TW200903161A - Photosensitive resin composition, photosensitive transfer material, separation wall and method of producing the same, substrate with separation wall, color filter and method of producing the same, and display apparatus - Google Patents

Abstract

The invention provides: a photosensitive resin composition from which release of a fluorine-containing compound component is suppressed upon heat treatment; a photosensitive transfer material using the composition; a separation wall using the photosensitive resin composition or the photosensitive transfer material, and a method of producing the separation wall; a substrate provided with the separation wall; a color filter using the separation wall and a method of producing the color filter; and a display apparatus using the color filter. The photosensitive resin composition includes an initiator, an ethylenically unsaturated compound, and a fluorine-containing compound, in which the mass of the fluorine-containing compound decreases due to heat by 30% by mass or less when the composition is heated at 150 DEG C for 30 minutes.

Description

200903161 IX. The invention relates to a photosensitive resin composition, a photosensitive growth transfer material using the same, a painting wall and a method for forming the same, a substrate with a painting wall, and a color filter. Light sheet and its manufacturing method and display device. [Prior Art] In recent years, the demand for liquid crystal display devices for personal computers and liquid crystal color televisions has been increasing, and the demand for improvement in characteristics and cost reduction of color filters which are indispensable for such displays has increased. At present, as a method of producing a color filter, a dyeing method, a pigment dispersion method, an electrodeposition method, a printing method, and the like are carried out. For example, the dyeing method is to form a water-soluble polymer material layer of a dyeing material on a transparent substrate, and after patterning it into a desired shape by a lithography step, the resulting pattern is immersed in a dyeing bath to obtain a coloring. pattern. By repeating this step three times, a coloring layer formed of three coloring portions of R (red), G (green), and B (blue) can be formed. Further, the method of the pigment dispersion method which has been popular in recent years is to form a monochromatic pattern by patterning a photosensitive resin layer in which a pigment is dispersed on a transparent substrate. By repeating this step three times, a coloring layer formed of three coloring portions of R, G, and B can be formed. Further, the electrodeposition method is to pattern a transparent electrode on a transparent substrate, and immerse it in an electrodeposition coating liquid to which a pigment, a resin, an electrolytic solution or the like is added to electrodeposit the first color. By repeating this step three times, a coloring layer formed of three coloring portions of R, G, and B can be obtained, and finally, simmering is performed. 200903161 The printing method is a method in which a pigment is dispersed in a thermosetting resin, and R, G, and b are respectively applied by repeating printing three times, and then the resin is thermally cured to form a colored layer. In order to form three-color pixels of red, green, and blue, the temple method must repeat the same step three times' cost is common. Further, since the number of steps is large, there is a problem that the yield is easily lowered. In order to overcome this, in recent years, a color filter method for producing RGB pixels by an inkjet method has been reviewed by forming a black matrix (off-paint wall) by a pigment dispersion method. In the ink jet method, R, G, and B colors are sequentially applied to the concave portions of the black matrix (out of the wall) to form a pixel. The method using the ink jet method has the advantages of simple process and low cost. Further, the ink jet method is not limited to the production of a color filter, and can be applied to the production of other optical elements such as an electroluminescence element. In the ink jet method described above, it is necessary to prevent the occurrence of ink mixed color or the like between adjacent pixel regions or the phenomenon in which the ITO solution or the metal solution in the portion other than the designated region is solidified and adhered. Therefore, it is required that the partition wall (out of the wall) has a property of discharging water or an organic solvent such as an inkjet discharge liquid, that is, so-called water repellency and oil repellency. As a resin for forming such a partition wall (a wall), there is disclosed a coating composition comprising a vinyl polymer obtained by polymerizing a monomer composition containing a vinyl monomer having a fluoroalkyl group. A photosensitive resin and an organic solvent, wherein the ethylene-based polymer contains a polymer having a fluorine atom content of 0.1 to 5% by mass (see, for example, JP-A-9-54432). As a technique for imparting water repellency and oil repellency, for example, The invention discloses a copolymerization of a vinyl monomer obtained by polymerizing a monomer composition containing a vinyl monomer having 200,903,161 fluoroalkyl groups, or a vinyl monomer such as hexafluoropropylene, and a copolymerization of three or more other vinyl monomers. (for example, refer to Patent Document 1, 2). Further, there is disclosed a photoresist composition comprising a monomer composition comprising a vinyl monomer having 4 to 6 fluoroalkyl groups to obtain a polymer or a photoreceptor, wherein the fluorine atom of the vinyl polymer is contained 7 to 35 mass% (for example, refer to Patent Document 3). Further, as a substrate to which a black matrix containing an ink-repellent agent is attached, there is a control angle of 30 ° by the upper top of the color matrix by controlling the thermal hardening temperature of the black matrix or the heat hardening time color matrix ( For example, refer to Patent Document 4). On the other hand, there is an example of a water-soluble photosensitive resin which is disclosed in a tertiary amine of a resin having a bromoacetic acid unit (for example, refer to the patent document, however, when a photosensitive resin is used in which a photosensitive resin is added to form a black matrix, it contains The black matrix of the fluorine-containing compound is generally high in baking, hardening, etc., and is subjected to a baking treatment or the like. Therefore, the pixel forming region surrounded by the black matrix is inked to the glass surface, and the coloring is given. In the case of an ink for forming a pixel, there is a problem that a glass ink is applied, and a colored pixel of a desired quality cannot be formed, and the filter cannot be formed. Further, the copolymer of the copolymer described in Patent Document 6 is synthesized. In the case of the composition, the coating film formed by the coating film tends to have oil repellency. Further, in the case of the ethylene-based polymerization described in Patent Document 3, the visibility of the developing solution and the adhesion at the time of development are insufficient. The tendency of the patented carbon number of the patented stationery base is the method of making the black-60. The addition of 5) ° to the shape of the temperature treatment stop is rejected as a color ratio of all the deficiencies. 20 [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In one aspect, the problem is that the water-repellent property and the ink-repellent property of the upper surface of the pattern image (the exposed surface on the side opposite to the contact surface of the substrate) can be maintained while being used as a pattern image (for example, a wall). In this case, the adhesion between the image and the substrate on which the pattern image is formed is maintained, and the photosensitive resin composition in which the fluorine-containing compound component (including the decomposition component) is released during the heat treatment is suppressed. Further, in a certain aspect of the present invention, it is an object of the present invention to provide a water-repellent and ink-repellent property U capable of maintaining a pattern image (for example, a wall) formed by transfer, and maintaining the pattern and formation well. The adhesiveness of the substrate having the pattern image, and the photosensitive transfer material having a uniform photosensitive resin layer which is suppressed from being repelled at the time of application. Further, in one aspect of the present invention, it is an object of the present invention to provide a wettability of a region which can be maintained while holding a colored liquid, and to form an ink-dissipating property and to suppress the spread of the colored liquid to be applied. A method of forming a wall and a painting wall formed by the forming method and a method of manufacturing the same. Further, in a certain aspect of the present invention, the problem is to provide a coloring liquid which is provided in a concave portion between the walls of the drawing having a width of 200,903,161 s, and to suppress the coloring liquid from being held while maintaining the coloring liquid between the walls of the painting. The wettability of the given area is attached to the substrate of the painted wall. Further, the present invention provides a high-grade color filter which suppresses display unevenness during color mixing, whitening, and image display, and a method of manufacturing the same. Further, the present invention provides a display device capable of displaying a high-quality image in which display unevenness is suppressed in a certain aspect. The invention is based on the following knowledge, and is based on the knowledge. In other words, a pattern of a black matrix or the like is formed in advance by using a resin composition to which an ink-repellent is added, and then a high-temperature treatment such as baking treatment (for example, 150° C. or higher) is applied to the pattern. The component contained in the fluorine-containing compound flows out of the system and adheres to the substrate surface, and the wettability of the ink applied to the substrate surface tends to be lowered. However, the specific fluorine-containing compound can suppress the black matrix. Adhesion of the substrate surface after formation. In order to achieve the above problems, the specific means are as follows. (1) A photosensitive resin composition comprising an initiator, an ethylenically unsaturated compound, and a fluorine-containing compound, and the heat-reducing rate of the above-mentioned fluorine-containing compound is 30% by mass or less when held at 150 ° C for 30 minutes. (2) The photosensitive resin composition as described in (1), wherein the fluorine-containing compound contains a repeating unit' main chain structure having a fluorine atom in a side chain, and has a C-linked chain. (3) The photosensitive resin composition as described in (1), wherein the fluorine-containing compound 200903161 contains a repeating unit having a fluorine atom in a side chain, and a repeating unit represented by the following formula:

General formula (1)

R2 In the formula (1), 'R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R2 represents a hydrogen atom: an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number of 2 to 2 An alkane group of 5; L1 represents a single bond or a divalent organic linking group; X represents a chlorine atom, a bromine atom or an iodine atom; and Υ represents an extended aryl group, a divalent heterocyclic residue, a carbonyl group, or an oxycarbonyl group. . (4) The photosensitive resin composition according to the item (3), wherein the repeating unit having a fluorine atom in a side chain has three or more fluorine atoms. (5) The photosensitive resin composition according to (3), wherein the repeating unit represented by the above formula (1) is a repeating unit represented by the following formula (2): -10-200903161 R1

General formula (2)

Z1——L2——Y——CH—X

In the formula (2), R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number of 2 to 5; An alkano group; Z1 represents an ester group or a guanamine group; L2 represents a single bond or a divalent organic linking group; X represents a chlorine atom, a bromine atom, or an iodine atom; and Y represents an exoaryl group, a divalent impurity a ring residue, a carbonyl group, or an oxycarbonyl group. (6) The photosensitive resin composition according to the above formula (1), wherein the repeating unit represented by the above formula (1) is a repeating unit represented by the following formula (3): R1 1

General formula (3)

Z2——Y—CH—X

In the formula (3), R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or carbon-11-200903161 Alkyl group of 2 to 5; Z2 represents a single bond; a aryl group; and X represents a chlorine atom, a bromine atom, or an iodine atom group, a divalent heterocyclic residue, a carbonyl group, or an oxycarbonyl group. (7) The photosensitive resin composition according to (2), wherein the repeating unit having a fluorine atom has a carbon number of 4 to 7. (8) The L 1 system of the photosensitive resin composition according to the above (3), which contains at least one of an ester bond and a guanamine bond, and the L 1 system of the photosensitive resin composition as described in (3) A single bond, an extended aryl group or a divalent heterocyclic residue. (1) The photosensitive resin composition according to (1) further has a repeating unit having an acidic group. (1) The component of the photosensitive resin composition according to (1), wherein the content of the fluorine-containing compound is 5% by mass. (12) A photosensitive transfer material, which is a method for forming a photosensitive wall (13) of the photosensitive resin composition described in (1), which has a method of forming (1) to (1) 1) The photosensitive transfer material described in the photosensitive material according to any one of the above, wherein the photosensitive resin layer is exposed, the exposed photosensitive resin layer is exposed, and the image is formed by the photosensitive image layer. The obtained pattern image heat treatment (14) is a painting wall which is a group described in (13) or a divalent heterocyclic residue; and Y represents a repeating single of the fluoroalkyl group in the side chain. The divalent organic linking group in the above formula (1). In the above formula (1), the above-mentioned fluorine-containing compound, wherein the total solid is 0.1% by mass to 1 0, has a resin layer on the support. . The composition of the composition, or (1 2) lipid layer, formed by the method of forming the wall -12- 200903161. (15) A substrate having a painting wall attached thereto, comprising a substrate, and a painting wall formed by the method of forming the painting wall described in (13) on the substrate. (16) The substrate having the paint wall according to (15), wherein the water contact angle on the wall of the paint wall is 60° or more when measured according to a wettability test method of a known substrate glass surface. In the substrate surface on the side of the substrate on which the wall is formed, the portion of the substrate which is not formed with the drawing wall has a droplet diameter of 20 μm or more immediately after dropping the propylene glycol monomethyl ether acetate. (17) A method of producing a color filter comprising the step of applying a colored liquid composition to a colored portion by a concave portion on a substrate divided by the drawing wall as described in (14). (18) The method of producing a color filter according to (17), wherein the coloring liquid composition is applied by ejecting a droplet of the colored liquid composition by an inkjet method. (19) A color filter produced by the method of producing a color filter according to (18). (20) A display device comprising the color filter described in (19). Advantageous Effects of Invention According to the present invention, it is possible to provide water-repellent and ink-repellent properties of a pattern image (for example, an image-exposed surface) while maintaining an upper surface of the pattern image (the exposed surface on the opposite side of the contact surface between the substrate and the substrate). The photosensitive resin composition in which the release of the fluorine-containing compound component (including the decomposition component) is suppressed during the heat treatment while maintaining the adhesion between the pattern image and the substrate on which the pattern image is formed is good. According to the present invention, it is possible to provide a water-repellent and ink-repellent property of the upper surface of the pattern image (200903161, for example, the wall of the painting) which is formed by transfer, while maintaining the adhesion between the pattern image and the substrate on which the pattern image is formed. It is a photosensitive transfer material which has a uniform photosensitive resin layer which suppresses the occurrence of rejection (non-sticking) at the time of coating. According to the present invention, it is possible to provide a method for forming an off-paint wall which can maintain the wettability of a region imparted by a colored liquid while forming an ink-repellent property and suppress the spread of the colored liquid to be applied, and form the same. The painting wall formed by the method and the manufacturing method thereof. According to the present invention, it is possible to suppress the spread of the coloring liquid while the coloring liquid is applied to the concave portion between the ink-removing walls, while maintaining the wettability of the region given by the colored liquid between the walls of the painting. According to the present invention, a high-grade color filter capable of providing color mixing, whitening, and display unevenness in image display and a method of manufacturing the same can be provided according to the present invention, and display unevenness can be provided. A display device that displays high-quality images. BEST MODE FOR CARRYING OUT THE INVENTION A photosensitive resin composition, a photosensitive transfer material using the same, a painting wall and a method for forming the same, a substrate with a painting wall, and a color filter, which will be described in detail below And its manufacturing method and display device. Photosensitive Resin Composition The photosensitive resin composition of the present invention contains at least an initiator, a bivalent unsaturated compound, and a fluorine-containing compound, and is kept at 150 ° C for 30 minutes - 14 - 200903161, a fluorine-containing compound The heat reduction rate is suppressed to 30% or less. The photosensitive resin composition of the present invention contains a fluorine-containing compound whose temperature reduction rate at 30 ° C for 30 minutes is suppressed to 30% or less. Therefore, for example, heat treatment at a high temperature (for example, 150 k or more) after film formation In this case, the release of the fluorine-containing component can be suppressed. For example, a film is formed on the substrate, and after the pattern is formed, the heat treatment is performed for ink repellency and thermal curing of the pattern to prevent adhesion of the fluorine-containing component to the film non-formed surface. Thereby, the wettability to the liquid in the region where the photosensitive resin composition is not provided can be maintained, for example, in the case where the color filter is formed, the non-formation region of the image forming wall of the substrate on which the black matrix or the like is formed is formed. (a concave portion on the substrate isolated from the wall of the drawing), when the colored liquid composition is applied (for example, the ink is applied by an inkjet method) to form a colored region (coloring pixels such as RGB), the liquid can be prevented The color filter and the display device capable of displaying high-quality images, which are suppressed in the occurrence of whitening in the colored region and the occurrence of uneven display during image display, are obtained. 1) Initiator The photosensitive resin composition of the present invention contains at least one type of initiator. η ^ as a method of curing the photosensitive resin composition, generally a thermal initiation system using a thermal initiator or a photoinitiator using a photoinitiator, but in the present invention, the surface shape of the painted wall after hardening is It is important that the cross-sectional shape becomes a shape of a non-tapered rectangle, and therefore it is preferable to use a photoinitiator. The photopolymerization initiator is irradiated with radiation (also referred to as exposure) of visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, or the like, and can be used to initiate polymerization of an ethylenically unsaturated compound described later. The compound of the active species' can be appropriately selected from a well-known photopolymerization initiator or photopolymerization initiator-15-200903161. Examples of the photopolymerization initiator or the photopolymerization initiator include a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a bisimidazole compound, a tritrap compound, and a benzoin compound. A benzophenone compound, an α-diketone compound, a polynuclear oxime compound, a xanthone compound, a diazo compound, or the like. Specifically, a trihalomethyl-substituted trihalomethylcarbazole derivative or an s-trictylene derivative described in JP-A-2001-117230, and a trihalomethyl group described in the specification of U.S. Patent No. 4,239,850 can be mentioned. -s-tri-trap compound, a trihalomethyl-containing compound such as a trihalomethyl oxadiazole compound described in the specification of U.S. Patent No. 4,212,976; 9-phenyl acridine, 9-pyridyl acridine, 9 -pyridyl acridine, 1,2-bis(9-acridinyl)ethane, 1,3-bis(9-acridinyl)propane, I,4-bis(9-acridinyl)butane 1,5-bis(9-acridinyl)pentane, 1,6-bis(9-acridinyl)hexane, 1,7-bis(9-acridinyl)heptane, 1,8- Bis(9-acridinyl)octane, 1,9-bis(9-acridinyl)decane, 1,1 fluorene-bis(9-acridinyl)decane, 1,1 1-double (9 - acridinyl)undecane>: acridine compound such as bis(9-acridinyl)alkane such as 1,1 2 -bis(9-acridinyl)dodecane; 6-( p-Methoxyphenyl)-2,4-bis(trichloromethyl)-s-tripper, 6-[p-(indolyl bis(ethoxycarbonylmethyl)amino)phenyl]-2 ,4-bis(trichloromethyl)-s- '6-[4,-(N,N-bis(ethoxycarbonylmethyl)amino)-3,-phenyl]-2,4-bis(trichloromethyl)-s-triad Triple well compound; other, 9,10-dimethylbenzophenan trap, Michler's ketone, benzophenone / Michler's ketone, hexaarylbisimidazole/mercaptobenzimidazole, benzyldimethyl Ketal, thioxanthone/amine, 2,2,_bis(2,4-dichlorophenyl)- -16- 200903161 4,4',5,5'-tetraphenyl-1,2'-double Imidazole and the like. In the above, from the viewpoint of sensitivity, at least one selected from the group consisting of a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a bisimidazole compound, and a triple well compound is preferable. It is particularly preferred to contain at least one selected from the group consisting of a trihalomethyl group-containing compound and an acridine compound. Trihalomethyl-containing compounds and guanidine D-based compounds are also useful in versatility and low cost. Particularly preferably, for the same reason as described above, the trihalomethyl group-containing compound is 2-dichloromethyl-5-(p-phenylethylphenylbenzene)-1,3,4-anthracenequinone Oral compound is 9-local Iff卩' and 6-[p-(N,N-bis(ethoxymethyl)amino)phenyl]-2,4-bis(trichloromethane) , s, tris, 6-[4,-(Ν,Ν-bis(ethoxycarbonylmethyl)amino)-3'-phenyl]-2,4-bis(trichloromethyl)_3 _ triterpene, 2-(p-butoxystyryl)-5-trichloromethyl·ι, 3,4-oxadiazole-containing trihalomethyl-containing compound 'the aforementioned three-tillage compound system 6- [p-(Ν, Ν-bis(ethoxycarbonylmethyl)amino)phenyl]-2,4-bis(trichloromethyl)_s-triazine, the above-mentioned oral acridine compound is 9-phenylindole Acridine, the aforementioned acetophenone-based compound is rice bran (IV) 'The above-mentioned biimidazole-based compound is 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5,-tetraphenyl- 1,2'-bisimidazole. The photopolymerization initiator may be used singly or in combination of two or more. The total amount of the initiator (especially the photopolymerization initiator) in the photosensitive resin composition is preferably from 0.1 to 20% by mass based on the total solid content (mass) of the resin composition. 〇% by mass. When the total amount is within the above range, photohardening of the resin composition can be performed efficiently, and an image pattern in which no peeling or surface cracking occurs during development can be obtained. When the total amount is 0.1 mass -17 to 200903161% or more, the photocuring efficiency of the composition can be improved, and the exposure time can be shortened. When the total amount is 20% by mass or less, the image pattern formed during development can be suppressed from falling off. Or the occurrence of cracks on the surface of the pattern. In the present invention, the total solid content (mass) of the photosensitive resin composition means all components other than the solvent in the resin composition. The photopolymerization initiator may be formed by using a hydrogen donor. The hydrogen donor is preferably a thiol compound or an amine compound as described below from the viewpoint that the sensitivity can be further improved. The term "hydrogen donor" as used herein refers to a compound which can supply a hydrogen atom to a radical generated from the photopolymerization initiator by exposure. The thiol compound is a compound having a benzene ring or a hetero ring as a nucleus and having one or more sulfhydryl groups directly bonded to the nucleus (hereinafter referred to as "thiol hydrogen donor"). It is preferably 1 to 3, more preferably 1 to 2. In addition, the amine compound is a compound having a benzene ring or a hetero ring as a core, and having one or more amine groups bonded to the core (hereinafter referred to as "amine-based hydrogen donor"), the amine group It is preferably 1 to 3, more preferably 1 to 2. Further, the hydrogen donor may have both a mercapto group and an amine group. Specific examples of the thiol-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and 2,5-dimercapto-1. 3,4-thiadiazole '2-mercapto-2,5-dimethylaminopyridine and the like. Among them, 'preferably 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, particularly preferably 2-mercaptobenzothiazole. Specific examples of the amine-based hydrogen donor include 4,4'-bis(dimethylamino)benzophenone and 4,4,-bis(diethylamino)benzophenone, and 4 -Diethylamine-18- 200903161 Acetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4- Dimethylaminobenzonitrile and the like. Among them, preferred are 4,4'-bis(dimethylamino)benzophenone, 4,4,-bis(diethylamino)benzophenone, and particularly preferably 4,4. '-Bis(diethylamino)benzidine can be used alone or in combination of two or more kinds, and the formed image is not easily peeled off from the permanent support during development, and the strength and sensitivity are Further, it is preferable to use one or more types of thiol-based hydrogen donors and one or more kinds of amine-based hydrogen donors in combination. Specific examples of the combination of the above-described thiol-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole/4,4'-bis(dimethylamino)benzophenone, and 2 -mercaptobenzothiazole/4,4'-bis(diethylamino)benzophenone, 2-mercaptobenzoxazole/4,4'-bis(dimethylamino)benzophenone 2, nonylbenzazole/4,4'-bis(diethylamino)benzophenone. A more preferred combination is 2-mercaptobenzothiazole/4,4'-bis(diethylamino)benzophenone, 2-mercaptobenzoxazole/4,4'-bis(diethylamino) A particularly preferred combination of benzophenone is 2-mercaptobenzothiazole/4,4'-fluorene bis(diethylamino)benzophenone. When the thiol-based hydrogen donor and the amine-based hydrogen donor are combined, the mass ratio (Μ: Α) of the thiol-based hydrogen donor (Μ) to the amine-based hydrogen donor (Α) is generally preferably 1: 1 ~ 1 : 4, more preferably 1: 1 ~ 1 : 3. The total amount of the hydrogen donor in the photosensitive resin composition is preferably from 0 to 1 to 20% by mass based on the total solid content (mass) of the photosensitive resin composition, particularly preferably 〇. 5 to 1 0 by mass. %. 2) Ethylene unsaturated compound The photosensitive resin composition of the present invention contains at least one kind of ethylenic non--19-200903161 saturated compound. As the ethylenically unsaturated compound, the following compounds may be used singly or in combination with other monomers. Specific examples thereof include tert-butyl (meth)acrylate, ethylene glycol di(meth)acrylic acid vinegar, (meth)acrylic acid 2-propane vinegar, and triethylene glycol di(meth)acrylic acid. Ester, trimethylolpropane tri(meth)acrylate, 2-ethyl-2-butylpropanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate , dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxyethylated trimethylolpropane tri (meth) acrylate, tris (2-(methyl) propylene oxime Ethyl ethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxybenzene di(meth)acrylate, decamethyl glycol di(meth)acrylate, benzene Ethylene, diallyl fumarate, triallyl trimellitate, lauryl (meth)acrylate, (meth)acrylamide, benzyldimethylbis(meth)acrylamide, and the like. Further, a compound having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or polyethylene glycol mono(meth)acrylate may be used. A reaction product with a diisocyanate such as isocyanate, toluene diisocyanate or xylene diisocyanate. Among them, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris(2-propenyloxyethyl)isocyanurate are particularly preferred. The content of the ethylenically unsaturated compound in the resin composition is preferably from 5 to 80% by mass, particularly preferably from 10 to 70% by mass, based on the total solid content (mass) of the resin composition. When the content of the ethylenically unsaturated compound is within the above range, the resistance of the exposed portion of the composition to the alkali developing solution can be ensured. -20-200903161 'When it is a resin composition', the increase in adhesiveness can be suppressed to ensure operability. 0 3) Fluorine-containing compound The photosensitive resin composition of the present invention contains at least one of a compound containing a fluorine atom as a fluorine-containing compound and having a heat reduction rate of 30% by mass or less. The fluorine-containing compound has a small amount of a fluorine-containing component which is released from a heat treatment (e.g., 150 ° C or higher), and is a compound which imparts a function of a fluorine functional group such as water-repellent property and interface activity. Specifically, when heat treatment is performed after exposure and development, and a pattern (for example, a black wall or the like) is formed on the substrate, water-repellent and oil-repellent properties are imparted to the surface of the pattern (for example, a black matrix or the like). In contrast, it is possible to suppress the adhesion of the fluorine component to the substrate pattern (for example, the black matrix or the like), and to maintain the wettability of the substrate surface (no watering) 〇 In the present invention, the wettability refers to the degree of wetness expansion when the liquid is dropped onto a plane, for example, the concave portion surrounded by the paint wall of the substrate on which the black matrix or the like is formed (ie, becomes a colored pixel). The substrate surface of the region), when inkjet is applied to the liquid composition of the colored liquid composition, that is, the ink composition, the degree of wetting of the ink droplets is enlarged. More specifically, the ink composition of the drop is dropped between the walls of the painting, and the diameter of the circle formed by the droplet is used as an index of the degree of wetness expansion. The heat reduction rate refers to a mass reduction rate after heating of the fluorine-containing compound at 15 (TC for 30 minutes, before heating). In the present invention, the heat reduction rate is 30% by mass or less. It is preferably 25% by mass or less, more preferably 20% by mass or less. -21- 200903161 If the heat reduction rate is within the above range, the residual amount after heat treatment of the photosensitive resin composition can be ensured, and the composition after heat treatment can be given. Good water repellency and oil repellency on the surface of the object. For example, when the photosensitive resin composition is exposed, developed, or thermally cured on a substrate to form a cured resin, the exposed surface of the substrate can be maintained (for example, when a black matrix is formed on the substrate, black) The wettability of the concave portion on the substrate surrounded by the matrix, thereby preventing the non-sticking when the liquid (the colored liquid composition containing ink or the like) is exposed to the substrate. The fluorine-containing compound of 30% by mass or less can be selected from a compound group containing a repeating unit having a fluorine atom, and can impart water-repellent and ink-repellent properties. Among them, even heat treatment (for example, a temperature of 150 ° C or higher) In the present invention, it is preferred that the compound is selected from the group consisting of a repeating unit having a fluorine atom in a side chain and a main chain having a linking chain of an acrylic acid. The repeating unit having a fluorine atom is preferably a repeating unit of a side chain having a fluorine atom. Further, the repeating unit having a fluorine atom preferably has three or more fluorine atoms. Preferably, it is a fluoroalkyl group having a total carbon number of 2 to 8, more preferably a fluoroalkyl group having a total carbon number of 4 to 7. Since the total carbon number of the fluoroalkyl group is within the above range, it can be maintained as a fluorine functional group. The fluoroalkyl group may be a linear or a bond. The repeating unit having a fluorine atom in the present invention is preferably a repeating unit represented by the following formula (A). 22- 200903161

In the above formula (A), R11 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the present invention, 'R11 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. In the above formula (A), 'L11 represents a single bond or a divalent organic linking group. In the present invention, L11 is preferably a divalent organic linking group. The organic linking group is preferably an organic linking group selected from a group consisting of an alkyl group, an aryl group, an ester bond, a guanamine bond, and a divalent heterocyclic residue, or a combination thereof. The above-mentioned stretching base is preferably a stretching base having a total carbon number of 1 to 10, more preferably an alkylene group having a total carbon number of 1 to 6. Specific examples thereof include a methylene group, an ethyl group, a butyl group, a heptyl group, a hexyl group, and a decyl group. As the above-mentioned aryl group, a aryl group having a total carbon number of 6 to 15 is preferable, and an aryl group having a total carbon number of 6 to 10 is more preferable. Specific examples thereof include a phenylene group, an anthranyl group, a fluorenyl group, a phenylene group, a dialkyl phenyl group, etc., which may be a hydrazine-substituted compound, a P-substituted compound, and/or a m-substituted group. Things. The ester bond is preferably a carboxylate bond, a sulfonate bond, a phosphate bond or the like, and more preferably a carboxylate bond. The guanamine bond is preferably a guanamine bond, a sulfonate oxime bond, a guanamine phosphate bond or the like, and more preferably a guanamine bond. -23-200903161 The divalent heterocyclic residue is preferably a 5-membered heterocyclic ring derived from a 5-membered ring or a 6-membered ring containing a nitrogen atom or an oxygen atom as a ring member. Preferably, it is a pyridine ring, a pyrimidine ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, an indazole ring, a benzoxazole ring, an isoxazole ring, a pyrazole ring, an imidazole ring, a quinoline ring or a thiadiazole. The divalent heterocyclic residue derived from the ring is preferably a divalent heterocyclic residue derived from a pyridine ring or a thiadiazole ring. In the above formula (A), Rf represents a fluoroalkyl group having three or more fluorine atoms. Rf in the present invention is preferably a fluoroalkyl group having a total carbon number of 2 to 8, more preferably a fluoroalkyl group having a total carbon number of 4 to 7. The aforementioned Rf may be a straight chain or a bond. More preferably, Rf is a fluoroalkyl group represented by any one of the following formulae (A-1) to (A-3). /cf3

XCmF2# ] ~fCmF2mH] - CmF2iTr-CF CF3 General formula (A-1) Formula (A-2) Formula (A-3) wherein 'm represents an integer of 4 to 8, preferably 4 to 7 The integer. The following concrete examples of the repeating unit represented by the general formula (A) include V repeating units 0-1) to (a-34), but the present invention is not limited thereto. Further, in the following specific examples, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. -24- 200903161 R- (a-1) (a-2) R1 (a-3)

R

O 'fcFs (a-4) CF,

C4F8—CF ri (a-5) 〆 c cT^

R (a-6)

R (a-7)

Enter ^CeFl3. Into cT C7F15

Rl (a-8) PF3

'C4F8-CF CF3

Rl (a-9)

〇入〇YY^C4F9 OH

Rl (a-10)

(a-11) Ό 丫 C ~ C6F13 OH

C4F8—CF CF, CF3

Rl (a-12)

R (a-13) 丨人 ~CeFi 3 ~C7pi5

H

H

R

(a-14) H

R

(a-15)

Y H, C4F9 丫〇, 13 -25- 13200903161

(a-16) Η Η Ο CT CT^N, A- Υ, C4Fs

(a-17) Η H 0 person "X6F

(a-18) (a-20)

-26- 200903161

C4f9

(a-30)

O o

hrH

The repeating unit having three or more fluorine atoms -27 to 200903161 represented by the formula (A) in the present invention is preferably a hydrogen atom of R11 or a methyl group of L11 derived from a carboxylic acid, an ether bond, or the like. a divalent organic linking group consisting of a combination of a single or a complex group selected from the group consisting of an exoaryl group and an alkylene group, and a Rf-based tetrafluorocarbon group having a carbon number of 4 to a carbon number of 7 (Cd9 to CtF^), preferably The R11 hydrogen atom 'L11 is a divalent organic linking group composed of a combination of a carboxylate bond and an alkylene group, and Rf is a perfluoroalkyl group having 4 to 6 carbon atoms (C4F9 to C6F13). Further, the repeating unit having a fluorine atom in the side chain preferably has a total carbon number of 2 to 12, more preferably a total carbon number of 2 to 8, and particularly preferably a fluoroalkyl group having a total carbon number of 4 to 7. Repeat unit. Since the total carbon number of the fluoroalkyl group is within the above range, the performance as a fluorine functional group can be maintained while reducing the load on the environment. The fluoroalkyl group may be a straight chain or a bond. The above repeating unit ′ having a fluorine atom in the side chain is more preferably the following structural formula (A). R1

Xk丄 Rf Structural Formula (A) In the above structural formula (A), R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the above structural formula (A), 'a' represents a mass ratio (% by mass) of the structural formula (A) which is contained in the total mass of the fluorine-containing compound. In the above structural formula (A), 'X1' represents an ether group, an ester group, a decylamino group, an extended aryl group, or a divalent heterocyclic residue. -28- 200903161 The exoaryl group represented by X1 is preferably a aryl group having a total carbon number of 6 to 20, and examples thereof include a phenyl group, a naphthyl group, a fluorenyl group, and a phenyl group. Etc. may also be a hydrazine-substituent, a hydrazine-substituent, and/or an m-substituent. Among them, it is more preferably a aryl group having a carbon number of 6 to 12, particularly preferably a phenyl group and a phenyl group. The heterocyclic residue represented by X1 is, for example, preferably a divalent heterocyclic residue derived from a 5-membered or 6-membered heterocyclic ring containing a nitrogen atom or an oxygen atom as a constituent of the ring. As a specific example, a pyridine ring, a pyrimidine ring, a pyridinium ring, a thiazole ring, a benzothiene ring, an anthracene ring, a benzofluorene ring, a heterofluorene ring, a hydrazine ring, an imidazole ring, a quinoline ring A thiadiazole ring or the like is suitable, and a divalent heterocyclic residue derived from a pyridine ring or a thiadiazole ring is more preferable. In the above, "X1" is preferably a linking group having the following structure or at least one linking group having the following structure.

Here, 'R represents a hydrogen atom, a group having a total carbon number of 1 to 12, or an aryl group having a total carbon number of 6 to 20. Examples of the fluorenyl group having a total carbon number of 1 to 1 2 represented by RX include an unsubstituted alkyl group such as a methyl 'ethyl group, a propyl 'butyl group, a hexyl group, an octyl group, and a dodecyl group, and the like. A substituted alkyl group having a substituent of an ether group, a thioether group, an ester group, a decylamino group, an amine group, a carbamate group, a thiol group or the like. Among them, it is preferable that the base group of the total carbon number of 1 to 8 is more preferably a methyl group, a butyl group or an octyl group. -29-200903161 Examples of the aryl group having a total carbon number of 6 to 20 represented by Rx include a phenyl group, a naphthyl group, a methylphenyl group, a methoxyphenyl group, and a nonylphenyl group. Among them, an aryl group having a total carbon number of 6 to 15 is preferable, and a phenyl group or a nonylphenyl group is more preferable. As RX, a methyl group, a butyl group, an octyl group, a phenyl group or a nonylphenyl group is preferred from the viewpoint of water-repellent/oil-repellent properties. In the above structural formula (A), L 1 is preferably a linking group having the following structure or at least one linking group having the following structure.

0H

RY represents a hydrogen atom or a methyl group. η represents an integer of 2 to 20, preferably an integer of 4 to 12. The ruthenium is preferably a single bond, a linking group having the following structure, or at least one linking group having the following structure C ^ . -30- 200903161

η represents an integer of 2 to 20, preferably an integer of 4 to 12. R3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom. In the above structural formula (Α), Rf represents a fluorine-containing group. The Rf in the present invention is preferably a fluorine-based group having a total carbon number of 2 to 8, more preferably a fluorine-based group having a total carbon number of 4 to 7. The aforementioned Rf may be a straight chain or a bond. Rf is preferably a fluorine-containing group having the following structure or a fluorine-containing group having a group having the following structure.

Ten CmF2# j ^CmF2mH

-31-200903161 m represents an integer of 1 to 20', preferably an integer of 4 to 12', more preferably an integer of 4 to 7.

(Rx is a methyl group, a butyl group, or an octyl group "a linking group of the above-described structure or a linking group having at least one of the above structures (R3 is a hydrogen atom)", and Rf is a fluorine-containing group having the above structure or having the aforementioned structure In the above "a compound having a repeating unit having a fluorine atom in a side chain and having a main chain structure having an acrylic linking chain", it is preferred to contain a repeating unit having a fluorine atom in a side chain and The fluorine-containing compound of the repeating unit represented by the above formula (1). Further, the repeating unit having a fluorine atom in the side chain is as described above, and the preferred embodiment is also the same.

General formula (1)

L1—Y—CH—X R2 In the above formula (1), R1 represents a hydrogen atom or an alkyl group having a carbon number of 丨5, and R2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 6 to 10. An aryl group or an alkano group having a carbon number of 2 to 5. -32-200903161 Examples of the base of the carbon number of 1 to 5 represented by the above R1 include a methyl group, an ethyl group, a propyl group and the like. R2 preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferred examples thereof are a hydrogen atom, a methyl group, a phenyl group, a propyl group and an ethyl fluorenyl group. R1 and R2 each independently preferably represent a hydrogen atom or a methyl group. L1 represents a single bond or a divalent organic linking chain. The divalent organic linking chain represented by L1 is preferably a single organic linking group selected from the group consisting of an alkyl group, an aryl group ester bond, an ether bond, a guanamine bond, and a divalent heterocyclic residue. Or an organic linking group composed of such combinations. In the present invention, from the viewpoint of the polymerizability of the repeating unit, the solubility of the polymer, or the cost, a divalent organic linking group containing an ester bond and/or a guanamine bond is preferred. Further, L1 is preferably a single bond, an extended aryl group or a divalent heterocyclic residue from the viewpoint of polymerizability of a repeating unit, heat resistance of a polymer, or cost. The alkylene group as the divalent organic linking group represented by L 1 is preferably an alkylene group having a total carbon number of 1 to 1 Å, more preferably an alkylene group having a total carbon number of 1 to 6. Specific examples thereof include a methylene group, an ethyl group, a butyl group, a heptyl group, a hexyl group, and a twelfth group. The extended aryl group of the divalent organic linking group represented by L1 is preferably an extended aryl group having a total carbon number of 6 to 15, more preferably an extended aryl group having a total carbon number of 6 to 10. Specific examples thereof include a phenylene group, an anthranyl group, a fluorenyl group, a phenylene group, a dialkyl phenyl group, etc., which may also be oxime-substituted, p-substituted, and/or m- Substitute. The ester group of the divalent organic linking group represented by L1 is preferably a carboxylate group, a sulfonate group or a phosphate group, and more preferably a carboxylate group. The guanamine group as the organic linking group represented by L 1 is preferably a carboxylic acid decylamine-33-200903161 group, a sulfonium sulfonate group, a guanidinium phosphate group or the like, and more preferably a carboxylic acid guanamine group. The ether group as the organic linking group represented by L1 is preferably an oxygen ether group or a thioether group, and more preferably an oxygen ether group. The divalent heterocyclic residue of the divalent organic linking group represented by L1 is preferably a 2-membered heterocyclic ring derived from a 5-membered ring or a 6-membered ring containing a nitrogen atom or an oxygen atom as a ring member. More preferably, the residue is a pyridine ring, a pyrimidine ring, a pyridinium ring, a thiazole ring, a benzothiazole ring, an indazole ring, a benzoxazole ring, an isoxazole ring, a pyrazole ring, an imidazole ring, or a quinoline ring. The divalent heterocyclic residue derived from a thiadiazole ring or the like is particularly preferably a divalent heterocyclic residue derived from a pyridine ring or a thiadiazole ring. In the above formula (1), X represents a chlorine atom, a bromine atom, or an iodine atom. In particular, a chlorine atom or a bromine atom is preferred from the viewpoint of stability of the liquid crystal holding voltage, suppression of discoloration, and availability in forming a color filter or a liquid crystal display element, and more preferably a chlorine atom. γ represents an extended aryl group, a divalent heterocyclic residue, a carbonyl group, or an oxycarbonyl group. The aryl group represented by Y is preferably an extended aryl group having a total carbon number of 6 to 15 and more preferably an extended aryl group having a total carbon number of 6 to 10. Specific examples thereof include a phenylene group, a naphthyl group, a fluorenyl group, a phenylene group, a dialkyl phenyl group, etc., which may also be a ruthenium-substituent, a p-substituent, and/or m- Substitute. As the divalent heterocyclic residue represented by Y, for example, a divalent heterocyclic residue from a 5-membered ring or a 6-membered ring containing a nitrogen atom or an oxygen atom as a ring member is preferable. From a pyridine ring, a pyrimidine ring, a pyr trap ring, a thiophene ring, a benzothiazole ring, an oxazole ring, a benzoxazole ring, an isoxazole ring, a pyrazole ring, a oxime ring, a porphyrin ring or a thiadiazole The cyclic divalent heterocyclic residue 'better'-34-200903161 is a divalent heterocyclic residue derived from a pyridine ring or a thiodiazepine ring. Among the above, γ is preferably a phenyl group, a naphthyl group, or a carbonyl group. The commercial product of the compound which can form the repeating unit represented by the above-mentioned general formula (1), the SEIMI CHEMICAL Co., Ltd. product: CMS-P series (trade name), etc. are mentioned. The following concrete examples of the repeating unit represented by the general formula (1) show repeating units (h-Ι) to (h_37), but the present invention is not limited thereto. Further, in the following specific examples, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. -35- 200903161

(h-4) (h-3)

(h-6)

(h-8)

(h-11)

O-36- 200903161

L (h-12) (h-14) (h-15) (h-16) (h-17) (h-18) (h-19) (h-20)

-37- 200903161 (h-21) R1

0

O (h-22)

O

(h-25) (h-24)

ο

ϊ"1 200903161 (h-26) (h-27)

(h-32) H (h-33)

H is a repeating unit represented by the above formula (1) in the invention, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, a methyl group or a phenyl group, an X-based chlorine atom or a bromine-39-200903161 atom, Y Is a aryl group or a carbonyl group having 6 to 10 carbon atoms; the L1 series single bond, an extended aryl group, a divalent heterocyclic residue or a divalent organic linking group containing an ester bond and/or a guanamine bond is preferably an R1 hydrogen group. An atom, an R 2 -based hydrogen atom, an X-based chlorine atom, a γ-based carbonyl group, and an L 1 -based ester bond. Among them, a fluorine-containing compound having a repeating unit having a fluorine atom in a side chain and a repeating unit represented by a formula (2) in τ is preferable. Further, the repeating unit having a fluorine atom in the side chain is as described above, and the preferred embodiment is also the same.

In the above formula (2), R1 represents a hydrogen atom or a group of carbon number 1-5, and R2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a aryl group having 6 to 1 carbon atoms. A group or an alkano group having 2 to 5 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom 'Υ represents an extended aryl group, a divalent heterocyclic residue, a carbonyl group, or an oxycarbonyl group. R1, R2, X, and Y are the same as Ri, r2, χ, and γ in the above formula (1), and preferred embodiments are also the same. In the formula (2), 'Z1' represents an ester group or a guanamine group. The ester group is preferably a carboxylate group, a sulfonate group, a phosphate group or the like, more preferably a carboxylate group. The guanamine group is preferably a ruthenium carboxylate group, a sulfonium sulfonate group, a phosphonium hydride group - 40 - 200903161 amine group, etc., more preferably a ruthenium carboxylate group. As Z1, a carboxylate group or a carboxylic acid amine group is preferred. Further, L2 represents a single bond or a divalent organic linking chain. The divalent organic linking chain represented by L2 is preferably an organic organic linking group selected from the group consisting of an alkylene group, an extended aryl group, and a divalent heterocyclic residue, or an organic combination thereof. Linkage base. The alkylene, aryl, and divalent heterocyclic residues herein are synonymous with the alkyl, aryl, and divalent heterocyclic residues of L1 in the above formula (1), preferably The same is true. As L2', it is preferably a methylene group or an ethyl group. Further, it is more preferably a fluorine-containing compound containing a repeating unit having a fluorine atom in a side chain and a repeating unit which is not in the following formula (3). Further, the repeating unit having a fluorine atom in the side chain is as described above, and the preferred embodiment is also the same. R1 Ί

General formula (3)

Z2—Y—CH—X

In the above formula (3), 'R1 represents a hydrogen atom or an alkyl group having 1 to US carbon atoms, and R2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 1 carbon atoms, or a carbon number of 2 An alkyl group of ～5, X represents a chlorine atom, a bromine atom or a ruthenium atom, and Y represents an extended aryl group, a divalent heterocyclic residue, a carbonyl group or an oxycarbonyl group. Rl, -41- 200903161 R, X, and Y are synonymous with Ri, r2, X, and γ in the above formula (1), and preferred embodiments are also the same. In the formula (3), 'Ζ2' represents a single bond, an extended aryl group or a heterocyclic residue. The aryl group represented by Ζ2 is preferably an extended aryl group having a total carbon number of 6 to 丨5, more preferably an extended aryl group having a total carbon number of 6 to 10. Specific examples thereof include a phenylene group, an anthranyl group, a fluorenyl group, a phenylene group, a dialkyl phenyl group, etc., which may also be a ruthenium-substituent, a P-substituent, and/or m- Substitute. The heterocyclic residue represented by Z2 is preferably, for example, a divalent heterocyclic residue from a 5-membered ring or a 6-membered ring containing a nitrogen atom or an oxygen atom as a ring member, and more preferably a pyridine. Ring, pyrimidine ring, pyridinium ring, thiazole ring, benzothiazepine ring, anthracene ring, benzo Bf π ring, isoindole ring, fluorene d ring, im n ring, quinoline ring, thiophene The divalent heterocyclic residue derived from the oxadiazole ring or the like is particularly preferably a divalent heterocyclic residue derived from a pyridine ring or a thiadiazole ring. As Z2, it is preferred that the single bond is a phenyl group or a pyridine ring residue. In the above, the fluorine-containing compound of the present invention is particularly preferably a repeating unit having a fluorine atom in a side chain from the viewpoint of water-repellent and oil-repellent properties; and a repeating unit represented by the above formula (3) The fluorine-containing compound, in the above formula (3), R1 is a hydrogen atom, R2 is a hydrogen atom, X is a chlorine atom, a Y-based single bond, and a Z2-based oxycarbonyl group. Further, the fluorine-containing compound in the present invention may contain a repeating unit of a structure other than those exemplified herein, as long as the heat resistance is not impaired as needed. In general, a fluorine-containing compound having a repeating unit having a small molecular weight is often unfavorable in heat resistance, and therefore, a fluorine-containing compound having a repeating unit having a large molecular weight is used in order not to impair heat resistance. The repeating unit having a large molecular weight of -42 to 200903161 may, for example, be a repeating unit having a polyether structure in a side chain. Examples of the repeating unit having a polyether structure in the side chain include polyethylene oxide, polypropylene oxide, polytetrahydrofuran, and the like. These may be plurally combined, and the following structural formula (B) is more preferable. .

- Μ1" R4 In the above structural formula (B), R2 represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, a methyl group or a hydroxymethyl group. In the above structural formula (B), η is preferably from 6 to 40, more preferably from 9 to 30, particularly preferably from 12 to 24. In the above structural formula (Β), L2 is preferably a single bond or a divalent linking group. The (/divalent linking group) is more preferably the following structural formula.

L2 is preferably a single bond. In the above structural formula (B), Μ represents a repeating unit of polyethylene oxide, a repeating unit of polypropylene oxide, or a repeating unit of polytetrahydrofuran. Further, as the hydrazine, a group having the following structure is more preferable. -43- 200903161

R5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 1 represents an integer of 2 to 20, preferably an integer of 4 to 12. The oxime is preferably an ethylene oxide chain represented by the above (a), and r5 is preferably a hydrogen atom. In the above structural formula (B), R4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group of 6 to 15, and the alkyl group or the aryl group may have a substituent. The alkyl group of R4 is preferably a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group or an octadecyl group, more preferably a methyl group or an octyl group. The aryl group of R4 is preferably a phenyl group, a methylphenyl group, a nonylphenyl group or a methoxyphenyl group, and more preferably a phenyl group or a nonylphenyl group. R4 is preferably an alkyl group or an aryl group. These are referred to as capped polyether structures and are best constructed. R4 is most preferably methyl or phenyl. Commercial products of the vinyl compound having the polyether structure include Japanese fats and oils: Blenmer PME200, PME 550, PME1000, 50POEP-800P, ALE800, PE1300, ANE1300, PSE-1300, PMEP -1200B041MA, PE3 5 0, PP 800, Xinzhongcun Chemical Co., Ltd.: NK Ester AM130G, M230G, OC-18E, A-SAL-9E, A-CMP-5E, Kyoeisha Co., Ltd.: Light Ester 041MA, etc. (all of the above). Repeating unit having an acidic group -44-200903161 The fluorine-containing compound in the present invention preferably has the above repeating unit having a fluorine atom in a side chain, and a repeating unit represented by the above formula (1), and having an acidity The repeating unit of the base. The above repeating unit having an acidic group preferably has an acidic group in the side chain. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, a phosphinic acid group, and a phosphoric acid group. The acidic group in the present invention is preferably a carboxyl group. The monomer ' which can form a repeating unit having a carboxyl group in a side chain is not particularly limited and can be appropriately selected from well-known monomers. Examples of well-known monomers include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, and α. - an addition reaction of a cyanocinnamic acid, an acrylic acid dimer, a hydroxyl group-containing monomer with a cyclic acid anhydride, ω-carboxy-polycaprolactone mono(meth)acrylate, or the like. These may be used by a suitable manufacturer or a commercial product. The hydroxyl group-containing monomer used for the addition reaction of the hydroxyl group-containing monomer and the cyclic acid anhydride may, for example, be 2-hydroxyethyl (meth)acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic anhydride. As the aforementioned commercial products, the East Asian Synthetic Chemical Industry Co., Ltd. can be cited: Aronix Μ- 5 3 00, Aronix Μ-5 400, Aronix Μ- 5 5 00, Aronix M- 5 600, Xinzhongcun Chemical Industry Co., Ltd. System: NK Ester CB-1, NK Ester CBX-1, Kyoeisha Oil Chemical Industry Co., Ltd.: HOA-MP, HOA-MS, Osaka Organic Chemical Industry Co., Ltd.: Biscoat #2100, etc. Product name). Among them, (meth)acrylic acid or the like is preferred from the viewpoint of excellent imageability and low cost -45 to 200903161. The fluorine-containing compound of the present invention may further have a repeating unit other than the repeating unit having the acidic group, in addition to the above-mentioned repeating unit having a fluorine atom and the repeating unit represented by the above formula (1). The monomer capable of forming another repeating unit may be a copolymer of a repeating unit having a fluorine atom and a repeating unit represented by the above formula (1), and examples thereof include a (meth) acrylate. Classes, styrenes, vinyl alkanoates, and the like. As the copolymerizable (meth) acrylate, a methacrylic acid alkyl ester having 1 to 50 carbon atoms which may have a substituent, and a aryl group having 6 to 30 carbon atoms which may have a substituent are preferable. A acrylate, a polyoxyalkylene (methyl) having a carbon number of 2 to 50. Further, an alkyl (meth) acrylate having a carbon number of 1 to 40 and a polyalkylene group having a carbon number of 50 to 50 are more preferably, for example, methyl (meth)acrylate or ethyl (meth)acrylate. , (meth) propyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, caprolactone modification (A Acrylate, polyethylene oxide (meth) oxime acrylate, polypropylene oxide (meth) acrylate, and the like. The above-mentioned copolymerizable styrene is preferably a phenyl group having a vinyl group of 6 to 20 carbon atoms, a naphthyl group having a vinyl group of 1 to 20 carbon atoms, and a vinyl group having a carbon number of 14 to 20 The thiol substituent may also have a substituent other than a vinyl group. Further, more preferably, the vinyl group is substituted with a phenyl group having a carbon number of 6 to 10, a naphthyl group having a vinyl group of 15 to 15 or a fluorenyl group having a carbon number of 14 to 18 is preferred. It is styrene, butyl styrene, methoxy styrene, α-methyl styrene 'vinyl naphthalene, vinyl - 46- 200903161 蒽. The above-mentioned copolymerizable vinyl alkanoate is preferably an alkyl vinyl ester having 4 to 20 carbon atoms or an aryl vinyl ester having 9 to 20 carbon atoms. Further, an alkyl vinyl ester having 4 to 10 carbon atoms or an aryl vinyl ester having 9 to 15 carbon atoms is preferable, and examples thereof include vinyl acetate, vinyl butyrate, vinyl dodecanoate, and vinyl benzoate. The content of the fluorine-containing compound in the photosensitive resin composition is preferably from 1 to 30% by mass, particularly preferably from 0.05 to 20% by mass, more preferably from 0.1 to 30% by mass, based on the total solid content of the resin composition. ~10% by mass. When the content of the fluorine-containing compound is within the above range, more water-repellent and ink-repellent properties can be obtained, and adhesion to a region where the composition does not exist can be suppressed, and when the film is formed on the substrate, the substrate adhesion can be improved. For example, when a coloring agent containing a black pigment or the like is formed to form a black matrix or the like, the ink is applied to the liquid droplets to form a colored region, thereby suppressing the spread of the ink on the paint wall. Prevents color mixing, and at the same time, it can produce a wall with high substrate density and high color density. In the fluorine-containing compound of the present invention, it is preferred that the repeating unit having a fluorine atom in a side chain is the above-mentioned repeating unit (a·1), (a·2), (a_6), (a_9), (a- 10) or (a-15), the repeating unit represented by the above formula (1) is the above repeating units (h-1), (h-5), (h-10), (h-11), (h) -15) or (h-21), a repeating unit having an acidic group is acrylic acid. Further, in the fluorine-containing compound of the present invention, 'preferably, the content of the repeating unit having a fluorine atom in the side chain' is 30 to 7 % by mass based on the total weight of the fluorine-containing compound, and the above formula (1) The content of the repeating unit shown is '1 to 30% by mass to 47 to 200903161 for the total weight of the fluorine-containing compound, and the content of the repeating unit having an acidic group, for the total of the fluorine-containing compound In terms of weight, it is 〇30% by mass. Specific examples of the fluorine-containing compound of the present invention are shown below. However, the invention is not limited by these. Further, the composition ratio of each component can be selected within the range of the above preferred composition ratio.

200903161

Br

C4F g Ο

Ο^ΌΗ

. Eight OH O into CH3

Enter ΟΗ 〇"^. 181~137

(C2H40)n-CH3 -49- 200903161

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O^X) (C2H40)n-CH3 4) Adhesive -51- 200903161 The photosensitive resin composition of the present invention may be formed by using at least one type of binder in addition to the above components. As the binder, a polymer having a polar group such as a carboxylic acid group or a carboxylate group in a side chain is preferred. As an example, JP-A-59-44 6 1 5, JP-A-54- 3 4 3 2 7 , JP-A-58-127, and JP-A-54- A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, and a maleic acid copolymer described in JP-A-59-53848, JP-A-59-53836, and JP-A-59-71048 a partially esterified maleic acid copolymer or the like. Further, a cellulose derivative having a carboxylic acid group in a side chain may also be mentioned. Further, it is also preferred to use a cyclic anhydride in which a polymer having a hydroxyl group is added. Moreover, as a particularly preferable example, a copolymer of benzyl (meth)acrylate and (meth)acrylic acid or a benzyl (meth)acrylate described in the specification of U.S. Patent No. 4 1 3 93 9 1 may be mentioned. A multicomponent copolymer with (meth)acrylic acid and other monomers. These polar group-containing binder polymers may be used singly or as a composition of a usual film-forming polymer. The content of the binder in the resin composition is generally 20 to 50% by mass, preferably 25 to 45 mass% / 〇, based on the total solid content of the resin composition. 5) Color material The photosensitive resin composition of the present invention can be formed using at least one color material. As the color material, a well-known coloring agent (dye, pigment, etc.) -52 to 200903161 can be used, and specifically, it can be suitably used in the publication [0038] to [0054] of JP-A-2005-1776. The pigments and dyes of the above-mentioned pigments, and the coloring agents described in JP-A-2005-17521 [0080] to [00 8 8] Wait. In the photosensitive resin composition of the present invention, an organic pigment, an inorganic pigment, a dye or the like can be suitably used. In particular, when forming a light-blocking paint wall using the photosensitive resin composition of the present invention, a metal oxide powder such as a carbon material (such as carbon black), titanium oxide or triiron tetroxide, or a metal can be used. A light-shielding material such as a sulfide powder or a metal powder, or a mixture of pigments such as red, blue, and green. Among them, carbon black is preferred. When a pigment is used, it is preferably uniformly dispersed in the photosensitive resin composition. The content of the color material in the resin composition is preferably from 30 to 70% by mass, particularly preferably from 40 to 60%, from the viewpoint of shortening the development time, with respect to the total solid content of the resin composition. The mass% is more preferably 5 0 to 5 5 mass%. The pigment is preferably used as a dispersion. The dispersion can be prepared by adding and dispersing a composition obtained by preliminarily mixing a pigment and a pigment dispersant in an organic solvent (or a vehicle) to be described later. The vehicle liquid refers to a portion of the medium which disperses the pigment when the coating is in a liquid state, and includes a portion (adhesive) which is bonded to the liquid pigment to solidify the coating film, and a component (organic solvent) for dissolving and diluting the pigment. The disperser used in the case of dispersing the above-mentioned pigments is not particularly limited, and examples thereof include those described in the "Pigment of the Pigment" (asakura, the first edition, the Asakura Bookstore, 2000, p. 438). Kneader, roll mill, vertical ball mill, super honing machine, dissolving -53-200903161, homomixer, sand mill and other conventional dispersers. Further, the particle diameter of the pulverized material (pigment) may be micro-pulverized by mechanical grinding by the mechanical grinding described on page 310 of the document, and the number average particle diameter is preferably 0 from the viewpoint of dispersion stability. . 001~ο. Ίμιη, better 0_01~0. 08μιη. In addition, the "particle size" refers to the diameter when the electron micrograph of the microparticles is taken as the circle of the same area, and the "number average particle diameter" refers to the particle diameter of one particle, and the average of the average is obtained. value. 6) Other In the photosensitive resin composition, the following solvents, surfactants, thermal polymerization inhibitors, ultraviolet absorbers, and the like may be added in addition to the components of the above 1) to 5). Further, other components such as "adhesion aid" described in JP-A No. 1 1 - 1 3 3 600 or other additives may be added. Solvent In the photosensitive resin composition of the present invention, a solvent can be further used in addition to the above components. Examples of the solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, and ethyl lactate. Methyl lactate, caprolactam, and the like. In the photosensitive resin composition of the present invention, it is preferred to appropriately contain the interface activity in the photosensitive resin composition from the viewpoint of controlling the uniform film thickness and effectively preventing coating unevenness. Agent. The surfactant disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. -54-200903161 Thermal polymerization inhibitor The photosensitive resin composition of the present invention preferably contains a thermal polymerization inhibitor 〇 as an example of a thermal polymerization inhibitor, and examples thereof include hydrogen styrene, hydroquinone monomethyl ether, and p-methoxy group. Phenol, di-tert-butyl-p-cresol 'pyrophenol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol)' 2, 2'-methylenebis(4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, morphine trap, and the like. Ultraviolet absorber In the photosensitive resin composition of the present invention, an ultraviolet absorber may be contained as needed. Examples of the ultraviolet ray absorbing agent include a compound described in JP-A No. 5-72724, a salicylate type, a benzophenone type, a benzotriazole type, a cyanoacrylate type, and a nickel chelate type. Hindered amines and the like. Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5,-di-third-4'- may be mentioned. Hydroxybenzoate, 4-tert-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- n-Octyl benzophenone, 2-(2'-hydroxy-5,-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-- Phenyl)-5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenylacrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Butyl dithiocarbamate, bis(2,2,6,6-tetramethyl-4-pyridine)-sebacate, 4-tert-butylphenyl salicylate, salicylic acid Phenyl ester, 4-hydroxy-2,2,6,6-tetramethyl piperidine condensate, succinic acid-bis(2,2,6,6-tetramethyl-4-piperidinyl)-ester, 2 -[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 7-{[4-chloro--55- 200903161 6-(diethylamine Base)-5-trin-2-yl]amino}-3-phenylcoumarin. Photosensitive transfer material The photosensitive transfer material of the present invention is composed of a photosensitive resin layer formed by using at least the photosensitive resin composition of the present invention on the temporary support. Since the photosensitive transfer material is used, the paint wall can be formed easily and at low cost. Further, if necessary, a protective layer capable of blocking oxygen (hereinafter also referred to as "oxygen barrier layer") or another layer such as a thermoplastic resin layer may be provided between the temporary support and the photosensitive resin layer. When the oxygen barrier layer is used, the photosensitive resin layer is protected by the oxygen barrier layer to prevent the atmosphere, and thus automatically becomes an oxygen-poor atmosphere. Therefore, the exposure does not have to be carried out under an inert gas or under reduced pressure, and the current step can be utilized as it is, and the advantages of high sensitivity and high hardness can be obtained. As will be described later, a temporary support can also be used as the "protective layer capable of blocking oxygen". In this case, it is not necessary to provide an oxygen barrier layer, which contributes to the reduction in the number of steps. The details of the oxygen barrier layer will be described later. In the photosensitive transfer material, a thermoplastic resin layer may be provided between the temporary support and the oxygen barrier layer between the temporary support and the photosensitive resin layer or when the oxygen barrier layer is provided. The thermoplastic resin layer is a resin component which is alkali-soluble and contains at least a resin component having a substantial softening point of 80 ° C or less, and has a cushioning property. By providing such a thermoplastic resin layer, good adhesion to the permanent support can be obtained. Examples of the alkali-soluble thermoplastic resin having a softening point of 80 ° C or less include a saponified product of an ethylene and an acrylate copolymer, a saponified product of a styrene and a (meth) acrylate copolymer, a vinyl toluene and a (methyl group). a saponified product of a saponified product of an acrylate copolymer, a poly(meth)acrylate, a butyl (meth)acrylate, or a (meth)acrylate copolymer such as vinegar-56-200903161 vinyl acetate. In the thermoplastic resin layer, at least one of the above thermoplastic resins can be appropriately selected, and a "Plastic Performance Fact Sheet" can be used. (The Japan Plastics Industry Alliance, the All-Japan Plastic Forming Industry Association, edited by the Industrial Research Association, 1 9 6 8 years 1 〇 2 2 5) The softening point is about 80 ° C below the organic polymer in the soluble in aqueous solution. Further, in the case of an organic polymer material having a softening point of 80 ° C or higher, a substantial softening point is reduced to 80 by adding various plasticizers compatible with the polymer material to the organic polymer material. It can also be used below °C. Further, in the organic polymer material, for the purpose of adjusting the adhesion to the temporary support, various polymers or supercooled substances may be added in a range where the substantial softening point does not exceed 80 ° C. Adhesive modifier, surfactant, release agent, etc. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, and tolyl diphenyl phosphate. , biphenyl diphenyl phosphate and the like. The temporary support constituting the photosensitive transfer material can be appropriately selected from those composed of chemically and thermally stable flexible materials. Specifically, it is preferably a Teflon (registered trademark), a polyethylene terephthalate, a polycarbonate, a polyethylene, a polypropylene, or the like, a sheet or a laminate thereof. The thickness of the temporary support is suitably 5 to 300 μm, preferably 20 to 150 μm. If it is within this thickness range, it can be easily peeled off without causing the temporary support to be broken, and the exposure with good resolution can be performed even with the temporary support. Among the above specific examples, a 2-axis stretched polyethylene terephthalate-57-200903161 film is particularly preferred. It is preferable to provide a thin cover sheet on the photosensitive resin layer for protection against contamination or damage during storage. The cover sheet, although formed of the same or similar material as the temporary support, must be easily separable from the photosensitive resin layer. As the cover sheet material, for example, polyoxynized paper, polyolefin or polytetrazole is suitable. Further, the thickness of the cover sheet is generally 4 to 40 μm, preferably 5 to 30 μm, and particularly preferably 10 to 25 μm. Substrate In the present invention, as the substrate (permanent support), glass, ceramic, synthetic resin film or the like can be used. Particularly preferred is a glass or synthetic resin film which is transparent and has good dimensional stability. BACKGROUND OF THE INVENTION The method for forming a painting wall according to the present invention comprises at least the following steps: using (on at least one side of the substrate) the photosensitive resin composition of the present invention or the photosensitive conversion of the present invention a printing material, a photosensitive resin layer forming a photosensitive resin layer; an exposure for exposing the formed photosensitive resin layer; a development of developing the exposed photosensitive resin layer; and a photosensitive resin obtained by development The pattern image formed by the layer is subjected to heat treatment of heat treatment. The painting wall of the present invention is formed by the method for forming a painting wall according to the present invention. In the case of two or more pixel groups (for example, a pixel group of plural colors having different hue), the pixels are generally separated from each other. It is black (dark), but not limited to black. The coloring agent is preferably an organic substance (a dye or a carbon material such as a dye or a pigment) or an inorganic substance. Further, the substrate with the drawing wall of the present invention is formed by forming a wall on at least one side of the substrate by the method for forming the wall of the present invention, from the substrate to the substrate. A spacer wall formed by the method for forming a wall of the present invention is provided. Photosensitive resin layer forming step The photosensitive resin layer forming step 'for example, by using the photosensitive resin composition of the above-described resin composition of the present invention on at least the surface of the substrate' or by using the aforementioned The photosensitive transfer material of the invention forms a photosensitive resin layer. The method of forming the photosensitive resin layer using the photosensitive resin composition is not particularly limited. For example, it can be formed by applying a photosensitive resin composition onto a substrate by a well-known coating method such as slit coating. Further, it can be pre-baked after coating as needed. The method of forming a photosensitive resin layer using a photosensitive transfer material is not particularly limited. For example, it can be formed as follows. That is, on the temporary support body, a light-transmitting material in which an oxygen barrier layer, a photosensitive resin layer, and a cover sheet for protecting the photosensitive resin layer are provided in this order is prepared from the side of the temporary support. First, after the cover sheet is peeled off, the surface of the exposed photosensitive resin layer is bonded to a substrate which is a permanent support, and laminated by a laminator or the like by heating or pressurization (layered body). The laminator can be appropriately selected from conventional laminators, vacuum laminators, and the like, and an automatic cutting laminator can be used in order to further improve productivity. Then, the temporary support and the oxygen barrier layer are peeled off, and the temporary support is removed from the laminate to form a photosensitive resin layer and an oxygen barrier layer on the substrate. -59- 200903161 Exposure step and development step In the exposure step, the removal surface (the acid barrier layer) after removal of the temporary support of the laminate is disposed face to face with a desired mask (for example, a quartz exposure mask). When the laminated body and the photomask are vertically erected, the distance between the mask surface and the photosensitive resin layer is appropriately set (for example, 200 Å for exposure. For example, a proximity type exposure machine having an ultrahigh pressure mercury lamp is used for exposure. (For example, Hi-Tech Hi-Tech Engineering Co., Ltd.), etc., the exposure amount can be selected suitably (for example, 300 mJ/cm2). As a light source for exposure, a medium-pressure to ultra-high pressure mercury lamp, a xenon lamp, and a metal halide can be cited. From the point of view of improving the light sensitivity, that is, the degree of hardening, it is preferable to expose the photosensitive resin layer in an oxygen-poor atmosphere and then develop it. Here, the oxygen-poor atmosphere is Refers to the following under the inert gas, decompression, oxygen-protective protective layer (hereinafter also referred to as "oxygen barrier layer"). The above-mentioned inert gas means inertness exposed to N2, h2, co2, etc. Gas In the atmosphere of a rare gas such as He, Ne, or Ar, etc., the inert gas is preferably N2 in terms of safety, ease of availability, and cost. The above-mentioned reduced pressure means 500 hPa. In the following, it is preferably in a state of 10 〇〇hPa or less. As the protective layer capable of occluding oxygen, for example, it is described in each of the publications of Japanese Patent Publication No. Sho 4-6-2 1 2 1 or Japanese Patent Publication No. 56-40824 Polyvinyl ether/maleic anhydride polymer, water-soluble salt of carboxyalkyl cellulose, water-soluble cellulose-60-200903161 ether, water-soluble salt of brothel source powder, polyethyl alcohol, polyethyl b Pyridoxone, various polyacrylamides, various water-soluble polyamines, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, water-soluble salts of various starches and their analogues, benzene A copolymer of ethylene/maleic acid, a maleate resin, a combination of two or more of these, etc. Among them, 'preferably a combination of polyvinyl alcohol and polyvinylpyrrolidone. The saponification rate of polyvinyl alcohol is preferably 80% or more, and the content of polyvinylpyrrolidone is The solid content of the photosensitive photosensitive resin layer is preferably from 1 to 75% by mass, particularly preferably from 1 to 50% by mass, more preferably from 10 to 40% by mass. Further, in the oxygen barrier layer Various films can be used. For example, polyesters such as PET, polyamines such as Nile, and ethylene-vinyl acetate copolymers (EVA) can also be used. The stretching is preferably 5 to 300 μm in thickness, preferably 20 to 150 μm. In particular, when a photosensitive transfer material is used to form the paint wall, a temporary support can be suitably used as the oxygen barrier layer. When the temporary support is used as the oxygen barrier layer, the temporary support system remains (not peeled off), and the temporary support is disposed face to face with a desired mask (for example, a quartz exposure mask) to make the laminate When the body and the reticle are vertically erected, the distance between the exposure mask surface and the temporary support (for example, 200 μm) is appropriately set for exposure. The oxygen permeability coefficient of the oxygen barrier layer (the oxygen barrier layer) is preferably 2000 cm 3 /(m 2 , day. Below atm), more preferably ΙΟΟοιη3"!^. . Below "^", the best is 50cm3/(m2_day. Atm) below. -61- 200903161 When the oxygen permeability is within the above range, photohardening is favorably performed by oxygen barrier, and the desired shape is effectively formed on the wall. Next, a developing step is applied, and the exposed photosensitive resin layer is subjected to development processing using a predetermined developing solution. Then, as needed, a water washing process is performed to obtain a pattern image (a pattern of the wall). Further, it is preferable to spray pure water from the shower nozzle before the development to uniformly wet the surface of the photosensitive resin layer or the oxygen barrier layer. As a developing solution used for development processing, a thin aqueous solution of an alkaline substance is used, but an organic substance which is miscible with water may be added in a small amount. Solvent. Examples of the basic substance include alkali metal hydroxides (for example, sodium hydroxide or potassium hydroxide), alkali metal carbonates (for example, sodium carbonate and potassium carbonate), and alkali metal bicarbonates (for example, hydrogen carbonate). Sodium, potassium bicarbonate), alkali metal silicates (such as sodium citrate, potassium citrate), alkali metal bismuth citrates (such as sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, Monoethanolamine, morpholine, tetraammonium hydroxide (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0. 0 1 to 30% by mass, and the pH is preferably 8 1 4 〇 As the above-mentioned "organic solvent which is miscible with water", for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, and the like are mentioned. Acetyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ - Butyrolactone, dimethylformamide, dimethylacetamide, hexamethylsulfonamide, ethyl lactate, methyl lactate, caprolactam, hydrazine-methylpyrrolidone, and the like. The concentration of the organic solvent which is miscible with water is preferably 0. 1 to 30% by mass. Further, a conventional surfactant may be added, and the concentration of the surfactant is preferably 〇·〇 1 to 10% by mass. The developing solution can also be used as a bath or as a spray. In the case where the uncured portion of the photosensitive resin layer is removed, a method of combining a rotary brush or a wet sponge to brush or the like in the developing liquid can be employed. The liquid temperature of the developing solution is preferably from the vicinity of the usual room temperature (20 ° C) to 40 ° C. The development time depends on the composition of the photosensitive resin layer, the alkalinity or temperature of the developing solution, the type and concentration of the organic solvent, and the like, but it is usually about 10 seconds to 2 minutes. When the development time is within the above range, the development of the non-hardened portion (non-exposed portion in the negative type) is good, and the cured portion (the exposed portion in the case of the negative type) is not etched, and a good shape is obtained. The point of painting the wall is effective. Further, after the development process, a water washing step may also be added. In the heat treatment step, by the heat treatment (also referred to as baking treatment), the pattern image (the pattern wall pattern) formed by the photosensitive resin layer obtained in the above-described development step can provide a better water repellency and ink repellency. Painting the wall. In the heat treatment, the pattern image (from the wall pattern) formed by exposure and development is heated and hardened, and the fluorine functional groups are arranged on the surface by heat, whereby the water repellency and ink repellency of the fluorine-containing compound can be further exhibited. As a method of heat treatment, various conventional methods can be used. That is, for example, a method in which a plurality of substrates are housed in a cassette, a method of processing by a convection oven, a method of processing each sheet by heating, and an infrared heater is used. Further, the baking temperature (heating temperature) is usually 150 to 280 ° C, preferably -63 to 200903161 180 to 25 ° C. The heating time can be appropriately selected in accordance with the above-mentioned baking temperature. For example, when the baking temperature is 240 ° C, it is preferably 10 to 12 minutes, more preferably 30 to 90 minutes. Further, in the heat treatment step of the method of forming the wall, the film is formed by the exposure and development steps, and the film is prevented from being thinned by unevenness, thereby preventing the UV absorber from being contained in the photosensitive resin layer. From the viewpoint of precipitation of components, etc., post-exposure can also be performed before the heat treatment. When the post-exposure is applied before the heat treatment, the defects of the bulging of the minute foreign matter can be effectively prevented during the lamination. Here, the aforementioned post exposure is briefly explained. The light source used for the post-exposure may be appropriately selected as long as it can irradiate light having a wavelength range (for example, 3 65 nm '405 nm) which can cure the photosensitive resin layer. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or the like can be given. As the exposure amount, it is sufficient to supplement the exposure amount of the exposure, and is usually 50 to 5000 mJ/cm 2 ', preferably 200 to 2000 mJ/cm 2 , more preferably 500 to 1 000 mJ/cm 2 ° by the painting wall of the present invention. The paint wall which can be produced by the formation method preferably has a high optical density at 555 nm. In particular, when a black matrix constituting a color filter as a partition wall is formed, the optical density is preferably 2. From the viewpoint of imparting a light-shielding property to display a more vivid and clear multicolor image. 5 or more, especially good 2. 5~10. 0, more preferably 2. 5~6. 0, especially good is 3 · 0 ~ 5 · 0. -64- 200903161 Further, the photosensitive resin layer is preferably hardened by a photoinitiating system. For the exposure wavelength (generally the ultraviolet region), the optical density is also important. That is, it is preferably 2. 0~10. 0, more preferably 2. 5~6. 0, especially good 3. 0~5_0. If it is within the above preferred range, the wall of the desired shape can be formed. In addition, the width and the height of the wall (ie, the spacing between the pixels and the pixels when the color filter is formed) are preferably 15 to 10 Å, and the height (ie, the substrate surface in the normal direction of the substrate). Preferably, the distance to the apex of the painting wall is 1. 0~5. 0μιη. The shape described in the paragraphs [0054] to [0055] of the paragraph of the drawing is also suitable for the present invention. Further, the substrate with the painting wall of the present invention contains a substrate and an ink-repellent, and has a water contact angle of 60 on the wall when measured by the method described in the wettability test method of the surface of the substrate glass. . The above-mentioned drawing wall has a droplet diameter of 2〇0111 or more immediately after the propylene glycol monomethyl ether acetate is not formed in the portion of the substrate on which the wall is formed, and the portion of the substrate is not formed. The way to form. Conventionally, a film is formed by using a composition containing an ink-repellent agent, and after heat treatment after exposure and development to produce a paint wall having a black matrix such as ink-repellent property, the ink-repellent component flows out during heat treatment. Outside the film system, the surface of the substrate exposed by the contamination is liable to lower the wettability to the liquid. However, in the substrate with the paint wall of the present invention, the pattern film formed by the ink-repellent agent is inked. And heat hardening, etc., even after heat treatment (for example, high temperature treatment at 150 ° C or higher), the exposed substrate surface (film non-formed surface) prevents the adhesion of the fluorine-containing component of -65-200903161, keeping the liquid moist For example, when a color filter is produced, a coloring liquid composition is given to a non-formed region of the image forming wall of the substrate of the black matrix or the like (a recess on the substrate separated from the wall). For example, when ink droplets are applied by an inkjet method to form a colored region (coloring pixels such as RGB), it is possible to prevent liquid from sticking, and it is possible to suppress occurrence of whitening in a colored region and image display. display The furnace can be significantly were light colored sheet does not smell image quality and a display device. In the past, the ink-repellent component adhered to the heat treatment is not easily removed even if it is subsequently washed and removed. However, if the adhesion itself associated with the heat treatment can be suppressed according to the present invention, a high-quality color filter and display can be easily obtained. Device. The painting wall of the present invention is a resin hardened wall (for example, black) having a water contact angle of 60° or more on the wall after the heat treatment, as measured by a method described in a well-known method for testing the wettability of a substrate glass surface. The matrix or the like can be formed by forming a film using a (photosensitive) resin composition containing an ink repellent in advance, and then forming a film by heat treatment (for example, 150 ° C or higher). The heat treatment is preferably carried out mainly for thermal curing and imparting ink repellency, and can be appropriately selected in the range of 150 °C to 250 °C. As described above, the property of repelling water and other solvents is called ink repellency. When the ink repellency is less than 60°, the ink repellency from the surface of the wall is insufficient, and the exposed portion of the substrate (the concave portion on the substrate surrounded by the black matrix) is not formed by the inkjet method. When a liquid (for example, a droplet of a colored liquid composition (for example, an ink of RGB or the like) for forming a colored pixel constituting a color furnace sheet is applied, it is impossible to prevent color mixing. -66- 200903161 From the point of view of preventing the spread of liquid on the wall of the painting and preventing color mixing, the ink repellency is preferably 70. the above. The exposed surface of the substrate which is away from the drawing wall is not formed, and from the viewpoint of obtaining the effect of the present invention, it is desirable that the liquid wettability to the liquid is high, and the substrate with the drawing wall of the present invention has The wettability of the droplet diameter immediately after dropping a drop of propylene glycol monomethyl ether acetate on the exposed surface of the substrate was 20 μm or more. If the droplet diameter is less than 20 μm, the degree of variation of the dropped liquid is large, for example, by giving a colored liquid composition (for example, ink droplets are given by an inkjet method) to form a colored region (coloring of RGB, etc.) In the case of a pixel, the substrate repels the ink "cannot suppress the occurrence of whitening in the colored region and display unevenness during image display. In the present invention, 'wetability refers to the degree of wetting expansion when a liquid is dropped onto a plane, for example, a concave portion surrounded by a wall of a substrate on which a substrate of a black matrix or the like is formed (ie, becomes a colored pixel). The substrate surface of the region), when inkjet is applied to the liquid composition of the colored liquid composition, that is, the ink composition, the degree of wetting of the ink droplets is enlarged. More specifically, one drop of the ink composition was dropped between the walls of the painting, and the diameter of the circle formed by the droplet was used as an index of the degree of wetness expansion. The droplet diameter refers to an optical photograph taken at an arbitrary magnification, and the diameter thereof is measured, and the actual size is calculated from the magnification. When the solvent is dropped, since the minute droplets evaporate rapidly, it is necessary to take a photograph quickly after dropping. Measurement of contact angle from the painted wall Printing of the painted wall (for example, black matrix) before and after the heat treatment (baking treatment) -67- 200903161 The change of the ink contact angle and the water contact angle is important. The method of measuring the contact angle here is based on the consortium. 方法 方法 JI JI JI JI 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 The method described in the "static drop method". More specifically, using a contact angle measuring device (contact angle meter CA-A (trade name) manufactured by Kyowa Interface Science Co., Ltd.), ink droplets and water droplets of a size of 20 scales are produced, and ink droplets and water droplets are dripped from the needle tip. The ink droplets and water droplets were formed in contact with the upper surface of the partition wall, and after standing for 10 seconds, the shape of the ink droplets and the water droplets were observed from the peephole of the contact angle meter to obtain a contact angle of 25 ° C. . Here, "after heat treatment" means that after heating at 250 ° C for 50 minutes, the latter is left to stand at room temperature for 1 hour. Here, the upper surface of the painting wall will be described with reference to Fig. 1 . The upper surface of the painting wall refers to the exposed surface (the upper surface 4 of Fig. 1) on the opposite side of the surface of the wall which is in contact with the substrate 6. Further, the side surface of the painting wall refers to a surface other than the upper surface of the drawing wall from the exposed surface of the drawing wall (the side surface 5 of Fig. 1). Further, the concave portion on the substrate refers to a concave portion (the concave portion 3 in Fig. 1) which is formed by the side surface of the drawing wall and the substrate surface on which the substrate is not formed, which is surrounded by the drawing wall. Contact angle 値 The photosensitive resin composition of the present invention is used to measure the water contact angle of the pattern image (for example, the image wall) formed by using the photosensitive resin composition by the above method, before applying heat treatment The water contact angle on the pattern of the pattern (for example, the pattern of the wall before the heat treatment) is taken as A° 'to be heated at 240 ° C for 50 minutes and left to cool for 1 hour (for example, from the painting -68- 200903161 wall) The water contact angle above is taken as B. Time' contact angle difference b°-A. Must be 20° or more. The aforementioned contact angle difference is B〇-A. More preferably 3 inches. Above, the best is 4〇. The above 〇 ‘from the point of view of the adhesion between the painting wall and the substrate, A. Preferably, it is 0 to 60 °, more preferably 〇 55. , especially good for 〇 ~ 5 〇. . Further, 'B' is preferably from 65 to 180 from the viewpoint of more effectively suppressing the color mixture in the production of the color filter. More preferably 80~180. , especially good for 90 ~ 180 〇. Color enamel sheet and method of manufacturing the same The method for producing a color filter of the present invention includes preparing a substrate with a drawing wall of the present invention or a method of manufacturing the substrate with the detachable wall of the present invention a substrate having a wall away from the wall and a concave portion (a region for forming a colored region) defined by a wall of the substrate on which the wall is attached, and a colored liquid composition (preferably two or more colors) is formed to form (preferably two or more colors) a plurality of colored regions (for example, red, green, blue, white, purple, etc.). The method for producing a color filter of the present invention is based on a substrate having a drawing wall (for example, a black matrix) using the fluorine-containing compound of the present invention, and a colored liquid composition is applied to form a colored region, so that the printing can be avoided. The color mixture accompanying the spread of the ink on the wall of the painting, the concave portion (the region for forming the colored region) on the substrate divided by the drawing wall, prevents the non-sticking of the coloring liquid composition, and also suppresses the drawing. If the wall is peeled off or defects occur, it is possible to produce a color filter of high-69-200903161 grade with suppressed image failure such as color mixing, color unevenness, and whitening. Since the color filter of the present invention also has a painting wall using the fluorine-containing compound of the present invention, it suppresses image failure such as whitening, and has clear and clear display characteristics. The coloring liquid composition is not particularly limited, and a well-known method such as a coating method such as an inkjet method, a slit coating method or a strip-shaped orifice method can be suitably employed. The strip-type orifice coating method is a method of forming a strip-shaped pixel by using a mouth plate which has a hole for discharging a fine droplet to apply a droplet to a substrate. In the present invention, it is particularly preferable to use an inkjet method. The inkjet method as the inkjet method can employ a method in which a charged ink is continuously ejected and controlled by an electric field, and a method of intermittently ejecting ink using a piezoelectric element is used to heat the ink and foam the same. Various methods such as a method of intermittently spraying. The ink can be either oily or water-based. Further, the coloring agent containing the ink can be used together with the dye 'pigment, and it is more preferable to use a pigment from the viewpoint of durability. Further, it is also possible to use a colored ink for coating in the production of a conventional color filter (for example, the coloring described in paragraphs [0034] to [0063] of JP-A-2005-1883 The resin composition is a conventional ink such as the colored ink described in Japanese Laid-Open Patent Publication No. 2004-325736, and the ink described in JP-A-2002-372613. In the ink used in the ink jet method, in consideration of the step after the application, it is possible to harden by heating or to add an energy ray-hardenable component such as ultraviolet rays. -70- 200903161 As a component for heat curing, various thermosetting resins are widely used, and as an energy ray-hardenable component, for example, a photoreaction is added to an acrylate derivative or a methyl acrylate derivative. Agent. In particular, it is considered that the heat resistance is more preferably a plural propylene fluorenyl group or a methacryl fluorenyl group in the molecule. These acrylate derivatives and methacrylate derivatives are preferably water-soluble, and emulsification or the like can be used even if it is poorly soluble in water. In this case, a photosensitive composition containing a coloring agent such as a pigment of the photosensitive composition can be suitably used. In the color filter of the present invention, it is preferable that a color filter of a colored liquid composition is ejected onto a substrate by an inkjet method to form a color filter having a colored region (for example, a pixel), preferably having a color filter. A color filter of at least three color-colored pixels of at least RGB 3-color ink discharged by the inkjet method. The pattern shape of the color filter is not particularly limited, and is generally a black matrix shape or a line shape, and may be a lattice shape or a Δ (d e 11 a) array. In the color filter to be produced, in order to improve the resistance, there is a case where the overcoat layer is provided in an all-round manner. The overcoat layer protects the colored areas (such as RGB pixels) while flattening the surface. However, from the viewpoint of increasing the number of steps, it is preferable not to provide an overcoat layer. The resin (the c-coating agent) for forming the overcoat layer may, for example, be an acrylic resin composition, an epoxy resin composition, a polyimine resin composition or the like. In particular, the resin component of the curable composition constituting the color filter is excellent in transparency in the visible light range. Generally, the acrylic component is contained as a main component, and the acrylic resin composition is preferable from the viewpoint of excellent adhesion. As an example of the overcoat layer, those described in paragraphs - 71-200903161 [0018] to [0028] of JP-A-2002-2009 The product is "OptmerSS6699G" (trade name) manufactured by JSR. Further, a transparent electrode 'alignment film or the like may be provided on a colored region (for example, RGB pixels) as needed. Specific examples of the transparent electrode include an ITO film. Moreover, as a specific example of an alignment film, a polyimine is mentioned. Display device The display device of the present invention is constructed by providing the color filter of the present invention described above. The color filter obtained by the method for producing a color filter of the present invention can be used as a liquid crystal display element, an electrophoretic moving display element, an electrochromic display element, or a display element combined with PLZT (lead lanthanum zirconium titanate) or the like. . It can also be used in color TV cameras or other applications that use color filters. Examples of the display device include a display device such as a liquid crystal display device, a plasma display device, an organic electroluminescence (EL) display device, and a CRT (cathode ray tube) display device. The definition of the display device or the description of each display device is, for example, "Electronic display device (sasaki Sasaki, "Investigation" Industrial Research Association issued in 1990)", "Display device (Ibuki Shunzhang, Industrial Book (share)) It is described in the issue of "). A display device comprising the color filter of the present invention is preferably a liquid crystal display device. The liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (Edited by Uchida Natsuo, Co., Ltd., Ltd., issued in 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and for example, it can be applied to the liquid crystal display devices of the respective types described in the above-mentioned "second-generation liquid crystal display technology". Among them, it is particularly effective for a liquid crystal display device for a color τ F Τ mode. A liquid crystal display device of a color TFT (thin film transistor type) is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a horizontal electric field driving method such as IPS (in-plane switching) or a pixel division method such as MVA (multi-domain vertical alignment) is expanded. These methods are described, for example, on page 43 of "EL, PDP, LCD Display Technology, and the Latest Trends in the Market (Dongli Research Center Survey Research Division, 2001)". The liquid crystal display device is composed of a wide variety of members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film, in addition to the color filter. The color filter of the present invention can be applied to a liquid crystal display device composed of these conventional members. These components are described, for example, in the "94" liquid crystal display peripheral material. The market for chemicals (Island Kentaro, issued by CMC in 1994), and the status quo of the 2003 LCD-related market and future prospects (volume) (Former Liangji, (share) Fuji Chimera, 2003, etc.). The application is applicable to portable terminals such as televisions, personal computers, liquid crystal projectors, game machines, and mobile phones, digital cameras, and vehicle navigation systems, and is not particularly limited. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited by the following examples as long as it does not exceed its gist. Further, the molecular weight means the polystyrene equivalent weight -73 - 200903161 measured by gel permeation chromatography (GPC), and "%" and "parts" are masses unless otherwise specified. Benchmark. Synthesis Example The synthesis method of a compound (hereinafter also referred to as a halide monomer) which can form a repeating unit represented by the formula (1) is shown below. Synthesis of a fluorine-containing compound Synthesis of a halide monomer (1) In a 300-ml three-necked flask equipped with a dropping funnel, 50 g of ethyl methyl ketone [MEK, manufactured by Wako Pure Chemical Industries, Ltd.] and 26. 1 g of hydroxyethyl methacrylate [HEMA, manufactured by Tokyo Chemical Industry Co., Ltd.], and the internal temperature was cooled to 5 ° C in a water bath containing ice. Place 1 in it. 2 g of pyridine [P y, manufactured by Tokyo Home Economics Co., Ltd.], for stirring. Drop through the dropping funnel so that the internal temperature of the flask does not exceed 10 ° C. 6 g of chloroethyl chloroform [CAC, manufactured by Wako Pure Chemical Industries, Ltd.]. The reaction was followed by NMR, and it was confirmed that the disappearance of HEMA was stirred at room temperature for 2 hours. The reaction was added to 2 L of distilled water with stirring and extracted with diethyl ether. The extracted organic layer was washed with baking soda and saturated brine, and the organic layer was dried over magnesium sulfate, and filtered to remove insolubles. The obtained filtrate was concentrated, and 3 5 - 4 g (yield: 8 6 %) of a halide monomer (1) was obtained by distillation under reduced pressure. In the synthesis method of the halide monomer (2), in addition to the method of synthesizing the halide monomer (1), HEMA is changed to hydroxyethyl acrylate [HEA, manufactured by Tokyo Chemical Industry Co., Ltd.], in accordance with the halide monomer. The synthesis method of (1), synthesizing a halide monomer (2). The yield was 88%. Method for synthesizing halide monomer (3) -74- 200903161 In addition to the method for synthesizing halide monomer (1), CAC is changed to bromoethene bromide [BAB, manufactured by Tokyo Chemical Industry Co., Ltd.), in accordance with A method for synthesizing a halide monomer (1), synthesizing a halide monomer (3). The yield was 79%. In addition to the method for synthesizing the chelating monomer (1), the HEMA is changed to Aronix M152 [AX-M152, manufactured by Toagos Corporation), in accordance with the halide monomer ( The synthesis method of 1) synthesizes a halide monomer (4). The yield was 88%. In the synthesis method of the halide monomer (5), in addition to the method for synthesizing the halide monomer (1), HEMA is changed to Aronix M154 [AX-M154, manufactured by Toagos Corporation), in accordance with a halide monomer ( The synthesis method of 1) synthesizes a halide monomer (5). The yield was 87%. In the synthesis method of the halide monomer (6), in addition to the method of synthesizing the halide monomer (1), HEMA is changed to Blenmer PE200 [BL-PE200, manufactured by Nippon Oil & Fats Co., Ltd.], in accordance with a halide monomer ( The synthesis method of 1) synthesizes a halide monomer (6). Yield 90% 〇' Synthesis of fluorine-containing compound (1) Under a nitrogen stream, 25 g of propylene glycol monomethyl ether acetate [MMPG-Ac, manufactured by DAICEL Chemical Industry Co., Ltd.] was placed in a 300 ml line equipped with a cooling tube. In the three-necked flask, the internal temperature was heated to 70 ° C in a paraffin-added water bath. In this case, it is also dissolved by a plunger pump for 2 hours and dissolved in 40 g of MMPG-Ac. 5 g of acrylic acid [AA, Tokyo Chemical Industry Co., Ltd.], 25 g of 2-(perfluorohexyl)-ethyl acrylate [FAAC6, NOK (share) system], 17. 5 g of polyethylene glycol monomer [AM23 0G, Xinzhongcun Chemical Co., Ltd.] -75- 200903161, 5. 0 g of the above-mentioned halide monomer (1), and 0-88 g of 2-ethylhexyl isopropyl propionic acid [EHMP, manufactured by Tokyo Chemical Industry Co., Ltd.], and dissolved in gram MFGAc. 3 34 g of a solution of 2,2'-azobis(isovaleronitrile) [trade name: V65, manufactured by Wako Pure Chemical Industries, Ltd.]. After completion of the dropwise addition, the mixture was stirred for 5 hours, and the disappearance of the residual monomer was confirmed by 'H-NMR. Copolymerization of 2-(perfluorohexyl)-ethylpropionic acid ester [FAAC6], acrylic acid [AA], polyethylene glycol monomer [AM2 3 0G], and halide monomer (1) as above And FAAC6/AA/AM230G/halide monomer (1) = 50/5/35/10 (mass ratio) of fluorine-containing compound (1). The weight average molecular weight is 1.  60000. Since the monomer disappeared and a high molecular weight component was formed, the synthesis of a fluorine-containing resin having a side chain of 6 ester chains was confirmed. Synthesis of Fluorine-Containing Compound (2) The synthesis of the fluorine-containing compound (2) is carried out in accordance with the synthesis of the above-mentioned fluorine-containing compound (1). The respective copolymerization components and composition ratios are as follows: • Fluorine-containing compound (2): FAAC6/AA/AM23 0G = 5 0/5 /4 5 (mass ratio) i Synthesis of fluorine-containing compound (3) The synthesis of the fluorine-containing compound (3) is carried out in accordance with the synthesis of the above fluorine-containing compound (1). Regarding the respective copolymerization components and composition ratios, the following are as follows: Fluorine-containing compound (3): FAMAC6/MAA/M23 0G = 5 0/5/4 5 (mass ratio) The synthesis of the fluorine-containing compound (4) to (5) is carried out in accordance with the synthesis of the above-mentioned fluorine-containing compound (1). Synthesis of fluorine compounds (4) to (5). The respective copolymerization components and composition ratios are as follows: • Fluorine-containing compound (4): R1 420/MAA/M23 0G = 50/5/45 (mass ratio) -76- 200903161 • Fluorine-containing compound (5) : FAMAC6/MAA/M90G = 50/5/45 (mass ratio) Evaluation 1 (1) The heat reduction rate is determined by using fluorine-containing compounds (1) to (5) in such a manner that they are not affected by other components of the composition. Heat reduction rate. The obtained fluorine-containing compound was weighed by 1 g in a vacuum oven, and a thermogravimetric analyzer (trade name: DTG-60, manufactured by Shimadzu Corporation) was used to measure at 15 (TC retention). The weight reduction rate after 30 minutes. The measurement results are shown in the following Table 3. The synthesis method of the fluorine-containing compound (6) to (18) According to the synthesis example of the fluorine-containing compound (1), another fluorine-containing compound (6) is carried out. Synthesis of ~(18). Regarding the respective copolymerization components and composition ratios, the following are as follows: Fluorine-containing compound (6) FAAC6/AA/AM23 0G/halide monomer (2) = 50/ 5/43/2 ( Mass ratio) Fluorine-containing compound (7) FAAC6/AA/AM230G/halide monomer (2) = 50/ 5/40/5 (mass ratio) Fluorine-containing compound (8) FAAC6/AA/AM230G/halide monomer (2) = 40/ 5/3 5/20 (mass ratio) Fluorine-containing compound (9) FAAC6/AA/AM230G/halide monomer (2) = 30/ 5/55/10 (mass ratio) Fluorine-containing compound (10) FAAC6/AA/AM230G/halide monomer (2) = 50 /5/35/10 (mass ratio) Fluorine-containing compound (11) FAAC6/AA/FA5/firmate monomer (2) = 40/ 5/ -77- 200903161 45/10 (mass ratio) containing fluoride (12) Quantity ratio FAAC6/AA/FA5/CMS-P = 40/5/45/1 0 (Fluorine-containing compound (1 3 ) 1〇 (mass ratio) FAAC6/AA/AM23 0G/CMS-P = 40/5/45/ Fluorine-containing compound (14) /5/35/10 (mass ratio) FAAC6/AA/AM230G/halide monomer (3) = 50 Fluorine-containing compound (1 5 ) /5/35/ 10 (mass ratio) FAAC6/AA/AM230G/halide monomer (4) = 50 fluorochemical (16) /5/35/10 (mass ratio) FAAC6/AA/AM230G/halide monomer (5) = 50 Fluorine-containing compound (1 7) FAM AC6/MAA/M23 0G/halide monomer (6) = 50/5/35/10 (mass ratio) Fluorine-containing compound (1 8 ) /1 〇 (mass ratio) FAAC6 /AM230G /halide monomer (2) = 50/40 Synthesis method of fluorine-containing compound (19) to (20) According to the synthesis example of the above fluorine-containing compound (1), fluorine-containing compound (19) to (20) is carried out. For the respective copolymerization components and composition ratios, the following are as follows: Fluorine-containing compound (19) 35/10 (mass ratio) TFA/AA/AM130G/halide monomer (2) = 50/5/ Fluorine-containing Compound (20) FAAC6/AA/V# 1 60 = 50/5/45 (mass ratio) Add propylene glycol monomethyl ether acetate to adjust each of the above-mentioned synthesized fluorine The solid content concentration of compound that became 25%. Further, the symbols of the respective copolymerization components (monomers) constituting the fluorine-containing compound are as follows: fluorine-containing monomer. FAAC6: 2-(perfluorohexyl)-ethyl acrylate [manufactured by NOK Co., Ltd.] • FAMAC6: 2-(perfluorohexyl)-ethyl methacrylate [manufactured by NOK Co., Ltd.]. R1 420: 2-(perfluorobutyl)-ethyl acrylate [manufactured by DAIKIN Industrial Co., Ltd.] Other monomers • AA: Acrylic [Tokyo Chemical Co., Ltd.]. MAA: Methacrylic acid [Tokyo Chemical Co., Ltd.] • AM23 0G: Polyethylene glycol (23-mer) of monomethyl acrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.] • M230G: Polyethylene glycol (23-polymerization) Monomethyl methacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.] • M90G: Polyethylene glycol (9-mer) monomethyl methacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.] In each of the fluorine-containing compounds (1) and (6) to (20), the copolymerization component, the copolymerization ratio, and the mass average molecular weight are as shown in Table 1 below. Further, propylene glycol monomethyl ether acetate was added to adjust the solid content concentration of each fluorine-containing compound to 25 %. -79- 200903161 [Table 1] Fluorinated compound Fluoromonomer monomer having an acidic group Other monomer Halide monomer copolymerization ratio (mass ratio) Mass average molecular weight (1) FAMAC6 MAA M90G (1) 50/5 /35/10 1. 60,000 (6) FAAC6 AA AM230G (2) 50/5/43/2 1_5 million (7) FAAC6 AA AM230G (2) 50/5/40/5 1. 40,000 (8) FAAC6 AA AM230G (2) 40/5/35/20 1. 50,000 (9) FAAC6 AA AM230G (2) 30/5/55/10 1_2 million (10) FAAC6 AA AM230G (2) 50/5/35/10 1_4 million (11) FAAC6 AA FA5 (2) 40/5 /45/10 0. 60,000 (12) FAAC6 AA FA5 CMS-P 40/5/45/10 0_7 million (13) FAAC6 AA AM230G CMS-P 40/5/45/10 1. 0 million (14) FAAC6 AA AM230G (3) 50/5/35/10 1. 50,000 (15) FAAC6 AA AM230G (4) 50/5/35/10 1. 10,000 (16) FAAC6 AA AM230G (5) 50/5/35/10 1. 20,000 (17) FAMAC6 MAA AM230G (6) 50/5/35/10 1. 60,000 (18) FAAC6 - AM230G (2) 50/40/10 1. 90,000 (19) TFA AA AM130G (2) 50/5/35/10 1. 80,000 (20) FAAC6 AA V#160 - 50/5/45 1. 40,000 [Example 1] Preparation of photosensitive resin composition First, the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate described in Table 2 below were measured at a temperature of 24 ° C (±2). °C), stirring, stirring at 150 ° rpm for 10 minutes, and then measuring the amount of methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2, respectively, as described in Table 2 below. , 4-bis(trichloromethyl)-6-[4'-(丨1 diethoxycarbonylmethylamino)-3'-bromophenyl]-s-three tillage, surfactant 1, and the above The obtained fluorine-containing compound (1) -80-200903161 'added in this order at a temperature of 25 ° C (± 2 ° C), and stirred at 15 ° C for 30 minutes at a temperature of 40 ° C (± 2 ° C) to prepare Photosensitive resin composition K1. At this time, the ratio of the fluorine-containing compound (1) to the mass of the solid component in the photosensitive resin composition K 1 was 5%. Further, the amounts described in Table 2 are mass parts, and the details are as follows. K pigment dispersion 1 • Carbon black (trade name: Nipex35, manufactured by Degussa) 13. 1% • The following dispersant 1 0. 65% • Polymer (benzyl methacrylate/methacrylic acid = 72/2 8 molar ratio of random copolymer, molecular weight 3 .  70,000) 6. 72% • Propylene glycol monomethyl ether acetate 79. 5 3 % dispersant 1

Adhesive 2 • Polymer (benzyl methacrylate / methacrylic acid (= 78 /2 2 [mole ratio]) random copolymer, molecular weight 38,000) 27% • Propylene glycol monomethyl ether acetate Ester 73% DPHA liquid • Dipentaerythritol hexaacrylate (containing 500 ppm polymerization inhibitor -81- 200903161 DPHA)

MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD 7 6% • Propylene glycol monomethyl ether acetate 24% 3 0% 7 0% Surfactant 1 • The following structure 1 • Methyl ethyl ketone structure Object 1

—(CH o=co=c —(CH2-〒 Η)4〇— o=c OCH2CH2CnF2n+1 Ο(Ρ0)7Η 0(Ε0)7Η (n = 6,x = 55,y = 5, M w = 3 3 9 4 0, M w / Μ n = 2 · 5 PO : propylene oxide, EO : ethylene oxide) t -82- 200903161 [Table 2] Photosensitive resin composition Κ 1 Κ Pigment dispersion 1 30 Propylene glycol Monomethyl ether acetate 15 methyl ethyl ketone 34 binder 2 12 DPHA liquid 5.4 2,4-bis(trichloromethyl)-6-[4,-(11 bis ethoxymethylamino) -3'-Bromophenyl]-s-triterpene 0.2 Hydroquinone monomethyl ether 0.006 Surfactant 1 0.06 Fluorinated compound (1 ) 3.0 Unit: Part of the wall of the painting is washed by a UV cleaning device After the alkali-free glass substrate is cleaned with a detergent, ultrasonic cleaning is performed with ultrapure water, and the substrate is heat-treated at 120 ° C for 3 minutes to stabilize the surface state. After the glass substrate was cooled and the temperature was adjusted to 23 ° C, the photosensitive resin composition K1 was applied by a glass substrate coater (manufactured by FAS Asia, trade name: MH-1600) having a slit nozzle. , in the vacuum drying device VCD (Tokyo should 30 minutes in a chemical company, the solvent was partially dried to lose fluidity, and then prebaked at 120 ° C for 3 minutes to form a photosensitive resin composition layer K1 having a film thickness of 2.3 μm. -83- 200903161 Resin layer forming step). Secondly, using a proximity type exposure machine (made by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, on a glass substrate and a photomask (a quartz exposure mask with an image pattern) In a state in which it is vertically erected, the distance between the mask surface and the photosensitive resin composition layer K1 is set to 200 μm, and the exposure is performed at a exposure amount of 300 mJ/cm 2 in a nitrogen atmosphere (exposure step). The pure water is sprayed from the shower nozzle so that the surface of the photosensitive composition layer K1 is uniformly wetted, and then the KOH-based developing liquid (containing KOH, nonionic surfactant, trade name: CDK-1, Fuji) The film electronic material (manufactured by the film) was diluted by 100 times at a flat nozzle pressure of 0.04 MPa and sprayed at 23 ° C for 80 seconds to obtain a patterned image (development step). Then, by ultra high pressure Wash the nozzle, Ultrapure water was sprayed under a pressure of 9.8 MPa to remove the residue, and post-exposure was performed at an exposure amount of 200 00 mJ/cm 2 in the atmosphere, followed by post-baking at 50 ° C for 50 minutes (heat treatment step) to obtain a film thickness. 2.0 μιη, optical density 4.0, strip-shaped black matrix of the opening of ΙΟΟμπι wide (away from the wall). Hereinafter, the glass substrate on which the image wall is formed is referred to as "substrate with the image wall attached". Evaluation 2 (2) Wettability For the obtained substrate with the paint wall attached, the wettability was evaluated as follows, and the concave portion surrounded by the paint wall with the substrate on the paint wall was used.

The ink jet head SE-128' manufactured by Dimatix Co., Ltd. sprayed droplets under the conditions of a driving voltage of 50 V and a driving frequency of 50 Hz. From the beginning of the drop to the time point of 2 sec -84-200903161, the size of the droplet, the average 値' of 10 points is obtained as the droplet diameter. When the droplet diameter is 40 μm or more, it is a preferable state in which the wettability is maintained. The propylene glycol monomethyl ether acetate was sprayed on the concave portion surrounded by the wall of the substrate with the wall of the painting, using an inkjet head SE-I28 manufactured by Dimatix Co., Ltd. under the conditions of a driving voltage of 50 V and a driving frequency of 50 Hz. 1 drop each. The droplet size immediately after the drop was measured by optical microscopic observation, and the average enthalpy of 10 points was obtained to obtain the droplet diameter. Tables 3 and 4 show 値. (3) Water repellency and ink repellency from the wall of the painting The ink repellency of the obtained substrate with the paint wall was evaluated as follows. Using a contact angle meter (contact angle meter (CA-A) manufactured by Kyowa Interface Science Co., Ltd.), ion-exchanged water was prepared into a water sample having a size of 20 marks, and the water sample was dropped from the needle tip by When the frame edge portion of the painting wall was touched, water droplets were formed at the edge of the frame wall, and the shape of the ink droplet was observed by the peephole of the contact angle meter to obtain a contact angle 2 of 25 °C.値 is shown in Table 4 below. In the same manner as described above, the photosensitive resin composition layer K1 formed in the same manner as described above was exposed in the same manner as described above, except that in the examples 5 to 2 and the comparative examples 3 to 4, The operation up to the post-baking treatment (heat treatment step) under the same conditions was carried out to obtain a photosensitive resin composition layer for the test. Thereafter, the test photosensitive composition layer was left to stand at room temperature for 1 hour after the post-baking treatment, and then a contact angle meter (Kyowa Interface Science Co., Ltd. contact angle meter, trade name: CA-) was used. A) A liquid sample (ink sample) having a size of 20 marks is used for the coloring ink composition of the above-mentioned R pixel, and is dropped from the needle tip to make contact with the test photosensitive resin group -85-200903161 On the test photosensitive resin composition layer, droplets (ink droplets) of the colored ink composition for R pixels were formed. Then, the shape of the ink droplet was observed by the peephole of the contact angle meter. The ink contact angle Θ1 of the ink droplet after being left for 10 seconds from the drop was determined at 25 °C. Further, the ink droplets having the measured contact angles were changed to water droplets, and the water contact angle Θ2 was measured in the same procedure. The sputum after baking was evaluated as an index for evaluating the water repellency and ink repellency, and was evaluated according to the following evaluation criteria. The allowable range is A grade and B grade. The evaluation results are shown in Tables 5 and 6 below. Evaluation criteria .A grade: ink contact angle 2 50 °, water contact angle $ 1 〇〇. .B grade: ink contact angle 2 4 0 °, water contact angle 2 9 0. • Class C: ink contact angle g 35°, water contact angle g 80. • Class D: Ink contact angle < 3 5 °, water contact angle < 8 0 (4) Substrate adhesion from the painted wall except that the exposure is completed under the same conditions as in the above-mentioned "Formation of the painted wall" In the three glass substrates up to the step, the development time was increased to 90 seconds, 100 seconds, and 1 10 seconds, and the development process was performed under the same development conditions, and the following evaluation criteria were used. Visually evaluate 1 画 a single pixel part 'observation of each imaging time to see if there is a defect in the wall of the painting. The allowable range is A grade and B grade. The evaluation results are shown in Tables 5 and 6 below. Evaluation criteria • Class A: There is no defect at all from the wall. • Class B: 1 to 2 places are missing from the wall. -86- 200903161 .C Level: There are 3~1 defects in the painting wall. .D grade: There are more than 1 place defects in the painting wall. Production of color filter (1) Preparation of a pigmented ink composition for a pixel The following components were used: 'First mixed pigment' polymer dispersant and solvent, and a three-roll and bead mill was used to obtain a pigment dispersion liquid. While the pigment dispersion liquid was sufficiently stirred by a dissolver or the like, a small amount of other material was added to prepare a colored ink composition for red (R) pixels. Composition of colored ink composition for red pixel • Pigment (CI Pigment Red 254) 5 parts. Polymer dispersant (trade name: S〇lsPass 24000, manufactured by AVECIA) 1 part • Benzyl methacrylate/A Acrylic acid (= 7 2/2 8 [mole ratio]) random copolymer (molecular weight 37,000, binder) 3 parts • novolak type epoxy resin (trade name: Epicoat 154, manufactured by Oiled Shell Co., Ltd. 2 parts • Neopentyl glycol diglycidyl ether (epoxy resin) 5 parts • Trimellitic acid (hardener) 4 parts • Ethyl 3-ethoxypropionate (solvent) 80 parts, in addition to In place of the C. I. Pigment Red 2 5 4 in the above composition, the same amount of CI Pigment Green 36 is used, and the green (G) pixel coloring printing is prepared in the same manner as in the case of the R pixel using the colored ink composition. Ink composition. Further, in place of the C. I. Pigment Red 2 5 4 in the above composition, the same amount of C. I. Pigment Blue 1 5 : 6 is used, and the same as in the case of the R-picture pigmented ink composition. - 200903161 'Modified blue (B) pixels with colored ink composition. (2) Formation of a coloring pixel Next, 'the coloring ink composition for a pixel of R, G, and B described above is used' in the region of the above-mentioned obtained off-paint wall of the substrate with the painting wall ( The ink jet type recording apparatus is used to discharge the ink composition to a desired concentration, and a pattern (coloring pixel) composed of R, G, and B is formed. Color filter. Then, the color filter was baked in an oven at 230 ° C for 30 minutes to obtain a color filter substrate which was completely hardened from the wall and each of the pixels. Evaluate 3 (5) color filter color mixing and / or whitening the resulting color filter substrate, from the opposite side of the color filter forming pixel side, with a 200x optical microscope Visually observe whether there is color mixing and/or whitening between pixels. The evaluation system observes 1 000 pixels and divides them into the following levels. The allowable range is A grade and B grade. • Class A: There is no color mixing and/or whitening at all. • Class B: Mixed colors and/or whitening are seen in 1 to 2 places on the periphery of the display. • Class C: Mixed color and/or whitening in 1 to 2 places on the display unit • D level: Mixed color and/or whitening liquid crystal display device of 2 or more places is seen on the display unit. On the obtained color filter substrate, R pixels, G pixels, and B pixels, and a transparent electrode on the wall of the painting, and further ITO (indium tin oxide 88·200903161) were formed by sputtering. The electric resistance of this ITO (measured by a four-probe method using a resistivity measuring apparatus (trade name: Loresta) manufactured by Mitsubishi Chemical Corporation) was measured and found to be 12 Ω/□, which showed a very low enthalpy. In the same manner as described above, the coating liquid for a photosensitive resin layer for forming a spacer pattern is applied onto the ITO of the color filter, and dried to form a photosensitive property. Resin layer SP 1. Formulation of coating liquid for photosensitive resin layer s P 1 • Methacrylic acid / allyl methacrylate copolymer (mol ratio = 20/80, weight average molecular weight 40,000; high molecular substance) 108 parts • dipentaerythritol hexaacrylic acid Ester 6 4.7 parts of polymerizable monomer • 2,4-bis(trichloromethyl)_6_[4,_(N,N_bisethoxycarbonylmethylamino)-3'_bromophenyl]-s - Three wells 6.24 parts. Hydroquinone monomethyl ether 0.03 3 6 parts • Victoria blue (trade name: BOHM, manufactured by Hodogaya Chemical Co., Ltd.) 1 0.874 parts • Surfactant (trade name: Mega fa c F780F, Dainippon Ink Chemistry Industrial (stock) system 0.856 parts • methyl ethyl ketone 3 28 parts. 1-methoxy 2 propyl acetate 47 5 parts • methanol 1 6.6 parts followed by 'specified mask, by super The high pressure mercury lamp is exposed for close proximity at 300 mJ/cm2. After the exposure, the photosensitive layer of the unexposed portion was dissolved and removed using a 100-fold dilution of κ〇Η imaging solution [CDK--89-200903161 1 (trade name) (ρΗ = 11·8), manufactured by Fujifilm Co., Ltd.] Resin layer. Next, at 2 3 (TC baking for 30 minutes, a columnar spacer pattern having a diameter of μ6 μm and an average height of 3.7 μm was formed on the portion of the glass substrate on the upper portion of the ruthenium film which was on the enamel film. The aligning film formed of the polyimine is provided. The liquid crystal alignment splitting projection is formed by applying the coating liquid for a photosensitive resin layer to be described below to the color filter substrate by the same slit coater as described above. In the enamel, a photosensitive resin layer for forming a protrusion is formed by drying. Then, a coating liquid for an intermediate layer formed by the following prescription Ρ1 is used on the photosensitive resin layer for protrusions, and an intermediate layer having a dry film thickness of 1.6 μm is provided. Prescription of the coating liquid for the photosensitive resin layer for protrusions A • Positive-type photoresist liquid 5 3 . 3 parts (made by Fujifilm Electronic Materials Co., Ltd., trade name: FH-2413F) • 46.7 parts of methyl ethyl ketone • The surfactant 1 0.04 part of the coating solution for the intermediate layer is p 1 .PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree 88%, degree of polymerization 550) 32.2 parts • polyvinylpyrrolidone 1 4.9 parts (ISP·Japan (share) system, Product name: FK-30) *Distilled water 5 2 4 parts •Methanol 429 parts -90- 200903161 Next, a proximity exposure machine is disposed so that the distance between the mask and the surface of the photosensitive resin layer for protrusions is 100 μϊ, The photomask is exposed by a high-pressure mercury lamp with an irradiation energy of 150 m J / cm 2 . Then, a 2.3 8% aqueous solution of tetramethylammonium hydroxide is sprayed on the substrate at a temperature of 30 ° by a spray-type developing device. The second side image is developed to remove unnecessary portions (exposure portions) of the photosensitive tree layer for protrusions. Thus, the color filter substrate is located on the upper portion of the R, G, and B pixels on the ITO film. Forming a protrusion formed by the photosensitive resin layer patterned by the desired shape. Then, the color filter substrate on which the protrusion is formed is baked at 240 ° C for 50 minutes' on the color filter substrate A protrusion for the alignment division having a height of 1.5 μm and a fish plate shape in a longitudinal section is formed. Further, in the color filter substrate obtained as described above, the side substrate and the liquid crystal material are driven by the group to form a vertical alignment type alignment liquid. Display element. Specifically, as a drive a side substrate on which a TFT substrate and a pixel electrode (conductive layer) are formed, and the TFT substrate and the color filter substrate obtained above are provided with a surface on the side of the TFT substrate on which the electrode or the like is provided, and color The surface of the filter substrate on which the side of the alignment protrusion is formed is disposed in a relatively opposed manner, and the gap is provided by the spacer formed as described above, and the gap is fixed by the liquid crystal material in the gap. The liquid crystal layer was displayed to obtain a liquid crystal cell. On both sides of the liquid crystal cell obtained here, a polarizing HLC 2-2518 manufactured by Sanritz Co., Ltd. was adhered. Then, the backlight of the cold cathode tube is placed on the side opposite to the side on which the polarizing plate is provided on the unit cell (back side), and becomes an alignment vertical alignment type liquid crystal display device. Cheng Chao borrows 3 3 fat to divide the crystal into a crystal, and cuts into a material such as a plate liquid cut-91- 200903161. Evaluation 4 (6) Display unevenness of the liquid crystal display device for the liquid crystal display device produced by the above, input gray When the signal was tested, the visual observation was not observed. The presence or absence of display unevenness was evaluated according to the following evaluation criteria. Evaluation criteria • A: No display unevenness, and a very good display image. • B: The edge of the glass substrate is slightly uneven, but it does not affect the display. The image is good. • C: There is a slight unevenness in the display section, but it is within the range that is practically permissible. • D : Unevenness is seen on the display, and the displayed image is slightly worse. • E : Strong unevenness is seen on the display, and the displayed image is very poor. Example 2 The photosensitive transfer material K 1 was formed on a polyethylene terephthalate film temporary support (PET: temporary support) having a thickness of 75 μm, and was coated with a slit nozzle to be composed of the following prescription HI. The coating liquid for a thermoplastic resin layer is dried to form a thermoplastic resin layer. Then, a coating liquid for an intermediate layer composed of the following prescription P1 was applied onto the thermoplastic resin layer, and dried to form an intermediate layer. Further, the photosensitive resin composition K1 prepared in Example 1 was applied to dry the photosensitive resin layer. Thus, on the temporary support, a thermoplastic resin layer having a dry film thickness of 14.6 Pm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry film-92-200903161 photosensitive resin layer having a thickness of 2.3 μm were provided. 'The final pressure-sensitive protective film (thickness polypropylene film). In this manner, a photosensitive transfer material in which a photosensitive resin layer of a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and black (K) is integrated is prepared, and the sample name is a photosensitive transfer material K 1 . . Formulation of coating solution for thermoplastic resin layer • 1 • Methanol 1 1.1 parts • Propylene glycol monomethyl ether acetate 6.3 6 parts • Methyl ethyl ketone 52.4 parts • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (mole ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg and 70. (:) 5.83 parts • styrene / acrylic acid Copolymer (copolymerization composition ratio (mole ratio) == 63 / 3 7, average molecular weight = 10,000, Tg and 100 ° C) 13.6 parts • 2,2-bis[4-(methallyloxy group Ethoxy)phenyl]propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9_1 parts • The aforementioned surfactant 1 0.5 4 parts of coating solution for intermediate layer: prescription P 1 . Polyvinyl alcohol (trade name: PVA-205, Kuraray (s), saponification degree = 88%, degree of polymerization 5 5 0) 32.2 parts. Polyvinylpyrrolidone (trade name: K-30, ISP, manufactured by Japan) 1 4.9 parts • 524 parts of distilled water - 93 - 200903161 • Spray 429 parts of methanol to the alkali-free glass substrate (hereinafter referred to as "glass substrate") by adjusting the glass detergent liquid adjusted to 25 by a shower. Wash with a bristled brush, spray with pure water, and spray the decane coupling solution (Ν-β (aminoethyl) γ-aminopropyltrimethoxy) with a shower. The decane 0.3% aqueous solution 'product name: ΚΒΜ603, manufactured by Shin-Etsu Chemical Co., Ltd.) was washed with pure water for 20 seconds, and the glass substrate was heated at 1 Torr for 2 minutes by a substrate preparation heating device. The glass substrate after the coupling treatment is removed from the photosensitive transfer material K 1 obtained as described above, and the photosensitive resin layer exposed after the surface of the photosensitive resin layer is brought into contact with the surface of the glass substrate. For the glass substrate after the decane coupling treatment, a laminator (manufactured by Hitachi Industrial Co., Ltd., trade name: Lamic II type) was used, and the glass substrate was subjected to a rubber roller temperature of 130 ° C, a linear pressure of 10 O/cm, and a conveying speed of 2 to 2 m/ After laminating, the polyethylene terephthalate film temporary support is peeled off at the interface with the thermoplastic resin layer to remove the temporary support. After the temporary support is peeled off, by having an ultrahigh pressure The proximity type exposure machine of the mercury lamp (manufactured by Hitachi High-Tech Electronics Co., Ltd.) 'the substrate and the photomask (the quartz exposure mask having the image pattern) are vertically erected'. The mask surface and the photosensitive resin layer are formed. The distance between them was set to 200 μm η > and the exposure was 70 mJ/cm 2 as a pattern. Next, a 100-fold dilution of KOH imaging solution [CDK-1 (trade name, manufactured by Fujifilm)) (pH= l 1.8)] The image of the 'unexposed portion of the photosensitive resin layer and the underlying intermediate layer, thermoplastic resin layer' was formed to form a black matrix pattern on the glass substrate -94 - 200903161. Then, under the atmosphere, the surface of the substrate was post-exposed by 2000 mJ/cm 2 from the surface of the substrate by an aligner, and then post-baked at 240 ° C for 50 minutes to obtain an optical density of 4.0. Wall (with a substrate off the wall). Then, a color filter and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation as in the description of Example 1 was carried out. The evaluation results are shown in Tables 3 and 4 below. Example 3 In the same manner as in Example 2, except that the fluorine-containing compound (1) used in the preparation of the photosensitive resin composition K 1 was replaced with the fluorine-containing compound (2), in the same manner as in Example 2, The substrate, the color filter, and the liquid crystal display device were separated from the wall, and the same evaluation was performed. The evaluation results are shown in Tables 3 and 4 below. [Example 4] In the same manner as in Example 2 except that the fluorine-containing compound (1) used in the preparation of the photosensitive resin composition K1 was replaced with the fluorine-containing compound (3) in Example 2, The substrate of the wall, the color filter, and the liquid crystal display device were evaluated in the same manner. The evaluation results are shown in Tables 3 and 4 below. Comparative Example 1 In the same manner as in Example 2, except that the fluorine-containing compound (1) used in the preparation of the photosensitive resin composition κ1 was replaced with the fluorine-containing compound (4), The substrate of the wall, the color filter, and the liquid crystal display device were evaluated in the same manner. The results of the evaluation -95-200903161 are shown in Tables 3 and 4 below. Comparative Example 2 In the same manner as in Example 2, except that the fluorine-containing compound (1) used in the preparation of the photosensitive resin composition κ 1 was replaced with the fluorine-containing compound (5), The substrate of the wall, the color filter, and the liquid crystal display device were drawn, and the same evaluation was performed. The evaluation results are shown in Tables 3 and 4 below. 【table 3】

Fluorine-containing compound (1) Heat reduction rate Droplet diameter whitening unevenness (%) (μιη) Example 1 Fluorine-containing compound (1) ^ Coating_ηΕ 45 AB Example 2 Fluorine-containing compound (1) Transfer 17 48 AA Example 3 Fluorine-containing compound (2) Transfer 23 43 AB Example 4 Fluorine-containing compound (3) Transfer 27 40 BB Comparative Example 1 Fluorine-containing compound (4P transfer ^ 34 ' 15 DC Comparative Example 2 Fluorine-containing Compound (5) Transfer 35 13 DD [Table 4] Inking agent droplet diameter dialing water whitening unevenness (μιη) (°) Example 1 Fluorinated compound (1) Coating 43 109 Example 2 Fluorine-containing Compound (1) Transfer 45 114 1 AA Example 3 Fluorine-containing compound (2) Transfer 39 110 BA Example 4 Fluorine-containing compound (3) Transfer 28 103 BB Comparative Example 1 Fluorine-containing compound (4) Transfer 14 92 DD Comparative Example 2 Fluorine-containing compound (5) Transfer 11 91 DD As shown in the above Tables 3 and 4, in the embodiment, the black matrix can have a good ink repellent property while maintaining black color -96-200903161 The wettability of the composition of the colored ink composition between the matrices of the color pixels can be prevented The occurrence of whitening and suppression of high-quality image display showing unevenness. In contrast, in the comparative example, the wettability of the pigmented ink composition for the pixel is impaired, and the occurrence of whitening and image cannot be prevented. In the first embodiment, the photosensitive resin was prepared in the same manner as in Example 1 except that the content of the fluorine-containing compound (1) was changed from 5% to 1% in Example 1. In the composition K2, a color filter and a liquid crystal display device were produced, and the same evaluation was carried out. The results are not shown in the following Table 5. Example 6 Except that in Example 1, the content of the fluorine-containing compound (1) was changed from The photosensitive resin composition K3 was prepared in the same manner as in Example 1 except that 5% was changed to 0.1%, and a color filter 'liquid crystal display device was produced, and the same evaluation was performed. The evaluation results are shown in Table 5 below. 7 to 1 9 In addition to the fifth embodiment, the fluorine-containing compound (1) was replaced with the fluorine-containing compound (6) to (18) of the present invention obtained above (the fluorine-containing compound of the present invention). 2 Similarly, the photosensitive resin group is prepared The color filter and the liquid crystal display device were produced and the same evaluation was performed. The evaluation results are shown in Table 5 below. Comparative Example 3 In addition to the fluorine-containing compound in Example 5 In addition to the fluorine-containing compound (1 9) of the above-mentioned comparative use -97-200903161, @ & Μ < g & ^ In the case of Example 5, the salty resin composition Κ17 was prepared to produce color filter The sheet and the liquid crystal display device were subjected to the same evaluation. The evaluation results are shown in Table 5 below. Comparative Example 4 A photosensitive resin composition Κ 1 8 was prepared in the same manner as in Example 5 except that the fluorine-containing compound (1) was replaced with the fluorine-containing compound (20) for comparison. The same evaluation was performed on the filter and the liquid crystal display device. The evaluation results are shown in Table 5 below. -98- 200903161 [Table 5]

Fluorine-containing compound water-repellent and ink-repellent color mixing white substrate adhesion display uneven content content (%) post-baking ink contact angle Θ1 post-baking water contact angle Θ3 Example 1 (1) 5 A (58.) A (110.) AAB Example 5 (1) 1 A (56.) B (105.) AAA Example 6 (1) 0.1 B (49.) A (101.) BAA Example 7 (6) 1 B (45.) B (99.) BAB Example 8 (7) 1 A (50.) A (101.) AAA Example 9 (8) 1 A (51.) A (100.) AAA Example 10 ( 9) 1 B (48.) B (98.) BBA Example Π (10) 1 A (54.) A (103°) BAA Example 12 (11) 1 A (60.) A (105°) AAA Example 13 (12) 1 A (54.) A (102°) AAA Example 14 (13) 1 A (52.) A (100.) AAA Example 15 (14) 1 A (51.) A ( 100°) AAA Example 16 (15) 1 A (52.) A (102°) AAA Example Π (16) 1 A (59.) A (109.) ABA Example 18 (17) 1 A (50 A) (101.) AAB Example 19 (18) 1 B (41.) B (97.) BBB Comparative Example 3 (19) 1 D (34.) B (96.) CCC Comparative Example 4 (20) 1 C (38 °) A (100.) C C C * represents the content of the table for the mass ratio of solid content. As shown in the above Table 5, in the examples, the water-repellent and ink-repellent property on the off-paint wall after the heat treatment was excellent, the color mixture did not occur, and the substrate adhesion was also good from -99 to 200903161. Further, when the liquid crystal display device is produced and displayed, the occurrence of display unevenness is also suppressed, and an image having excellent display characteristics is obtained. On the other hand, in the comparative example, the water-repellent/inking property on the paint wall after the heat treatment was inferior, the color mixture preventing effect was insufficient, and the substrate adhesion was also inferior. Therefore, in the liquid crystal display device, it is difficult to display an image which does not occur in display unevenness. Example 2 0 A glass cleaner liquid adjusted to 25 ° C was sprayed onto an alkali-free glass substrate (hereinafter referred to as "glass substrate") by a shower for 20 seconds while using a rotary brush having a bristles resistance. After washing, washing with pure water spray, spray a decane coupling solution (N-β (amine ethyl) γ-aminopropyltrimethoxydecane 〇· 3 % aqueous solution by a shower, trade name: ΚΒΜ 603, Shin-Etsu Chemical Co., Ltd.) 20 seconds, and then washed with pure water spray. After washing, the glass substrate was heated by a substrate preparation heating device for 2 minutes. In the glass substrate after the decane coupling treatment, the surface of the photosensitive resin composition layer exposed by the cover film is removed from the photosensitive transfer material Κ2 described below; 'the layer is overlapped with the surface of the glass substrate, and the layer is used. The machine (product name: Lamic II type, manufactured by Hitachi Industrial Co., Ltd.) was laminated at a rubber roll temperature of 130 ° C, a line pressure of 100 N/cm, and a conveying speed of 2.2 m/min. Next, the PET temporary support was peeled off at the interface with the thermoplastic resin layer. After the temporary support was peeled off, the glass substrate and the photomask (the quartz exposure mask having the portrait pattern) were vertically erected by a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultrahigh pressure mercury lamp. The state 'sets the distance between the exposure mask surface and the photosensitive resin composition layer to -100-200903161 to 200 μm, and exposes the pattern with an exposure amount of 7 〇 mJ/cm 2 . Next, the KOH imaging liquid [1K ( dilution (CD = 1 1.8) of CDK-1 (trade name) made by Fujifilm Co., Ltd.) was used to remove the photosensitive resin composition layer. The unexposed portion and the underlying intermediate layer, thermoplastic resin layer 'form a pattern on the glass substrate. Subsequently, the entire surface of the glass substrate was post-exposed at 2000 m:T/cm 2 from the pattern forming surface side of the glass substrate by means of an aligner under the atmosphere, and then post-baked at 240 ° C for 50 minutes. In the same manner as in the first embodiment, a color filter and a liquid crystal display device were produced in the same manner as in the first embodiment, and the same evaluation as in the first embodiment was carried out. The evaluation results are shown in Table 6 below. The photosensitive transfer material K2 was formed on a polyethylene terephthalate film temporary support (PET temporary support) having a thickness of 75 μm, and a thermoplastic resin layer composed of the following prescription HI was applied using a slit nozzle. The coating liquid is dried to form a thermoplastic resin layer. Then, a coating liquid for an intermediate layer composed of the following prescription P 1 is applied onto the formed thermoplastic resin layer, and dried to laminate an intermediate layer (oxygen barrier film). Further, the photosensitive resin composition K5 prepared in Example 8 was applied onto the intermediate layer, and the photosensitive resin composition layer K5 of black (K) was dried and laminated. At this time, the ratio of the fluorine-containing compound (7) in the photosensitive resin composition K5 to the mass of the solid component was 1.% by weight. Thus, on the PET temporary support, a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a photosensitive resin having a dry film thickness of 2.3 μm were laminated on -101 to 200903161. The composition layer was further formed by a temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin composition layer 2 by pressure-bonding a protective film (polypropylene film having a thickness of 12 μm) on the surface of the photosensitive resin composition layer. The photosensitive transfer material Κ2 is integrally formed. Formulation of coating solution for thermoplastic resin layer •1 • Methanol 1 1.1 parts • Propylene glycol monomethyl ether acetate 6 _ 3 6 parts • Methyl ethyl ketone 52.4 parts. Methyl propyl sulphuric acid vinegar / propylene acid 2 -ethylhexyl ester / methyl propyl vinegar / methacrylic acid copolymer (copolymerization composition ratio (mole ratio) = 55 / 1 丨. 7 / 4.5 / 28.8, molecular weight = 100,000, Tg and 70. (:) 5.83 parts. Styrene/acrylic acid copolymer (copolymerization composition ratio (mo: ear ratio) = 63/37, average molecular weight = 10,000, Tg and 100 ° c) 1 3 · 6 parts. 2, 2- Bis[4-(methylallyloxypolyethoxy)phenyl]propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts • The aforementioned surfactant 1 0.54 parts of the coating solution for the intermediate layer P 1 • 32.2 parts of polyvinyl alcohol (trade name: PVA205 'Kelly's saponification degree 48%, degree of polymerization 550). Polyvinylpyrrolidone 14.9 parts (ISP. Japan company, trade name: K-30 Distilled water 524 parts • Methanol 429 parts -102- 200903161 Example 2 1~2 3 In addition to the preparation of the photosensitive transfer material of Example 20, 'replaces the fluorine-containing compound (1) The photosensitive resin composition K2' contains photosensitive resin compositions K11, K13, and K1 which respectively contain the fluorine-containing compounds (1 1 ), (1 3 ), and (15) of the present invention. In the same manner as in Example 20, the photosensitive transfer materials K3 to 5 were produced, and a color filter or a liquid crystal display device was produced. The same evaluation as in Example 1 was carried out, and the following Table 6 shows Evaluation results. [Table 6]

Fluorine-containing compound water-repellent. Ink-repellent color mixing · Whitening substrate adhesion shows uneven content content (%) Post-baking ink contact angle Θ1 Post-baking water contact angle Θ3 Example 20 (7) 1 A (52. A (101.) AAA Example 21 (11) 1 A (58.) A (103.) AAA Example 22 ---- (13) 1 A (53.) A (101.) AAA Example 23 (15) 1 A (53.) A (102.) AAA As shown in the above Table 6, in the examples, the water-repellent/ink-removing property on the paint wall after the heat treatment is excellent, and the color mixture does not occur, the substrate The adhesion is also good. Further, when a liquid crystal display device is produced and displayed, it is also effective to suppress the occurrence of display unevenness, and an image having excellent display characteristics is obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view for explaining a color filter such as a top surface of a drawing wall, a side surface of a drawing wall, and a concave portion on a substrate in the present invention. -103- 200903161 [Main component symbol 1 Off the painting wall 2 Color painting 3 Concave part 4 Off the painting wall 5 Off the painting wall 6 Base plate Description] Prime (colored area) Upper side

Claims (1)

200903161 X. Patent application scope: 1 . A photosensitive resin composition containing an initiator compound and a fluorine-containing compound, and maintaining a heat reduction rate of a fluorine compound at 30 ° C for 30% by mass or less. 2. The photosensitive resin group according to the first aspect of the invention, wherein the fluorine compound contains a repeating chain having a fluorine atom in a side chain. 3 _ The photosensitive resin group fluorine compound according to the first aspect of the patent application includes a repeating unit represented by the repeating formula (1) having a fluorine atom in a side chain: when the ethylenic unsaturated is 30 minutes, the content is The unit includes a main chain structure, wherein the unit and the following In the general formula (1), R1 represents a hydrogen atom or a C 1 to 5 hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkylene group having 6 to 2 carbon atoms; and L1 represents a single bond, or 2 X represents a chlorine atom, a bromine atom, or an iodine atom; a group, a divalent heterocyclic residue, a carbonyl group, or an oxycarbonyl group. R2 represents an aryl group of 10 or a carbon-valent organic linking group; and Y represents an aromatic-105-200903161 4. A photosensitive resin composition as in the third claim of the patent application 'where the side is The repeating unit having a fluorine atom in the chain has three or more fluorine atoms. 5. The photosensitive resin composition of claim 3, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following formula (2): In the formula (2), R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number; 2 to 5 alkyl alkene; Z1 represents an ester group or a guanamine group; L2 represents a single bond or a divalent organic linking group; X represents a chlorine atom, a bromine atom, or an iodine atom; and Y represents an extended aryl group, A divalent heterocyclic residue, a carbonyl group, or an oxycarbonyl group. 6. The photosensitive resin composition of claim 3, wherein the repeating unit represented by the stomach formula (1) is a repeating unit represented by the following formula (3): -106- 200903161 General formula (3) Z2—Y—CH—XR2 In the formula (3), R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 6 An aryl group of ～10 or an alkano group having a carbon number of 2 to 5; Z2 represents a single bond, an extended aryl group, or a divalent heterocyclic residue; X represents a chlorine atom, a bromine atom, or a monument atom; and γ represents An aryl group, a divalent heterocyclic residue, a carbonyl group, or an oxycarbonyl group. The photosensitive resin composition of the second aspect of the invention, wherein the repeating unit having a fluorine atom in the side chain has a repeating unit of a fluoroalkyl group having 4 to 7 carbon atoms. 8. The photosensitive resin composition of claim 3, wherein the L1 in the formula (1) contains at least one of a divalent organic linking group of an ester bond and a guanamine bond. 9. The photosensitive resin composition of claim 3, wherein the L1 in the general formula (1) is a single bond, an extended aryl group or a divalent heterocyclic residue. The photosensitive resin composition of claim 1, wherein the fluorine-containing compound further has a repeating unit having an acidic group. -107-200903161 1 1 The photosensitive resin composition of claim 1 wherein the content of the fluorine-containing compound is 0.1% by mass to 1% by mass based on the total solid content. A photosensitive transfer material comprising a photosensitive resin layer using the photosensitive resin composition of the first aspect of the patent application on the temporary support. A method for forming a paint wall, comprising: "using a photosensitive resin composition according to any one of claims 1 to 11 or a photosensitive transfer according to item 12 of the patent application; The photosensitive resin layer is formed by a printing material, the photosensitive resin layer is exposed, the exposed photosensitive resin layer is developed, and the pattern image obtained by the development is heat-treated. 1 4. An off-paint wall formed by a method of forming a paint wall 第 according to item 13 of the patent application. A substrate having a painting wall attached thereto, comprising a substrate, and a drawing wall formed on the substrate by a method of forming a drawing wall as in the first aspect of the patent application. 1 6 · If the substrate of the painting wall is attached to the wall of the painting, in the case of the wettability test method according to the well-known substrate glass surface, the water contact angle above the wall of the painting wall is 60. As described above, in the substrate surface on the side of the substrate on which the wall is formed, there is no portion which forms the image-removing wall -108-200903161, and the droplet diameter immediately after dropping the propylene glycol monomethyl ether monoacetate is 20 μm or more. A method of producing a color filter comprising the step of applying a colored liquid composition to form a colored region in a concave portion on a substrate divided by a drawing wall as disclosed in claim 14 of the patent application. The method of producing a color filter according to the seventh aspect of the invention, wherein the coloring liquid composition is applied by ejecting a droplet of the colored liquid composition by an inkjet method. A color filter produced by the method of producing a color filter according to claim 18 of the patent application. A display device comprising a color filter according to claim 19 of the patent application. -109-