JP2010085904A - Alkali-developable photosensitive resin composition, and display element barrier rib formed by using the same, and display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-developable photosensitive resin composition having excellent compatibility with an ink repelling agent, having a favorable surface appearance and pattern shape and excellent surface ink repelling property after the film of the composition is formed, and capable of maintaining the surface ink repelling property even when the film is subjected to normal cleaning or the time elapses. <P>SOLUTION: The alkali-developable photosensitive resin composition includes a fluorine-containing resin (A) composed of a copolymer having an acidic group and a substituent having a structure expressed by formula (1), and an alkali-developable photosensitive component which reacts with UV light, wherein the fluorine-containing resin (A) includes the substituent of formula (1) by 15 to 50 wt.%, and has an acid number of 10 to 100 mgKOH/g and an average molecular weight in the range from 2,000 to 20,000; and the proportion of the fluorine-containing resin (A) to total 100 parts by weight of the composition excluding the solvent is 0.05 to 10 parts by weight in the composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an alkali-developable photosensitive resin composition, partition walls formed using the same, and a display element, and more particularly, an alkali-developable photosensitive resin composition suitable for forming partition walls of a display element in an ink jet printing method and the same. And a 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 silicon-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 weight 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 = CH (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 weight. 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.

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

  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). For display elements that have 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. The present invention provides a photosensitive resin composition suitable for partition wall formation.

  That is, the present invention is as follows.

また、組成物中、溶剤を除く成分の合計１００重量部に対する含フッ素樹脂（Ａ）の割合が０．０５〜１０重量部であることを特徴とするアルカリ現像感光性樹脂組成物。 (1) A fluorine-containing resin (A) comprising a copolymer having an acidic group and a substituent having a structure represented by the following formula (1), and an alkali developing photosensitive component that reacts with ultraviolet light (300 nm to 450 nm) And the fluorine-containing resin (A) has a weight ratio of 15 to 50% by weight of the substituent of the structure represented by the formula (1), and The acid value is 10 to 100 mg KOH / g and the average molecular weight is in the range of 2000 to 20000,

Moreover, the ratio of the fluorine-containing resin (A) with respect to a total of 100 weight part of components except a solvent in a composition is 0.05-10 weight part, The alkali developing photosensitive resin composition characterized by the above-mentioned.

  (2) In addition to the fluororesin (A), the following components (B) to (D); (B) an alkali-developable oligomer having an acidic group and two or more ethylenic double bonds in one molecule; The alkali-developable photosensitive resin according to the above item (1), comprising (C) a photopolymerizable monomer having at least 3 ethylenic double bonds in one molecule, and (D) a photopolymerization initiator as essential components. Composition.

  (3) The alkali-developable photosensitive resin composition as described in (1) or (2) above, wherein the fluororesin (A) has an ethylenic double bond.

(4) The fluororesin (A) is 30 to 80 parts by weight of at least one monomer represented by the following general formula (2), and at least one 1 to 1 monomer having an alkali-soluble group. The alkali-developable photosensitive resin composition according to any one of (1) to (3) above, wherein 30 parts by weight are copolymerized.
CH ₂ = C (Rn) -COO-Y-O-Rf (2)
(In the formula, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, and Rf represents a fluorine-containing group represented by the formula (1)).

（式中、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ｒ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１〜３０の数である。） (5) The fluororesin (A) is a random or block copolymer represented by the following general formula (3), according to any one of (1) to (4) above, Alkali developing photosensitive resin composition.

(In the formula, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, Rf represents a fluorine-containing group represented by formula (1), 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 may be the same or different from each other, and p, q, r, and s represent the respective copolymer units. And p, q, and r are numbers from 0 to 30, the sum of p and q is 1 or more, and r is a number from 1 to 30.)

（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０〜１０の整数である） (6) The component (B) is a polybasic product of 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 item (2), which is an alkali-developable unsaturated group-containing oligomer obtained by reacting with an acid carboxylic acid or an anhydride thereof.

(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 0 to 10)

  (7) At least one selected from the group consisting of (E) a black organic pigment, a mixed color organic pigment, and a light-shielding material with respect to the alkali development photosensitive resin composition according to any one of (1) to (6) above A light-shielding photosensitive resin composition, wherein a light-shielding dispersion liquid is added and 25 to 60 parts by weight of component (E) is blended with respect to 100 parts by weight of the total solid content .

  (8) The photosensitive resin composition for partition formation for display elements as described in said (7) term.

  (9) The photosensitive resin composition for forming color filter partition walls as described in (8) above.

  (10) The photosensitive resin composition described in the above item (8) or (9) is applied on a substrate and dried, then (a) exposure with an ultraviolet exposure device, (b) development with an aqueous alkaline solution, and ( c) A partition wall for a display element, which is obtained by using each step of thermal baking as essential, and has a film thickness of 1.5 to 3 μm.

  (11) A display element in which pixels are formed in the partition wall according to the above (10) by an ink jet printing method.

  According to the present invention, in a resist composition containing a photosensitive component that reacts with 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 having excellent ink repellency and suitable for forming barrier ribs 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 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 (2). 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 (2)
(In the formula, Rn represents hydrogen or a methyl group, Y represents a divalent organic group not containing a fluorine atom, and Rf represents a fluorine-containing group of formula (1)).

  The monomer represented by the general formula (2) 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 alkyl group, a polyethylene glycol group, and a phenyl group. Further, the fluorine-containing resin (A) component is prepared by copolymerizing such a fluorine-containing monomer and a non-fluorine-containing monomer.

（式中、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ｒ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１〜３０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 (3) can be obtained.

(In the formula, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, Rf represents a fluorine-containing group represented by formula (1), 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 may be the same or different from each other, and p, q, r, and s represent the respective copolymer units. And p, q, and r are numbers from 0 to 30, the sum of p and q is 1 or more, and r is a number from 1 to 30.)

  The fluorine-containing resin (A) needs to contain a substituent having the structure of the formula (1) in the range of 15 to 50% by weight. If it is less than 15% by weight, a sufficient ink repellency cannot be obtained even after the alkali-developable photosensitive resin composition is cured, or if the desired ink repellency is obtained, the amount of component (A) added is increased. Thus, the alkali developability of the composition is impaired.

  Further, the fluororesin (A) has an acidic group and has an acid value of 10 to 100 mgKOH / g. If the acid value is less than 10 mg KOH / g, a residue tends to remain on the substrate after development, and if it exceeds 100 mg KOH / g, the ink repellency after development is not stable. In addition, the acid value of this (A) component is represented as mg number of KOH required in order to neutralize the acidic group in 1 g of resin.

  As a means for introducing an acidic group, a vinyl monomer having a carboxyl group or an acid anhydride group is copolymerized, or a polymer having a hydroxyl group in the side chain is prepared in advance and an acid anhydride is added. There is. Examples of this include acidic monomers such as methacrylic acid and maleic anhydride, and maleic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride as acid anhydrides.

  The fluorine-containing resin (A) component can be prepared by copolymerizing such a fluorine-containing monomer and an acidic group-containing monomer with a non-fluorine-containing monomer. Examples of such non-fluorine-containing monomers include ordinary acrylic acid esters, methacrylic acid esters, styrene derivatives, maleic acid esters, and the like. 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 weight used in the fluorine-containing resin (A) is preferably 30% by weight or more. If it is less than 30% by weight, 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. On the other hand, when the content exceeds 80% by weight, the obtained copolymer is poorly compatible with the solvent used for preparing the resist or the components (B) and (C), and causes the generation of a gel product.

  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 for reacting an acrylate or methacrylate compound having an isocyanate group, an acid anhydride group, an ethylene oxide group or the like as a bonding group 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. .

  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.

  In addition, the ratio of the fluororesin (A) to 0.05 to 10 parts by weight with respect to 100 parts by weight of the total solid content of the alkali-developable photosensitive resin composition excluding the solvent is adjusted to be 0.05 to 10 parts by weight. If the proportion of the fluorine-containing resin (A) is less than 0.05 parts by weight, the ink repellency becomes insufficient. Conversely, if it exceeds 10 parts by weight, the pattern formation of the original alkali development photosensitive resin composition is affected. There is a risk.

  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０〜１０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-, a 9,9-fluorenyl group represented by the following formula

Or it indicates absence, and n is an integer of 0 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. be able to.

  Since 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, color The photosensitive resin composition for forming filter barrier ribs is provided with excellent photocurability, good developability, and patterning characteristics, and improves the physical properties of the light-shielding barrier ribs.

  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) dimethyl Silane, 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 or the like, or X in the formula (4) is the 9,9-fur 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene which is a rhenyl group, 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 compounds such as 4,4′-biphenol, 3,3′-biphenol, and the like.

  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. Further, when the bisphenols are glycidyl etherized, oligomer units are mixed. If the average value of n in the general formula (4) is in the range of 0 to 10, preferably 0 to 2, the present resin There is no problem with the performance of the composition.

  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 in the side chain and 3) another ethylenically unsaturated monomer in a solvent in which a peroxide and a chain transfer agent coexist. Alkali developability having an ethylenic double bond by using a copolymer obtained by copolymerization as a binder resin to which a monounsaturated compound having a functional group that can be added to the side chain of 2) is further added. It can also be an oligomer.

  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 this component (B) is expressed as the number of mg of KOH necessary to neutralize the carboxyl group in 1 g of 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, trimethylolethanetri (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 photocur this, a photopolymerization initiator is used as component (D). 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 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 Tylamino-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 -Trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine Halomethyl-S-triazine compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 2- And benzyl-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.

  The amount of the photopolymerization initiator used as the component (D) is suitably 5 to 40 parts by weight based on the total of 100 parts by weight of the components (A), (B) and (C). When the blending ratio of component (D) is less than 5 parts by weight, the rate of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, when it exceeds 40 parts by weight, 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 developing 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. Can do. 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, the ratio of the pigment or light-shielding material contained in (E) component may be mix | blended 25-60 weight part with respect to 100 weight part of total solid of the photosensitive resin composition. preferable. When the amount is less than 25 parts by weight, the light shielding property is not sufficient. When the amount exceeds 60 parts by weight, 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, it is preferable to use a solvent separately from 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, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl Glycol ethers such as ether and 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 silicon-based, fluorine-based, and acrylic-based 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 monomers that become solid content after curing), the total of components (A) to (E) is 70 wt% or more, preferably 80 wt%, more preferably 90 wt% or more It is desirable to include. 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 wt%.

  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 light exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a deep ultraviolet lamp, and the resin composition for black resist in the coating film 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 weakly alkaline aqueous solution containing 0.05 to 3% by weight of a 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 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. The compound abbreviations listed in the table are shown below.
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
CFnMA: CH 2 = C (CH} 3) COOCH 2 CH 2 (CF 2) a mixture of _n CF _{3 n} = _4~10
CF9PHSt: CH ₂ = CHC ₆ H ₄ OC ₉ F ₁₇
PHSt: Parahydroxystyrene
IBMA: Isobornyl methacrylate 2-HEMA: 2-hydroxyethyl methacrylate
GMA: Glycidyl methacrylate
4-HBMA: 4-hydroxybutyl methacrylate
MA: Methacrylic acid
NPMI: n-phenylmaleimide
BzMA: benzyl methacrylate
AIBN: Azobisisobutyronitrile
LM: Lauryl mercaptan

<Synthesis example A1> Fluorine-containing resin A-1
CF9PEMA (60.0 g), IBMA (18.45 g), 4-HBMA (18.45 g), MA (3.10 g), polymerization initiator AIBN (0.69 g), and chain transfer to a 1 liter reactor equipped with a stirrer Agent LM (1.70 g) was charged, and propylene glycol monomethyl acetate (PGMEA) was further added so that the solid content concentration was 40 wt%, and polymerization was performed at 90 ° C. for 14 hours while stirring in a nitrogen atmosphere. After cooling, the solution was diluted with PGMEA so that the solid content concentration was 20 wt% to obtain a solution of fluororesin A-1. This solution exhibited a uniform solution even when left at room temperature. The weight average molecular weight of the fluororesin A-1 was 8400, and the acid value was 20 mgKOH / 1g polymer. However, the weight average molecular weight was determined by GPC using THF as a developing solvent (in terms of polyethylene glycol).

<Synthesis Examples A2 to A14 and Comparative Synthesis Examples a1 to a2>
In the synthesis of fluorinated resin A-1, the fluorinated resins A-2 to A-14 and a-1 to a-4 were prepared in the same manner except that the amount of raw materials was changed as shown in Tables 1 and 2. Obtained. In any fluorine-containing resin A, the content of the substituent having the structure shown in Formula (1) is 20 to 50% by weight. In addition, the unit of the numerical value described in the column of each component shown in Table 1 and Table 2 is “g”. The properties were the same as in Synthesis Example 1 and showed the weight average molecular weight, acid value, and PGMEA solubility (20 ° C.).

<Synthesis Example A-15> Preparation of fluorinated resin A-15 In a 1 liter reactor equipped with a stirrer, IBMA (27.4 g), 4-HBMA (13.5 g), MA (4.60 g), polymerization initiator Charge AIBN (0.69 g) and chain transfer agent LM (1.70 g), add propylene glycol monomethyl acetate (PGMEA) to a solid content of 40 wt%, and stir in a nitrogen atmosphere at 90 ° C. For 14 hours. After cooling, 19.1 g of [(CF ₃ ) ₂ CF] ₂ C═CFCF ₃ and 4 g of triethylamine were added, and the mixture was further stirred at 40 ° C. for 12 hours. After the constant temperature, the solution was poured into methanol, and 50 g of fluororesin A-15 was obtained by filtration under reduced pressure.

<Synthesis Example A-1s> Introduction of double bond (Preparation of fluororesin A-1s solution)
100 g of 20 wt% PGMEA solution of A-1 and 1.64 g of 2-acryloyloxyethyl isocyanate (MW = 141.12, isocyanate group / hydroxyl group in A-1 = 0.5 mol / mol), 1,4-diazabicyclo [2 , 2,2] octa 0.03 g, and stirred at 50 ° C. for 12 hours and cooled to room temperature. This polymer solution A-1s was confirmed to have lost NCO absorption (2730 nm) by IR.

<Synthesis Examples A-2s to A-15s> Preparation of fluororesin A-2s to A-15s solution Using 100 g of the 20 wt% PGMEA solution of each of the aforementioned A-2 to A-14 polymers, the hydroxyl groups of each polymer Each solution of polymers A-2s to A-14s was obtained in the same manner as in Synthesis Example A-1s except that 2-acryloyloxyethyl isocyanate was charged so as to be 0.5 mol / mol.

<Synthesis example A-2s2> Introduction of double bond-2 (Preparation of fluororesin A-2s2 solution)
100 g of 20 wt% PGMEA solution of A-1 and 4.1 g of 2-acryloyloxyethyl isocyanate (MW = 141.12, isocyanate group / hydroxyl group in A-1 = 1 mol / mol), 1,4-diazabicyclo [2,2 , 2] Octa 0.03 g was mixed, stirred at 50 ° C. for 12 hours, and cooled to room temperature. This polymer solution A-2s2 was confirmed to have lost NCO absorption (2730 nm) by IR.

<Examples 1 to 25 and Comparative Examples 1 to 4>
First, the components (B) to (F) excluding the component (A) are mixed in the proportions (parts by weight) described in Tables 3 and 4, and propylene glycol monomethyl ether acetate is added so that the solid content concentration becomes 20% by weight. did. Subsequently, component solution (A) was added in parts by weight shown in Tables 3 and 4. 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 Tables 3 and 4, the blending ratio with respect to the total solid content is shown in wt% in () of the component (A) and the component (B). The blending ratio of component (E) is shown in the separate column as (pigment / total solids) wt% with respect to the total solids.

Here, the compounding component used by manufacture of the alkali image development photosensitive resin composition of an Example and a comparative example is as follows.
(B) -1: propylene glycol monomethyl ether acetate solution of an acid anhydride polycondensate of an epoxy acrylate having a fluorene skeleton (resin solid content concentration = 56.1% by weight, trade 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 30,000 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-01 (Ciba Specialty Chemicals)
(D) -2: IRGACURE OXE-02 (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 Shin-Etsu Chemical Co., Ltd.)

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. After that, the exposure gap is adjusted to 150 μm, a negative photomask is put on the dried coating film, and 100 mj / cm ² of ultraviolet light is irradiated with an ultrahigh pressure mercury lamp with an I-line illuminance of 30 mW / cm ^2. A curing 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. Evaluation items and methods in Examples and Comparative Examples are as follows.

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 to the substrate and the pattern edge portion were not observed was evaluated as ◯ <good>, and the case where it was recognized was evaluated as x <bad>.
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 <bad> 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 pattern-formed substrate is subjected to a PCT (pressure cooker) test under conditions of 121 ° C, 100% RH, 2 atm, and 24 hours, and then cellophane tape is applied to the 20 µm pattern. 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 black square pattern of 10 mm × 10 mm × 2.1 μm was formed on the glass substrate after development by the same method as described above. The static contact angle of water was measured using butyl carbitol acetate (BCA) on this coating film or on the glass surface which was removed by development.
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 onto 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: Grain 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 ink drying residue remains on the matrix. I observed it.

  As a result, in the examples, all the characteristics as the light-shielding color filter partition were satisfied, and the static contact angle was 40 ° or more even in butyl carbitol acetate (BCA). On the other hand, in the comparative example, the obtained fluororesin had low solubility, and it was difficult to obtain a smooth coating film. In Comparative Example 2 and Comparative Example 4, a sufficient contact angle could not be obtained, and a phenomenon in which ink leaked from BM during IJ coating was observed. In Comparative Example 3, a residue was observed on the substrate after development, and a problem was observed in ink spreadability during IJ coating.

<Examples 26 to 30>
First, components (B) to (D) excluding component (A) and YX-4000H (manufactured by Showa Shell; tetramethyldiphenyl epoxy resin) are mixed in the proportions (parts by weight) shown in Table 5 to produce propylene glycol monomethyl ether acetate. To a solid content concentration of 20% by weight. Subsequently, the component solution (A) was added in parts by weight shown in Table 5. Subsequently, it filtered by 0.2 kg / cm < ² > pressurization using a ² micrometer polypropylene membrane filter, and prepared alkali development photosensitive resin composition.

  Subsequently, a matrix having openings of 300 μm × 100 μm, a BM line of 30 μm, and a film thickness of 2.1 μm was formed in the same manner as in the previous example, and the same evaluation was performed. This partition also showed a sufficient static contact angle in butyl carbitol acetate, and the IJ coating characteristics were also good.

Claims (11)

A fluorine-containing resin (A) comprising a copolymer having an acidic group and a substituent having a structure represented by the following formula (1), and at least an alkali developing photosensitive component that reacts with ultraviolet light (300 nm to 450 nm) An alkali development photosensitive resin composition contained,
The fluorine-containing resin (A) has a weight ratio of 15 to 50% by weight of the substituent having the structure represented by the formula (1), an acid value of 10 to 100 mgKOH / g, and an average molecular weight. In the range of 2000 to 20000,

Moreover, the ratio of the fluorine-containing resin (A) with respect to a total of 100 weight part of components except a solvent in a composition is 0.05-10 weight part, The alkali developing photosensitive resin composition characterized by the above-mentioned. In addition to the fluororesin (A), the following components (B) to (D):
(B) an alkali-developable oligomer having an acidic group and two or more ethylenic double bonds in one molecule;
(C) a photopolymerizable monomer having three or more ethylenic double bonds in at least one molecule, and (D) a photopolymerization initiator,
The alkali developing photosensitive resin composition according to claim 1, comprising:   The alkali-developable photosensitive resin composition according to claim 1, wherein the fluororesin (A) has an ethylenic double bond. The fluororesin (A) is 30 to 80 parts by weight of at least one monomer represented by the following general formula (2) and 1 to 30 parts by weight of at least one monomer having an alkali-soluble group. The alkali-developable photosensitive resin composition according to any one of claims 1 to 3, wherein
CH ₂ = C (Rn) -COO-Y-O-Rf (2)
(In the formula, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, and Rf represents a fluorine-containing group represented by the formula (1)). The alkali-developable photosensitive resin composition according to any one of claims 1 to 4, wherein the fluororesin (A) is a random or block copolymer represented by the following general formula (3). .

(In the formula, Rn represents hydrogen or a methyl group, Y represents a divalent organic group containing no fluorine atom, Rf represents a fluorine-containing group represented by formula (1), 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 may be the same or different from each other, and p, q, r, and s represent the respective copolymer units. And p, q, and r are numbers from 0 to 30, the sum of p and q is 1 or more, and r is a number from 1 to 30.) The component (B) is a polybasic acid carboxylic acid obtained by further reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols represented by the following general formula (4) with (meth) acrylic acid. 3. The alkali-developable photosensitive resin composition according to claim 2, which is an oligomer containing an alkali-developable unsaturated group obtained by reacting with an anhydride thereof.

(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 0 to 10) For the alkali-developable photosensitive resin composition according to claim 1,
(E) A light-shielding dispersion liquid in which at least one selected from the group consisting of black organic pigments, mixed color organic pigments and light-shielding materials is dispersed is added, and component (E) is added to 100 parts by weight of the total solid content. Is blended in an amount of 25 to 60 parts by weight, a light-shielding photosensitive resin composition.   The photosensitive resin composition for partition formation for display elements of Claim 7.   The photosensitive resin composition for color filter partition formation of Claim 8.   Each step of (a) exposure with an ultraviolet exposure device, (b) development with an alkaline aqueous solution, and (c) thermal baking after the photosensitive resin composition according to claim 8 or 9 is applied on a substrate and dried. A partition for a display element, characterized in that the thickness is 1.5 to 3 μm.   The display element which formed the pixel in the partition of Claim 10 with the inkjet printing method.