JP2011209443A - Alkali-developable photosensitive resin composition, barrier rib for display element formed using the same, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-developable photosensitive resin composition which is excellent in compatibility of an ink repellent, ensures good surface appearance and pattern shape after film production, exhibits excellent surface ink repellency, and can retain the surface ink repellency even after usual cleaning and after a lapse of time.SOLUTION: The alkali-developable photosensitive resin composition contains: a fluorine-containing resin (A) as an ink repellent; and an alkali-developable photosensitive component reacting with ultraviolet radiation whose wavelength is 300-450 nm, wherein the fluorine-containing resin (A) is a predetermined random or block copolymer and has an average molecular weight Mw in the range of 2,000-20,000, and a proportion of the fluorine-containing resin (A) to a total of 100 pts.mass of the composition except solvent is 0.05-1 pt.mass.

Description

  The present invention relates to an alkali-developable photosensitive resin composition, partition walls formed using the same, and a display element, and more specifically, an alkali-developable photosensitive resin composition suitable for forming partition walls of a display element by an ink jet printing method, and the same. The present invention relates to a partition wall formed using the display element and the display element.

  A color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet, and then sequentially applies three or more different hues such as red, green and blue in a striped or mosaic shape. It is formed with a color pattern. The pattern size varies depending on the use of the color filter and each color, but is about 5 to 700 μm. Further, the positional accuracy of superposition is several μm to several tens of μm, and it is manufactured by a fine processing technique with high dimensional accuracy.

  Typical methods for producing a color filter include a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method. Among these, in particular, a pigment dispersion method for forming a color filter image by applying a photopolymerizable composition containing a color material on a transparent substrate and repeating image exposure, development, and curing as necessary is a color filter pixel. Is widely used because of its high accuracy of position, film thickness, etc., excellent durability such as light resistance and heat resistance, and few defects such as pinholes.

  On the other hand, a black matrix is generally arranged in a grid, stripe, or mosaic pattern between red, green, and blue color patterns. This improves contrast by suppressing color mixing between colors or prevents TFT malfunction due to light leakage. It plays a role to prevent. For this reason, the black matrix is required to have high light shielding properties. Conventionally, the black matrix is generally formed of a metal film such as chromium, or is formed by a photolithography method using a photosensitive resin containing a light shielding material.

  However, when a color pattern is formed using the above-described method, an exposure and development process must be performed for each color, which requires at least three photo processes and is expensive. Therefore, an inkjet method that can provide a color filter at low cost has been proposed. This is a method in which red, blue and green inks are sprayed and applied to only the necessary pixels at the same time, and cured to form the pixels. There has been proposed a method of discharging ink to the portion. However, with this method, bleeding of each color region and color mixing between adjacent regions can occur. Therefore, the material that constitutes the partition walls is required to have a property that suppresses the spread of the colorant outside the coloring target region. For example, Patent Document 2 exemplifies that color mixing can be effectively avoided if the static contact angle between the ink and the partition wall surface is 40 to 55 °. On the other hand, when considering the dynamic contact angle, it is considered preferable that the advancing angle between the ink and the partition wall surface is large.

  In addition, when the ink ejected from the ink jet head overlaps with the inside of the pixel and on the partition wall, a self-repairing action is required in which the ink on the surface of the partition wall returns to the pixel due to surface ink repellency. In particular, in the demand for higher definition where pixels are miniaturized, the frequency of droplets ejected from the inkjet overlapping the black matrix increases, and in order to compensate for the ink spreadability at the corners in each color region, they overlap with the partition walls. It is also considered to strike (see Patent Document 7). When the ink that has overlapped the partition wall returns to the inside of the pixel, it is predicted that it is preferable that the falling angle of the ink is small. Similarly, when forming a display element using a coating type organic EL material, a means for coating the coating type organic EL material in the partitioning by an ink jet coating method after forming the partitioning by a photo process has been proposed.

  As a photoresist composition for providing a partition material for such purposes, a method of mixing a fluorine-based or silicone-based compound as a component imparting ink repellency has been proposed. For example, Patent Document 1 discloses a photoresist composition containing a copolymer of a fluoroalkyl group-containing (meth) acrylate monomer and a silicone chain-containing ethylenically unsaturated monomer. However, the addition amount of the copolymer is 0.001 to 0.05% by mass with respect to the solid content of the photoresist composition, and ink repellency is insufficient at such a low content.

  Patent Document 2 exemplifies a composition of a copolymer of hexafluoropropylene, an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, and a fluorine organic compound. However, in order to obtain a polymer of hexafluoropropylene, polymerization at high pressure is indispensable, and its molecular weight is as small as 2000 or less. Moreover, the fluorine organic compound which assists this is also a surfactant system, and a problem arises in its ink repellency persistence.

Patent Document 3 discloses that CH ₂ = C (R ¹ ) COOXR ^f (R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms) as a monomer and a fluorine atom content of 7 to 35% by mass. The resist composition characterized by the fluorine-containing resin is illustrated. In this case, the R ¹ group is limited to H, CH ₃ or CF ₃ . Further, Patent Document 4 discloses an alkali-soluble photosensitive resin having an acidic group and three or more ethylenic double bonds in the molecule, and a carbon number of 20 or less in which at least one hydrogen atom is substituted with a fluorine atom. A negative photosensitive resin composition containing a polymer unit having an alkyl group and an ink repellent agent comprising a polymer obtained by copolymerizing a polymer unit having an ethylenic double bond is described. The fluorine-containing polymer unit in this ink repellent is also equivalent to that of Patent Document 3. In either case, when the ratio of the fluorine-containing compound in the photoresist solid content is increased, it is pointed out that the adhesion to the support substrate is lowered and the surface smoothness is deteriorated.

In Patent Document 5, an ink repellent agent containing silicon and / or fluorine atoms having a low affinity with a resin contained in a black matrix is used, and the black matrix is baked at 150 to 230 ° C. after development to obtain the ink repellent agent. A method for producing a surface ink-repellent black matrix is described in which the contact angle with the colored ink is controlled to 30 to 60 ° by transferring to the surface. Among these, specific examples of the ink repellent agent include those having an organic silicone in the main chain or side chain, and a fluororesin by copolymerization with a fluorine-containing monomer such as vinylidene fluoride. However, silicone-containing oligomers such as surfactants and fluorine-based oligomers have a problem that even if they move to the surface after firing, their ink repellency decreases with subsequent washing and the passage of time. Patent Document 8 discloses an ink repellent containing an Rf group and an acidic group (carboxyl group, phenolic hydroxyl group, sulfonic acid group) having a polyfluoroether structure, and Patent Document 9 describes CH ₂ = C (Rn) COOYRf (Rn is The resist composition containing the ink repellent agent which uses a C2 or more organic group or chlorine) as a monomer is illustrated. Since these two examples have good alkali developability and good patternability, a decrease in ink repellency accompanying development can be seen. Therefore, in order to have sufficient ink repellency, addition of a certain amount or more is indispensable, and therefore contamination by the ink repellant in the pixel opening is inevitable.

  In addition, as a photoresist suitable for forming a light-shielding resin matrix, in Patent Document 6, a reaction product of a specific aromatic epoxy compound and (meth) acrylic acid is further added with a polybasic acid carboxylic acid or an anhydride thereof. The black resist containing the unsaturated group-containing compound obtained as a result of the reaction as a resin main component has a high light-shielding rate, and it is easy to form a fine pattern by a photolithography method. It has been reported that the composition for forming a light-shielding thin film is excellent in adhesion and room temperature storage stability. However, in this patent document 6, the ink repellency is not mentioned, and there is no mention about compatibility.

JP-A-9-54432 JP-A-11-281815 JP 2005-315984 A WO 2004-42474 JP 2006-251433 A JP-A-8-278629 JP 2006-343518 A JP 2009-35745 A JP 2009-37233 A

  Therefore, the object of the present invention is to solve the above-mentioned problems, that is, to make the ink repellent agent compatible in a resist composition (photosensitive resin composition) containing a photosensitive component that reacts with ultraviolet light (300 nm to 450 nm). Display element with excellent surface appearance and pattern shape after film formation, and excellent surface ink repellency, while maintaining surface ink repellency even after normal cleaning and time A photosensitive resin composition suitable for forming a partition wall is provided.

〔式中、Ｒはアルコール性水酸基又はフェノール性水酸基を有した有機基を示し、Ｒｎは水素又はメチル基を示し、Ｙはフッ素原子を含まない２価の有機基を示し、Ｒｆは下記式（１）で表される含フッ素基を示し、Ａｒは芳香族環を示し、Ｘ及びＺは水素原子、芳香族基、アルキル基、アルケニル基、又はフッ素原子を含まないエステル基を示して、互いに同じでも異なってもよく、ｐ、ｑ、ｒ及びｓはそれぞれの共重合単位の総数であって、このうちｐ、ｑ及びｓは０〜３０の数であり、ｐ及びｑの合計は１以上であり、rは１〜４０の数である。また、一般式（２）の共重合体中に含まれる式（１）の含フッ素基の割合は、質量換算で１５〜５０質量％である。〕

That is, the present invention is as follows.
(1) An alkali-developable photosensitive resin composition comprising a fluorine-containing resin (A) as an ink repellent agent and an alkali-developable photosensitive component that reacts with ultraviolet light having a wavelength of 300 to 450 nm. The fluororesin (A) is a random or block copolymer represented by the following general formula (2), the average molecular weight Mw is in the range of 2000 to 20000, and the content is 100 parts by mass relative to the total components excluding the solvent. The ratio of a fluororesin (A) is 0.05-1 mass part, The alkali developable photosensitive resin composition characterized by the above-mentioned.

[Wherein R represents an organic group having an alcoholic hydroxyl group or a phenolic hydroxyl group, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, and Rf represents the following formula ( 1) represents a fluorine-containing group, Ar represents an aromatic ring, X and Z represent a hydrogen atom, an aromatic group, an alkyl group, an alkenyl group, or an ester group containing no fluorine atom, P, q, r, and s are the total number of copolymerized units, and p, q, and s are numbers from 0 to 30, and the sum of p and q is 1 or more. And r is a number from 1 to 40. Moreover, the ratio of the fluorine-containing group of Formula (1) contained in the copolymer of General formula (2) is 15-50 mass% in mass conversion. ]

(2) the fluororesin (A), (B) an alkali developable oligomer having an acidic group and two or more ethylenic double bonds in one molecule, and (C) three or more in one molecule. The alkali-developable photosensitive resin composition according to the above item (1), comprising a photopolymerizable monomer having an ethylenic double bond, and (D) a photopolymerization initiator.

〔但し、式中、Ｒ₁及びＲ₂は水素原子、炭素数１〜５のアルキル基又はハロゲン原子であり、互いに同じであっても異なってもよく、Ｘは−CO−、−SO₂−、−C(CF₃)₂−、−Si(CH₃)₂−、−CH₂−、−C(CH₃)₂−、−O−、下記式で表される9,9−フルオレニル基、又は不存在を示し、ｎは１〜１０の整数である〕

(3) The component (B) is a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (4) and (meth) acrylic acid, The alkali-developable photosensitive resin composition according to the above item (2), which is an alkali-developable unsaturated group-containing oligomer obtained by reacting with a polybasic acid carboxylic acid or an anhydride thereof.

[Wherein, R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and may be the same or different, and X is —CO—, —SO ₂ —. _{, -C (CF 3) 2 -} , - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, 9,9- fluorenyl group represented by the following formula, Or indicates absence, and n is an integer of 1 to 10.

(4) The alkali-developable photosensitive resin composition according to any one of the above items (1) to (3), selected from the group consisting of (E) a black organic pigment, a mixed color organic pigment, and a light shielding material. While adding the light-shielding dispersion liquid which disperse | distributes at least 1 sort (s), the said (E) component is mix | blended in the ratio of 25-60 mass parts with respect to 100 mass parts of total solids, It is characterized by the above-mentioned. A light-shielding alkali-developable photosensitive resin composition.

(5) The photosensitive resin composition for partition formation for display elements as described in said (4) term.

(6) The photosensitive resin composition for color filter partition formation as described in said (5) term.

(7) The photosensitive resin composition described in the above item (5) or (6) is applied on a substrate and dried, then (a) exposure with an ultraviolet exposure device, (b) development with an alkaline aqueous solution, and ( c) A partition wall for a display element, which is obtained by using each step of thermal firing as essential, and has a film thickness of 1.5 to 3 μm.

(8) A display element, wherein pixels are formed in the partition wall according to (7) by an ink jet printing method.

  According to the present invention, in a resist composition containing a photosensitive component that reacts to ultraviolet light (300 nm to 450 nm), the ink repellent agent has excellent compatibility, and the surface appearance and pattern shape after film formation are good. A photosensitive resin composition excellent in surface ink repellency and suitable for forming partition walls for display elements can be provided. For this reason, for example, in a method for manufacturing a display element by an inkjet process, it is possible to achieve a reduction in cost that does not require a facility for surface ink repellency treatment using atmospheric pressure plasma, and to suitably provide a material that contributes to an improvement in yield. . In particular, it can be suitably used in liquid crystal display devices and organic EL color filters prepared by ink jet printing, and can also be applied to fluid-driven electronic paper applications.

Hereinafter, the present invention will be described in detail.
The fluorine-containing resin (A) in the photosensitive resin composition of the present invention is an ink repellent and is a fluorine-containing resin (A) having a substituent having the structure of the following formula (1).

As a method for introducing a substituent represented by the formula (1), a known means can be used, and specifically, a means represented by the following formula (5) can be used.

Usually, the fluorine-containing product represented by the above formula (5) may contain the following isomer skeleton (1b), but it has the same effect as the substituent having the structure represented by the formula (1). As shown, the effect can be treated as the content in the present invention as the fluorine-containing group.

  P-OH in the above formula (5) is a compound having a primary hydroxyl group or a phenol group. Therefore, in order to obtain the desired fluororesin (A), method (i): a polymer having a primary hydroxyl group or phenol group in the side chain is used as a precursor, and this is achieved by means shown in formula (5). And a method (ii): a method of copolymerizing a monomer having a fluorine-containing substituent represented by the formula (1) with another monomer. Among these, the method (ii) is preferable for introducing a fluorine group quantitatively into the molecular chain as compared with the method (i).

  Specific examples of the method (i) include a method in which a copolymer with a (meth) acrylic acid ester derivative such as 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, and 6-hydroxybutyl methacrylate is used as a precursor, p-hydroxy Examples thereof include a copolymer with a vinyl compound having a phenol group such as styrene.

Specific examples of the method (ii) include a method in which a fluorine group is previously introduced into p-hydroxystyrene by the formula (5) and then copolymerized with another monomer, or represented by the following general formula (3). And a method in which a monomer unit formed from a (meth) acrylate monomer is copolymerized with another monomer.
CH ₂ = C (Rn) -COO-Y-O-Rf (3)
[Wherein, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, and Rf represents a fluorine-containing group of the formula (1). ]

  The monomer represented by the general formula (3) is one in which Rf is linked to a polymer main chain having an α-position substituent (Rn) by an organic group Y that functions as a spacer. Examples of the organic group Y include an alkylene group, a polyethylene glycol group, and a phenylene group. For example, the group which has a functional group which can connect carboxyl groups, such as (meth) acrylic acid, and the fluorine-containing product obtained by said Formula (5) is mentioned. Furthermore, a fluorine-containing resin (A) component is prepared by copolymerizing such a fluorine-containing monomer and a non-fluorine-containing monomer.

（式中、Rはアルコール性水酸基もしくはフェノール性水酸基を有する有機基を示し、Rnは水素またはメチル基を示し、Yはフッ素原子を含まない２価の有機基を示し、Rfは式（１）に示す含フッ素基を示し、Arは芳香族環を示し、X及びZは水素原子、芳香族基、アルキル基、アルケニル基、又はフッ素原子を含まないエステル基を示して、互いに同じか異なってもよく、p、q、r及びsはそれぞれの共重合単位の総数であり、p、q及びsは０〜３０の数であって、p及びqの合計は１以上であり、rは１〜４０の数である。） By using the method (i) or (ii), for example, a fluororesin (A) composed of a random or block copolymer represented by the following general formula (2) can be obtained.

(In the formula, R represents an organic group having an alcoholic hydroxyl group or a phenolic hydroxyl group, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, and Rf represents the formula (1). In which Ar represents an aromatic ring, X and Z represent a hydrogen atom, an aromatic group, an alkyl group, an alkenyl group, or an ester group that does not contain a fluorine atom, and are the same or different from each other. P, q, r, and s are the total number of copolymerized units, p, q, and s are numbers from 0 to 30, and the sum of p and q is 1 or more, and r is 1 A number of ~ 40.)

  In the fluororesin (A), it is necessary to contain a substituent having the structure of the formula (1) in the range of 15 to 50% by mass. If the amount is less than 15% by mass, sufficient ink repellency cannot be obtained even after the alkali-developable photosensitive resin composition is cured, or if a desired ink repellency is to be obtained, the amount of component (A) added is large. As a result, the alkali developability of the composition is impaired.

  The fluororesin (A) has a hydroxyl group as an essential component. By having a hydroxyl group, the compatibility of the fluororesin (A) with the alkali developer can be slightly improved, and the residue on the development substrate can be reduced. As a method for introducing a hydroxyl group, (meth) acrylic acid ester derivatives such as 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, and 6-hydroxybutyl methacrylate are generally used as monomers. It is not limited to.

  Furthermore, a functional group that can introduce a vinyl group into the molecular chain of the fluororesin (A) as required, for example, a hydroxyl group or a carboxyl group is preferably present. By introducing a vinyl group, it is possible to contribute to maintaining the ink repellency on the surface of the exposed area after development at the time of forming a partition by a photolithography method, which is preferable when a particularly strong developer is used. Specific examples of the introducing means include known means in which an acrylate or methacrylate compound having an isocyanate group, an ethylene oxide group or the like as a bonding group is reacted with a hydroxyl group or a carboxyl group in the fluororesin. For example, when an isocyanate group is used as a linking group, the amount is less than the same equivalent to the hydroxyl group in the fluorine-containing resin (A) obtained in advance. This is because the remaining linking group may impair the storage stability of the composition. When the ethylene oxide group is used as a linking group, it reacts with the carboxyl group in the fluororesin (A) obtained in advance, so that the acid value of the fluororesin (A) is adjusted to 10 to 100 mg. .

  Moreover, a fluorine-containing resin (A) can also be prepared by copolymerizing a normal (meth) acrylic acid ester, a styrene derivative, a maleic acid ester, etc. as a non-fluorine-containing monomer. From the viewpoint of maintaining compatibility with an alkali-developable resin and maintaining ink repellency, it is preferable to copolymerize with a methacrylic acid ester, and the side chain alcohol residue is preferably a bulky group such as a benzyl group, an isobornyl group or an adamantane group . The proportion of the fluorine-containing mass in the fluorine-containing resin (A) is preferably 30% by mass or more. If it is less than 30% by mass, sufficient ink repellency is not exhibited, and the ink repellency may be lost at the time of forming the black matrix and immediately before applying the inkjet ink. Moreover, when it exceeds 80 mass%, the compatibility of the obtained copolymer with the solvent used for resist preparation, or (B) and (C) component will be bad, and will cause a gel thing generation | occurrence | production.

  The weight average molecular weight of this fluororesin (A) component is set so that the polyethylene glycol equivalent weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) method is in the range of 2000-20000. When the molecular weight is 2000 or less, the ink repellency is lowered in the partition forming process, or it is difficult to continue the ink repellency. When the molecular weight (Mw) exceeds 20000, it is not preferable because of dissolution delay in an alkaline developer.

  Further, the ratio of the fluororesin (A) to 100 parts by mass of the total solid content of the alkali developing photosensitive resin composition excluding the solvent is set to 0.05 to 1 part by mass. When the proportion of the fluororesin (A) is less than 0.05 parts by mass, the ink repellency becomes insufficient. On the other hand, when it exceeds 1 part by mass, the pattern formation of the original alkali developing photosensitive resin composition is affected. May cause effects.

  Next, the components (B) to (E) used in the photosensitive resin composition (negative resist composition) containing a photosensitive component that reacts with ultraviolet light (300 nm to 450 nm) will be described.

  Examples of the alkali-developable oligomer having an acidic group and two or more ethylenic double bonds in one molecule as component (B) are epoxy having two glycidyl ether groups derived from bisphenols. Mention may be made of alkali-developable unsaturated group-containing oligomers obtained by further reacting a reaction product of a compound with (meth) acrylic acid with a polybasic carboxylic acid or its anhydride.

〔但し、式中、Ｒ₁及びＲ₂は水素原子、炭素数１〜５のアルキル基又はハロゲン原子のいずれかであり互いに同じか異なってもよく、Ｘは−CO−、−SO₂−、−C(CF₃)₂−、−Si(CH₃)₂−、−CH₂−、−C(CH₃)₂−、−O−、下記式で表される9,9−フルオレニル基、又は不存在を示し、ｎは１〜１０の整数である〕

Here, as an epoxy compound which has two glycidyl ether groups induced | guided | derived from bisphenol, the epoxy compound represented by following General formula (4) is mentioned preferably.

[In the formula, R ₁ and R ₂ are either a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and may be the same or different from each other, and X is —CO—, —SO ₂ —, _{-C (CF 3) 2 -,} - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, 9,9- fluorenyl group represented by the following formula, or It indicates absence, and n is an integer of 1 to 10.]

  An epoxy compound having two glycidyl ether groups derived from these bisphenols is reacted with (meth) acrylic acid (which means “acrylic acid and / or methacrylic acid”), and the resulting hydroxy An epoxy (meth) acrylate acid adduct obtained by reacting a compound having a group with a polybasic acid carboxylic acid or an anhydride thereof is used as an alkali-developable unsaturated group-containing oligomer as component (B) of the present invention. can do.

  The alkali-developable oligomer having an ethylenic double bond as the component (B) has both an ethylenically unsaturated double bond and an acidic group such as a carboxyl group, a hydroxyl group, a sulfonic acid group, and a phosphoric acid group. When used for forming color filter partition walls, the photosensitive resin composition is provided with excellent photocurability, good developability, and patterning characteristics, and improves the physical properties of the light-shielding partition walls.

  The alkali-developable oligomer having an ethylenic double bond as component (B) is preferably derived from an epoxy compound represented by the above formula (4). This epoxy compound is derived from bisphenols. Therefore, by explaining bisphenols, an alkali-developable unsaturated group-containing oligomer can be understood, and preferred specific examples will be explained using bisphenols.

  Examples of bisphenols that give preferred alkali-developable unsaturated group-containing oligomers include the following. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, Bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2- Bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, etc. And 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl), wherein X in the formula (4) is the 9,9-fluorenyl group. ) Fluor 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5 -Dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene and the like, and further compounds such as 4,4'-biphenol and 3,3'-biphenol.

  The alkali-developable oligomer having an ethylenic double bond as the component (B) can be obtained from an epoxy compound derived from bisphenols as described above, but in addition to such an epoxy compound, a phenol novolac-type epoxy compound or Also, a cresol novolac type epoxy compound can be used as long as it contains a compound having two glycidyl ether groups significantly. In addition, when bisphenols are converted to glycidyl ether, oligomer units are mixed. If n in the general formula (4) is 0 to 10, preferably 0 to 2, There is no problem in performance.

  In addition, as the polybasic acid carboxylic acid or its acid anhydride that can react with the hydroxy group in the epoxy (meth) acrylate molecule obtained by reacting such an epoxy compound with (meth) acrylic acid, for example, Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid and the acid anhydride thereof, Furthermore, aromatic polyvalent carboxylic acids such as benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid dianhydrides thereof can be used. And about the usage-amount of an acid anhydride and an acid dianhydride, the ratio suitable for forming a fine pattern by exposure and alkali image development operation can be selected.

  About the alkali developable oligomer which has an ethylenic double bond of (B) component, even if it uses only 1 type, it can also use 2 or more types of mixtures. Moreover, reaction with an epoxy compound and (meth) acrylic acid, reaction with the epoxy (meth) acrylate obtained by this reaction, and a polybasic acid or its acid anhydride employ | adopt a well-known method by the said patent document 6 grade | etc.,. However, it is not particularly limited.

  As another method for obtaining the component (B), 1) an ethylenically unsaturated monomer having one or more carboxyl groups, 2) a hydroxy group or an acid anhydride group capable of introducing an unsaturated group after polymerization. , A monomer mixture containing an ethylenically unsaturated monomer having a glycidyl group or the like in the side chain, and 3) another ethylenically unsaturated monomer in a solvent in which a peroxide and a chain transfer agent coexist. After obtaining a copolymer obtained by radical copolymerization, an ethylenic double bond is formed by using a binder resin in which a monounsaturated compound is added to a functional group that can be added to the side chain of 2) above. It can also be set as the alkali developable oligomer which has.

  Examples of the ethylenically unsaturated monomer having at least one carboxyl group that can be used as the monomer mixture include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid. Unsaturated monocarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and the like; Examples include unsaturated polycarboxylic acids (anhydrides). Of these, acrylic acid and methacrylic acid are preferable. These carboxyl group-containing ethylenically unsaturated monomers may be used alone or in combination of two or more.

  3) Other ethylenically unsaturated monomers which are another component of the monomer mixture include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, methoxystyrene; methyl acrylate, methyl Methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate , Unsaturated carboxylic acids such as octadecyl methacrylate, docosyl methacrylate, eicosyl methacrylate Stealth; Unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Vinyl acetate and vinyl propionate Carboxylic acid vinyl esters such as vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, cyanide Vinyl cyanide compounds such as vinylidene chloride; acrylamide, methacrylamide, α-chloroacrylamide, N-hydroxyethyl acetate Examples thereof include unsaturated amides or unsaturated imides such as rilamide, N-hydroxyethylmethacrylamide and maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene. Of these, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate are preferable. These other unsaturated monomers may be used alone or in combination of two or more.

  The acid value of the component (B) is expressed as the number of mg of KOH necessary for neutralizing the carboxyl group in 1 g of the resin, and the development processing time and pattern shape at the time of image pattern formation, the adhesion of the cured film From the viewpoint of the above, it is preferable to be 50 to 150 (KOHmg / g). If it is less than 50, pattern formation with an alkali developer becomes impossible, and when a crosslinking agent is used, crosslinking with an epoxy resin as a crosslinking agent becomes insufficient, resulting in a decrease in heat resistance and adhesion in an organic solvent. Defects occur. If the acid value exceeds 150, surface roughness during alkali development, poor development adhesion of the fine line pattern, and moisture resistance of the cured film become problems.

  Examples of the photopolymerizable monomer having three or more ethylenically unsaturated bonds in at least one molecule as component (C) include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol. (Meth) acrylates such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, Only one of them can be used alone, or two or more can be used in combination.

  The alkali-developable photosensitive resin composition of the present invention contains a photopolymerizable compound such as component (B) or component (C). In order to photocure this, photopolymerization is initiated as component (D). An agent may be included. Component (D) generates radical species upon irradiation with ultraviolet light, particularly 300 to 450 nm, and is added to a photopolymerizable compound to initiate radical polymerization and cure the resin composition.

  As the photopolymerization initiator of component (D), benzophenone, Michler's ketone, N, N'-tetramethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone , Aromatic ketones such as 2-ethylanthraquinone and phenanthrene, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5 -Phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3 Halomethylthiazole compounds such as 2,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2,4,6-tris (trichloromethyl) -1 , 3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3,5-triazine 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroR methyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-triazine Methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. Halomethyl-S-triazine compounds, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 2-benzyl- Examples include 2-dimethylamino-1- [4-morpholinophenyl] -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone.

  These photoinitiators can be used individually or in mixture of 2 or more types. In addition, although it does not act as a photopolymerization initiator or sensitizer by itself, it is also possible to add a compound that can increase the ability of the photopolymerization initiator or sensitizer by using in combination with the above compound. it can. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

  (D) As for the usage-amount of the photoinitiator of a component, 5-40 mass parts is suitable on the basis of a total of 100 mass parts of each component of (A), (B) and (C). When the blending ratio of the component (D) is less than 5 parts by mass, the rate of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, when it exceeds 40 parts by mass, the sensitivity is too strong and the pattern line The width becomes thicker than the pattern mask, and there is a possibility that a line width that is faithful to the mask cannot be reproduced, or that the pattern edge does not become jagged and sharp.

  By adding a pigment or the like to the alkali-developable photosensitive resin composition containing the components (A) to (D) according to the purpose, a photosensitive resin composition for forming a partition for a display element is obtained. be able to. Particularly in the case of color filter partition walls, a light-shielding dispersion (component E) can be preferably used for the purpose of shielding the TFT element.

  The black organic pigment, mixed color organic pigment, and light-shielding material contained in the light-shielding dispersion liquid as component (E) are preferably excellent in heat resistance, light resistance, and solvent resistance. Here, examples of the black organic pigment include perylene black and cyanine black. Examples of mixed color organic pigments include those obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like into a pseudo black color. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Two or more types can be appropriately selected and used. The surface smoothness, dispersion stability, and compatibility with the resin are preferable. One or more selected from these pigments or light-shielding materials can be dispersed in an organic solvent with a dispersant and a dispersion aid as required to obtain a light-shielding dispersed facial liquid.

  (E) About the mixture ratio of a component, 25-60 mass parts is mix | blended with respect to 100 mass parts of total solid of the photosensitive resin composition about the ratio of the pigment or light-shielding material contained in (E) component. Is preferred. When the amount is less than 25 parts by mass, the light shielding property is not sufficient. When the amount exceeds 60 parts by mass, the content of the photosensitive resin as the original binder is decreased, so that an undesired problem that the development characteristics are impaired and the film forming ability is impaired.

  In the photosensitive resin composition for forming a display element partition according to the present invention, a solvent may be used separately in addition to the solvents contained in the components (A) to (E). Examples of other solvents used herein include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N- Ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether Ter, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, Examples include acetic acid esters such as propylene glycol monoethyl ether acetate, and a uniform solution-like composition can be obtained by dissolving and mixing them.

  Moreover, the photosensitive resin composition for forming a display element partition according to the present invention is blended with additives such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a belling agent, and an antifoaming agent as necessary. be able to. Among these, the thermal polymerization inhibitor can include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, etc., and the plasticizer can include dibutyl phthalate, dioctyl phthalate, tricresyl, etc. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and leveling agent include silicone, fluorine, and acrylic compounds.

  In particular, when adding materials having surface activity such as leveling agents and antifoaming agents used for improving surface properties, it is necessary to add them to the extent that they do not impair the surface ink repellency after curing, preferably all solids in the composition It is added at a lower content than the ink repellent at a concentration relative to the minute.

  The partition-forming photosensitive resin composition for display elements of the present invention contains the above components (A) to (E) or these and a solvent as main components. In the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after curing), the components (A) to (E) are 70% by mass or more in total, preferably 80% by mass, more preferably 90%. It is desirable to contain at least mass%. The amount of the solvent varies depending on the target viscosity depending on the coating method, but is preferably in the range of 30 to 90% by mass.

  In order to form the partition for display elements or the color filter partition of the present invention, it is formed by the photolithography method using the above-described alkali development photosensitive resin composition of the present invention. As the manufacturing process, first, the photosensitive resin composition is applied to the substrate surface as a solution, and then the solvent is dried (prebaked), and then a photomask is applied on the coating thus obtained, Examples include a method in which an exposed portion is cured by irradiating ultraviolet rays, a pattern is formed by performing development in which an unexposed portion is eluted with an alkaline aqueous solution, and post-baking is performed as post-drying.

  As a substrate on which the solution of the photosensitive resin composition is applied, a glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) on which a transparent electrode such as ITO or gold is deposited or patterned is used. It is done.

  As a method for applying the solution of the photosensitive resin composition to the substrate, any method such as a method using a roller coater machine, a land coater machine, or a spinner machine as well as a known solution dipping method and spray method can be adopted. be able to. After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate or the like. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent to be used, for example, at a temperature of 60 to 120 ° C. for 1 to 10 minutes.

  The exposure performed after pre-baking is performed by an exposure machine, and only the resist corresponding to the pattern is exposed by exposing through a photomask. The exposure machine and the exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a deep ultraviolet lamp, and the photosensitive resin composition is photocured.

  The alkali development after the exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. Particularly, sodium carbonate, potassium carbonate, carbonate It is preferable to develop at a temperature of 20 to 30 ° C. using a weak alkaline aqueous solution containing 0.05 to 3% by mass of carbonate such as lithium, and a fine image using a commercially available developing machine or ultrasonic cleaner. Can be formed precisely.

  After the development as described above, a heat treatment (post-bake) is performed at a temperature of 160 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-baking. The patterned light-shielding film (partition wall) of the present invention is formed through each step by the above photolithography method.

  In addition, the photosensitive resin composition for forming a partition of the present invention can be used as a color filter by forming a predetermined color pattern by providing pixels by various means after forming a light-shielding color filter partition by, for example, the above method. Can be obtained. In particular, since the color filter partition formed using the photosensitive resin composition of the present invention has excellent adhesion to the substrate and excellent ink repellency, the ink-jet printing method is used in the obtained light-shielding color filter partition. It is suitable for forming a pixel to obtain a color filter.

  Embodiments of the present invention will be specifically described below based on examples and comparative examples. In addition, this invention is not limited only to these Examples.

<Synthesis Examples A-1 to A-6, Comparative Synthesis Examples a-1 and a-2>
A 1 liter reactor equipped with a stirrer was charged with the monomers, polymerization initiator, and chain transfer agent shown in Table 1, and propylene glycol monomethyl acetate (PGMEA) so that the solid content concentration was 40% by mass. And polymerized at 90 ° C. for 14 hours while stirring under a nitrogen atmosphere. After the temperature was lowered, the solution was diluted with PGMEA so that the solid content concentration was 20% by mass to obtain a solution of fluorine-containing resins A-1 to A-6, a-1, and a-2. The weight average molecular weight was determined by GPC using tetrahydrofuran as a developing solvent (in terms of polyethylene glycol). In addition, the unit of the numerical value described in the column of each component shown in Table 1 is “g”. Further, the fluorine-containing group weight (%) is a value obtained by calculating the theoretical weight of fluorine atoms contained in one molecule from the average molecular weight based on the charging ratio. Further, the meanings of the abbreviations in Table 1 are as follows.

CF9BuMA: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ CH ₂ CH ₂ OC ₉ F ₁₇
CF9PEMA: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ OCOC ₆ H ₄ OC ₉ F ₁₇
2-HEMA: 2-hydroxybutyl methacrylate
4-HBMA: 4-hydroxybutyl methacrylate
MMA: Methyl methacrylate
IBMA: Isobornyl methacrylate
4-HBAGE: 4-hydroxybutyl acrylate glycidyl ether
AIBN: Azobisisobutyronitrile
LM: Lauryl mercaptan

<Synthesis Examples A-1s to A-6s, Comparative Synthesis Examples a-1s, a-2s> (Introduction of Double Bond)
With respect to the fluororesin (A) prepared in the above “Synthesis Examples A-1 to A-6, Comparative Synthesis Examples a-1 and a-2”, 2-acryloyloxyethyl with respect to 100 g of a 20 mass% PGMEA solution. Isocyanate (Mw = 141.12) was added so that isocyanate group / hydroxyl group in fluororesin (A) = 0.5 mol / mol, and 1,4-diazabicyclo [2,2,2] octane 03 g was mixed, stirred at 50 ° C. for 12 hours, and cooled to room temperature. Each of the obtained polymer solutions A-1s to A-6s, a-1s, and a-3s confirmed the disappearance of NCO absorption (2730 cm ⁻¹ ) by IR.

<Examples 1-14 and Comparative Examples 1-2>
First, the components (B) to (F) excluding the fluororesin (A) component and YX-4000H (made by Showa Shell; tetramethyldiphenyl epoxy resin) were mixed in the proportions (parts by weight) shown in Tables 2 and 3. Then, propylene glycol monomethyl ether acetate was added to make the solid content concentration 20% by mass. Then, (A) component solution was added by the mass part as described in Table 2 and Table 3. Subsequently, it filtered by 0.2 kg / cm < ² > pressurization using a ² micrometer polypropylene membrane filter, and prepared alkali development photosensitive resin composition. In Table 2 and Table 3, the blending ratio with respect to the total solid content is shown in mass% in () of the component (B). Moreover, about the mixture ratio of (E) component, it showed in the separate column as (pigment / total solid content) mass% with respect to the total solid content. Furthermore, the meanings of the abbreviations in Tables 2 and 3 are as follows.

(B) -1: Propylene glycol monomethyl ether acetate solution of acid anhydride polycondensate of epoxy acrylate having a fluorene skeleton (resin solid content concentration = 56.1% by weight, product name V259ME manufactured by Nippon Steel Chemical Co., Ltd.)
(B) -2: N-ethylmaleimide / methacrylic acid / benzyl methacrylate copolymer propylene glycol monomethyl ether acetate solution having a weight average molecular weight of 30000 and an acid value of 100 (KOHmg / g) (resin solid content concentration = 36.7% by weight) (N-ethylmaleimide: methacrylic acid: benzyl methacrylate = 29:20:51 mol%)
(C) -1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D) -1: IRGACURE OXE-02 (Ciba Specialty Chemicals)
(D) -2: IRGACURE OXE-01 (Ciba Specialty Chemicals)
(E) -1: Propylene glycol monomethyl ether acetate dispersion with a carbon black concentration of 20% by weight and a polymer dispersant concentration of 5% by weight (solid content 25%)
(F) -1: Silane coupling agent S-510 (manufactured by Chisso Corporation)

The alkali-developable photosensitive resin compositions obtained in the above examples and comparative examples were applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking was 2.1 μm, Dry at 80 ° C. for 1 minute. Thereafter, the exposure gap is adjusted to 150 μm, a negative photomask is put on the dried coating film, and an ultraviolet ray of 100 mJ / cm ² is irradiated with an ultrahigh pressure mercury lamp with an I-line illuminance of 30 mW / cm ² . A photocuring reaction was performed. The photomask used forms a matrix with x-direction 50 μm lines + 350 μm openings and y-direction 20 μm lines + 180 μm openings. Next, this exposed coated plate is subjected to 1 kgf / cm ² pressure shower development at 23 ° C. for 60 seconds or 80 seconds and 5 kgf / cm ² pressure spray water washing in an aqueous solution of 0.05% potassium hydroxide. The unexposed portion was removed to form a pixel pattern on the glass substrate, and then heat post-baked at 230 ° C. for 30 minutes using a hot air dryer. The evaluation items and methods in Examples and Comparative Examples are as follows, and the evaluation results of each item are shown in Table 2 and Table 3.

Film thickness: measured using a stylus film thickness meter (trade name Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.).
Coated foreign matter: A case where radial streaks were observed in the coating film after spin coating was evaluated as x <defect>, and a case where no radial streaks were observed was evaluated as o <good>.
Developability: The pixel pattern after development was observed with a microscope, and the case where peeling with respect to the substrate or the pattern edge portion was not recognized was evaluated as ○ <good>, and the case where it was recognized was evaluated as x <defect>.
Coated surface roughness: The surface roughness (Ra) of the coated film after development and thermal baking was evaluated as ○ <good> when the surface roughness was less than 150 mm and x <defect> when the value was 150 mm or more.
Pattern adhesion: A case where peeling of a 20 μm pattern was not recognized in a peeling test was evaluated as “good”, and a case where it was recognized was evaluated as “poor”.
PCT adhesion: A post-baked patterned substrate is subjected to a PCT (pressure cooker) test under the conditions of 121 ° C, 100% RH, 2 atm, and 24 hours, and then cellophane tape is applied to the 20 µm pattern area. Pattern adhesion was evaluated by performing a peeling test.
OD measurement: When a black pigment was mixed as the component (E), it was measured using an OD meter manufactured by Otsuka Electronics Co., Ltd. using a 2.1 μm coating film after post-baking and described as an OD value per 1 μm.
Contact angle measurement: A square pattern of 10 mm × 10 mm × 2.1 μm was formed on a glass substrate after development by the same method as described above. The static contact angle on this coating film was measured using butyl carbitol acetate (BCA). When this static contact angle was 40 ° or more, it was evaluated as “good”, and when it was less than 40 °, it was evaluated as “poor”.
IJ (inkjet) ink coating characteristics: Into the obtained matrix, using a TOSHIBA TEC inkjet head, a green ink for a color filter having a viscosity of 10 mPa.sec and a solid content concentration of 20% was applied as follows. After drying at ° C for 1 minute, post-baking was further carried out at 230 ° C, and the coating state was observed with an optical microscope.
Drawing condition 1: 42 pl of green ink was dropped on the center of 350 × 180 μm pixel glass. At this time, a sample exhibiting a liquid spread on the glass surface equivalent to that of the comparative example to which no ink repellent was added was marked with ◯.
Drawing condition 2: Green ink is dropped into the matrix so that the average film thickness after post-baking is 1.8 μm. After post-baking, light leakage occurs near the matrix, or there is ink drying residue on the matrix. I observed it.

  As a result of the above, in the examples, all the characteristics as the color filter partition walls were satisfied, and the static contact angle was 40 ° or more even in butyl carbitol acetate (BCA). On the other hand, in Comparative Example 1, a residue was observed on the substrate after development, and a problem was observed in the ink spreadability during IJ coating. In Comparative Example 2, a sufficient contact angle was not obtained, and a phenomenon in which ink leaked from the partition walls during IJ coating was observed.

Claims (8)

An alkali-developable photosensitive resin composition comprising a fluorine-containing resin (A) as an ink repellent agent and an alkali-developable photosensitive component that reacts with ultraviolet light having a wavelength of 300 to 450 nm,
While the fluororesin (A) is a random or block copolymer represented by the following general formula (2), the average molecular weight Mw is in the range of 2000 to 20000, and relative to 100 parts by mass of the total component excluding the solvent. The alkali-developable photosensitive resin composition, wherein the ratio of the fluororesin (A) is 0.05 to 1 part by mass.

[Wherein R represents an organic group having an alcoholic hydroxyl group or a phenolic hydroxyl group, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, and Rf represents the following formula ( 1) represents a fluorine-containing group, Ar represents an aromatic ring, X and Z represent a hydrogen atom, an aromatic group, an alkyl group, an alkenyl group, or an ester group containing no fluorine atom, P, q, r, and s are the total number of copolymerized units, and p, q, and s are numbers from 0 to 30, and the sum of p and q is 1 or more. And r is a number from 1 to 40. Moreover, the ratio of the fluorine-containing group of Formula (1) contained in the copolymer of General formula (2) is 15-50 mass% in mass conversion. ]

  The fluororesin (A), (B) an alkali-developable oligomer having an acidic group and two or more ethylenic double bonds in one molecule, and (C) three or more ethylenic groups in one molecule. The alkali-developable photosensitive resin composition according to claim 1, comprising a photopolymerizable monomer having a double bond and (D) a photopolymerization initiator. The component (B) comprises a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (4) and (meth) acrylic acid, a polybasic acid The alkali-developable photosensitive resin composition according to claim 2, which is an alkali-developable unsaturated group-containing oligomer obtained by reacting with a carboxylic acid or an anhydride thereof.

[Wherein, R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and may be the same or different, and X is —CO—, —SO ₂ —. _{, -C (CF 3) 2 -} , - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, 9,9- fluorenyl group represented by the following formula, Or indicates absence, and n is an integer of 1 to 10.

  The alkali-developable photosensitive resin composition according to any one of claims 1 to 3, wherein (E) at least one selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light shielding material is dispersed. A light-shielding alkali-developable photosensitive material, wherein the component (E) is blended in an amount of 25 to 60 parts by mass with respect to 100 parts by mass of the total solid content. Resin composition.   The photosensitive resin composition for barrier rib formation for display elements of Claim 4.   The photosensitive resin composition for color filter partition formation of Claim 5.   Each step of (a) exposure with an ultraviolet exposure device, (b) development with an aqueous alkali solution, and (c) thermal baking after the photosensitive resin composition according to claim 5 or 6 is applied on a substrate and dried. A partition for a display element, having a thickness of 1.5 to 3 μm.   A display element, wherein pixels are formed in the partition wall according to claim 7 by an ink jet printing method.