JP5346509B2 - Photosensitive resin composition for forming color filter partition walls, light-shielding color filter partition walls and color filters formed using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, maintaining surface ink repellency even after ordinary washing or a lapse of time, and forming a barrier plate having excellent adhessive to a support substrate. <P>SOLUTION: This photosensitive resin composition for forming color filter barrier plate contains: (A) alkali developing unsaturated group-containing oligomer obtained by further reacting a reactant of an epoxy compound having two glycidyl ether groups derived from visphenols and (meth)acrylic acid with polybasic acid carboxylic acid or its anhydride; (B) ink repellent (meth)acrylic polymer having a main chain having 4-6 carbon atoms, and having polymer unit in which at least seven of hydrogen atoms are substituted by fluorine atoms; (C) photopolymerizable monomer having three or more ethylenic double bond at least in one molecule; (D) a photopolymerization initiator; and (E) light shielding dispersion pigment containing at least one kind selected from a black organic pigment, a mixed color organic pigment and a light shielding material. The (B) component of 0.2-10 pts.wt. is mixed with total solid of 100 pts.wt. in the composition. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  TECHNICAL FIELD The present invention relates to a photosensitive resin composition for forming color filter partition walls, a light-shielding color filter partition wall and a color filter formed using the same, and particularly to a color filter partition wall forming photosensitive material suitable for manufacturing a color filter by an ink jet printing method. The present invention relates to a light-sensitive resin composition, a light-shielding color filter partition formed using the same, and a color filter.

  A color filter usually forms a black matrix (black matrix) on the surface of a transparent substrate such as glass or plastic sheet, and then successively forms three or more different hues such as red, green, blue, etc. in stripes or It is formed with a color pattern such as a mosaic. 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 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 coating a photopolymerizable composition containing a color material on a transparent substrate and repeating image exposure, development, and curing as necessary is a color filter. It is widely used because it has high accuracy such as pixel position and film thickness, 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. The black matrix is generally formed by etching a metal film such as chromium or by a photolithographic method using a photosensitive resin containing a light-shielding pigment.

  However, when a color pattern is formed using the pigment dispersion method, radiation and other irradiation steps and development steps must be performed for each color, which requires at least three photo steps 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, in this method, bleeding of each color region and color mixture between adjacent regions can occur. Therefore, the material constituting this partition wall is required to have a property that suppresses the spread of the colorant (ink) outside the target coloring area. 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 inkjet head overlaps with the inside of the pixel and on the partition wall, a so-called self-repairing action is required in which the ink on the partition surface returns to the inside of the pixel due to surface ink repellency. In particular, in the demand for higher definition in which pixels are miniaturized, the frequency of droplets ejected from the ink jet overlapping with the black matrix increases, and in order to compensate for the developability of ink at the corners in each color region, Overstrikes are also being studied (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.

  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. Patent Document 1 discloses a photoresist composition containing a fluoroalkyl group-containing (meth) acrylate monomer and a silicone chain-containing ethylenically unsaturated monomer. However, the amount of the copolymer added is as follows. The content is 0.001 to 0.05% by weight based on the solid content of the photoresist composition, and such a low content results in insufficient ink repellency.

  Patent Document 2 exemplifies a composition of an alkali-developable 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.

In Patent Document 3, CH ₂ = CH (R ¹ ) COOXR ^f (R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms) is used as a monomer, and the fluorine atom content is 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 .

  Patent Document 4 discloses an alkali-soluble photosensitive resin having an acidic group and three or more ethylenic double bonds in the molecule, and an alkyl having 20 or less carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. A negative photosensitive resin composition containing, as an ink repellent, a polymer obtained by copolymerizing a polymer unit having a group and 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 surface is transferred to the surface and the contact angle with the colored ink is controlled to 30 to 60 °. Among these, specific examples of the ink repellent agent include those having an organic silicone in the main chain or side chain, and fluororesins by copolymerization with a fluorine-containing monomer with vinylidene fluoride or the like. 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.

  On the other hand, it is described in Macromolecules, 38 (2005), page 5699 (nonpatent literature 1) regarding the dynamic contact angle by the molecular chain length of a fluorine-containing side chain using an acrylic ester polymer. There is a description that when the number of carbon atoms in the fluorine-containing molecular chain length exceeds 6, the receding angle becomes large and the falling angle becomes small due to crystallization of the side chain. However, the EPA recommends a policy to reduce the production of fluorine compounds having fluoroalkyl (Rf) groups with 8 or more carbon atoms (long chain) by 95% by 2010, with a small falling angle at 6 or less carbon atoms. An ink repellent fluorine-containing compound is desired.

Further, 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 reacted with a polybasic acid carboxylic acid or an anhydride thereof. The black resist containing the unsaturated group-containing compound as a main component of the resin has a high light-shielding rate, and it is easy to form a fine pattern by a photolithography method. In addition, insulation, heat resistance, adhesion It has been reported that it is a composition for forming a light-shielding thin film having excellent properties and room temperature storage stability. However, Patent Document 6 does not mention the ink repellency, nor does it mention compatibility.
JP-A-9-54432 JP-A-11-281815 JP 2005-315984 A WO2004-42474 pamphlet JP 2006-251433 A JP-A-8-278629 JP 2006-343518 A Macromolecules, 38 (2005), 5699

  Therefore, the object of the present invention is to solve the above-mentioned problems, that is, the surface ink repellency is excellent and the surface ink repellency can be maintained even after a normal cleaning and time elapses. It is in providing the photosensitive resin composition which can form the partition excellent also in the property. Another object of the present invention is to provide a color filter partition formed using this photosensitive resin composition, and the color filter partition obtained thereby is an ink repellency when forming a color pattern. And excellent adhesion to the support substrate. Furthermore, another object of the present invention is to provide a color filter formed using this color filter partition wall.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have further obtained a reaction product of an aromatic epoxy compound derived from bisphenols and (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof. When used in combination with a predetermined amount of an ink-repellent (meth) acrylic polymer, mainly the unsaturated group-containing compound obtained by the reaction, the ink-repellent agent has excellent compatibility even in the photosensitive resin composition for forming a color filter partition wall. The surface appearance and pattern shape after film formation are good, and the surface ink repellency is excellent. On the other hand, the surface ink repellency is maintained even after normal cleaning and time passes, and the adhesion reliability with the transparent substrate is excellent. The present inventors have found that a photosensitive resin composition for forming color filter partition walls can be provided.

（但し、式中、Ｒ ₁ 及びＲ ₂ 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、Ｘは-C(CH ₃ ) ₂ ‐又は下記式で表される9,9-フルオレニル基

を示し、ｎは０〜１０の整数である）で表されるエポキシ化合物と、（メタ）アクリル酸との反応物を更に多塩基酸カルボン酸又はその無水物と反応させて得られたアルカリ現像性不飽和基含有オリゴマー、
（B）下記一般式(2)
CH ₂ ＝C（Rn）−COO−Y−Rf (2)
（式中、Rnは炭素数２以上の有機基又は塩素を示し、Yは炭素数1〜6のフッ素原子を含まない２価の有機基を示し、Rfは、炭素数4〜6のパーフルオロアルキル基を示す。）で表される重合単位を有する撥インキ性（メタ）アクリル重合体、
(C)少なくとも１分子中に３個以上のエチレン性二重結合を有する光重合性モノマー、
(D)光重合開始剤、
(E)黒色有機顔料、混色有機顔料及び遮光材から選ばれた少なくとも１種を含む遮光性分散顔料、
を必須成分として含むカラーフィルター隔壁形成用感光性樹脂組成物であり、組成物中全固形分100重量部に対して、(B)成分が0.2〜10重量部配合されていることを特徴とする遮光性のカラーフィルター隔壁形成用感光性樹脂組成物である。 The present invention
(1) The following components (A) to (E)
(A) The following general formula (1)

(In the formula, R ₁ and R ₂ are any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom, and X is represented by —C (CH ₃ ) ₂ — or the following formula: , 9-Fluorenyl group

And n is an integer of 0 to 10), and an alkali development obtained by further reacting a reaction product of (meth) acrylic acid with a polybasic acid carboxylic acid or an anhydride thereof. An unsaturated group-containing oligomer,
(B) The following general formula (2)
CH ₂ = C (Rn) −COO−Y−Rf (2)
(In the formula, Rn represents an organic group having 2 or more carbon atoms or chlorine, Y represents a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms, and Rf represents perfluoro having 4 to 6 carbon atoms. An ink repellent (meth) acrylic polymer having a polymerization unit represented by :
(C) a photopolymerizable monomer having at least 3 ethylenic double bonds in at least one molecule;
(D) a photopolymerization initiator,
(E) a light-shielding dispersion pigment comprising at least one selected from black organic pigments, mixed-color organic pigments and light-shielding materials,
Is a photosensitive resin composition for forming a color filter partition wall as an essential component, wherein 0.2 to 10 parts by weight of component (B) is blended with respect to 100 parts by weight of the total solid content in the composition. It is a light-sensitive photosensitive resin composition for forming color filter partition walls.

Furthermore, the present invention is as follows.
(3) 2 to 10 parts by weight of component (D) and 25 to 60 parts by weight of component (E) are mixed with 100 parts by weight of the total solid content in the tourism resin composition for forming color filter partition walls. (1) or (2) has a light-shielding photosensitive resin composition for forming color filter partition walls.

(4) The light-shielding photosensitive resin composition for forming a light-shielding color filter partition according to any one of claims (1) to (3), wherein the light-shielding dispersed pigment is a carbon black dispersion.

(5) After applying and drying the photosensitive resin composition for forming a color filter partition wall according to any one of (1) to (4) above on a transparent substrate, (a) exposure by an ultraviolet exposure device, (b) A light-shielding color filter partition obtained by developing each step with an alkaline aqueous solution and (C) thermal baking, and having a thickness of 1.5 to 3 μm.

(6) A color filter formed by ink jet printing in the light-shielding color filter partition wall according to (5).

  According to the present invention, the compatibility of the ink repellent agent is excellent, the surface appearance and pattern shape after film formation are good, and the surface ink repellency is excellent. The photosensitive resin composition for color filter partition formation which can maintain ink property can be provided. For this reason, in particular, in a method for producing a color filter by an ink jet process, it is possible to achieve a cost reduction that does not require a surface ink repellency treatment facility using atmospheric pressure plasma, and to suitably provide a material that contributes to an improvement in yield. .

（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、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） Hereinafter, the present invention will be described in detail.
It is obtained by further reacting a reaction product of (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols, which is component (A), and a polybasic acid carboxylic acid or its anhydride. As the epoxy compound having two glycidyl ether groups derived from bisphenols in the alkali-developable unsaturated group-containing oligomer, an epoxy compound represented by the following general formula (1) is preferably exemplified.

(In the formula, R ₁ and R ₂ are any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom, 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)

  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 its anhydride is used as an alkali-developable unsaturated group-containing oligomer which is the component (A) of the present invention. be able to. The alkali-developable oligomer of the component (A) thus obtained has both an ethylenically unsaturated double bond and a carboxyl group, and therefore has excellent photocurability in the photosensitive resin composition for forming a color filter partition wall, Gives good developability and patterning characteristics, and improves the physical properties of the light-shielding partition.

  As described above, the alkali-developable oligomer as component (A) is preferably derived from an epoxy compound represented by the above formula (1), that is, the 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 (1) 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 as component (A) can be obtained from an epoxy compound derived from bisphenols as described above. In addition to such an epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, etc. Can be used as long as it contains a compound having two glycidyl ether groups significantly. In addition, when bisphenols are glycidyl etherified, oligomer units are mixed. If the average value of n in the general formula (1) is in the range of 0 to 0, preferably 0 to 2, this 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. Moreover, the epoxy (meth) acrylate obtained by making such an epoxy compound and (meth) acrylic acid react may use only 1 type, or may use 2 or more types, polybasic acid carboxylic acid A copolymer can also be obtained by reacting with an acid or an acid anhydride thereof.

  About the alkali developable oligomer of (A) component, even if it uses only 1 type, the mixture of 2 or more types can also be used. 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 (A), 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 cinnamon. Unsaturated monocarboxylic acids such as acids: maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids (anhydrides): 3 or more And unsaturated polyvalent carboxylic 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 component (A) 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 during image pattern formation, and the adhesion of the cured film From the viewpoint of the above, it is preferable to be 70 to 150 (KOHmg / g). If it is less than 70, 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. When 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.

The ink repellent (meth) acrylic polymer (B) of the present invention is an ink repellent and is a polymer unit having 4 to 6 carbon atoms in which at least 7 of hydrogen atoms, more preferably 9 are substituted with fluorine atoms. A fluorine-containing (meth) acrylic polymer having ink repellency. Specifically, what has a monomer unit formed from a monomer as represented by following General formula (2) can be illustrated.
_{CH 2 = C (Rn) -COO} -Y-Rf (2)
(In the formula, Rn represents an organic group having 2 or more carbon atoms or chlorine, Y represents a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms, and Rf represents perfluoro having 4 to 6 carbon atoms. Represents an alkyl group.)

  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. When the carbon number of the perfluoroalkyl group (Rf) exceeds 6, the surface ink repellency is excellent, but the compatibility with the negative resist composition is lowered, and the surface appearance is poor during slit coating or after curing. The surface becomes rough. Further, perfluoroalkyl groups having more than 6 carbon atoms are not preferred from the environment. On the other hand, if the carbon number of Rf is smaller than 4, it is not preferable because the ink-inking property is lowered.

  On the other hand, if the α-position substituent Rn is low in volume corresponding to hydrogen or a methyl group, the side chain crystallinity of the perfluoroalkyl group having 6 or less carbon atoms is destroyed during firing of the black matrix, and the ink repellency is fired. On the other hand, when the organic group has 2 or more carbon atoms, it is preferable to maintain the ink repellency due to the side chain by constraining the mobility of the main chain. In this case, it is preferable that the Y group as a spacer has 6 or less carbon atoms in order to maintain the surface ink repellency of the main chain on the side chain perfluoroalkyl group after washing and curing.

Specific examples of the fluorine-containing monomer unit that can provide such an ink-repellent (meth) acrylic polymer include those in which the Rn group is —CH ₂ CH ₃ , —CH (CH ₃ ) ₂ , —CH ₂ C _6. H ₅ , —COO—Rm, —CH ₂ COO—Rm (Rm represents an organic group such as an alkyl group, a phenyl group, or an alkoxy group or chlorine, and may contain oxygen, silicon, or a fluorine element), Rf There _{-C 4 F 9, -C 5 F} 11, -C 6 F 13, Y groups are _{-CH 2 CH 2 -, - CH} 2 CH 2 O-, with _{-CH 2 CH (OH) CH 2} O- etc. Some can be mentioned.

  Furthermore, an ink-repellent (meth) acrylic polymer (B) component is prepared by copolymerizing such a fluorine-containing monomer and a non-fluorine-containing monomer. Examples of such non-fluorine-containing monomers include ordinary acrylic acid esters, methacrylic acid esters, styrene derivatives, maleic anhydride esters, and the like. From the viewpoint of compatibility with an alkali-developable resin and maintaining ink repellency, copolymerization with a methacrylic acid ester is preferable, and the side chain alcohol residue is preferably a bulky group such as a benzyl group, an isobornyl group or an adamantane group. . The ratio of the fluorine-containing monomer unit used in the ink-repellent (meth) acrylic polymer (B) is 30 mol% or more, preferably 50 mol% or more. If it is less than 30%, 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.

  The weight average molecular weight of the ink-repellent (meth) acrylic polymer needs to have a polystyrene-reduced weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) in the range of 4000 to 20000. When the molecular weight is 4000 or less, the ink repellency is lowered in the partition forming process, or the continuation of the ink repellency becomes difficult. The upper limit of the molecular weight is not preferable because of a delay in dissolution in an alkaline developer.

  This ink repellency (meth) acrylic polymer (B) is added for the purpose of imparting surface ink repellency to the partition walls, but is added within a range not impairing other properties of the composition of the present invention and its cured product. The component (B) is used in the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the total solid content in the resin composition. When the blending ratio of component (B) is less than 0.2 parts by weight, sufficient surface ink repellency is not exhibited. On the other hand, when it exceeds 10 parts by weight, the developability is affected and the pattern edge becomes jagged. It is not preferable for the flatness of the coating film, and adversely affects the moisture-resistant adhesion of the coating film. Furthermore, the coating film surface roughness increases and the surface smoothness may deteriorate. The total solid content of the photosensitive resin composition represents the total amount of components remaining as a solid content after curing.

  Examples of the photopolymerizable monomer having at least three ethylenic double bonds in one molecule of component (C) include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tetramethylene. Glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Mention may be made of (meth) acrylic esters such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc. Things, in addition to use only that alone can be used in combination of two or more.

  The monomer of component (C) needs to be added within a range that does not impair the properties of the composition of the present invention and its cured product, and preferably 100 weights in total of component (A), component (B) and component (C). The component (C) is preferably used in the range of 15 to 50 parts by weight with respect to parts. When the blending ratio of component (C) is less than 15 parts by weight, the ratio of the photoreactive functional group in the resin is small and the photosensitivity is insufficient, so the formed pattern becomes thinner than the target line width. Or patterns are easily lost. On the other hand, if it exceeds 50 parts by weight, the development speed is too fast, and the line width faithful to Mauku cannot be reproduced, or the developability deteriorates, so the pattern edge does not become jagged and sharp. Problems may arise.

  The photosensitive resin composition for forming color filter partition walls of the present invention contains a photopolymerizable compound such as the component (A) or the component (C), but is photopolymerized as the component (D) in order to photocure it. Contains initiator. 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 the 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 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-to 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- And photopolymerization initiators such as 2-dimethylamino-1- [4-morpholinophenyl] -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone. Further, oxime ester photoinitiators (OXE01 and OXE02) manufactured by Ciba SC are preferably used.

  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 7 to 20 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 7 parts by weight, the rate of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, when it exceeds 20 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 Mauku cannot be reproduced, or that the pattern edge does not become jagged and sharp.

  As the light-shielding pigment used for the light-shielding dispersed pigment such as the black organic pigment, the mixed color organic pigment, or the light shielding material as the component (E), it is preferable that it is 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 light-shielding pigments can be made into a light-shielding dispersed pigment by dispersing them in an organic solvent together with a dispersant and a dispersion aid as required.

  (E) About the mixture ratio of a component, it is preferable that 25-60 weight part is mix | blended with respect to 100 weight part of total solid content of the photosensitive resin composition. 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 color filter partition walls of the present invention, it is preferable to use a solvent in addition to the components (A) to (E). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as 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, Glycol ethers such as reethylene 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, propylene glycol mono Examples include acetic acid esters such as ethyl ether acetate, and the like, and these can be dissolved and mixed to form a uniform solution-like composition.

  Further, the photosensitive resin composition for forming a color filter partition wall of the present invention includes a coupling agent, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, etc. as necessary. Additives can be blended. The coupling agent improves the moisture resistance adhesion between the partition walls and the transparent substrate, and a siloxane compound having an alkoxy group as well as any one of glycidyl group, metalloyl group and isocyanate group can be preferably used. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl, and the like. Can include glass fiber, silica, mica, alumina and the like. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, 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 photosensitive resin composition for forming color filter partition walls 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%.

  The color filter partition of the present invention is formed by photolithography using the above-described photosensitive resin composition for forming a color filter partition 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 used, and for example, the heating is performed at a temperature of 80 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 color filter partition wall of the present invention is formed into a light-shielding color filter partition wall by, for example, the above method, and then a pixel is provided by various means to form a predetermined color pattern. A color filter 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.

Hereinafter, based on an Example , a reference example, and a comparative example, embodiment of this invention is described concretely. Here, the compounding components used in the production of the black matrix of Examples , Reference Examples and Comparative Examples are as follows.

<Synthesis Example 1>
An epoxy compound (epoxy equivalent 258) starting from 9,9-bis (4-hydroxyphenyl) fluorene is heated at 120 ° C. for 12 hours with 1.01 equivalent of acrylic acid and a catalytic amount (0.05 equivalent) of tritetraethylammonium bromide. Thereafter, the mixture was diluted with propylene glycol monomethyl ether acetate to obtain an epoxy acrylate compound solution (solid content concentration = 50% by weight). To 100 g of this solution, add 11.1 g of biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride and 5.76 g of tetrahydroxyphthalic anhydride, add propylene glycol monomethyl ether acetate, and add solid content concentration Was 56.5%, and the mixture was stirred and heated at 90 ° C. for 4 hours to obtain an alkali-developable unsaturated group-containing oligomer solution (A-1, acid value 55.0 mgKOH / g).

<Synthesis Example 2>
Alkaline-developable unsaturated group-containing oligomer solution (A-2, solid content concentration 56.5%, acid content) as in Synthesis Example 1, except that it was the same as the epoxy compound used in Synthesis Example 1 and the epoxy equivalent was 288 Value 56 mg KOH / g).

<Synthesis Example 3>
In the same manner as in Synthesis Example 1, except that biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride was changed to 8.9 g and tetrahydroxyphthalic anhydride was changed to 6.9 g. An oligomer solution (A-3, solid content concentration 56.5%, acid value 55.5 mgKOH / g) was obtained.

<Synthesis Example 4>
An epoxy compound (epoxy equivalent 272) using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene instead of 9,9-bis (4-hydroxyphenyl) fluorene was prepared, and biphenyl-3,3 Synthesis was performed in the same manner as in Synthesis Example 1 except that 10.7 g of ', 4,4'-tetracarboxylic dianhydride and 5.5 g of tetrahydroxyphthalic anhydride were used, and an alkali-developing unsaturated group-containing oligomer solution was prepared. (A-4, solid content concentration 56.5%, acid value 53 mgKOH / g) was obtained.

<Synthesis Example 5>
Three pairs of an epoxy compound (epoxy equivalent 258) having 9,9-bis (4-hydroxyphenyl) fluorene as a skeleton and an epoxy compound (epoxy equivalent 240) having 2,2-bis (4-hydroxyphenyl) propane as a skeleton In the same manner as in Synthesis Example 1 except that 1 part by weight and 12.0 g of biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride and 6.2 g of tetrahydroxyphthalic anhydride were mixed. Then, an alkali-developable unsaturated group-containing oligomer solution (A-5, solid content concentration 56.5%, acid value 57.2 mgKOH / g) was obtained.

<Synthesis Example 6>
Ink repellent B-1
2MCA-bCF4 (352g), IBMA (43.4g), GMA (14.2g), MMA (8.6g) polymerization initiator V-70 (8.8g), chain transfer agent in a 5L reactor equipped with a stirrer 2-ME (4.4 g) was charged, PGMEA was further added so that the solid content concentration was 40 wt%, and polymerization was performed at 40 ° C. for 18 hours while stirring in a nitrogen atmosphere. After the temperature was lowered, the solution was diluted with PGMEA so that the solid content concentration was 20 wt% to obtain an ink repellent B-1 solution. The weight average molecular weight of the ink repellent B-1 was 7300. However, the weight average molecular weight was determined by GPC using THF as a developing solvent (PS conversion).

<Synthesis Examples 7 to 13>
In the synthesis of ink repellent agent B-1, ink repellent agents B-2 to B-6 and resin solution b-1 were obtained in the same manner except that the amount of raw materials was changed as shown in Table 1. Minor concentration 20wt%). In addition, the unit of the numerical value in the column of each component shown in Table 1 is “g”.

<Synthesis Examples 14-15>
The isobonyl methacrylate copolymer solution was synthesized using the same synthesis method as used in Synthesis Example 6 to obtain a-1 and a-2 (solid content concentration 36.7 wt%). Table 1 shows the composition of the raw materials.

CF6MA：CH₂=C(CH₃)COOCH₂CH₂(CF2)₅CF₃
CFnMA：CH₂=C(CH₃)COOCH₂CH₂(CF2)_nCF₃ n=4〜10の混合物
IBMA：イソボルニルメタクリレート
２−HEMA：２−ヒドロキシエチルメタクリレート
GMA：グリシジルメタクリレート
MMA: メチルメタクリレート
BzMA：ベンジルメタクリレート
V-70：2，2−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）
２−ME：２−メルカプトエタノール Here, the abbreviations of the compounds described above and in Table 1 are shown below.

CF6MA: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF2) ₅ CF _{3
CFnMA: CH 2 = C (CH} 3) COOCH 2 CH 2 (CF2) a mixture of _n CF _{3 n} = _4~10
IBMA: Isobornyl methacrylate 2-HEMA: 2-hydroxyethyl methacrylate
GMA: Glycidyl methacrylate
MMA: Methyl methacrylate
BzMA: benzyl methacrylate
V-70: 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile)
2-ME: 2-mercaptoethanol

<Examples 1-3, Reference Example 4, Examples 5-18, and Comparative Examples 1-4>
First, components (B) to (E) excluding component (A) are mixed in the proportions (parts by weight) shown in Table 2 and Table 3, and 0.23 parts by weight of silane coupling agent S-510 (manufactured by Shin-Etsu Chemical) ) And propylene glycol monomethyl ether acetate were added so that the solid concentration was 20% by weight. Subsequently, (A) component solution was added in parts by weight shown in Tables 2 and 3, and 0.005 part by weight of silicon-based surfactant SH3557 (manufactured by Kao) (G-2 component) was added (only in the case of Comparative Example 4). G-1 component). Subsequently, it filtered by 0.2 kg / cm < ² > pressurization using a ² micrometer polypropylene membrane filter, and prepared the photosensitive resin composition for color filter partition formation. In Table 2 and Table 3, 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 the component (E) is shown in a separate column as (pigment / total solid content) wt% with respect to the total solid content.

Here, the compounding component used by manufacture of the photosensitive resin composition of an Example, a reference example, and a comparative example is as follows.
(C) -1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(C) -2: Pentaerythritol tetraacrylate (trade name TMP-A, manufactured by Kyoeisha Chemical Co., Ltd.)
(C) -3: Trimethylolpropane triacrylate (trade name PE-4A manufactured by Kyoeisha Chemical Co., Ltd.)
(D) -1: OXE-01 (manufactured by Ciba Specialty Chemicals)
(D) -2: OXE-02 (manufactured by 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.)
(G) -1: Fluorosurfactant MegaFuck F-470 (Dainippon Ink)
(G) -2: Silicone surfactant SH3557 (manufactured by Kao)

The post-baking film thickness of the photosensitive resin composition for forming color filter partition walls obtained in the above Examples, Reference Examples, and Comparative Examples on a 125 mm × 125 mm glass substrate using a spin coater is 2.1 μm. And pre-baked at 80 ° C for 1 minute. Then, on the dried coating to adjust the exposure gap in 80 [mu] m, covered with a negative type photomask having a line / space = 20 [mu] m / 20 [mu] m, an ultrahigh-pressure mercury lamp of I-line irradiance 30 mW / cm ² of 100 mj / cm ² UV The photocuring reaction of the photosensitive part was performed.

Next, this exposed coated plate was subjected to 1 kgf / cm ² pressure shower development at 23 ° C. for 60 seconds or 80 seconds and spray water washing at 5 kgf / cm ² pressure in a 0.05% aqueous potassium hydroxide solution, and unexposed portions of the coating film. Then, a pixel pattern was formed on the glass substrate, and then heat post-baked at 230 ° C. for 30 minutes using a hot air dryer. Evaluation items and methods of black matrix in Examples, Reference Examples, and Comparative Examples are as follows.

[Film thickness] The film thickness was measured using a stylus-type film thickness meter (trade name Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.).
[Applied foreign matter] The case where radial streaks were observed in the coating film after spin coating was evaluated as x <defect>, and the case where it was not 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 <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 (Ra) was less than 150 mm and x <bad> when the value was 150 mm or more.
[Pattern Adhesiveness] In the peeling test, 20 μm pattern peeling was not recognized as ○ <good>, and what was recognized as x <bad>.
[PCT Adhesion] Post-baked pattern forming substrate is subjected to PCT (pressure cooker) test under the conditions of 121 ° C, 100% RH, 2atm, 24 hours, and then cellophane tape is applied to the 20μm pattern area. Pattern adhesion was evaluated by performing a peeling test.
[OD measurement] Measurement was performed using an OD meter manufactured by Otsuka Electronics using a 2.1 μm coating film after post-baking, and was described as an OD value per 1 μm.
[Measurement of Contact Angle] A black 10 mm × 10 mm × 2.1 μm square pattern was formed on the glass substrate after development by the same method as described above. The static contact angle was measured using water or butyl carbitol acetate (BCA) on the black coating film. Further, this black coating film was allowed to stand for 1 week at 23 ° C. and 50% humidity, and then the static contact angle was measured again.

  As a result of the above, all of the examples satisfy various characteristics as a light-shielding color filter partition wall, and the static contact angle is high also in water and butyl carbitol acetate (BCA). I couldn't see it. On the other hand, in Comparative Examples 1 and 2 using an ordinary copolymerized methacrylic acid binder, even if an ink repellent agent is added, the compatibility is not sufficient, the developability deteriorates, the surface roughness deteriorates, and the Comparative Example In No. 3, since the fluorine side chain was long, there were problems in plate making characteristics such as linearity. In Comparative Example 4, sufficient ink repellency could not be obtained with a surfactant level, and a tendency to decrease after standing for 1 week was observed.

<Example 19>
Using the resin composition obtained in Example 1, a matrix having an opening of 300 μm × 100 μm, a BM line of 30 μm, and a film thickness of 2.1 μm was formed. Then, after treatment with an oxygen atmospheric plasma for 3 seconds, it was performed for 3 seconds treatment at CF ₄ atmospheric pressure plasma. When static contact angles were measured using water or butyl carbitol acetate (BCA) on the black coating film, they showed 100 ° and 50 °, respectively. Using a TOSHIBA TEC inkjet head into this black matrix, ink of red, blue and green with a viscosity of 9 mPa · sec and a solid concentration of 20% is applied and post-baked at 230 ° C to form a color filter. did. The obtained color filter was a good color filter with no color mixing of ink in adjacent areas.

Claims (5)

The following (A) to (E) components,
(A) The following general formula (1)

(In the formula, R ₁ and R ₂ are any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom, and X is represented by —C (CH ₃ ) ₂ — or the following formula: , 9-Fluorenyl group

And n is an integer of 0 to 10), and an alkali development obtained by further reacting a reaction product of (meth) acrylic acid with a polybasic acid carboxylic acid or an anhydride thereof. An unsaturated group-containing oligomer,
(B) The following general formula (2)
CH ₂ = C (Rn) −COO−Y−Rf (2)
(In the formula, Rn represents an organic group having 2 or more carbon atoms or chlorine, Y represents a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms, and Rf represents perfluoro having 4 to 6 carbon atoms. An ink repellent (meth) acrylic polymer having a polymerization unit represented by :
(C) a photopolymerizable monomer having at least 3 ethylenic double bonds in at least one molecule;
(D) a photopolymerization initiator,
(E) a light-shielding dispersion pigment comprising at least one selected from black organic pigments, mixed-color organic pigments and light-shielding materials,
Is a photosensitive resin composition for forming a color filter partition wall as an essential component, wherein 0.2 to 10 parts by weight of component (B) is blended with respect to 100 parts by weight of the total solid content in the composition. Photosensitive resin composition for forming light-shielding color filter partition walls. In the tourism resin composition for forming color filter partition walls, 2 to 10 parts by weight of component (D) and 25 to 60 parts by weight of component (E) are blended with respect to 100 parts by weight of the total solid content. claim 1 Symbol placement of the light-shielding color filter forming barrier ribs for a photosensitive resin composition. 3. The light-shielding photosensitive resin composition for forming a color filter partition wall according to claim 1, wherein the light-shielding dispersion pigment is a carbon black dispersion. The photosensitive resin composition for forming a color filter partition wall according to any one of claims 1 to 3 is applied on a transparent substrate and dried, (a) exposure with an ultraviolet exposure device, (b) development with an alkaline aqueous solution, ( c) A light-shielding color filter partition wall obtained by subjecting each step of thermal firing as an essential component, and having a film thickness of 1.5 to 3 μm. The color filter formed in the light-shielding color filter partition of Claim 4 by the inkjet printing method.