which volatilized by heating etc. in the formation of a partition wall, such as solvent (D). However, the amount of total solids can also be calculated from the feed amount.

In the present specification, a film in which a negative photosensitive resin composition is applied is referred to as a "coating film", and a state in which it is dried is referred to as a "film", and a film obtained by curing is referred to as a "cured film". The negative photosensitive resin composition contains a black colorant, so that the surface of the substrate has been divided into partitions by "partition walls", which is called "black matrix", and the "partition wall" is divided into plural numbers by dividing the surface of the substrate. The cured film formed by the zone.

The term "ink" in the present specification means a general term for a liquid composition having, for example, an optical or electrical function after drying and hardening, and is not limited to a coloring material used in the prior art. Further, the "pixel" formed by injecting the above-described ink is similarly used as a distinguisher indicating that it is partitioned by a partition wall and has an optical or electrical function.

Embodiments of the present invention will be described below. However, in the case where it is not specifically described in the present specification, % means mass%.

[alkali soluble resin (A)]

The alkali-soluble resin (A) in the present invention is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. The alkali-soluble resin (A) has an ethylenic double bond in the molecule, whereby the exposed portion of the negative photosensitive resin composition can be borrowed The radical generated by the photopolymerization initiator (B) is polymerized and hardened. The exposed portion hardened by the above method cannot be removed by the alkali developer. Further, the alkali-soluble resin (A) has an acidic group in the molecule, whereby the unexposed portion of the uncured negative photosensitive resin composition can be selectively removed by the alkali developing solution. As a result, a partition wall can be formed.

The acidic group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group. These may be used alone or in combination of two or more.

The ethylenic double bond is not particularly limited, and examples thereof include a double bond having addition polymerization property such as a (meth) acryl fluorenyl group, an allyl group, a vinyl group, a vinyloxy group, and an oxyalkylene group. One type may be used alone or two or more types may be used in combination. Further, part or all of the hydrogen atoms of the ethylenic double bond group may be substituted by an alkyl group, and are preferably substituted by a methyl group.

The alkali-soluble resin (A) is not particularly limited, and examples thereof include a resin having a side chain having an acidic group and a side chain having an ethylenic double bond (A1-1); and an acid group and an ethylene group have been introduced into the epoxy resin. A resin (A1-2) having a double bond; and a monomer (A1-3) having a side chain having an acidic group and a side chain having an ethylenic double bond. These may be used alone or in combination of two or more.

The resin (A1-1) can be synthesized, for example, by the following method (i) or (ii).

(i) copolymerizing a monomer having a reactive group other than an acidic group in a side chain such as a hydroxyl group and a reactive group such as an epoxy group with a monomer having an acidic group in a side chain to obtain a side chain having a reactive group and a copolymer having an acidic group side chain. Next, the copolymer is reacted with a compound having a functional group capable of bonding to the above reactive group and an ethylenic double bond. Or, make the side chain have acid After the monomer such as a carboxyl group is copolymerized, a compound having a functional group capable of bonding an acidic group and an ethylenic double bond is reacted in an amount which remains after the reaction of the acidic group.

(ii) reacting a monomer having a reactive group other than the above acidic group in the side chain (i) with a compound having a functional group capable of bonding the reactive group and a protected ethylenic double bond . Next, after the monomer is copolymerized with a monomer having an acidic group in the side chain, the protection of the ethylenic double bond is removed. Alternatively, the monomer having an acidic group in the side chain is copolymerized with a monomer having a protected ethylenic double bond in the side chain, and the protection of the ethylenic double bond is removed.

However, (i) or (ii) is preferably carried out in a solvent.

In the present invention, the method (i) is preferably used in the above. Hereinafter, the method (i) will be specifically described.

Examples of the monomer having a hydroxyl group as a reactive group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. 4-hydroxybutyl methacrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono ( Methyl) acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl A diol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) acrylamide, and N,N-bis(hydroxymethyl)(meth) acrylamide.

When a monomer having a hydroxyl group as a reactive group is used in the above (i), the monomer having an acidic group copolymerized is not particularly limited. Other than the monomer having a carboxyl group, which will be described later, examples of the monomer having a phosphate group include 2-(meth)acryloyloxyethyl phosphate. a monomer having a carboxyl group as a reactive group The copolymerization of the monomer having an acidic group can be carried out by a conventionally known method.

Examples of the compound which reacts with the obtained copolymer and which has a functional group capable of bonding a hydroxyl group and an ethylenic double bond include an acid anhydride having an ethylenic double bond, a compound having an isocyanate group and an ethylenic double bond, And a compound having a ruthenium chloride group and an ethylenic double bond.

As the acid anhydride having an ethylenic double bond, there may be mentioned maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6- Tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, and the like.

As the compound having an isocyanate group and an ethylenic double bond, 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)propenyloxymethyl isocyanate) Ethyl ester and the like.

The compound having a ruthenium chloride group and an ethylenic double bond may, for example, be a (meth) acrylonitrile chloride.

Examples of the monomer having an epoxy group as a reactive group include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl acrylate.

In the case of a monomer which is copolymerized with a monomer having an epoxy group as a reactive group and has an acidic group, a monomer similar to that described above for a monomer having a carboxyl group as a reactive group may be used. The copolymerization of a monomer having an oxy group as a reactive group and a monomer having an acidic group can also be carried out by a conventionally known method.

As the compound which can react with the obtained copolymer and which has a functional group capable of bonding an epoxy group and an ethylenic double bond, there may be mentioned a compound having a carboxyl group and an ethylenic double bond. In the specific example of the compound, Examples thereof include acrylic acid, methacrylic acid, ethylene acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and the like. Alternatively, the hydroxyl group formed here may be reacted with an acid anhydride which forms a part of the cyclic structure in a dehydration condensation portion of the carboxylic acid, and a carboxyl group may be introduced into the resin (A1-1).

Examples of the monomer having a carboxyl group as a reactive group include acrylic acid, methacrylic acid, ethylene acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and the like. Further, these monomers can also be used as the above-mentioned monomer having an acidic group.

When a monomer having a carboxyl group as a reactive group is used, the monomer is polymerized as described above. The compound which reacts with the obtained polymer and has a functional group capable of bonding a carboxyl group and an ethylenic double bond may, for example, be a compound having an epoxy group and an ethylenic double bond. Examples of the compound include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl acrylate. In this case, the amount of the compound which can react with the copolymer having a carboxyl group and which has a functional group capable of bonding a carboxyl group and an ethylenic double bond is a carboxyl group which can be used as an acidic group in the polymer after the reaction. The amount of the side chain.

The resin (A1-2) can be synthesized by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond which will be described later, and then reacting with a polyvalent carboxylic acid or an anhydride thereof.

Specifically, an epoxy resin is reacted with a compound having a carboxyl group and an ethylenic double bond to introduce an ethylenic double bond into the epoxy resin. Next, a carboxyl group can be introduced by reacting a polyvalent carboxylic acid or an anhydride thereof in an epoxy resin into which an ethylenic double bond has been introduced.

The epoxy resin is not particularly limited, and examples thereof include a bisphenol A ring. Oxygen resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, phenolic methane type epoxy resin, epoxy resin having a naphthalene skeleton, represented by the following formula (A1-2a) An epoxy resin having a biphenyl skeleton, an epoxy resin represented by the following formula (A1-2b), and an epoxy resin represented by the following formula (A1-2c) and having a biphenyl skeleton.

(In the formula (A1-2a), v is an integer of 1 to 50, and preferably an integer of 2 to 10. Further, the hydrogen atom of the benzene ring may be independently substituted by an alkyl group having 1 to 12 carbon atoms or a halogen. An atom, or a portion of a hydrogen atom, may also be substituted with a phenyl group substituted with a substituent.)

(In the formula (A1-2b), R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and w is an integer of 0 or 1 to 10. )

(In the formula (A1-2c), the hydrogen atom of the benzene ring may be independently substituted by the number of carbon atoms The alkyl group of 1 to 12, a halogen atom, or a part of a hydrogen atom may be substituted with a phenyl group substituted with a substituent. u is 0 or an integer from 1 to 10. )

The compound which reacts with the epoxy resin and has a carboxyl group and an ethylenic double bond in order to introduce an ethylenic double bond is preferably acrylic acid, methacrylic acid, ethylene acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid. And such salts and the like, and preferably acrylic acid or methacrylic acid. That is, as the resin (A1-2), an epoxy (meth) acrylate resin to which an acidic group has been introduced is preferable.

The resin (A1-2) can be obtained by reacting a polyvalent carboxylic acid anhydride with an alcoholic hydroxyl group of a resin obtained by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond. As the polycarboxylic acid anhydride, a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride is preferably used. The molecular weight can be controlled by varying the ratio of the dicarboxylic anhydride and the tetracarboxylic dianhydride.

A commercially available product can be used for the resin (A1-2). For commercial products, all are listed under the trade name KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR- 1286H, ZAR-1535H, ZAR-2001H, ZAR-2002, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H ( The above, manufactured by Nippon Kayaku Co., Ltd., and EX1010 (manufactured by Nagase ChemteX Co., Ltd.).

Examples of the monomer (A1-3) include 2,2,2-tripropylene decanoate (NK Ester CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.).

As the alkali-soluble resin (A), it is preferred to use the resin (A1-2) in the following three points: it is possible to suppress peeling of the cured film during development and to obtain high resolution. The point of the pattern, the point where the linearity of the line is good, and the point at which the appearance after the post-baking step can be maintained and the smooth surface of the cured film is easily obtained.

The resin (A1-2) is preferably a resin having an acidic group and an ethylenic double bond introduced into a bisphenol A type epoxy resin, and a resin having an acidic group and an ethylenic double bond introduced into the bisphenol F type epoxy resin. a resin which has been introduced with an acidic group and an ethylenic double bond in a phenol novolak type epoxy resin, a resin which has been introduced with an acidic group and an ethylenic double bond in a cresol novolac type epoxy resin, and has been introduced into a phenolic methane type epoxy resin. A resin having a base and an ethylenic double bond, and a resin having an acidic group and an ethylenic double bond introduced into the epoxy resin represented by the formula (A1-2a) to (A1-2c). Further, as the resin (A1-2), an epoxy (meth) acrylate resin to which an acidic group has been introduced is particularly preferable.

The number of the ethylenic double bonds which the alkali-soluble resin (A) has in one molecule is preferably 3 or more on average, and more preferably 6 or more. When the number of the ethylenic double bonds is at least the lower limit of the above range, the alkali solubility of the exposed portion and the unexposed portion is likely to be different, and fine pattern formation can be performed with a small amount of exposure.

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1.5 × 10 ³ to 30 × 10 ³ , and particularly preferably 2 × 10 ³ to 20 × 10 ³ . Further, the number average molecular weight (Mn) is preferably 500 to 20 × 10 ³ , and more preferably 1 × 10 ³ to 10 × 10 ³ . When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are at most the lower limit of the above range, the curing property at the time of exposure is excellent, and if it is at most the upper limit of the above range, the developability is good.

The acid value of the alkali-soluble resin (A) is preferably from 10 to 300 mgKOH/g, and particularly preferably from 30 to 150 mgKOH/g. If the acid value is in the above range, the negative photosensitive tree The developability of the lipid composition is preferably.

The alkali-soluble resin (A) contained in the negative-type photosensitive resin composition may be used alone or in combination of two or more.

The content of the alkali-soluble resin (A) in the total solid content of the negative photosensitive resin composition is preferably from 5 to 80% by mass, particularly preferably from 10 to 60% by mass. When the content ratio is in the above range, the developability of the negative photosensitive resin composition is good.

[Photopolymerization Initiator (B)]

As the photopolymerization initiator (B) in the present invention, a compound which generates a radical by light can be used without particular limitation. As the above compound, specifically, there is an O-tellurium compound. For example, IRGACURE OXE01 (manufactured by BASF Corporation: equivalent to 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzamide))), ADEKA OPTOMER N-1919 ADEKA ARKLS NCI-831 and NCI-930 (made by ADEKA Corporation). Among the O-ruthenium compounds, a compound represented by the following formula (3) which is capable of producing a good shape of the partition wall even at a small amount of exposure is preferable. Hereinafter, the compound represented by the formula (3) is referred to as a photopolymerization initiator (3). The photopolymerization initiator (B) preferably contains one or more photopolymerization initiators (3), and is preferably formed only by the photopolymerization initiator (3).

In the formula (3), R ³ represents a hydrogen atom, R ⁶¹ or OR ⁶² , and R ⁶¹ and R ⁶² each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom in the cycloalkyl ring may be alkyl group. a substituted cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in the benzene ring may be substituted by an alkyl group in a phenyl group having 6 to 30 carbon atoms or a benzene ring. A hydrogen atom may be substituted by an alkyl group and has a phenylalkyl group having 7 to 30 carbon atoms.

R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 30 carbon atoms in which a hydrogen atom in the benzene ring may be substituted by an alkyl group. The hydrogen atom in the benzene ring may be substituted by an alkyl group, the phenylalkyl group having 7 to 30 carbon atoms, the alkanoyl group having 2 to 20 carbon atoms, or the hydrogen atom in the benzene ring may be substituted by an alkyl group. The benzoylcarbonyl group having 7 to 20 benzylidene groups, the alkoxycarbonyl group having 2 to 12 carbon atoms or the hydrogen atom in the benzene ring may be substituted with an alkyl group and having 7 to 20 carbon atoms or a cyano group.

R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom in the benzene ring may be substituted by an alkyl group, a phenyl group having 6 to 30 carbon atoms, or a hydrogen atom in a benzene ring may be substituted by an alkyl group. A phenylalkyl group having an atomic number of 7 to 30.

R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a cyano group, a halogen atom, a nitro group, R ⁶¹ , OR ⁶² , an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring. a benzylidene group having 7 to 20 carbon atoms which may be substituted by an alkyl group, a benzocarbonyl group having 7 to 20 carbon atoms and an alkyl group having 2 to 12 carbon atoms which may be substituted by an alkyl group. The oxycarbonyl group or the hydrogen atom in the benzene ring may be substituted with an alkyl group, and the phenoxycarbonyl group having 7 to 20 carbon atoms and the decylamino group having 1 to 20 carbon atoms may be substituted.

R ⁰ represents R ⁶¹ , OR ⁶² , a cyano group or a halogen atom. a is 0 or an integer from 1 to 3.

Further, in the photopolymerization initiator (3), a compound having the following aspect is preferred.

R ^{3 is} preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and examples thereof include a methyl group and an ethyl group. Propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl and phenyl. The alkyl group having 1 to 4 carbon atoms is preferred, and the alkyl group having 1 to 2 carbon atoms is more preferred, and the methyl group is particularly preferred.

R ^{4 is} preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. Heptyl, octyl, decyl, decyl, methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl. The alkyl group having 1 to 6 carbon atoms is preferred, and the alkyl group having 1 to 3 carbon atoms is more preferred, and the methyl group is particularly preferred.

As the photopolymerization initiator (3), Nos. 1 to 71 described in International Publication No. 2008/078678 can also be used.

Among the photopolymerization initiators (3), a compound of the following aspect is preferred.

In the formula (3), R ^{5 is} preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. . The alkyl group having 2 to 6 carbon atoms is preferred, and the ethyl group is particularly preferred.

As R ⁶ , R ⁸ and R ⁹ , a hydrogen atom or a nitro group is preferred.

As R ⁷ , a benzoyl group having 7 to 20 carbon atoms or a hydrogen atom in a benzene ring in which a hydrogen atom in the benzene ring may be substituted by an alkyl group may be substituted with an alkyl group and have 7 to 20 carbon atoms. Benzylcarbonyl or nitro is preferred, and is benzylidene, 2-methylbenzhydryl, 2-methyl-4-tetrahydropyranylmethoxybenzylidene, 2-methyl- 5-tetrahydrofuranylmethoxybenzylidene, 2-methyl-5-tetrahydropyranylmethoxybenzylidene, benzylcarbonyl, 1,3,5-trimethylcarbonyl and nitro .

A indicating the number of R ⁰ is 0.

Specific examples of the photopolymerization initiator (3) include compounds (3-1) to (3-10), etc., and in the formula (3), R ³ to R ⁹ are each the following groups. And indicates that the number of R ⁰ is 0.

R ³ : phenyl, R ⁴ : octyl, R ⁵ : ethyl, R ⁶ , R ⁸ , R ⁹ : a hydrogen atom and R ⁷ : a benzylidene group compound (3-1); R ³ : methyl R ⁴ : octyl, R ⁵ :ethyl, R ⁶ , R ⁸ , R ⁹ : a hydrogen atom and R ⁷ : a benzylidene group compound (3-2); R ³ : methyl group, R ⁴ : a compound (3-3) wherein R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ⁹ : a hydrogen atom and R ⁷ : a benzylidene group; R ³ : a methyl group, R ⁴ : heptyl group, R ⁵ : Ethyl, R ⁶ , R ⁸ , R ⁹ : a hydrogen atom and R ⁷ : benzamidine group compound (3-4); R ³ : phenyl group, R ⁴ : octyl group, R ⁵ : ethyl group, R ⁶ a compound (3-5) wherein R ⁸ : R ⁹ : a hydrogen atom and R ⁷ : 2-methylbenzimidyl; R ³ : methyl, R ⁴ : octyl, R ⁵ : ethyl, R ⁶ , R ⁸ , R ⁹ : a compound of hydrogen atom and R ⁷ : 2-methylbenzhydryl (3-6); R ³ : methyl, R ⁴ : methyl, R ⁵ : ethyl, R ⁶ , R ^8. A compound (3-7) wherein R ^{9 is a} hydrogen atom and R ⁷ : 2-methylbenzhydryl group; R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ^9: a hydrogen atom and R ^7: 2- tetrahydropyran-methyl-4-ylmethoxy benzoyl group Compound (3-8); R ^3: methyl group, R ^4: methyl, R ^5: an ethyl ^{group, R 6, R 8, R} 9: a hydrogen atom and R ^7: 2- methyl-5-yl methyl tetrahydrofuran a compound of the oxybenzimidyl group (3-9); and R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : a hydrogen atom and R ⁷ : 2 Methyl-5-tetrahydropiperidylmethoxybenzylidene compound (3-10).

A commercially available product can be used as the photopolymerization initiator (3). In the case of the commercial product, IRGACURE OXE02 (manufactured by BASF Corporation: equivalent to the above compound (3-7)) is used.

The ratio of the photopolymerization initiator (B) in the total solid content of the negative photosensitive resin composition is preferably from 1 to 15% by mass, preferably from 2 to 10% by mass, particularly preferably from 3 to 6% by mass. Further, the ratio of the photopolymerization initiator (3) in the photopolymerization initiator (B) is preferably from 50 to 100% by mass, more preferably from 75 to 100% by mass, even more preferably from 100% by mass. When the ratio of the photopolymerization initiator (B) in the total solid content and the ratio of the photopolymerization initiator (3) in the photopolymerization initiator (B) are in the above range, the hardenability of the negative photosensitive resin composition is preferably And in the partition wall or the black matrix which is obtained by the exposure step and the development step after the formation of the coating film, the linear pattern or the line width can be formed to be close to the shape of the mask pattern at the time of exposure.

In the negative photosensitive resin composition of the present invention, the photopolymerization initiator (B) may contain both a photopolymerization initiator (3) and a photopolymerization initiator, and as the photopolymerization initiator, the following photopolymerization may be employed. Initiator.

Examples of the photopolymerization initiator which may be used in combination with the photopolymerization initiator (3) include methylphenylglyoxylate and α-diketones such as 9,10-phenanthrenequinone; Affinity; benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; thioglycol, 2-chlorothiarone, 2-methyl Thiolone, 2,4-dimethylthiaxanone, isopropylthione onion, 2,4-diethylthiane, 2,4-dichlorothiazepine, 2, 4-diisopropylthione ketone, and squalene such as squalene-4-decanoic acid; diphenyl ketone, 4,4'-bis(dimethylamino)diphenyl ketone, And diphenyl ketones such as 4,4'-bis(diethylamino)diphenyl ketone; acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, Dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2 - Lolinyl-1-propanone, and 2-benzyl-2-dimethylamino-1-(4- Acetophenones such as phenylphenyl)-butan-1-one; anthracene such as hydrazine, 2-ethyl hydrazine, hydrazine, and 1,4-naphthoquinone; 2-dimethylamine benzoic acid Ester, ethyl 4-dimethylamine benzoate, 4-dimethylammonium benzoic acid (n-butoxy)ethyl ester, 4-dimethylammonium benzoate isoamyl ester, and 4-dimethylaminobenzene An amine benzoate such as 2-ethylhexyl formate; a halogen compound such as benzamidine methyl chloride or trihalomphenyl; a fluorenylphosphine oxide; a di-tertiary butyl peroxide; An oxide; an aliphatic amine such as triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, and diethylaminoethyl methacrylate; and 2-anthracene benzoate Imidazole, 2-anthracene Azole, 2-hydrazinobenzothiazole, 1,4-butanol bis(3-mercaptobutyrate), ginseng (2-fluorenyloxyethyl)trimeric isocyanate, and pentaerythritol bismuth (3-mercapto) A thiol compound such as butyrate).

[black colorant (C)]

The negative photosensitive resin composition of the present invention contains a black coloring agent (C) in a ratio of more than 20% by mass based on the total solid content thereof.

Examples of the black colorant (C) include carbon black, aniline black, an anthraquinone black pigment, an anthraquinone black pigment, and a methine azo black pigment, and specific For example, C.I. Pigment Black 1, 6, 7, 12, 20, 31 and the like can be mentioned. As the black colorant (C), a mixture of an organic pigment such as a red pigment, a blue pigment, a green pigment, and a yellow pigment, or an inorganic pigment can also be used. Specific examples of the organic pigment include C.I. Pigment Blue 15:6, Pigment Red 254, Pigment Green 36, and Pigment Yellow 150. As the black colorant (C), it is preferable that the organic pigment is preferable from the viewpoint of electrical characteristics, and carbon black is preferable from the viewpoint of price and light-shielding. The carbon black is preferably a surface treated with a resin or the like, and in order to adjust the color tone, a blue pigment or a violet pigment may be used in combination. On the other hand, in the partition wall used for the pixel portion of the organic EL element, an organic pigment is preferable from the viewpoint of good electrical characteristics and contrast improvement.

As the organic pigment, from the viewpoint of the shape of the black matrix, the specific surface area calculated by the BET method is preferably from 50 to 200 m ² /g. When the specific surface area is 50 m ² /g or more, the black matrix shape is not easily deteriorated. If it is 200 m ² /g or less, the organic pigment is not excessively adsorbed to the dispersing aid, and it is not necessary to blend a large amount of dispersing aid in order to visualize the physical properties.

Further, the average primary particle diameter of the organic pigment under the observation of a transmission electron microscope is preferably from 20 to 150 nm. When the average primary particle diameter is 20 nm or more, the negative photosensitive resin composition can be dispersed in a high concentration, and a negative photosensitive resin composition having good stability over time can be easily obtained. If it is 150 nm or less, the black matrix shape is not easily deteriorated. Further, as the average secondary particle diameter observed under a transmission electron microscope, it is preferably 80 to 200 nm.

The black colorant (C) content ratio in the total solid content of the negative photosensitive resin composition is more than 20% by mass as described above. Let the content ratio exceed 20% by mass, thereby It is possible to sufficiently ensure the optical density (OD) which is a value of the light-shielding property of the obtained partition wall and the black matrix, and it is possible to perform high contrast using a color filter made of a partition wall and a black matrix. The content ratio of the black colorant (C) is preferably from 20 to 65 mass%, and particularly preferably from 25 to 65 mass%. When it is at most the upper limit of the above range, the curable property of the negative photosensitive resin composition is good, and a cured film having a good appearance can be obtained.

In order to enhance the dispersibility of the black colorant (C) in the negative photosensitive resin composition, it is preferred to contain a polymer dispersant. From the viewpoint of affinity for the black colorant (C), the polymer dispersant is preferably a compound having a basic functional group. When the basic functional group has a primary, secondary or tertiary amine group, it has particularly excellent dispersibility.

Examples of the polymer dispersant include urethane type, polyimide type, alkyd type, epoxy type, unsaturated polyester type, melamine type, phenol type, acrylic type, vinyl chloride type, and chlorine. A compound such as an ethylene vinyl acetate copolymer, a polyamine or a polycarbonate. Among them, ethyl urethane-based and polyester-based compounds are particularly preferred.

The polymer dispersant is preferably used in an amount of 5 to 30% by mass, more preferably 10 to 25% by mass, based on the black coloring agent (C). When the amount used is at least the lower limit of the above range, the dispersion of the black colorant (C) is preferable, and if it is at most the above upper limit of the above range, the developability is good.

[solvent (D)]

The negative photosensitive resin composition of the present invention contains a solvent (D). In addition, the solvent (D) contains a solvent (D1) of a compound represented by the following formula (1) in a ratio of 20 to 100% by mass based on the total amount of the solvent (D).

R ¹ O(C ₂ H ₄ O) ₂ R ² ...(1)

In the formula (1), R ¹ represents a methyl group, and R ² represents an alkyl group having 2 or 3 carbon atoms. The solvent (D) is not reactive with the alkali-soluble resin (A), the photopolymerization initiator (B), the black colorant (C), and any component contained in the negative photosensitive resin composition. Composition of the compound. Further, the solvent (D) has a function of uniformly dissolving the solid components uniformly even in a composition containing a black colorant (C) in a ratio of more than 20% by mass based on the total solid content. The mixture is dispersed to have a moderate viscosity, and the coating of the negative-type photosensitive composition on the substrate forming the partition wall can be uniformly and efficiently performed. Further, the solvent (D) has a property of dissolving the dried cured product of the same composition in the negative photosensitive resin composition, that is, imparting resolubility.

The content ratio of the solvent (D) in the negative photosensitive resin composition differs depending on the composition or use of the negative photosensitive resin composition and the coating method when forming a partition wall or the like on the surface of the substrate. However, it is preferably blended in a negative photosensitive resin composition at a ratio of 50 to 99% by mass, preferably 60 to 95% by mass, more preferably 65 to 90% by mass.

The resolubility in the negative photosensitive resin composition is particularly required in the case where the composition is applied to the surface of the substrate by a slit coating method. In the slit coating method, there is a problem in that a negative photosensitive resin composition adhering or remaining in a slit nozzle during repeated use is dried and solidified to form a projection, and the direction of the nozzle is generated in the coating. The ribs, or the dried solidified material, are dropped to allow foreign matter to be mixed into the coating film. In order to prevent this, it is required that the negative photosensitive resin composition has resolubility.

Further, the appropriate viscosity for uniformly and simply applying the negative photosensitive composition varies depending on the coating method to be used. When the slit coating method is used as the coating method, the viscosity varies depending on the coating speed, but the viscosity of the negative photosensitive composition is preferably less than 3.5 mPa‧s, and particularly preferably less than 3 mPa‧s. The lower limit is 1 mPa ‧ or more.

In the negative photosensitive resin composition of the present invention, the solvent (D) contains the solvent (D1) of the above compound (1) in the above ratio, whereby the black colorant (C) can be contained in a high concentration, and at the same time, it is ensured The viscosity and resolubility of the negative photosensitive resin composition required for the slit coating method.

The compound (1) is hydrophilic by the -OC ₂ H ₄ -OC ₂ H ₄ -O- structure in the formula (1), and the solubility with respect to the alkali-soluble resin (A) having hydrophilicity can be optimized. Further, ^one of the terminal groups represented by R ¹ and R ² (R ¹ ) is a methyl group and the other (R ² ) is an alkyl group having 2 or 3 carbon atoms, that is, an ethyl group, a propyl group and an isopropyl group. By. The terminal groups represented by R ¹ and R ² have moderate lipophilicity. The compound (1) is a compound having two amphiphilic properties by a structure having both the lipophilic group and the hydrophilicity described above.

The compound (1) may, for example, be diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether or diethylene glycol isopropyl methyl ether. Among them, diethylene glycol ethyl methyl ether and diethylene glycol isopropyl methyl ether are preferred, and diethylene glycol ethyl methyl ether is preferred.

Here, the boiling point of the compound (1) is in the range of 176 to 200 ° C and the viscosity is in the range of 1 to 1.5 mPa ‧ s. When the negative photosensitive resin composition is applied by the slit coating method, the solvent to be used preferably has a boiling point of 150 ° C or higher in order to prevent the composition from drying and solidifying in the slit nozzle at the time of coating. Again, from It seems that the drying speed of the coated film after application is fast, and the upper limit of the boiling point of the solvent to be used is preferably about 220 °C. Further, the negative photosensitive resin composition used in the slit coating method differs depending on the viscosity of the solid component used or the amount of the solvent relative to the solid component, but the solvent is used. The viscosity should be below 2.5 mPa‧s. The compound (1) is a compound which satisfies both the boiling point and the viscosity characteristics required for the solvent in the negative photosensitive resin composition used in the above slit coating method.

As the solvent (D1), one type of the compound (1) may be used, or two or more types may be used in combination. The content of the solvent (D1) in the solvent (D) is 20 to 100% by mass, preferably 30 to 90% by mass, more preferably 30 to 80% by mass. The content of the solvent (D) in the negative photosensitive resin composition is in the above range, and the solvent (D1) content is in the above range with respect to the total amount of the solvent (D), whereby the following negative photosensitive resin can be obtained. Composition: a negative photosensitive resin containing a black coloring agent (C) at a high concentration of more than 20% by mass based on the total solid content of the alkali-soluble resin (A) and the photopolymerization initiator (B) The re-solubility is excellent, and the occurrence of defects in the coating film applied by the slit coating method can be suppressed, and the viscosity can be applied by the slit coating method.

In the negative photosensitive resin composition of the present invention, as the solvent (D), a solvent (D1) and a solvent (D2) are preferably used in combination, and the solvent (D2) is an aliphatic cyclic compound (D2-1), which contains one or more. A carbon atom bonded to an oxygen atom by a double bond serves as a ring constituent atom, and may also contain an oxygen atom. The ratio of the solvent (D2) is preferably from 10 to 40% by mass, particularly preferably from 15 to 30% by mass, based on the total amount of the solvent (D).

From the point of view of boiling point and melting point, aliphatic cyclic compounds The number of rings in (D2-1) is preferably 3~7, and it is especially good for a 5-member ring or a 6-member ring. The aliphatic cyclic compound (D2-1) constitutes an atomic carbon atom or an etheric oxygen atom of the ring, and the number of etheric oxygen atoms may also be zero. Further, it has a relationship between the number of carbon atoms and the number of oxygen atoms in the ether. At least one of the carbon atoms constituting the ring is bonded to one oxygen atom through a double bond. All of the carbon atoms constituting the ring and the oxygen-bonded bonds are bonded to the two hydrogen atoms.

Hereinafter, a group consisting of a carbon atom constituting a ring and an oxygen atom bonded thereto by a double bond is referred to as "a carbonyl group constituting a ring". In the aliphatic cyclic compound (D2-1), the number of the carbonyl groups constituting the ring may be one or more, and preferably one.

In the negative photosensitive resin composition of the present invention, by using the solvent (D2) together with the solvent (D1) as the solvent (D), the resolubility of the negative photosensitive resin composition can be further improved. . Since the aliphatic cyclic compound (D2-1) of the solvent (D2) has a carbonyl group which is a polar group and does not have a terminal alkyl group, it is highly hydrophilic, thereby optimizing the solubility to the hydrophilic alkali-soluble resin (A). . However, the aliphatic cyclic compound (D2-1) has a high viscosity as compared with the above compound (1), whereby the viscosity of the resulting negative photosensitive resin composition can be adjusted, and thus the solvent (D) It is preferred to use the above blending amount.

The aliphatic cyclic compound (D2-1) may, for example, be a cyclic ester or a cyclic ketone.

Examples of the cyclic ester include lactones such as α-lactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Examples of the cyclic ketone include cycloalkanones such as cycloacetone, cyclobutanone, cyclopentanone, cyclohexanone, and cycloheptanone.

Among them, as a solvent (D2), from the point of view of ease and boiling point It appears that cyclohexanone and γ-butyrolactone are preferred.

One type of the above-mentioned aliphatic cyclic compound (D2-1) may be used as the solvent (D2), or two or more types may be used in combination.

The negative photosensitive resin composition of the present invention may contain, as a solvent (D), a solvent (D3) other than the solvent (D1) and the solvent (D2) as needed. The solvent (D3) may, for example, be a solvent used in the synthesis of the above alkali-soluble resin (A) or the following ink-repellent (E), and may be blended with an alkali-soluble resin (A) or an ink-repellent (E). A solvent or the like of a negative photosensitive resin composition.

Further, as the solvent used in the synthesis of the alkali-soluble resin (A) or the ink-repellent (E), the solvent (D1) or the solvent (D2) may be used. When the negative photosensitive resin composition contains the solvent (D1) or the solvent (D2) derived from the blending components, it is individually adjusted so as to contain the solvent (D1) and the solvent (D2). The content of the solvent (D1) and the solvent (D2) in the solvent (D) calculated in each of the total amounts may be within the above range.

The solvent (D3) is not particularly limited as long as it is used together with the solvent (D1) and the solvent (D2) to be used as required, and does not inhibit the above function as the solvent (D). Therefore, when the alkali-soluble resin (A) or the ink-repellent agent (E) is blended with the solvent used in the synthesis thereof to the negative-type photosensitive resin composition, it is preferable to select not to impair the above functions as the solvent (D). The solvent is used as a solvent for the synthesis.

Examples of the solvent (D3) include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; acetone, 2-butanone, and methyl isobutyl ketone. Ketones; 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol, etc.; 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol And 2-(2-butyl Carbitol such as oxyethoxy)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 Ester, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol An ester such as an acid ester, 3-methyl-3-methoxybutyl acetate or triacetin; and diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, Diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and dibutyl ether.

The content of the solvent (D3) in the solvent (D) is the amount of the solvent (D1) and the solvent (D2) minus the amount of the solvent (D), specifically, the total amount of the solvent (D). The ratio of ~70% by mass is preferably, and preferably 20 to 70% by mass.

Further, as the specific aspect of the solvent (D), it may be a form composed only of the solvent (D1) and a solvent (D1) and a solvent (D2) and/or a solvent (D3). When the solvent (D) is an ideal blend ratio (mass ratio) of the solvent (D1) and the solvent (D2), as the solvent (D1): solvent (D2) = 85: 15 to 70: 30. When the solvent (D) is an ideal blend ratio (mass ratio) of the solvent (D1) and the solvent (D3), it is, for example, a solvent (D1): a solvent (D3) = 30:70 to 80:20. Further, when the solvent (D) is a solvent (D1), a solvent (D2), and a solvent (D3), a desired blend ratio (mass ratio) is as follows: solvent (D1): solvent (D2): solvent (D3) )=30~80:10~30:0~60.

[Ink (E)]

The negative photosensitive resin composition of the present invention may further contain an ink repellent (E) as an optional component. The ink repellent (E) may, for example, be an alkyl group having at least one hydrogen atom substituted with a fluorine atom and having 1 to 20 carbon atoms (however, the alkyl group may have an etheric oxygen atom between carbon atoms) And/or a polymer (E1) or the like containing a group represented by the following formula (4).

(In the formula (4), R ¹¹ and R ¹² each independently represent a methyl group or a phenyl group. n represents an integer of from 1 to 200.)

As the ink-repellent agent (E), one type of the polymer (E1) may be used alone or two or more types may be used in combination. When the negative photosensitive resin composition is blended with the ink-repellent (E), the ink-repellent property can be imparted to the partition wall or the upper surface of the black matrix which is produced. When the ink is injected by an inkjet method into a region (dot) which is partitioned by a partition or a black matrix, the color mixture of the ink between adjacent dots can be prevented.

The number average molecular weight (Mn) of the polymer (E1) is preferably 1,500 to 50,000, more preferably 10,000 to 50,000. When the number average molecular weight (Mn) is in the above range, alkali solubility and developability are preferable. From the viewpoint of ink repellency and barrier formability, the content of fluorine atoms in the polymer (E1) when the polymer (E1) contains a fluorine atom is preferably 5 to 35 mass%, more preferably 10 to 30 mass%. . Moreover, from the viewpoint of ink repellency and barrier formability, the ruthenium content in the polymer (E1) when the polymer (E1) contains a ruthenium atom is 0.1 to 25% by mass. Preferably, 0.5 to 10% by mass is particularly preferred.

The polymer (E1) preferably has an ethylenic double bond in the side chain at a ratio of from 3 to 100 molecules per molecule. When the polymer (E1) has an ethylenic double bond in the side chain, the ratio is preferably from 6 to 30 molecules per molecule. The polymer (E1) is immobilized on the upper portion of the partition wall by an alkali-soluble resin (A) which is free-radically polymerizable in the negative photosensitive resin composition by having an ethylenic double bond.

Further, the polymer (E1) preferably has an acidic group, for example, at least one acidic group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfo group. The reason is as follows: by having alkali solubility, it is possible to prevent the polymer (E1) having the ink repellent property from remaining in a region (dot matrix) which is partitioned by a partition wall or a black matrix on a substrate, and which is printed when ink is injected. The wet spread of the ink is good. From this point of view, the acid value of the polymer (E1) is preferably from 10 to 400 mgKOH/g, and particularly preferably from 20 to 300 mgKOH/g.

The ink-repellent (E) content ratio in the total solid content of the negative photosensitive resin composition is preferably 0.01 to 30% by mass, and more preferably 0.05 to 20% by mass. When the content ratio is at least the lower limit of the above range, sufficient ink repellency can be imparted to the partition wall formed by the negative photosensitive resin composition or the upper surface of the black matrix. When it is less than or equal to the upper limit of the above range, the adhesion between the partition walls or the black matrix and the substrate is preferably good.

[crosslinking agent (F)]

The negative photosensitive resin composition of the present invention may further contain a crosslinking agent (F) as an optional component for promoting radical hardening. As the crosslinking agent (F), a compound having two or more ethylenic double bonds in one molecule and having no acidic group is preferred. The negative photosensitive resin composition contains a crosslinking agent (F), thereby enhancing exposure The hardenability of the negative-type photosensitive resin composition at the time of light can form a partition wall even at a small amount of exposure.

Examples of the crosslinking agent (F) include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and neopentyl glycol. (Meth) acrylate, 1,9-nonanediol di(meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, neopentyl Alcohol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, B Oxidized isocyanuric acid triacrylate, ε-caprolactone modified ginseng-(2-propenyl oxiranyl) trimer isocyanate, bis{4-(allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine)phenyl}methane, N,N'-meta-indole-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯imine), and urethane acrylate. From the viewpoint of photoreactivity, it is preferred to contain a large number of ethylenic double bonds. In addition, these may be used alone or in combination of two or more.

As the crosslinking agent (F), a commercially available product can be used. For the commercial products, KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.; a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ESTER A-9530 (product) Name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)), NK ESTER A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.; ethoxylated) Cyanuric acid triacrylate), NK ESTER A-9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.; ε-caprolactone modified ginseng-(2-propenyl oxiranyl) trimeric isocyanate), BANI-M (trade name, Maruzen Petrochemical Co., Ltd.; Double {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenimidate)phenyl}methane) and BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.; N , N'-meta-diyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)) and the like. As the urethane acrylate, for example, the KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., the specific trade names are: UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, and UX. -5002D-P20 and so on.

The content ratio of the crosslinking agent (F) in the total solid content of the negative photosensitive resin composition is preferably from 3 to 50% by mass, and particularly preferably from 5 to 40% by mass. In the above range, the alkali developability of the negative photosensitive resin composition is good.

[Microparticles (G)]

The negative photosensitive resin composition of the present invention may contain fine particles (G) as required. The negative photosensitive resin composition contains fine particles (G), whereby the partition wall obtained from the negative photosensitive resin composition can be a partition wall excellent in heat resistance against thermal collapse.

Although various inorganic and organic fine particles can be used as the fine particles (G), it is preferable to use a negatively charged person from the viewpoint of the adsorption energy of the basic polymeric dispersant.

Examples of the inorganic system include cerium oxide, zirconium oxide, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO). Examples of the organic system include polyethylene and polymethyl methacrylate (PMMA). In consideration of heat resistance, inorganic fine particles are preferred, and in view of ease of handling and dispersion stability, cerium oxide or zirconium oxide is particularly preferable. In addition, if the exposure sensitivity of the negative photosensitive resin composition is considered, the fine particles (G) do not absorb the exposure. The light to be irradiated is preferably light, and is preferably an i-line (365 nm), an h-line (405 nm), and a g-line (436 nm) which do not absorb the main light-emitting wavelength of the ultrahigh-pressure mercury lamp.

The particle diameter of the fine particles (G) is preferably 1 μm or less from the viewpoint of smoothness of the surface of the partition walls, and particularly preferably 200 nm or less.

As the fine particles (G), cerium oxide is preferred. In the case of cerium oxide, colloidal cerium oxide is preferred. In general, as the colloidal cerium oxide, if there is an organic cerium oxide sol which has been dispersed in water and an organic cerium oxide sol which is replaced by an organic solvent, and an organic cerium oxide sol which uses an organic solvent as a dispersion medium, good.

As the organic cerium oxide sol, a commercially available product can be used, and in the case of a commercial product, a product name manufactured by Nissan Chemical Industries Co., Ltd. can be cited as PMA-ST (cerium dioxide particle size: 10 to 20 nm, two Solid content of cerium oxide: 30% by mass and propylene glycol monomethyl ether acetate: 70% by mass), NPC-ST (particle diameter of cerium oxide: 10 to 20 nm, solid content of cerium oxide: 30% by mass and n-propyl group Sai Lu Su: 70% by mass) and IPA-ST (cerium oxide particle size: 10 to 20 nm, cerium oxide solid content: 30% by mass, and isopropyl alcohol (2-propanol): 70% by mass).

The fine particle (G) content ratio in the total solid content of the negative photosensitive resin composition is preferably 5 to 35% by mass, and more preferably 10 to 30% by mass. When the content ratio is at least the lower limit of the above range, thermal collapse of the partition wall due to post-baking can be prevented, and if it is at most the upper limit of the above range, the storage stability of the negative photosensitive resin composition is excellent.

[Chane coupling agent (H)]

The negative photosensitive resin composition of the present invention may also contain as needed Decane coupling agent (H). The negative photosensitive resin composition contains a decane coupling agent (H), whereby the substrate adhesion of the cured film formed from the negative photosensitive resin composition can be improved.

The decane coupling agent (H) may, for example, be tetraethoxy decane, 3-glycidoxypropyltrimethoxy decane, methyltrimethoxy decane, vinyltrimethoxy decane or 3-methylpropenyl propyloxypropyl group. Trimethoxy decane, 3-chloropropyltrimethoxy decane, 3-mercaptopropyltrimethoxy decane, heptafluorooctylethyltrimethoxy decane, triethoxy decane containing polyoxyalkylene chain, imidazolium, and the like. These may be used alone or in combination of two or more.

As the decane coupling agent (H), a commercially available product can be used. For the commercial product, KBM5013 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.; 3-propenyloxypropyltrimethoxysilane) may be mentioned.

The content ratio of the decane coupling agent (H) in the total solid content of the negative photosensitive resin composition is preferably from 0.1 to 20% by mass, particularly preferably from 1 to 10% by mass. When the content is at least the lower limit of the above range, the adhesion of the substrate to the cured film formed of the negative photosensitive resin composition can be improved.

[thermosetting agent (I)]

The negative photosensitive resin composition of the present invention may contain a thermosetting agent (I) as required. The negative photosensitive resin composition contains a thermosetting agent (I), whereby the heat resistance and water permeability of the partition walls can be improved.

Examples of the thermosetting agent (I) include an amine resin, a compound having two or more epoxy groups, a compound having two or more mercapto groups, a polycarbodiimide compound, and two or more. A compound of an oxazoline group, a compound having two or more indole cyclopropyl groups, a polyvalent metal, a compound having two or more mercapto groups, and a polyisocyanate compound. From the viewpoint of improving the resistance of the formed partition wall, an amine resin, a compound having two or more epoxy groups, or two or more The oxazoline group compound is particularly preferred.

The content ratio of the thermosetting agent (I) in the total solid content of the negative photosensitive resin composition is preferably from 0.1 to 20% by mass, particularly preferably from 1 to 20% by mass. In the above range, the developability of the negative photosensitive resin composition obtained is excellent.

[phosphoric acid compound (J)]

The negative photosensitive resin composition of the present invention may contain a phosphoric acid compound (J) as required. When the negative photosensitive resin composition contains the phosphoric acid compound (J), the adhesion to the substrate can be improved.

The phosphoric acid compound may, for example, be mono(methyl)propenyloxyethyl phosphate, di(meth)acryloxyethyl phosphate or tris(meth)acryloxyethyl phosphate.

The content ratio of the phosphoric acid compound (J) in the total solid content of the negative photosensitive resin composition is preferably from 0.1 to 10% by mass, particularly preferably from 0.1 to 1% by mass. In the above range, the adhesion between the cured film formed of the negative photosensitive resin composition obtained and the substrate is excellent.

[Surfactant (K)]

The negative photosensitive resin composition of the present invention may contain a surfactant (K) as needed. When the negative photosensitive resin composition contains the surfactant (K), the thickness of the cured film can be made uniform.

The above-mentioned ink-repellent (E) usually also functions as a surfactant. For forming an optical element such as pixel formation by a method other than the inkjet method The negative photosensitive resin composition of the partition wall usually does not contain an ink repellent, and therefore it is preferred to use a surfactant. As the surfactant (K), the same polymer as the ink-repellent (E) can be used, and examples thereof include a fluorine-based surfactant, a rhodium-based surfactant, and an acrylic surfactant.

Commercially available products can also be used as the surfactant (K). All of them are BYK-306 (polyether modified polydimethyl siloxane: 12% by mass, xylene: 68% by mass, and monophenylethylene glycol: 20% by mass). , BYK-307 (polyether modified polydimethyl siloxane), BYK-323 (aralkyl modified polymethyl alkyl siloxane), BYK-320 (polyether modified polymethyl alkyl) Acetone: 52% by mass, white oil solvent: 43% by mass, PGMEA: 5 mass%), and BYK-350 (acrylic copolymer).

The content ratio of the surfactant (K) in the total solid content of the negative photosensitive resin composition is preferably 0.01 to 30% by mass, and more preferably 0.05 to 20% by mass. In the above range, the uniformity of the film thickness of the negative photosensitive resin composition obtained is excellent.

[Other additives]

In the negative photosensitive resin composition of the present invention, a curing accelerator, a tackifier, a plasticizer, an antifoaming agent, an anti-cratering agent, and an ultraviolet absorber may be used depending on the demand.

[Negative photosensitive resin composition]

The negative photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a photopolymerization initiator (B), and a black colorant (C) and a solvent (D) in a ratio of more than 20% by mass based on the total solid content. In addition, it may also contain ink-repellent (E), cross-linking agent (F), fine particles (G), decane coupling agent (H), and heat hardening according to requirements. Agent (I), phosphoric acid compound (J), surfactant (K) and other additives.

The method for producing the negative photosensitive resin composition of the present invention is not particularly limited, and it can be produced by weighing a predetermined amount of each of the above components and mixing them in a usual manner.

The negative photosensitive resin composition of the present invention is used as a material such as photolithography in the same manner as a normal negative photosensitive resin composition, and the obtained cured film can be used as a partition wall or can be used as a black colorant especially in a high concentration. It is used as a black matrix having a high light-shielding property, or as a member of an optical element used for a cured film of a normal negative photosensitive resin composition. The negative photosensitive resin composition of the present invention containing the solid component and the solvent (D1) of the compound (1) as the solvent (D) contains a black colorant at a high concentration, and has excellent resolubility and has The viscosity of the coating by the slit coating method can be further improved.

Therefore, when the negative photosensitive resin composition of the present invention is formed by forming a cured film of a partition wall or the like on the substrate, a slit coating method is used for coating the negative photosensitive resin composition, that is, it has an appropriate viscosity, and The problem caused by the dry solidified material around the slit nozzle is eliminated, and thus it appears to be particularly suitable for forming a cured film from coating using a slit coating method.

(Ideal combination of negative photosensitive resin composition)

The negative photosensitive resin composition of the present invention is preferably selected in accordance with the use and required characteristics to appropriately select the composition and the blend ratio.

The ideal composition of various blending components in the negative photosensitive resin composition of the present invention is shown below.

<combination 1>

Alkali-soluble resin (A): at least one resin selected from the group consisting of a resin in which an acidic group and an ethylenic double bond have been introduced into a bisphenol A-type epoxy resin, and has been introduced into a bisphenol F-type epoxy resin. a resin having an acidic group and an ethylenic double bond, a resin having an acidic group and an ethylenic double bond introduced into a phenol novolak type epoxy resin, and a resin having an acidic group and an ethylenic double bond introduced into a cresol novolac type epoxy resin. a resin in which an acidic group and an ethylenic double bond are introduced to a phenol-methane type epoxy resin, and an acidic group and an ethylenic double bond which have been introduced in the epoxy resin represented by the above formula (A1-2a) to (A1-2c) The resin accounts for 10 to 60% by mass of the total solid content of the negative photosensitive resin composition; the photopolymerization initiator (B) is an O-lanthanoid compound and is a total of the negative photosensitive resin composition. 3 to 6% by mass of the solid component; black colorant (C): is selected from at least one coloring agent of carbon black and organic pigment, and accounts for 25~ of the total solid content of the negative photosensitive resin composition. 65% by mass; solvent (D): the solvent (D) accounts for 65 to 90% by mass in the negative photosensitive resin composition, and the solvent (D) contains a solvent (D1) in an amount of 30 to 80% by mass based on the total amount of the solvent (D) and a PGMEA in an amount of 20 to 70% by mass as a solvent (D3); and a crosslinking agent (F): having one molecule in one molecule a compound having two or more ethylenic double bonds and having no acidic group, and accounting for 5 to 40% by mass of the total solid content of the negative photosensitive resin composition; and a surfactant (K): selected from a fluorine-based interface activity At least one surfactant of the agent, the oxime-based surfactant, and the acrylic surfactant accounts for 0.05 to 20% by mass of the total solid content of the negative photosensitive resin composition.

<combination 2>

The alkali-soluble resin (A), the photopolymerization initiator (B), the black colorant (C), the crosslinking agent (F), and the surfactant (K) are the same as in the combination 1, and the solvent (D) is as follows.

Solvent (D): The solvent (D) accounts for 65 to 90% by mass in the negative photosensitive resin composition, and the solvent (D) contains 30 to 80% by mass based on the total amount of the solvent (D), respectively. Solvent (D1), solvent (D2) in an amount of 10 to 30% by mass, and PGMEA in an amount of 0 to 60% by mass as a solvent (D3).

[Partition and its manufacturing method]

The partition wall of the present invention is a partition wall formed by providing a partitioning region on the surface of the substrate, and is composed of the cured film of the negative photosensitive resin composition of the present invention. The partition wall of the present invention is suitable for use in an optical element, and since the negative photosensitive resin composition contains a black coloring agent (C), the obtained partition wall can be applied as a black matrix.

Since the negative photosensitive resin composition of the present invention contains a black coloring agent (C) at a high concentration, the black matrix which is a partition formed of the negative photosensitive resin composition has high light blocking property, specifically, optical density (OD) ) High light blocking at 2.5 or more. In the present invention, a black matrix having an optical density (OD) of 3 or more can also be provided by further adjusting the conditions. As long as it is a black matrix having an optical density (OD) of 2.5 or more and especially 3 or more, it can sufficiently contribute to, for example, high contrast of a color filter manufactured using the same.

The partition wall of the present invention can be applied to, for example, a partition wall (black matrix) for an optical element having a plurality of pixels on the surface of the substrate and a partition wall between the adjacent pixels.

As a method of producing the partition (black matrix) for an optical element of the present invention using the negative photosensitive resin composition of the present invention, for example, The next method.

The partition wall (black matrix) for an optical element of the present invention can be produced by applying the negative photosensitive resin composition of the present invention to the surface of the substrate to form a coating film (coating film forming step); The coating film is dried to form a film (drying step); and only a portion which is a partition wall in the film is exposed to light curing (exposure step); then, a film other than the photohardened portion is removed to form the film. The partition wall formed by the light-hardened portion (developing step); and then the above-mentioned formed partition wall or the like is further thermally cured (post-baking step). Further, a post-exposure step may be placed between the developing step and the post-baking step to further photoharden the above-described formed partition walls and the like.

The material of the substrate is not particularly limited, and various glass plates, polyester (polyethylene terephthalate or the like), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, and the like can be used. Thermoplastic plastic sheets such as polyfluorene, polyimine, and poly(meth)acrylic resins; and hardened sheets of thermosetting resins such as epoxy resins and unsaturated polyesters. In particular, from the viewpoint of heat resistance, a heat-resistant plastic such as a glass plate or a polyimide may be preferred. Further, since the back exposure may be performed from the back surface (substrate side) where the partition walls are not formed, it is preferable to use a transparent substrate.

The coated surface of the negative photosensitive resin composition of the substrate is preferably washed with alcohol, ultraviolet light, ozone cleaning or the like before application.

(coating film forming step)

The coating method is not particularly limited as long as it can form a coating film having a uniform film thickness, and examples thereof include a spin coating method, a spray coating method, a slit coating method, a roll coating method, a spin coating method, and a rod. Coating method, etc. are usually used in the formation of a coating film. law. In particular, a slit coating method capable of performing large-area coating at one time is preferred.

As described above, the negative photosensitive resin composition of the present invention is excellent in resolubility by using a black colorant (C) and a solvent (D) containing the solvent (D1) of the compound (1) at a high concentration. And it has a viscosity which can be coated by a slit coating method. Therefore, the problem caused by the dry solidified material around the slit nozzle can be eliminated, and the coating itself can be carried out without load by an appropriate viscosity, whereby the productivity can be well coated, and is particularly suitable for A cured film is formed from a coating using a slit coating method.

The film thickness of the coating film is determined by measuring the height of the partition wall finally obtained and the solid content concentration of the negative photosensitive resin composition. The film thickness of the coating film is preferably 500 to 2,000% of the height of the partition (black matrix) finally obtained, and particularly preferably 550 to 1,000%. The film thickness of the coating film is preferably from 0.3 to 100 μm, and particularly preferably from 1 to 50 μm.

(drying step)

The coating film formed on the surface of the substrate by the coating film forming step described above is dried to obtain a film. By drying, the volatile component including the solvent contained in the negative photosensitive resin composition constituting the coating film is volatilized and removed, and a film having no adhesiveness is obtained.

As the drying method, vacuum drying or heat drying (prebaking) is preferred. Further, in order to prevent the appearance of the film from being uneven and to dry efficiently, it is preferred to use vacuum drying and heat drying in combination.

The conditions for vacuum drying vary depending on the type of the components and the blending ratio, but it is preferably carried out at 10 to 500 Pa for 10 to 300 seconds.

Heating and drying should be carried out by heating the substrate together with the coating film by a hot plate and an oven. The device is operated at a temperature of 50 to 120 ° C for 10 to 2,000 seconds.

(exposure step)

A portion of the obtained film is exposed through a mask of a predetermined pattern. The negative photosensitive resin composition of the exposed portion is cured, and the negative photosensitive resin composition of the unexposed portion is not cured.

For the illumination, for example, visible light; ultraviolet light; far ultraviolet light; KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, and Exon lasers such as Ar ₂ excimer lasers; X-rays; and electron beams. Further, as the irradiation light, light having a wavelength of 100 to 600 nm is preferable, and light having a distribution in the range of 300 to 500 nm is preferable, and i-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable.

As the irradiation device, a known ultrahigh pressure mercury lamp or the like can be used. The exposure amount is preferably 5 to 1,000 mJ/cm ^{2 and more} preferably 10 to 200 mJ/cm ² based on the i-line. When the amount of exposure is at least the lower limit of the above range, the negative photosensitive resin composition of the partition wall is sufficiently cured, and it is less likely to be dissolved or peeled off from the substrate during subsequent development. If it is below the upper limit of the above range, high resolution can be obtained.

(development step)

The negative photosensitive resin composition of the unexposed portion is removed by development of a developing solution. As the developer, an alkali-containing aqueous solution containing an alkali such as an inorganic base, an amine, an alkanolamine or a quaternary ammonium salt can be used. Further, in order to improve the solubility and remove the residue, an organic solvent such as a surfactant or an alcohol may be added to the developer.

The development time (time to contact the developer) should be 5 to 180 seconds. Further, the development method may be, for example, a flooding method, a dipping method, or a shower method. After development, proceed It is washed with high pressure water or running water and air-dried with compressed air or compressed nitrogen, thereby removing moisture from the surface of the substrate.

(post exposure step)

Next, post exposure can be performed to meet the demand. The post-exposure can be performed from one of the surface on which the partition wall is formed or the back surface on which the partition wall is not formed (substrate side). Also, it can be exposed from both the front and back sides. The exposure amount is preferably 50 mJ/cm ² or more, more preferably 200 mJ/cm ² or more, still more preferably 1,000 mJ/cm ² or more, and particularly preferably 2,000 mJ/cm ² or more.

As the light to be irradiated, ultraviolet light is preferred, and as the light source, a known ultrahigh pressure mercury lamp or high pressure mercury lamp or the like can be used. These light sources are suitable for use because they emit light of 600 nm or less which contributes to the hardening of the partition walls and emit less than 200 nm of light which causes oxidative decomposition of the partition walls. Further, the quartz tube glass used for the mercury lamp preferably has an optical filter function of cutting off light of 200 nm or less.

A low-pressure mercury lamp can also be used as the light source. However, the low-pressure mercury lamp has a high luminous intensity at a wavelength of 200 nm or less and is liable to cause oxidative decomposition of the partition wall due to generation of ozone, so that it is not suitable for a large amount of exposure. The exposure amount is preferably 500 mJ/cm ² or less, and more preferably 300 mJ/cm ² or less.

(post-baking step)

Next, it is advisable to heat the next wall. The heat treatment is performed by a heating device such as a hot plate or an oven for 5 to 90 minutes, whereby a pattern formed by the partition walls and the regions (dot arrays) partitioned by the partition walls can be formed.

The heating temperature is preferably 150 to 250 ° C, and particularly preferably 180 to 250 ° C. If the heating temperature is above the lower limit of the above range, the hardening of the partition wall is sufficient and In the case where the ink is applied when the pixel is formed thereafter, the partition wall is not swollen or the ink is infiltrated due to the solvent contained in the ink. If it is below the upper limit of the above range, it is difficult to cause thermal decomposition of the partition walls.

The pattern formed of the negative photosensitive resin composition of the present invention preferably has a width of the partition walls of 100 μm or less on average, and is preferably 20 μm or less. The distance between the adjacent partition walls (the width of the dot matrix) is preferably 300 μm or less on average, and preferably 100 μm or less. The height of the partition wall is preferably 0.05 to 50 μm on average, and preferably 0.2 to 10 μm.

Examples of the optical element to which the partition wall (black matrix) of the present invention is applied include a color filter and an organic EL element.

[Manufacturing method of color filter]

As described above, after forming a partition wall (black matrix) on the surface of the substrate, an ink composed of a transparent colored photosensitive resin composition is used, and the same method (photolithography) as the partition wall is used to form a surface of the partition wall (black matrix). A color filter is fabricated by forming a pixel at a position between the partition walls (black matrix).

The ink used in the photolithography method mainly contains a coloring component, an initiator, a binder resin component, and a solvent. As the coloring component, pigments and dyes excellent in heat resistance and light resistance are preferably used.

As the binder resin component, a resin which is excellent in transparency and heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and an urethane resin. The water-based ink contains water and a water-soluble organic solvent as a solvent, and contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as required. Also, the oily ink contains organic solvents. As a solvent, the agent contains a resin soluble in an organic solvent as a binder resin component, and contains various auxiliary agents as required.

Further, ink may be injected into the region partitioned by the partition walls (black matrix) by an inkjet method using an ink jet device to form a pixel.

In the substrate on which the partition wall (black matrix) is formed, before the ink is placed in the region (dot matrix) partitioned by the partition wall (black matrix), for example, an alkali aqueous solution cleaning treatment, an ultraviolet cleaning treatment, and ultraviolet rays may be used. / Ozone cleaning treatment, excimer cleaning treatment, corona discharge treatment, and oxygen plasma treatment, etc., the ink-repellent treatment is performed on the surface of the substrate that has been exposed in the lattice.

The ink jet device is not particularly limited, and a device using various methods of continuously ejecting the charged ink and controlling it by a magnetic field, a method of intermittently ejecting the ink using the piezoelectric element, and printing the ink can be used. Heating is performed by a method in which foaming is intermittently performed by foaming.

The shape of the pixel can be any well-known arrangement such as a stripe type, a mosaic type, a triangular type, and a 4-pixel arrangement type.

The ink used in the ink jet method mainly contains a coloring component, a binder resin component, and a solvent. As the coloring component, pigments and dyes excellent in heat resistance and light resistance are preferably used.

As the binder resin component, a resin which is excellent in transparency and heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and an urethane resin. The water-based ink contains water and a water-soluble organic solvent as a solvent, and contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as required. Further, the oily ink contains an organic solvent as a solvent, and contains a resin soluble in an organic solvent as a binder tree. The fat component and various auxiliaries are required according to the requirements.

Further, in the ink jet method, after the ink is injected into the dot matrix by the above-described ink jet apparatus, the ink layer formed in the dot matrix can be subjected to drying, heat curing, ultraviolet curing or the like to form a pixel.

After the pixel is formed, a protective film layer is formed in response to the demand. The protective film layer is preferably formed for the purpose of improving surface flatness and blocking the elution of the ink from the partition wall (black matrix) or the pixel portion to the liquid crystal layer. When the protective film layer is formed, when the ink repellency of the partition walls (black matrix) is strong, it is preferable to remove the ink repellency of the partition walls (black matrix) beforehand. At this time, if the ink repellency is not removed, the coating liquid for the protective film may be pulled and the uniform film thickness may not be obtained. As a method of removing the ink repellency of the partition walls (black matrix), there are a plasma ashing treatment or a light ashing treatment.

Further, in order to increase the grade of a liquid crystal panel or the like manufactured by using a color filter, it is preferable to form a light spacer on a partition wall (black matrix).

The color filter of the present invention uses a partition having a high light-shielding property obtained by the above-described present invention as a black matrix, and thus is a color filter having sufficiently high contrast performance.

[Manufacturing Method of Organic EL Element]

Before the formation of the partition walls, a transparent electrode such as indium tin oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like, and the transparent electrode is etched into a desired pattern as needed. Next, a partition wall is formed using the negative photosensitive resin composition of the present invention, and a solution of the hole transporting material and the luminescent material is sequentially applied to the dot matrix by a vapor deposition method or an inkjet method, and dried to form electricity. Hole transport layer and luminescent layer. Thereafter, an electrode of aluminum or the like is formed by a vapor deposition method or the like, whereby a pixel of the organic EL element can be obtained. Forming holes using inkjet In the case of the transport layer and the light-emitting layer, the inking treatment of the dot matrix is performed before the formation in response to the demand.

Example

The invention will be further illustrated in the following examples, but the invention is not limited by the examples. Further, Examples 1 to 11 are examples, and Examples 21 to 28 are comparative examples.

The abbreviated names of the compounds used in the synthesis examples and examples are as follows.

(alkali soluble resin (A))

ZCR1642: a resin having an ethylenic double bond and an acidic group in an epoxy resin having a biphenyl skeleton represented by the above formula (A1-2a) (manufactured by Nippon Kayaku Co., Ltd.; trade name: ZCR-1642H; mass average molecular weight (Mw) ): 5,800, acid value: 100 mgKOH/g, solid content: 70% by mass, and PGMEA: 30% by mass).

(Photopolymerization initiator (B))

OXE02: ethanol, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetyl) (in formula (3) The compound represented by the formula is represented by the following: R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methylbenzene醯基.BASF company; trade name: OXE02).

NCI831: ADEKA company; trade name: ADEKA ARKLS NCI-831.

N1919: ADEKA company; trade name: ADEKA OPTOMER N-1919.

(black colorant (C) + polymer dispersion)

CB: carbon black dispersion (average secondary particle diameter: 120 nm, carbon black: 20% by mass, amine valence polymer dispersant having an amine price of 18 mgKOH/g: 5% by mass and PGMEA: 75% by mass).

Mixed organic pigment: a mixture of C.I. Pigment Blue 15:6, C.I. Pigment Red 254, C.I. Pigment Yellow 139, and polymer dispersant 10:5:5:5 (solid content: 25% by mass and PGMEA: 75% by mass).

(solvent (D)) (i) solvent (D1)

EDM: diethylene glycol ethyl methyl ether (boiling point: 176 ° C and viscosity: 1.2 mPa ‧ s).

IPDM: diethylene glycol isopropyl methyl ether (boiling point: 179 ° C and viscosity: 1.3 mPa ‧ s).

(ii) Solvent (D2)

CHN: cyclohexanone (boiling point: 155 ° C and viscosity: 2.1 mPa ‧ s).

4-BL: γ-butyrolactone (boiling point: 204 ° C and viscosity: 1.8 mPa ‧ s).

(iii) Solvent (D3)

MDM: diethylene glycol dimethyl ether (boiling point: 162 ° C and viscosity: 1.1 mPa ‧ s).

PGMEA: propylene glycol 1-monomethyl ether 2-acetate (boiling point: 146 ° C and viscosity: 1.3 mPa ‧ s).

EDE: diethylene glycol diethyl ether (boiling point: 189 ° C and viscosity: 1.3 mPa ‧ s).

BDM: diethylene glycol butyl methyl ether (boiling point: 212 ° C and viscosity: 1.5 mPa ‧ s).

DMM: dipropylene glycol dimethyl ether (boiling point: 171 ° C and viscosity: 1.0 mPa ‧ s).

CHXA: cyclohexyl acetate (cyclohexanol acetate; boiling point: 173 ° C and viscosity: 2.0 mPa ‧ s).

DPMA: dipropylene glycol monomethyl ether acetate (boiling point: 213 ° C and viscosity: 2.2 mPa ‧ s).

IPA: isopropanol (2-propanol; boiling point: 82 ° C and viscosity: 1.8 mPa ‧ s).

BA: butyl acetate (n-butyl acetate; boiling point: 126 ° C and viscosity: 0.9 mPa ‧ s).

(crosslinking agent (F))

UX5002: a polyfunctional urethane acrylate oligomer (manufactured by Nippon Kayaku Co., Ltd.; trade name: KAYARAD UX-5002D-P20; solid content: 80% by mass and PGMEA: 20% by mass).

(microparticle (G))

PMA-ST: trade name (manufactured by Nissan Chemical Industries Co., Ltd.; organic cerium oxide sol; solid content: 30% by mass and PGMEA: 70% by mass).

(decane coupling agent (H))

KBM5103: trade name (manufactured by Shin-Etsu Chemical Co., Ltd.; 3-propenyl methoxypropyltrimethoxy decane).

(thermosetting agent (I))

XD1000: Multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd.; trade name: XD1000).

(surfactant (K))

BYK-307: trade name (BYK Japan company; polyether modified polydimethylene Base oxane).

[Examples 1 to 11 and 21 to 28: Modulation of the composition of the negative photosensitive resin, formation and evaluation of the partition walls] (Preparation of negative photosensitive resin composition)

The alkali-soluble resin (A) (containing 30% by mass of PGMEA as a solvent), a photopolymerization initiator (B), and a black colorant (C) (containing 75% by mass) were blended at the ratios shown in Tables 1 and 2. PGMEA as solvent), solvent (D), crosslinking agent (F) (containing 20% by mass of PGMEA as solvent), fine particles (G) (containing 70% by mass of PGMEA as solvent), decane coupling agent (H), heat The hardener (I) and the surfactant (K) were used to prepare a negative photosensitive resin composition.

(formation of black matrix)

A negative photosensitive resin composition was applied onto the surface of a glass substrate (75 × 75 mm) using a spinner to form a coating film (coating film forming step).

Subsequently, the film was dried on a hot plate at 100 ° C for 2 minutes to obtain a glass substrate (1) having the following films: Examples 1, 2 and Examples 21 to 27 were films having a film thickness of 1.0 μm; 3 to 10 are films having a film thickness of 2.0 μm; and Example 11 is a film having a film thickness of 3.0 μm (drying step).

Then, an ultrahigh pressure mercury lamp was used to pass through a photomask having a linear opening of 10 μm × 10 mm, and the exposure amount was irradiated with light of 50 mJ/cm ² based on i line (365 nm) (exposure step).

Next, the unexposed portion was immersed in an inorganic alkali-type developing solution (manufactured by Yokohama Oil & Fats Co., Ltd.; trade name: 10-fold diluted aqueous solution of SEMICLEAN DL-A4), and the unexposed portion was rinsed with water and dried ( Development step).

Next, it was heated at 220 ° C for 1 hour on a hot plate, whereby a glass substrate (2) having a pattern (black matrix) formed on its surface was obtained (post-baking step).

(assessment)

The viscosity of the obtained negative photosensitive resin composition was measured and evaluated. Further, using the obtained glass substrate (1) and glass substrate (2), the resolubility and light blocking properties were measured and evaluated by the method shown below. The evaluation results are shown in Tables 1 and 2.

(1) Viscosity

The viscosity of the negative-type photosensitive resin composition was adjusted to 25°C using a TVE25L-shaped viscometer (manufactured by Toki Sangyo Co., Ltd.) which was calibrated with a standard solution for calibration of viscosity meter JS2.5 (manufactured by Japan GREASE Co., Ltd.). Determination. On the other hand, the viscosity of each compound used as the solvent (D) was measured in the same manner.

The obtained measured value was evaluated based on the following criteria based on the viscosity characteristics obtained in the slit coating method.

Those below 3.0 mPa ‧ are evaluated as ◎ (good), those below 3.5 mPa ‧ are evaluated as ○ (may), and those above 3.5 mPa ‧ are evaluated as × (bad)

(2) Resolubility

The film (0.1 mg) peeled off from the surface of the glass substrate (1) was added to a mixed liquid (40 g) corresponding to a solvent in which the solid content of the negative photosensitive resin composition was removed, and the mixture was stirred at room temperature for 10 minutes. A resolubilizing solution is obtained.

10 mL of the obtained re-dissolved solution was filtered through a membrane filter of 2.5 μm pores of polypropylene, and the precipitate attached to the membrane filter was observed by visual observation or optical microscopy.

Those who did not observe the precipitate were evaluated as ◎ (good), and although no precipitate was observed, the color filter of the membrane filter was evaluated as ○ (may), and those who observed the precipitate were evaluated as × (bad).

(3) Slit coating characteristics

The negative photosensitive resin composition used in Examples 1 and 22 was applied onto the surface of a glass substrate (370 mm × 470 mm) to form a coating film, and the coating property was evaluated by the slit coating method described below.

As the slit coating die, a mold made of SUS304 having a width of 370 mm, a height of 100 mm, and a thickness of 60 mm was used. The distance between the mold and the glass substrate was 100 μm, and a gear pump was used as a method of supplying the negative photosensitive resin composition to the mold. Under this condition, the mold was moved relative to the glass substrate at a relative speed of 50 mm/sec, and a coating film of a negative photosensitive resin composition was formed on the surface of the glass substrate. Next, the coating film was dried to form a film having a thickness of 1.0 μm. The slit coating die was allowed to stand for 5 minutes after coating, and the coating film was again formed by a slit coating method and dried to form a film. Repeat this 10 times. The obtained film was visually observed. The defect of the dry cured product in which no skeletal marks or photosensitive composition was observed was evaluated as ○ (good), and those who observed defects were evaluated as × (bad).

(4) Light blocking (optical density (OD))

The optical density (OD) on the pattern (black matrix) of the glass substrate (2) was measured using a white black transmission densitometer Ihca-T5 (manufactured by Ihara Electronics Co., Ltd.).

Those having an optical density of 2.5 or more were evaluated as ○ (good), and those below 2.5 were evaluated as × (bad).

As is clear from Table 1, the re-solubility and viscosity of the negative-type photosensitive resin composition of the present invention and the light-shielding property of the partition walls (black matrix) formed of the negative-type photosensitive resin composition were good. Among them, Examples 6 to 11 in which the solvent (D1) was used and the solvent (D2) was added as the solvent (D) were particularly excellent in resolubility.

On the other hand, in Table 2, in Examples 21 and 28 in which the solvent (D1) content was small, the resolubility was poor.

In Examples 23 to 27 containing no solvent (D1), the resolubility was also poor.

In the example 22, a negative photosensitive resin composition containing 47% by mass of a solvent of the formula (1) in which R ¹ and R ² are both methyl groups in the total solvent (D) was used, and the slit coating of Example 22 was used. As a result of poor cloth properties, it is presumed that if both of R ¹ and R ² are a methyl group, the boiling point is low and drying and solidification at the slit nozzle is caused, resulting in poor slit coating characteristics.

In the example 23, a negative photosensitive resin composition containing 47% by mass of a solvent of the formula (1) in which all of R ¹ and R ² are ethyl groups is used, and the resolubility from the example 23 is used. As a result of the failure, it is presumed that once the number of carbon atoms of the alkyl chain is increased, it becomes hydrophobic and has poor resolubility.

Further, in the same manner as in the example 24 of the negative photosensitive resin composition containing a solvent having a carbon number of 4 in which R ¹ is a methyl group and R ² is an alkyl chain, it is estimated that the result of poor resolubility is The same reason as in Example 23 caused poor resolubility.

Similarly, in Examples 25 to 27 in which a negative photosensitive resin composition containing 47% by mass of the solvent described in the prior art document in the total solvent (D) was used, the resolubility was also poor.

Industrial availability

The negative photosensitive resin composition of the present invention is suitable for producing a composition of a black matrix having a high light-shielding property containing a pigment, and a high-resolution color filter or an organic EL element can be produced by using the obtained black matrix. .

The entire disclosure of Japanese Patent Application No. 2011-187763, filed on Jan. 30, 2011, the entire content of

Claims (12)

A negative photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerization initiator (B), a black colorant (C), and a solvent (D), which is characterized by a total of the above composition The content of the black coloring agent (C) is more than 20% by mass, and the solvent (D) contains a solvent (D1) in a ratio of 20 to 100% by mass based on the total amount of the solvent (D). (D1) is a compound represented by the following formula (1): R ¹ O(C ₂ H ₄ O) ₂ R ² (1) In the formula (1), R ¹ represents a methyl group, and R ² represents a carbon number. 2 or 3 alkyl groups. The negative photosensitive resin composition of claim 1, wherein the solvent (D1) is diethylene glycol ethyl methyl ether. The negative photosensitive resin composition according to claim 1 or 2, wherein the solvent (D) further contains a solvent (D2) in a ratio of 10 to 40% by mass based on the total amount of the solvent (D). The solvent (D2) is an aliphatic cyclic compound containing one or more carbon atoms bonded to an oxygen atom by a double bond as a ring-constituting atom, and may also contain an etheric oxygen atom. The negative photosensitive resin composition of claim 3, wherein the aliphatic cyclic compound is a cyclic ester or a cyclic ketone. The negative-type photosensitive resin composition according to any one of the above-mentioned items, wherein the alkali-soluble resin (A) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (A) has been introduced into an acidic group. Epoxy (meth) acrylate resin. The negative photosensitive resin composition according to any one of claims 1 to 6, wherein the photopolymerization initiator (B) is an O-quinone compound. The negative photosensitive resin composition according to any one of claims 1 to 7, wherein the photopolymerization initiator (B) is an O-quinone compound represented by the following formula (3): In the formula (3), R ³ represents a hydrogen atom, R ⁶¹ or OR ⁶² , and R ⁶¹ and R ⁶² each independently represent an alkyl group having 1 to 20 carbon atoms, and a hydrogen atom in the cycloalkyl ring may be substituted by an alkyl group. a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a hydrogen atom in the benzene ring, or a phenyl group having 6 to 30 carbon atoms or a benzene ring substituted by an alkyl group A phenylalkyl group having 7 to 30 carbon atoms which may be substituted by an alkyl group; R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a benzene ring A phenyl group having 6 to 30 carbon atoms or a hydrogen atom in a benzene ring in which a hydrogen atom may be substituted by an alkyl group, or a phenylalkyl group having 7 to 30 carbon atoms and 2 to 20 carbon atoms may be substituted by an alkyl group. The alkanoyl group, the hydrogen atom in the benzene ring may be substituted by an alkyl group, the benzoyl group having 7 to 20 carbon atoms, the alkoxycarbonyl group having 2 to 12 carbon atoms or the hydrogen atom in the benzene ring may also be an alkane. a phenoxycarbonyl group having a carbon number of 7 to 20 or a cyano group; R ⁵ represents an alkyl group having 1 to 20 carbon atoms; and a hydrogen atom in the benzene ring may be substituted by an alkyl group; the number of carbon atoms is 6 to 30 The hydrogen atom in the phenyl or benzene ring may also be substituted by an alkyl group having 7 to 30 carbon atoms. Phenylalkyl; R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a cyano group, a halogen atom, a nitro group, R ⁶¹ , OR ⁶² , an alkanoyl group having 2 to 20 carbon atoms, and a benzene ring; The benzoyl group having 7 to 20 carbon atoms and the hydrogen atom in the benzene ring may be substituted by an alkyl group, and the benzocarbonyl group having 7 to 20 carbon atoms and a carbon number of 2 may be substituted by an alkyl group. The alkoxycarbonyl group of ~12, the hydrogen atom in the benzene ring may be substituted by an alkyl group, the phenoxycarbonyl group having 7 to 20 carbon atoms and the decylamino group having 1 to 20 carbon atoms; R ⁰ represents R ⁶¹ and OR ⁶² , cyano or halogen atom; a is 0 or an integer from 1 to 3. The negative photosensitive resin composition according to any one of claims 1 to 8, wherein the black colorant (C) is carbon black or an organic pigment. A partition wall formed by dividing a surface of a substrate into a plurality of divided regions for forming a pixel, wherein the partition wall is composed of a negative photosensitive resin according to any one of claims 1 to 9. It is composed of a cured film of matter. A black matrix characterized in that a surface of a substrate composed of a partition wall as in item 10 of the patent application is divided into a plurality of divided regions. An optical element having a plurality of pixels on a surface of a substrate and a partition wall between adjacent pixels, wherein the partition wall is formed by a partition wall of claim 10 of the patent application.