JP2008297344A - Photosensitive resin composition, and removable liquid-repellant layer formation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition easily forming a removable liquid-repellant layer useful in an inkjet method. <P>SOLUTION: The photosensitive resin composition containing a perfluoroalkyl group-containing resin (A) formed by at least copolymerizing a perfluoroalkyl group-containing polymerizable unsaturated monomer, a polymerizable unsaturated monomer having a carboxy group protected by a tertiary butyl group, and/or a polymerizable unsaturated monomer having a phenol group protected by a tertiary butyloxycarbonyl group; and an optical activator (B) producing an acid by the exposure to light. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition that can be easily formed with a removable liquid-repellent layer, which is useful when an inkjet method is used in the fields of flat panel displays, electronics, biochips, and the like. In the present specification, “liquid repellency” means water repellency and / or oil repellency.

  In recent years, the use of the inkjet method has been widely studied in the fields of flat panel displays, electronics, biochips and the like. For example, in the field of flat panel displays, R (red), G (green), and B (blue) inks are spray-applied in micro-partitions separated by partition walls, commonly referred to as black matrix, in the manufacture of color filters and the like. An ink jet method for forming a colored portion has been proposed. Also, in the manufacture of organic EL display elements, there is an ink jet method in which a hole transport material, a solution of a light emitting material is sprayed and applied in order to form a hole transport layer, a light emitting layer, and the like in a micro compartment separated by a partition wall. Proposed.

  By using such an ink jet method, a pattern such as a colored portion can be formed directly in a micro compartment. Therefore, the inkjet method can omit costly steps as compared with pattern formation by a so-called lithography method that requires repetition of processes such as etching and resist, and as a result, a pattern can be produced at low cost. There is an advantage.

  By the way, the colored portion formation of the color filter by the ink jet method is formed by discharging a plurality of colors of fluid ink and spraying it into a predetermined minute section on the substrate. Here, it is necessary to prevent the occurrence of ink color mixing between adjacent divided areas. Therefore, it is required that the partition walls separating the minute compartments have a property of repelling water or an organic solvent which is an ink jetting droplet, so-called liquid repellency. On the other hand, the liquid repellency of the partition wall may cause an adhesion failure after pattern formation by the ink jet method.

  Also in the fields of electronics, biochips, etc., pattern formation using an ink jet method is performed. For example, in the formation of a wiring pattern on a circuit board, which is an example of use in the electronics field, when forming a wiring pattern using an inkjet method, fluid ink containing a wiring material is ejected to a predetermined position on the board. By spraying, the wiring pattern can be formed directly on the substrate.

  This method also has an advantage that a costly process can be omitted as compared with pattern formation by a so-called lithography method, and as a result, a pattern can be produced at low cost. However, when droplets are ejected and adhered to the substrate, the adhered droplets spread depending on the characteristics of the substrate surface, and there is a problem that a desired wiring pattern cannot be obtained. Therefore, in the formation of the wiring pattern, a liquid repellent partition wall (also called a bank) that can be removed is provided in a portion where the wiring material is not formed, and the partition wall is removed after the pattern formation by the ink jet method. There is an advantage that it is possible to form a highly accurate wiring pattern.

  Japanese Patent Application Laid-Open No. 2005-315984 (Patent Document 1) describes a resist composition containing a fluorine-containing resin (Claim 1). Further, this resist composition is used to produce a color filter using an inkjet method. (Paragraph 0128 etc.). The resist composition described in Patent Document 1 is a negative resist composition that becomes insoluble in alkali when irradiated with light (paragraphs 0016 to 0022, paragraphs 0026 to 0122, and the like). The negative resist composition is a composition that is crosslinked or polymerized by light irradiation and cured. Therefore, when preparing a liquid-repellent partition using a negative resist composition, there is a problem that it is difficult to remove the liquid-repellent partition that is unnecessary after ink jet recording. The removal treatment of the cured negative resist composition is generally performed under extremely severe conditions as compared with the treatment with an alkali developer. Therefore, there is a problem that performing the removal treatment of the negative resist composition has a high possibility of adversely affecting the pattern formed by ink jet recording.

  In Japanese Patent Application Laid-Open No. 7-49414 (Patent Document 2), a light-repellent layer that is solubilized by exposure is applied on a light-transmitting substrate on which a black matrix is formed, and light is emitted by photolithography using the black matrix as a pattern mask. A method for producing a color filter is described, in which a repellent layer matching a black matrix pattern is formed by performing exposure and development processing from the transmissive substrate side (claims 1 and 2). This Patent Document 2 describes a method of forming a repellent layer on a black matrix using a so-called positive resist composition. In Patent Document 2, the formation of the repellent layer is carried out in two stages using a repulsive composition or a silicone rubber composition to which a fluorosurfactant is added and a positive photoresist separately, followed by exposure and development. Etc. (paragraphs 0038 to 0048). That is, in Patent Document 2, the repellent layer is formed by a two-step process using two components of a repellent composition and a positive photoresist. On the other hand, in the present invention, a removable liquid-repellent partition wall can be formed in one step using the photosensitive resin composition of the present invention. Is different. Moreover, in this invention, since the liquid-repellent partition which can be removed by one step can be formed, compared with the method described in patent document 2, it is simpler.

  In Japanese Patent Laid-Open No. 2000-35511 (Patent Document 3), after patterning a light shielding layer on a substrate, a positive resist layer for forming a convex portion is formed thereon, and the light shielding layer is used as a mask. The resist layer is exposed from the opposite surface of the substrate, and then the exposed resist layer is removed to form a convex portion by the resist layer, and an ink jet method is applied to the concave portion separated by the weir between the convex portion and the light shielding layer. The method for producing a color filter is characterized in that a colored layer is formed by spraying ink according to claim 1 (claim 1). In the formation of the convex portion, it is described that a method of patterning the convex portion by a method such as photolithography after ink repellent treatment with an ink repellent treatment agent is preferable (paragraph 0045, etc.). This method is also a method performed by a two-step process using two components, a positive resist and an ink repellent treatment agent. On the other hand, in the present invention, a removable liquid-repellent partition wall can be formed in one step using the photosensitive resin composition of the present invention. It is different and simpler than the method described in Patent Document 3.

  In JP-A-2006-163309 (Patent Document 4), a light shielding layer is formed on a transparent substrate using a printing method, a positive resist layer is formed, and then the positive resist layer is exposed from the back side of the transparent substrate. Then, development is performed and an ink repellent agent is formed on the positive resist layer to provide a partition wall in which the light shielding layer, the positive resist layer, and the ink repellent agent layer are laminated, and inkjet ink is discharged into the partition wall. A method of manufacturing a color filter is described. This method is also a method performed by a two-step process using two components, a positive resist and an ink repellent agent. On the other hand, in the present invention, a removable liquid-repellent partition wall can be formed in one step using the photosensitive resin composition of the present invention. It is different and simpler than the method described in Patent Document 4.

JP 2005-315984 A Japanese Unexamined Patent Publication No. 7-49414 JP 2000-35511 A JP 2006-163309 A

  The present invention solves the above-described conventional problems, and an object of the present invention is to easily form a removable liquid repellent layer (also referred to as a bank or a convex portion) that is useful in an ink jet method. It is in providing the photosensitive resin composition which can be manufactured.

The present invention
Polymerizable unsaturated monomer having a perfluoroalkyl group-containing polymerizable unsaturated monomer and a polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or a phenol group protected with a tertiary butyloxycarbonyl group A perfluoroalkyl group-containing resin (A) obtained by copolymerizing at least a monomer, and a photoactive agent (B) that generates an acid upon exposure to light
The photosensitive resin composition containing this is provided, and the said objective is achieved by this.

The perfluoroalkyl group-containing resin (A) is
5 to 74% by mass of a perfluoroalkyl group-containing polymerizable unsaturated monomer,
20 to 89% by mass of a polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or a phenolic group protected with a tertiary butyloxycarbonyl group, and other polymerizable compounds 6-75% by weight of unsaturated monomer,
(Provided that the total of the above monomers is 100% by mass)
And the photosensitive resin composition comprises 80 to 99.9 perfluoroalkyl group-containing resin (A) with respect to the total solid mass of the photosensitive resin composition. It is preferable to contain 0.1 to 20% by mass of the photoactivator (B) that generates an acid upon mass% and exposure.

The photosensitive resin composition further has an acrylic resin which does not have a perfluoroalkyl group and has a carboxyl group protected with a tertiary butyl group and / or a phenol group protected with a tertiary butyloxycarbonyl group. (C) comprises, and the difference between the SP value (SP _a) of the SP value of the acrylic resin (C) (SP _C) and the perfluoroalkyl group-containing resin (a) is not less than 0.3 preferable.

The photosensitive resin composition is based on the total solid mass of the photosensitive resin composition.
0.1-49.9 mass% of perfluoroalkyl group-containing resin (A),
0.1 to 20% by mass of the photoactive agent (B) that generates an acid upon exposure, and 50 to 99.8% by mass of the acrylic resin (C),
(Provided that the total of components (A), (B) and (C) is 100% by mass)
It is preferable to include.

  The photosensitive resin composition is preferably an alkali-soluble positive photosensitive resin composition.

The present invention also provides
Applying the photosensitive resin composition and then drying to obtain a photosensitive coating film, a photosensitive coating film forming step,
A pattern exposure step of irradiating the photosensitive coating film with light having a wavelength of 180 to 500 nm through a photomask;
Development process for developing a pattern-exposed coating film using an alkaline developer,
A method of forming a removable liquid repellent layer is also provided.

The present invention further includes
On the surface of the substrate having a black matrix, the photosensitive resin composition is applied and then dried to obtain a photosensitive coating film, a photosensitive coating film forming step,
A pattern exposure step of irradiating the photosensitive coating film with light having a wavelength of 180 to 500 nm from the surface side where the black matrix is not provided,
The pattern-exposed coating is developed using an alkaline developer to obtain a removable liquid repellent layer formed on the black matrix, and the resulting black matrix substrate is colored by an inkjet method. Forming a process,
A method for producing a color filter is also provided.

  The present invention further provides a color filter obtained by the method for producing a color filter.

  By using the photosensitive resin composition of the present invention, a removable liquid repellent layer can be easily formed. That is, by using the photosensitive resin composition of the present invention, it is possible to easily form a liquid repellent layer that can be easily removed after forming a colored part pattern or the like by an ink jet method. By forming such a liquid repellent layer in the ink jet method, the accuracy of ink jet recording can be improved. In addition, by using the photosensitive resin composition of the present invention, a color filter having good color separation and capable of being used for a high-definition display can be produced at low cost and with high productivity by an inkjet method. .

  The photosensitive coating film formed by the photosensitive resin composition of the present invention is a so-called positive photosensitive coating film in which only a portion irradiated with light having a wavelength of, for example, 180 to 500 nm is soluble in alkali. . In the prior art, there is almost no technology in which a positive resist composition itself contains a fluororesin. As a reason why the technology relating to a positive resist composition containing a fluororesin is hardly studied, by including a fluororesin in the positive resist composition, a liquid repellency is generated in the coating film itself obtained from the composition. By reducing the alkali detergency of the portion where the liquid repellency becomes soluble after light irradiation, it is considered that the alkali developability is lowered and development is impossible with high accuracy.

  On the other hand, a negative resist composition containing a fluororesin has been studied as a negative resist composition that becomes insoluble in alkali when irradiated with light (Patent Document 1, etc.). However, the negative resist composition is a composition that is cross-linked or polymerized by light irradiation and cured. Therefore, when preparing a liquid-repellent partition using a negative resist composition, there is a problem that it is difficult to remove the liquid-repellent partition that is unnecessary after ink jet recording. Further, the removal treatment of the cured negative resist composition needs to be performed under very severe conditions. Therefore, there is a problem that performing the removal treatment of the negative resist composition has a high possibility of adversely affecting the pattern formed by ink jet recording. On the other hand, as a method for removing the liquid repellency of the partition wall which has become unnecessary after ink jet recording while leaving the partition wall itself, for example, a method such as corona discharge (JP-A-10-62617) has been studied. However, such post-processing is very complicated, and such post-processing may also adversely affect a pattern formed by ink jet recording.

  According to the present invention, a liquid repellent layer that can be easily removed later can be formed with high accuracy. That is, according to the present invention, the performance of the ink jet recording technique can be enhanced, and a liquid repellent layer that can be easily removed after ink jet recording can be formed with high accuracy. By using the photosensitive resin composition of the present invention, a micro-order liquid repellent layer can be formed. The liquid-repellent layer formed according to the present invention can be easily removed by a gentle and widely used process in which the entire surface is exposed after ink jet recording and then washed with an alkaline developer. . By using the photosensitive resin composition of the present invention, the accuracy of the inkjet method can be further improved.

Photosensitive resin composition The photosensitive resin composition of the present invention contains at least a fluoroalkyl group-containing resin (A) and a photoactive agent (B) that generates an acid upon exposure. This photosensitive resin composition is a so-called alkali-soluble positive photosensitive resin composition.

Fluoroalkyl group-containing resin (A)
The fluoroalkyl group-containing resin (A) contained in the photosensitive resin composition of the present invention was protected with a perfluoroalkyl group, a carboxyl group protected with a tertiary butyl group, and / or a tertiary butyloxycarbonyl group. And a phenol group.
And this fluoroalkyl group containing resin (A),
A perfluoroalkyl group-containing polymerizable unsaturated monomer; and
A polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or a polymerizable unsaturated monomer having a phenol group protected with a tertiary butyloxycarbonyl group;
Of at least two components.

Examples of the perfluoroalkyl group-containing polymerizable unsaturated monomer used for the preparation of the fluoroalkyl group-containing resin (A) include unsaturated double bond-containing monomers having a C 1-12 perfluoroalkyl group. . Specific examples of the perfluoroalkyl group-containing polymerizable unsaturated monomer include, for example, the following formula 1
CH ₂ = CH (R ¹ ) COOXR ^f ... Formula 1
[Wherein, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents a divalent organic group having 1 to 10 carbon atoms, and R ^f represents a perfluoroalkyl group having 1 to 12 carbon atoms. Indicates. ]
The monomer represented by these is mentioned. X in Formula 1 may be a divalent organic group, and may have atoms other than carbon and hydrogen (for example, N, S, O atoms, etc.).

Specific examples of the monomer represented by the above formula 1 include the following monomers.
CH ₂ = CH (R ¹ ) COOR ² R ^f
CH ₂ = CH (R ¹ ) COOR ² NR ³ SO ₂ R ^f
CH ₂ = CH (R ¹ ) COOR ² NR ³ COR ^f
CH ₂ = CH (R ¹ ) COOCH ₂ CH (OH) R ⁴ R ^f
In the above formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, R ² represents an alkylene group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , R ⁴ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^f represents a perfluoroalkyl group having 1 to 12 carbon atoms.

Specific examples of R _{^2, -CH 2 -, - CH 2} CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH _{2 CH 3) -, - CH} 2 CH 2 CH 2 CH 2 -, - CH (CH 2 CH 2 CH 3) -, - CH 2 (CH 2) 3 CH 2 -, - CH (CH 2 CH (CH 3 ) ₂ )-and the like.

Specific examples of R ³ include —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₂ CH _{3 and the} like.

Specific examples of R ⁴ _{are, -CH 2 -, - CH 2} CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH _{2 CH 3) -, - CH} 2 CH 2 CH 2 CH 2 -, - CH (CH 2 CH 2 CH 3) - , and the like.

  In the above formula 1, X is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.

  Specific examples of the monomer represented by the above formula 1 include perfluorohexylethyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ) Ethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorodecyl) ethyl ( Acrylate), 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ) Ethyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro -7-methyloctyl) -2-hydroxypropyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoromethyl (meth) acrylate, and the like.

  In addition, a perfluoroalkyl group containing polymerizable unsaturated monomer may be used independently and may use 2 or more types together.

  A polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and a polymerizable unsaturated group having a phenol group protected with a tertiary butyloxycarbonyl group, used for the preparation of the fluoroalkyl group-containing resin (A) The tertiary butyl group and tertiary butyloxycarbonyl group possessed by the monomer are protecting groups that are cleaved in the presence of an acid. That is, the fluoroalkyl group-containing resin (A) in the present invention is a resin having a fluoroalkyl group and a carboxyl group and / or a phenol group protected by a protecting group that is cleaved by an acid.

  In the fluoroalkyl group-containing resin (A) of the present invention, the carboxyl group protected with a tertiary butyl group is cleaved by the generation of an acid upon exposure to regenerate the carboxyl group. Thereby, the fluoroalkyl group-containing resin (A) becomes alkali-soluble. Thus, the exposed portion is soluble in the alkaline developer and can be developed with the alkaline developer. In the fluoroalkyl group-containing resin (A) in the present invention, the phenol group protected by the tertiary butyloxycarbonyl group is cleaved by the generation of an acid upon exposure to regenerate the phenol group. Thereby, the fluoroalkyl group-containing resin (A) becomes alkali-soluble. Thus, the exposed portion is soluble in the alkaline developer and can be developed with the alkaline developer.

  As the polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group, tertiary butyl ester of an α, β-ethylenically unsaturated carboxylic acid can be used. Examples of α, β-ethylenically unsaturated carboxylic acids that form tertiary butyl esters include acrylic acid, methacrylic acid, crotonic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Monocarboxylic acids such as phthalic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; maleic anhydride and itaconic anhydride And tertiary butyl esters such as mono-esters of dicarboxylic acids such as monoethyl maleate, monoethyl fumarate and monoethyl itaconate; One of these may be used alone, or two or more may be mixed and used. Further, instead of using a polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group, for example, a hydroxyl group is introduced into the polymer by copolymerizing (meth) acrylic acid hydroxyalkyl ester, etc. A method in which an acid anhydride such as succinic acid or phthalic anhydride is reacted and then protected with a tertiary butyl group, or by introducing a glycidyl group into a polymer and reacting with a dicarboxylic acid or the like, an acid is contained in the resin. Examples thereof include a method of introducing a group and then protecting with a tertiary butyl group.

  As a polymerizable unsaturated monomer having a phenol group protected with a tertiary butyloxycarbonyl group, p-tertiary butoxycarbonyloxy-α-methylstyrene, p-tertiarybutoxycarbonyloxystyrene, tertiary butyl-p-vinyl Benzoate, tertiary butyl-p-isopropenyl phenyloxyacetate and the like can be used.

  In the preparation of the fluoroalkyl group-containing resin (A) in the present invention, the above-mentioned perfluoroalkyl group-containing polymerizable unsaturated monomer, the polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group, and / or tertiary. In addition to the polymerizable unsaturated monomer having a phenol group protected by a butyloxycarbonyl group, other polymerizable unsaturated monomers may be used.

  Other polymerizable unsaturated monomers that can be used, for example, substituted with styrene or α-, o-, m-, p-alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester of styrene Substituted derivatives; olefins such as butadiene, isoprene and neoprene; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, pentyl, neopentyl, isoamylhexyl, methacrylic acid or acrylic acid; Cyclohexyl, adamantyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, anthraquinonyl, piperonyl, salicyl, cyclohexyl, benzyl, phenethyl, cresyl, glycidyl, isobornyl, triphenylmethyl, dicyclopentanyl, Mil, 3- (N, N-dimethylamino) propyl, 3- (N, N-dimethylamino) ethyl, furyl or furfuryl ester; anilide or amide of methacrylic acid or acrylic acid, or N, N-dimethyl, N , N-diethyl, N, N-dipropyl, N, N-diisopropyl or anthranilamide; an ester of methacrylic acid or acrylic acid, the ester moiety containing an alkylene oxide group; an acrylonitrile; , Acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N -Methacryloyl phthalate An imide, N-acryloyl phthalimide, etc. can be used.

  As another polymerizable unsaturated monomer, a polymerizable unsaturated monomer having an acid group may be used. By preparing the fluoroalkyl group-containing resin (A) using a polymerizable unsaturated monomer having an acid group, the alkali developability of the resulting photosensitive resin composition can be further improved. Examples of the polymerizable unsaturated monomer having an acid group include methacrylic acid, acrylic acid, and substituted derivatives thereof substituted by α-position haloalkyl, alkoxy, halogen, nitro, or cyano. , M-, p-hydroxystyrene or substituted derivatives thereof substituted by alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester or carboxy; vinyl hydroquinone, 5-vinyl pyrogallol, 6-vinyl pyrogallol, 1- Polyhydroxyvinylphenols such as vinylphloroglicinol; o-, m-, p-vinylbenzoic acid or substituted derivatives thereof substituted by alkyl, alkoxy, halogen, nitro, cyano, amide or ester; maleic acid, anhydrous Ma Divalent unsaturated carboxylic acids such as inic acid, fumaric acid, fumaric acid anhydride, citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexenedicarboxylic acid or their methyl, ethyl, propyl, i-propyl, n- Mention may be made of butyl, sec-butyl, ter-butyl, phenyl, o-, m-, p-toluyl half ester or half amide.

  These other polymerizable unsaturated monomers may be used alone or in combination of two or more.

The preferred copolymerization ratio of the polymerizable unsaturated monomer used for the preparation of the perfluoroalkyl group-containing resin (A) is:
5 to 74% by mass of a perfluoroalkyl group-containing polymerizable unsaturated monomer,
20 to 89% by mass of a polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or a phenolic group protected with a tertiary butyloxycarbonyl group, and other polymerizable compounds 6-75% by weight of unsaturated monomer,
(Provided that the total of the above monomers is 100% by mass)
It is.

  The perfluoroalkyl group-containing resin (A) can be obtained, for example, by a method in which a monomer component is dissolved in a solvent, heated as necessary, and a polymerization initiator is added to cause a polymerization reaction. In this reaction, it is preferable that a chain transfer agent is present if necessary. You may add a monomer component, a polymerization initiator, a solvent, and a chain transfer agent continuously.

  Examples of the solvent that can be used in the copolymerization of the perfluoroalkyl group-containing resin (A) include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol, acetone, methyl isobutyl ketone, and cyclohexanone. Ketones, Cellsolves such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ) Carbitols such as ethanol, methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Over DOO, ethylene glycol diacetate, esters such as glycerol triacetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether. The amount of these solvents to be used is preferably 20 to 1000 parts by mass per 100 parts by mass of the total amount of monomers as reaction raw materials.

  As the polymerization initiator that can be used in the copolymerization of the perfluoroalkyl group-containing resin (A), those generally known as radical polymerization initiators can be used, for example, 2,2′-azobisisobutyrate. Azo compounds such as rhonitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide , Organic peroxides such as tert-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane, tertiary butylperoxy-2-ethylhexanoate; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be used as a redox initiator using a peroxide together with a reducing agent.

  Chain transfer agents that can be used in the copolymerization include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, chloroform, and the like. And alkyl halides such as carbon tetrachloride and carbon tetrabromide.

  The mass average molecular weight of the fluoroalkyl group-containing resin (A) used in the present invention is preferably 500 to 100,000, more preferably 1,000 to 50,000. The mass average molecular weight in this specification means a mass average molecular weight in terms of polystyrene. When the mass average molecular weight is less than 500, resolution and developability may be inferior. Moreover, when a mass average molecular weight exceeds 100,000, there exists a possibility that alkali developability may deteriorate.

Photoactivator that generates acid upon exposure (B)
The photosensitive resin composition of this invention contains the photoactive agent (B) which produces an acid by exposure. As the photoactive agent (B) that generates an acid upon exposure, a compound that generates a strong acid upon exposure can be used without particular limitation. The photoactivator (B) that can be used in the present invention is not particularly limited, but generally known onium salts and compounds that generate sulfonic acid upon exposure can be used. Examples of onium salts include diaryl iodonium salts, triaryl sulfonium salts, and triaryl selenium salts. Suitable counter anions include tetrafluoroborate, trifluoromethanesulfonate, hexafluoroantimonate, hexa Examples include compounds such as fluoroarsenates and hexafluorophosphates. Examples of compounds that generate sulfonic acid upon exposure include β-ketosulfone compounds, ester compounds of nitrobenzyl alcohol and arylsulfonic acid, ester compounds of oxime and arylsulfonic acid, N-hydroxyamide or imide and sulfonic acid. And ester compounds of benzoin and sulfonic acid. A photoactive agent (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

  By exposing the photosensitive resin layer, an acid is generated from the photoactivator (B), and this acid is a tertiary butyl (t-butyl) group and / or tertiary of the fluoroalkyl group-containing resin (A). The butyloxycarbonyl (t-butyloxycarbonyl) group will be cleaved.

  In one embodiment of the photosensitive resin composition of the present invention, the amount of the fluoroalkyl group-containing resin (A) and the photoactive agent (B) contained in the photosensitive resin composition is the total solid content of the photosensitive resin composition. In contrast, the perfluoroalkyl group-containing resin (A) is preferably 80 to 99.9% by mass and the photoactive agent (B) is preferably 0.1 to 20% by mass. When the amount of the photoactive agent (B) is less than the above range, the acid generation amount becomes poor and the alkali developability may be lowered. On the other hand, when the amount of the photoactive agent (B) is more than the above range, it is not preferable because sufficient film strength of the photosensitive coating film and the liquid repellent layer may not be obtained.

  In another embodiment of the photosensitive resin composition of the present invention, in addition to the perfluoroalkyl group-containing resin (A) and the photoactivator (B), the photosensitive resin composition does not have a perfluoroalkyl group and has tertiary butyl. And a photosensitive resin composition containing an acrylic resin (C) having a carboxyl group protected with a group and / or a phenol group protected with a tertiary butyloxycarbonyl group.

  The tertiary butyl group-protected carboxyl group and / or tertiary butyloxycarbonyl group of the acrylic resin (C) is cleaved in the presence of an acid as in the case of the fluoroalkyl group-containing resin (A). Protecting group. That is, the acrylic resin (C) in the present invention is a resin that has a carboxyl group and / or a phenol group protected by a protecting group that is cleaved by an acid, but does not have a fluoroalkyl group. The acrylic resin (C) becomes alkali-soluble by cleaving the protective group due to the generation of acid by exposure. Thus, the exposed portion becomes soluble in the alkali developer, and development with the alkali developer becomes possible.

  The acrylic resin (C) having no perfluoroalkyl group and having a carboxyl group protected with a tertiary butyl group and / or a phenol group protected with a tertiary butyloxycarbonyl group is a tertiary butyl group. A polymerizable unsaturated monomer having a carboxyl group protected with an alkyl group and / or a polymerizable unsaturated monomer having a phenol group protected with a tertiary butyloxycarbonyl group and another polymerizable unsaturated monomer are copolymerized. Can be prepared. A polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group, a polymerizable unsaturated monomer having a phenol group protected with a tertiary butyloxycarbonyl group, and other polymerizable monomers as described above Can be used respectively.

Preferred of the polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or the polymerizable unsaturated monomer having a phenol group protected with a tertiary butyloxycarbonyl group, and other polymerizable unsaturated monomers The ratio is
20 to 94% by mass of a polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or a polymerizable unsaturated monomer having a phenol group protected with a tertiary butyloxycarbonyl group
6-80% by mass of other polymerizable unsaturated monomers
It is. A more preferable copolymerization ratio of the unsaturated monomer used for the preparation of the acrylic resin (C) is, for example, a polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or a tertiary butyloxycarbonyl group. Examples of 20 to 94% by mass of polymerizable unsaturated monomer having a protected phenol group, 3 to 30% by mass of polymerizable unsaturated monomer having an acid group, and 3 to 50% by mass of polymerizable unsaturated monomer having no acid group Is mentioned. The total of the above monomers is 100% by mass.

  The acrylic resin (C) can be prepared in the same manner as the perfluoroalkyl group-containing resin (A). The lower limit of the acid value of the acrylic resin (C) is more preferably 20, and the upper limit is more preferably 200. Moreover, it is preferable that it is 500-100000, and, as for the mass mean molecular weight of an acrylic resin (C), it is more preferable that it is 1000-50000.

In another one embodiment of the photosensitive resin composition of the present invention, the difference between the SP value of the acrylic resin SP value of _(C) (SP C) and the perfluoroalkyl group-containing resin (A) and (SP _A) It is preferable that it is 0.3 or more. The SP value (SP _A ) of the perfluoroalkyl group-containing resin (A) is preferably lower than the SP value (SP _C ) of the acrylic resin (C). The difference in SP value is more preferably 0.5 or more, and further preferably 0.5 to 2.0. Here, “SP” means the solubility parameter (solubility parameter) of the resin. The solubility parameter is a scale indicating the degree of hydrophilicity or hydrophobicity of the resin, and is also an important scale for judging the compatibility between the resins. SP indicates that the larger the value, the higher the polarity, and the smaller the value, the lower the polarity.

  In general, it is considered that the compatibility starts to lose some compatibility when the difference in solubility parameter (SP) between the two types of resin components exceeds 0.3. And when the difference of solubility parameter (SP) exceeds 0.5, it is thought that the separation structure of a coating film begins to show clearly. In the photosensitive resin composition of the present invention, the perfluoroalkyl group-containing resin (A) having a perfluoroalkyl group which is a low polarity group is an acrylic resin (C) having no perfluoroalkyl group. The SP value is low compared. Therefore, when the photosensitive resin composition of the present invention is applied, the perfluoroalkyl group-containing resin (A) easily moves to the air layer side to form a resin layer. Thus, the difference in solubility parameter of each resin component is considered to be a driving force that causes separation of the resin layer. And in the photosensitive coating film obtained by applying the photosensitive resin composition of the present invention, the perfluoroalkyl group-containing resin (A) having a lower polarity moves to the air layer side, that is, the coating film surface side. It is considered that a photosensitive coating film having a perfluoroalkyl group-containing resin (A) localized on the surface can be obtained. In this way, the perfluoroalkyl group-containing resin (A) moves to the coating film surface side in the photosensitive coating film, whereby a partition wall having excellent liquid repellency can be formed.

  In such a photosensitive resin composition containing a perfluoroalkyl group-containing resin (A), a photoactivator (B), and an acrylic resin (C) having no perfluoroalkyl group, it is generally expensive. While suppressing the amount of the fluoroalkyl component used, excellent liquid repellency can be exhibited, and there is an advantage that it is excellent in economy. Such a photosensitive resin composition is further excellent in alkali developability, and has an advantage that a removable liquid repellent layer can be formed with higher accuracy.

  The solubility parameter of the perfluoroalkyl group-containing resin (A) and the acrylic resin (C) having no perfluoroalkyl group can be numerically quantified based on a turbidity measurement method known to those skilled in the art. it can. The solubility parameter can be measured, for example, by the following method [Reference: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].

Measurement temperature: 20 ° C
Sample: Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
solvent:
Good solvent: poor solvent such as dioxane, acetone, etc. n-hexane, ion-exchanged water, etc. Muddy point measurement: The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount of addition.

  The δ (SP value) of the resin is given by the following equation.

V _i : Molecular volume of solvent (ml / mol)
φ _i : Volume fraction of each solvent at cloud point δ _i : SP value of solvent ml: Low SP poor solvent mixed system mh: High SP poor solvent mixed system

In another embodiment of the photosensitive resin composition of the present invention, the amount of the fluoroalkyl group-containing resin (A), the photoactive agent (B) and the acrylic resin (C) contained in the photosensitive resin composition is photosensitive. For the total solid mass of the resin composition,
Perfluoroalkyl group-containing resin (A) 0.1-49.9% by mass,
0.1-20 mass% of photoactive agents (B) and 50-99.8 mass% of acrylic resins (C)
(Provided that the total of components (A), (B) and (C) is 100% by mass)
Is preferred. When the amount of the photoactive agent (B) is less than the above range, the acid generation amount becomes poor and the alkali developability may be lowered. On the other hand, when the amount of the photoactive agent (B) is more than the above range, it is not preferable because sufficient film strength of the photosensitive coating film and the liquid repellent layer may not be obtained.

  In the photosensitive resin composition according to another embodiment of the present invention, an acid is generated from the photoactive agent (B) by exposing the photosensitive resin layer, and the acid contains a fluoroalkyl group. The t-butyl group and / or t-butyloxycarbonyl group of the resin (A) and the acrylic resin (C) will be cleaved.

Preparation of photosensitive resin composition and formation of photosensitive coating film The photosensitive resin composition of the present invention has a fluoroalkyl group-containing resin (A), a photoactive agent (B), and a perfluoroalkyl group as required. It can prepare by melt | dissolving in a suitable solvent so that solid content concentration of resin solid content, such as an acrylic resin (C) which does not become may be 10-50 mass%. Suitable solvents for the photosensitive resin composition of the present invention include, for example, ethylene glycol monoalkyl ether and its acetate; propylene glycol monoalkyl ether and its acetate; diethylene glycol mono or dialkyl ether; alkyl propionate and alkoxy thereof. Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; acetates such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xylene; and ethyl lactate, diacetone alcohol, dimethylacetamide, dimethylformamide, N-methylpyrrolidone etc. are mentioned. These solvents may be used alone or in combination of two or more. In the photosensitive resin composition of the present invention, the components and the solvent are mixed at a temperature of, for example, 20 to 30 ° C. using a commonly used stirrer (for example, manufactured by TK Robotics (R) Primix Co., Ltd.). It can be prepared by stirring for 5 to 1 hour. Further, after dissolution, it may be filtered with a filter having a pore diameter of about 0.1 to 10 μm.

  In the photosensitive resin composition of the present invention, an antistatic agent, a storage stabilizer, an antihalation agent, an antifoaming agent, a leveling agent, an anti-repellent agent, a thickener, a plasticizer, a pigment, and the like are added as necessary. You can also.

In the present invention, a removable liquid repellent layer can be formed with high accuracy using the photosensitive resin composition. This removable liquid repellent layer is a photosensitive coating film forming step in which a photosensitive coating film is obtained by applying the photosensitive resin composition in the following step and then drying it.
A pattern exposure step of irradiating light having a wavelength of 180 to 500 nm to the resulting photosensitive coating film through a photomask, and a development step of developing the pattern-exposed coating film using an alkali developer ,
Can be formed.

  The material of the base material to which the photosensitive resin composition is applied is not particularly limited. Examples of the base material include various glass plates, polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and polyethylene, thermoplastic plastic sheets such as polycarbonate, polymethyl methacrylate, polysulfone, and polyimide, epoxy resins, polyester resins, and poly (meth) acrylic. Examples thereof include a thermosetting plastic sheet such as a resin. As a coating method when applying the photosensitive resin composition to the substrate, as a coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating and curtain are known. Application or the like can be used without any particular limitation.

  Next, a photosensitive coating film can be obtained by drying the photosensitive resin composition applied to the substrate. The photosensitive resin composition may be dried as necessary, for example, by pre-baking at 30 to 180 ° C. for 10 to 1200 seconds. Such pre-baking conditions can be widely changed according to the resin component and the type of solvent contained in the photosensitive resin composition, and the resin solid content.

The photosensitive coating film thus obtained is irradiated with light having a wavelength of 180 to 500 nm through a photomask having a predetermined pattern. This process is called a pattern exposure process. In this way, by partially exposing the photosensitive coating film, the exposed part becomes soluble in alkali, and the unexposed part maintains poor solubility in alkali. In addition, after exposure, you may heat for 10 to 1200 seconds at 50-180 degreeC as needed. By heating, the elimination reaction of the tertiary butyl group and / or tertiary butyloxycarbonyl group which component (A) and component (C) have can be promoted. As a light source used in pattern exposure, for example, ultraviolet rays from an ultra-high pressure mercury lamp, i-line with a wavelength of 365 nm, h-line with a wavelength of 405 nm, g-line with 436 nm, KrF excimer laser with a wavelength of 248 nm, ArF with a wavelength of 193 nm Examples include deep ultraviolet rays such as excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. As a more preferable light source in this exposure, an ultra-high pressure mercury lamp widely used for exposure apparatus applications can be mentioned. Using such a light source, it is preferable to expose in the range of the exposure amount of 5 to 1000 mJ / cm ² .

  Next, this pattern-exposed coating film is developed using an alkali developer (development process). Examples of the alkaline developer that can be used here include sodium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo An alkaline aqueous solution in which [4.3.0] -5-nonane or the like is dissolved may be mentioned. In addition, a water-soluble organic solvent (for example, alcohols such as methanol and ethanol) and / or an appropriate amount of a surfactant may be added to the alkaline aqueous solution or the like. As a developing method, a spray method, a dipping method, a rocking dipping method, or the like can be used. The development processing time is, for example, 10 to 300 seconds. Further, after development, water on the substrate can be removed by washing with running water as necessary and air-drying using compressed air or compressed nitrogen. Thus, a removable liquid repellent layer having a specific pattern is formed.

  The removable liquid repellent layer thus obtained serves as a partition wall that prevents the sprayed ink from spreading outside the desired position when the ink is sprayed and adhered to the desired position by the ink jet method. As an inkjet method, for example, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is intermittently ejected using a piezoelectric element, and an ink is heated and intermittently utilized by foaming. Various methods such as a spraying method can be adopted. As the ink used in the ink jet method, either oil-based ink or water-based ink can be used.

  The removable liquid repellent layer in the present invention can be easily removed by forming a desired pattern with high accuracy by an ink jet method and then exposing the liquid repellent layer and developing with alkali. The liquid repellent layer can be removed by exposing the entire surface of the liquid repellent layer with light having a wavelength of 180 to 500 nm and then developing with the above alkali developer. Such a removable liquid repellent layer is useful when using the inkjet method in the fields of flat panel displays, electronics, biochips and the like.

Method for Producing Color Filter The photosensitive resin composition of the present invention can be suitably used in the production of a color filter using an inkjet method. Examples of a method for producing a color filter include a method including the following steps:
On the surface of the substrate having a black matrix, the photosensitive resin composition is applied and then dried to obtain a photosensitive coating film, a photosensitive coating film forming step,
A pattern exposure step of irradiating the photosensitive coating film with light having a wavelength of 180 to 500 nm from the surface side where the black matrix is not provided,
The pattern-exposed coating is developed using an alkaline developer to obtain a removable liquid repellent layer formed on the black matrix, and the resulting black matrix substrate is colored by an inkjet method. Forming.

  As a substrate material of a substrate having a black matrix, a substrate material that is basically transparent and has solvent resistance to such an extent that transparency is not impaired by alkali development is preferably used. Specifically, a polyester film, a polyethersulfone film, a glass plate, or the like can be used as the substrate. A glass plate is preferably used as the substrate. The thickness of the substrate varies depending on the strength of the material used. For example, when a glass plate is used as the substrate, a thickness of 0.2 to 1.2 mm is preferable from the viewpoint of strength as a color filter material.

  In a general color filter, an electrode layer is formed on a substrate before forming a black matrix on the substrate. The electrode layer is made of, for example, a transparent electrode material such as ITO (mixed oxide of indium oxide and tin oxide) and a conductive polymer. The electrode layer can be formed on the substrate by a sputtering method, a spray method, a spin coating method, or the like.

  As an example of a method of forming a black matrix on a substrate, for example, a black layer that is a metal chromium film, a laminated black layer that is formed by laminating metal chromium and chromium oxide, or a black layer that is made of black pigment and resin such as carbon black is formed. Then, there is a method in which a black matrix is formed by applying a photoresist on the black layer and removing a portion of the resist to be a pixel portion by a photolithography method and then etching. As another example of the method of forming a black matrix on a substrate, for example, there is a method of forming a black film by applying a photoresist containing a black pigment and patterning it into a desired pattern by a photolithography method. This method is a cost-effective method.

  A photosensitive coating film is formed on the black matrix surface by applying the photosensitive resin composition of the present invention on the surface of the substrate having the black matrix, which can be obtained in this manner, on which the black matrix is provided. As an application method for applying the photosensitive resin composition, for example, a normal application method such as a spray method, a roll coating method, a spin coating method, or a bar coating method can be used without any particular limitation. Next, the photosensitive resin composition applied on the black matrix surface is dried. The photosensitive resin composition may be dried as necessary, for example, at 30 to 100 ° C. for 10 to 600 seconds. Such pre-baking conditions can be widely changed according to the resin component and the type of solvent contained in the photosensitive resin composition, and the resin solid content.

  Subsequently, the photosensitive coating film is irradiated with light having a wavelength of 180 to 500 nm from the surface side where the black matrix is not provided (pattern exposure step). In this irradiation, the black matrix functions as a light shielding mask (photomask). The light source and irradiation conditions that can be used in this step are the same as described above. And by this irradiation, the photosensitive coating film part on the area | region in which the black mask is not formed is exposed by the light which permeate | transmitted the board | substrate, and it becomes alkali-soluble. On the other hand, the photosensitive coating film portion on the black matrix is not exposed and maintains poor solubility in alkali. In this method, the black matrix thus functions as a photomask. The pattern-exposed coating film is then developed using an alkaline developer, whereby a liquid repellent layer is formed on the black matrix. The alkali developer and development conditions that can be used are the same as described above.

  In this method, the black matrix functions as a photomask in this way, so that a liquid repellent layer can be formed on the black matrix very easily. The liquid repellent layer formed on the black matrix can be easily removed after forming the colored pattern. The removal of the liquid repellent layer can be easily removed by a gentle and widely used process in which the entire surface of the liquid repellent layer is exposed and then washed with an alkaline developer.

  FIG. 1 shows a schematic diagram of the process until the liquid repellent layer is formed on the black matrix. (A) in FIG. 1 shows an outline of a substrate having a black matrix in which a black matrix (3) is provided on the substrate (1). (B) shows an outline of a state in which a photosensitive coating film (4) is formed on a substrate having a black matrix. (C) shows the outline of the pattern exposure which irradiates with respect to a photosensitive coating film from the surface side in which the black matrix is not provided. Next, by developing with an alkaline developer, a liquid repellent layer (5) formed on the black matrix (3) as shown in (D) is obtained.

  A colored pattern is formed by an ink jet method on the black matrix substrate in which the liquid repellent layer is thus formed on the black matrix. As an inkjet method, the inkjet head may be scanned and sprayed three times with R, G, and B, or a colored layer of RGB three colors may be sprayed simultaneously.

  The color pattern forming ink used for forming the color pattern contains a colorant such as a dye and a pigment, a binder resin for ink, a dispersant, a solvent, and the like.

  Specific examples of the pigment used in the coloring pattern forming ink include Pigment Red 177, 209, 254, 255, Pigment Blue 15, 60, Pigment Green 7, 36, Pigment Yellow 83, 138, 139, 150, Pigment. Examples include Orange 36 and Pigment Violet 23, but are not limited thereto. These pigments may be used alone or in combination of two or more.

  As the solvent for the colored pattern forming ink, those having a surface tension in a range suitable for the ink jet method, for example, 40 mN / m or less and a boiling point of 130 ° C. or more can be preferably used. When the surface tension exceeds 40 mN / m, there is a tendency to adversely affect the stability of the dot shape at the time of ink jet ejection, and when the boiling point is less than 130 ° C., the drying property near the nozzle becomes too high, There is a tendency to cause defects such as nozzle clogging. Suitable solvents include, for example, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl ether, 2- (2- And ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, 2-phenoxyethanol, and diethylene glycol dimethyl ether. . These solvents may be used alone or in combination of two or more. In addition to solubility, the solvent is required to have stability over time, drying property, and the like, and is appropriately selected according to the characteristics of the colorant and binder resin used.

  Examples of the binder resin that can be used in the colored pattern forming ink include casein, gelatin, polyvinyl alcohol, carboxymethyl acetal, polyimide resin, acrylic resin, epoxy resin, and melamine resin. These binder resins can be appropriately selected depending on the colorant used and the intended use. For example, acrylic resin is preferable when heat resistance and light resistance are required.

  In order to improve the dispersion of the pigment in the binder resin, a dispersant can be added to the colored pattern forming ink. Examples of the dispersant include a nonionic surfactant such as polyoxyethylene alkyl ether, and examples of the ionic surfactant include sodium alkylbenzene sulfonate, poly fatty acid salt, fatty acid salt alkyl phosphate, and tetra In addition to alkylammonium salts, organic pigment derivatives, polyesters, and the like can be given. A dispersing agent may be used independently and may mix and use 2 or more types.

  Moreover, the colored layer of each color can be formed, for example with the thickness of 1-2 micrometers.

  FIG. 2 shows a schematic diagram of an embodiment in which a colored pattern is formed by an inkjet method. The ink nozzle (7) of the ink jet recording apparatus is filled with a colored pattern forming ink (8) (for example, a red colored ink (8R), a green colored ink (8G), and a blue colored ink (8B)). Then, the colored ink (8R) is applied from the inkjet nozzle (7) (for example, the red inkjet nozzle (7R), the green inkjet nozzle (7G), and the blue inkjet nozzle (7B)) to a predetermined partition portion of the black matrix substrate. , (8G) and (8B) are sprayed to adhere to a predetermined arrangement. Since the sprayed colored inks (8R), (8G), and (8B) are separated from each other by the black matrix provided with the liquid repellent layer, they do not spread out to the adjacent partition portions, and the predetermined partitions It will stay in the club. As a result, it is possible to suppress the color mixture in which the colored inks (8R), (8G), and (8B) of each color are mixed, and further the occurrence of black defects derived from the color mixture. Furthermore, it is also possible to suppress the occurrence of uneven application of color patterns (white spots) and uneven color.

  As described above, by using the photosensitive resin composition of the present invention, a highly detailed color filter having good color separation and no color unevenness can be produced using an inkjet method. That is, by using the photosensitive resin composition of the present invention, a color filter that has good color separation and can be used for a high-definition display can be manufactured at low cost and with high productivity.

  After the colored pattern is formed in this way, it is desirable to remove the liquid repellent layer formed on the black matrix. This is because the liquid repellent layer formed on the black matrix can cause an adhesion failure when a flat panel display is produced using the obtained color filter. The liquid repellent layer is removed by exposing the entire surface of the liquid repellent layer with light having a wavelength of 180 to 500 nm and then washing with an alkali developer. The exposure conditions, usable alkali developer and development conditions are the same as described above. FIG. 3 is a schematic view showing a cross-sectional state of the color filter in a state where the liquid repellent layer is removed.

  The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on mass unless otherwise specified.

Production Example 1 Preparation of Perfluoroalkyl Group-Containing Resin (A-1) A 0.5 L glass reaction vessel containing 90 parts by mass of propylene glycol monomethyl acetate and equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel And a mixture of 17 parts by weight of methacrylic acid, 100 parts by weight of tertiary butyl methacrylate and 106 parts by weight of 2- (perfluorohexyl) ethyl methacrylate, and tertiary butyl peroxy-2-ethylhexanoate. A mixture of 6 parts by weight of ate and 20 parts by weight of propylene glycol monomethyl ether acetate was simultaneously added dropwise at a constant rate over 3 hours, and then reacted at 115 ° C. for 30 minutes. Thereafter, a mixture solution of 1 part by mass of tertiary butyl peroxy-2-ethylhexanoate and 10 parts by mass of propylene glycol monomethyl ether acetate was added dropwise at 115 ° C. over a period of 30 minutes, and then reacted at that temperature for 1 hour. To obtain a perfluoroalkyl group-containing resin (A-1). The obtained perfluoroalkyl group-containing resin (A-1) had an SP value (SP _A ) of 9.6. In addition, SP value in a present Example is a value measured according to the method described in this specification. The perfluoroalkyl group-containing resin (A-1) had an acid value of 50.

Production Example 2 Preparation of Perfluoroalkyl Group-Containing Resin (A-2) A 0.5 L glass reaction vessel containing 90 parts by mass of propylene glycol monomethyl acetate and equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel And a mixture of 30 parts by mass of methacrylic acid, 100 parts by mass of tertiary butyl methacrylate and 90 parts by mass of 2- (perfluorohexyl) ethyl methacrylate, and tertiary butyl peroxy-2-ethylhexano A mixture of 6 parts by weight of ate and 20 parts by weight of propylene glycol monomethyl ether acetate was simultaneously added dropwise at a constant rate over 3 hours, and then reacted at 115 ° C. for 30 minutes. Thereafter, a mixture solution of 1 part by mass of tertiary butyl peroxy-2-ethylhexanoate and 10 parts by mass of propylene glycol monomethyl ether acetate was added dropwise at 115 ° C. over a period of 30 minutes, and then reacted at that temperature for 1 hour. To obtain a perfluoroalkyl group-containing resin (A-2). The obtained perfluoroalkyl group-containing resin (A-2) had an SP value (SP _A ) of 10.3. The acid value of this perfluoroalkyl group-containing resin (A-2) was 100.

Production Example 3 Preparation of acrylic resin (C-1) having no perfluoroalkyl group After charging 149 parts of methyl isobutyl ketone into a reaction vessel and raising the temperature to 85C, 80 parts of t-butyl methacrylate, A monomer solution in which 10 parts of acid, 10 parts of diethylene glycol monoethyl ether acrylate and 1 part of t-butylperoxy-2-ethylhexanoate were mixed and dissolved was dropped into the reaction vessel over 2 hours, and further reacted for 4 hours. An acrylic resin (C) was obtained. The obtained acrylic resin (C) had an SP value (SP _C ) of 10.6. The acid value of the acrylic resin (C) was 68.

Production example 4 Preparation of acrylic resin (C-2) having no perfluoroalkyl group After charging 149 parts of methyl isobutyl ketone into a reaction vessel and raising the temperature to 85C, 25 parts of t-butyl methacrylate, A monomer solution in which 10 parts of acid, 65 parts of methyl methacrylate and 1 part of t-butylperoxy-2-ethylhexanoate are mixed and dissolved is added dropwise to the reaction vessel over 2 hours, and further reacted for 4 hours. (C) was obtained. The obtained acrylic resin (C) had an SP value (SP _C ) of 11.3. The acid value of the acrylic resin (C) was 61.

Comparative Production Example 1 Preparation of Resin (A ′) Having Perfluoroalkyl Group but No Carboxyl Group Protected with Tertiary Butyl Group Stirring Feather, Nitrogen Introduced with 90 Parts by Mass of Propylene Glycol Monomethyl Acetate A 0.5 L glass reaction vessel equipped with a tube, a condenser tube and a dropping funnel was heated to 115 ° C., where it was 17 parts by weight of methacrylic acid, 110 parts by weight of 2- (perfluorohexyl) ethyl methacrylate and cyclohexyl methacrylate 100. A mixture of parts by mass and a mixture of 6 parts by mass of tertiary butyl peroxy-2-ethylhexanoate and 20 parts by mass of propylene glycol monomethyl ether acetate are simultaneously added dropwise at a constant rate over 3 hours, and then at 115 ° C. for 30 parts. Reacted for 1 minute. Thereafter, a mixture solution of 1 part by mass of tertiary butyl peroxy-2-ethylhexanoate and 10 parts by mass of propylene glycol monomethyl ether acetate was added dropwise at 115 ° C. over a period of 30 minutes, and then reacted at that temperature for 1 hour. To obtain a perfluoroalkyl group-containing resin (A-3). The obtained perfluoroalkyl group-containing resin (A-3) had an SP value (SP _A ) of 9.3. The acid value of this perfluoroalkyl group-containing resin (A-3) was 50.

Examples 1-10 and Comparative Examples 1-3
Perfluoroalkyl group-containing resin (A), photoactivator (B) and acrylic resin (C) were blended in the proportions (parts by mass) shown in Tables 1 to 3 to obtain positive photosensitive resin compositions. .

The obtained positive photosensitive resin composition was applied onto a glass substrate using a spinner so that the dry coating thickness was 2.5 μm, and was heated and dried at 170 ° C. for 18 minutes to form a resist layer. . Next, 10 mJ / cm ² (near 365 nm) is exposed using an ultrahigh pressure mercury lamp (LE-4050A, manufactured by Hitachi Engineering Co., Ltd.) through a mask having a 10 μm line and space pattern, Heated at 130 ° C. for 10 minutes. This was developed by immersing and stirring at 35 ° C. for 1 minute and 40 seconds using a 5 mass% aqueous solution of dimethylethanolamine. By development, the exposed portion was eluted and a positive pattern was formed.

  About the obtained positive pattern, alkali developability, coating film appearance, and water / oil repellency were measured and evaluated by the following methods. The evaluation results are shown in Tables 1-3.

Alkali developability Evaluation was performed according to the following.
(Double-circle): It developed according to the pattern of the mask completely.
○: Development was possible to the extent that there was no practical problem, almost following the mask pattern.
Δ: There was a part that was not developed.
X: Many portions were not developed.

The appearance of the coating film was evaluated according to the following.
○: Appearance of the coating film is good.
○ △: White turbidity is confirmed in the coating film.
X: Remarkable cloudiness, bubble marks or radial streaks are confirmed on the coating film, or the film thickness is not uniform.

The contact angle of water and xylene contact angle on the surface of the coating film formed on the water- and oil-repellent glass substrate was measured using a contact angle meter Face analysis integrated system FAMAS manufactured by Kyowa Interface Chemical Co., Ltd. Pure water and xylene were used as measurement liquids. The measurement environment was a temperature of 20 ° C. and a relative humidity of 60%. The larger the contact angle value, the better the water / oil repellency of the coating film.

  As shown in Tables 1 to 3, the photosensitive coating obtained from the photosensitive resin composition of the present invention has excellent water repellency and oil repellency in combination with excellent alkali developability and coating appearance. It was confirmed that Since the photosensitive coating film obtained from the photosensitive resin composition of the present invention is excellent in alkali developability as described above, a removable liquid repellent layer that can be easily removed by performing overall exposure later is easily used. Can be formed. On the other hand, the photosensitive coating films obtained from the photosensitive resin compositions of Comparative Examples 1 and 2 that do not contain the perfluoroalkyl group-containing resin (A) have both water contact angles and xylene contact angles compared to those of the Examples. It was low. Moreover, it was confirmed that Comparative Example 3 using the resin (A ′) having a perfluoroalkyl group but not having a carboxyl group protected by a tertiary butyl group is inferior in alkali developability.

Color Filter Colored Pattern Formation by Inkjet Method Color pattern forming ink (R) is formed on the space portion of a positive pattern having 10 μm partition walls and space portions formed using the photosensitive resin compositions of Example 1 and Comparative Example 1. ), (G) and (B) (manufactured by Nippon Paint Co., Ltd., Exceled ED-R-1300, G-1300, B-1300) were sprayed to form a color filter coloring pattern. In the positive type pattern formed using the photosensitive resin composition of Example 1, no adhesion of ink onto the partition walls was confirmed, and no ink color mixing occurred. On the other hand, in the positive pattern formed using the photosensitive resin composition of Comparative Example 1, the occurrence of ink color mixture was confirmed.

  By using the photosensitive resin composition of the present invention, it is possible to easily form a liquid repellent layer that can be easily removed later before forming a colored portion pattern or the like by an inkjet method. By forming such a liquid repellent layer in the ink jet method, the accuracy of ink jet recording can be improved. In addition, by using the photosensitive resin composition of the present invention, a color filter having good color separation and capable of being used for a high-definition display can be produced at low cost and with high productivity by an inkjet method. .

It is the schematic of a process until forming a liquid repellent layer on a black matrix. It is the schematic of the aspect which forms a coloring pattern by the inkjet method. It is the schematic which shows the cross-sectional state of the color filter of the state which removed the liquid repellent layer.

Explanation of symbols

1 ... substrate,
3 ... Black matrix,
4 ... photosensitive coating film,
5 ... Liquid repellent layer,
7 ... Ink nozzle,
8: Colored ink,
10 Color filter.

Claims (8)

Polymerizable unsaturated monomer having a perfluoroalkyl group-containing polymerizable unsaturated monomer and a polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or a phenol group protected with a tertiary butyloxycarbonyl group A perfluoroalkyl group-containing resin (A) obtained by copolymerizing at least a monomer, and a photoactive agent (B) that generates an acid upon exposure to light
A photosensitive resin composition comprising: The perfluoroalkyl group-containing resin (A) is:
5 to 74% by mass of a perfluoroalkyl group-containing polymerizable unsaturated monomer,
20 to 89% by mass of a polymerizable unsaturated monomer having a carboxyl group protected with a tertiary butyl group and / or a phenolic group protected with a tertiary butyloxycarbonyl group, and other polymerizable compounds 6-75% by weight of unsaturated monomer,
(Provided that the total of the above monomers is 100% by mass)
80 to 99.9% by mass of the perfluoroalkyl group-containing resin (A) with respect to the total solid mass of the photosensitive resin composition, and an acid is generated by exposure. Containing 0.1 to 20% by mass of the photoactive agent (B),
The photosensitive resin composition of Claim 1. And an acrylic resin (C) having no perfluoroalkyl group and having a carboxyl group protected with a tertiary butyl group and / or a phenol group protected with a tertiary butyloxycarbonyl group, and the difference between the SP value of the acrylic resin _(C) (SP C) and the perfluoroalkyl group containing SP value of the resin _(a) (SP a) is 0.3 or more,
The photosensitive resin composition of Claim 1. For the total solid mass of the photosensitive resin composition,
0.1-49.9 mass% of perfluoroalkyl group-containing resin (A),
0.1 to 20% by mass of the photoactive agent (B) that generates an acid upon exposure, and 50 to 99.8% by mass of the acrylic resin (C),
(Provided that the total of components (A), (B) and (C) is 100% by mass)
The photosensitive resin composition of Claim 3 containing.   The photosensitive resin composition in any one of Claims 1-4 which is an alkali-soluble positive photosensitive resin composition. A photosensitive coating film forming step, wherein the photosensitive resin composition according to claim 1 is applied and then dried to obtain a photosensitive coating film,
A pattern exposure step of irradiating the photosensitive coating film with light having a wavelength of 180 to 500 nm through a photomask;
Development process for developing a pattern-exposed coating film using an alkaline developer,
Forming a removable liquid repellent layer comprising The photosensitive coating film which apply | coats the photosensitive resin composition in any one of Claims 1-5 on the surface provided with the black matrix of the board | substrate which has a black matrix, and then dries to obtain the photosensitive coating film Forming process,
A pattern exposure step of irradiating the photosensitive coating film with light having a wavelength of 180 to 500 nm from the surface side where the black matrix is not provided,
The pattern-exposed coating is developed using an alkaline developer to obtain a removable liquid repellent layer formed on the black matrix, and the resulting black matrix substrate is colored by an inkjet method. Forming a process,
A method for producing a color filter, comprising:   A color filter obtained by the method for producing a color filter according to claim 7.

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