JP2008208253A - Resin composition, photosensitive transfer material, partition wall and its forming method, color filter and method for producing the same, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of keeping well the adhesion between a pattern image and a substrate while retaining both the water repellency and ink repellency of the surface of the pattern image formed. <P>SOLUTION: The resin composition comprises (1) an initiator, (2) a binder and (3) an ethylenically unsaturated compound, and also a fluorine-containing compound composed of (a) recurring units each having ≥3 fluorine atoms and (b) recurring units each represented by general formula (B) (wherein, R<SP>21</SP>and R<SP>22</SP>are each H or a 1-5C alkyl; L<SP>21</SP>is a single bond or bivalent organic linkage group; X is a chlorine atom, bromine atom or iodine atom; and Y is an arylene group, bivalent heterocyclic group or carbonyl group). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition, a photosensitive transfer material, a separation wall and a method for forming the same, a color filter and a method for manufacturing the same, and a display device.

In recent years, the demand for liquid crystal displays for personal computers and liquid crystal color televisions has been increasing, and there has been an increasing demand for improved characteristics and cost reduction of color filters essential for such displays.
Conventionally, as a method for producing a color filter, a dyeing method, a pigment dispersion method, an electrodeposition method, a printing method, and the like have been performed.
For example, in the dyeing method, a water-soluble polymer material layer, which is a dyeing material, is formed on a transparent substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To obtain a colored pattern. By repeating this step three times, a colored layer comprising three colored portions of R (red), G (green), and B (blue) is formed.
In addition, the pigment dispersion method has been actively performed in recent years, and a monochromatic pattern is obtained by forming a photosensitive resin layer in which a pigment is dispersed on a transparent substrate and patterning the same. By repeating this process three times, a colored layer composed of colored portions of R, G, and B is formed.

In the electrodeposition method, a transparent electrode is patterned on a transparent substrate and immersed in an electrodeposition coating solution containing a pigment, a resin, an electrolytic solution, etc., and the first color is electrodeposited. This process is repeated three times to form a colored layer composed of three colored portions of R, G, and B, and finally fired.
In the printing method, a pigment is dispersed in a thermosetting resin, printing is repeated three times, R, G, and B are separately applied, and then the resin is thermally cured to form a colored layer. .
The point common to these methods is that it is necessary to repeat the same process three times in order to form red, green and blue three-color pixels, resulting in high costs. In addition, since the number of processes is large, there is a problem that the yield is likely to decrease.

In order to overcome these problems, in recent years, a color filter manufacturing method in which a black matrix (separation wall) is formed by a pigment dispersion method and RGB pixels are manufactured by an ink jet method has been studied. In this ink jet method, pixels are formed by sequentially applying R, G, and B colors to the recesses of the black matrix (separation wall). The method using the ink jet method has an advantage that the manufacturing process is simple and the cost is low.
In addition, the inkjet method is not limited to the manufacture of color filters, but can also be applied to the manufacture of other optical elements such as electroluminescence elements.

  In the inkjet method, it is necessary to prevent the occurrence of ink color mixing between adjacent pixel regions and the phenomenon that the ITO solution or the metal solution clumps and sticks to a portion other than a predetermined region. Therefore, the partition wall (separation wall) is required to have a property of repelling water, an organic solvent, and the like constituting the ink-jet coating liquid, so-called water and oil repellency.

  As a resin for forming such a partition wall (release wall), a vinyl polymer, a photosensitive resin and an organic solvent obtained by polymerizing a monomer composition containing a vinyl monomer having a fluoroalkyl group A coating composition containing a fluorine atom is disclosed, and the vinyl polymer is a polymer containing 0.1 to 5% by mass of fluorine atoms (see, for example, Patent Document 1).

  Also disclosed are a vinyl polymer obtained by polymerizing a monomer composition containing a vinyl monomer having a C 4-6 fluoroalkyl group, and a resist composition containing a photoreceptor. The vinyl polymer has a fluorine atom content of 7 to 35% by mass (see, for example, Patent Document 2).

On the other hand, an example of a water-soluble photosensitive resin obtained by adding a tertiary amine to a resin having an α-bromoacetic acid unit is disclosed (for example, see Patent Document 3).
JP-A-9-54432 JP 2005-315984 A JP 61-174202 A

  However, in the composition comprising the blending ratio of the copolymer described in Patent Document 1, there is a tendency that the water / oil repellency of the coating film formed thereby is insufficient. Furthermore, the vinyl polymer described in Patent Document 2 has a tendency that the developer resistance and the adhesion during development tend to be insufficient.

The present invention has been made in view of the above-described conventional problems, and an object thereof is to achieve the following object. The present invention maintains the water repellency and ink repellency of the upper surface of the pattern image (exposed surface opposite to the surface in contact with the substrate) when forming a pattern image (for example, a separation wall), It aims at providing the resin composition which can maintain favorable adhesiveness with the board | substrate with which a pattern image is formed.
In addition, the present invention maintains adhesion between the pattern image and the substrate on which the pattern image is formed while maintaining the water repellency and ink repellency of the upper surface of the transferred pattern image (for example, a separation wall). It is an object of the present invention to provide a photosensitive transfer material having a uniform photosensitive resin layer that can be kept in good condition and suppressed generation of repelling during application.
Furthermore, the present invention provides a separation wall that is excellent in water repellency and ink repellency on the upper surface, prevents the ink that has been ejected from riding on the separation wall, and has good adhesion to the substrate, and a method for producing the same. Providing a high-quality color filter in which the occurrence of mixed colors, white spots, color unevenness, and the like is suppressed, and a simple manufacturing method thereof, and the generation of display unevenness is suppressed, so that a high-quality image can be displayed. An object is to provide a display device that can be used.

As a result of intensive studies, the present inventors have made a pattern image (for example, using a resin composition containing a fluorine-containing compound having a repeating unit having 3 or more fluorine atoms and a repeating unit having a specific halogenated alkyl structure (for example, Forming a separation wall) reduces adhesion between the pattern image and the substrate, good developability, water and ink repellency, occurrence of repellency during application, and ink repellency at the time of droplet ejection. It was found that it is effective to suppress. It has been found that by using a composition containing the fluorine-containing compound, good water repellency and water repellency can be obtained without fluorine plasma treatment, and a high-quality color filter can be produced, and the present invention has been completed.
That is, specific means for solving the above problems are as follows.
<1> A resin composition comprising a fluorine-containing compound having (a) a repeating unit having 3 or more fluorine atoms and (b) a repeating unit represented by the following general formula (B).

In the general formula (B), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²² 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 alkanoyl groups, L ²¹ represents a single bond or a divalent organic linking group, X represents a chlorine atom, a bromine atom or an iodine atom, Y represents an arylene group, a divalent heterocyclic residue or Represents a carbonyl group.

<2> The resin composition according to <1>, wherein the repeating unit (a) having 3 or more fluorine atoms is a repeating unit having a fluoroalkyl group having 4 to 7 carbon atoms. .
<3> The resin composition according to <1> or <2>, wherein L ²¹ in the general formula (B) is a divalent organic linking group containing an ester bond and / or an amide bond. .
<4> The resin composition according to <1> or <2>, wherein L ²¹ in the general formula (B) is a single bond, an arylene group, or a divalent heterocyclic residue.
<5> The resin composition according to any one of <1> to <4>, wherein the fluorine-containing compound further includes (c) a repeating unit having an acidic group.

<6> In any one of the above items <1> to <5>, further comprising 1) an initiator, 2) a binder, and 3) an ethylenically unsaturated compound, and having photosensitivity. The resin composition as described.
<7> The resin composition according to any one of <1> to <6>, wherein a content of the fluorine-containing compound in a solid content is 0.1% by mass to 10% by mass. object.
<8> The resin composition according to any one of <1> to <7>, which is used for producing a color filter.
<9> A photosensitive transfer material having a photosensitive resin layer comprising the resin composition according to any one of <6> to <8> on a temporary support.

<10> A photosensitive resin using the resin composition according to any one of <6> to <8> or the photosensitive transfer material according to <9> on at least one surface of a substrate. A photosensitive resin layer forming step for forming a layer; an exposure step for exposing the photosensitive resin layer; a developing step for developing the exposed photosensitive resin layer to form a pattern image on the substrate; A heat treatment process for heat-treating the pattern image;
A separation wall having at least
<11> A separation wall formed by the method for forming a separation wall according to <10>.

<12> A method for producing a color filter, comprising a step of applying a colored liquid composition to the concave portions on the partitioned substrate by the separation wall according to <11>.
<13> The step of applying the colored liquid composition is a colored region forming step of forming a colored region by applying a droplet of the colored liquid composition by an ink jet method. Manufacturing method of color filter.

<14> A color filter manufactured by the method for manufacturing a color filter according to <12> or <13>.
<15> A display device comprising the color filter according to <14>.

According to the present invention, when a pattern image (for example, a separation wall) is used, the pattern image is maintained while maintaining the water repellency and ink repellency of the upper surface of the pattern image (exposed surface opposite to the surface in contact with the substrate). The photosensitive resin composition which can maintain favorable adhesiveness with the board | substrate with which this pattern image is formed can be provided.
Moreover, according to this invention, the resin composition which can comprise the said photosensitive resin composition can be provided.
In addition, according to the present invention, the pattern image and the substrate on which the pattern image is formed are adhered while maintaining the water repellency and ink repellency of the upper surface of the transferred pattern image (for example, the image separation wall). Therefore, it is possible to provide a photosensitive transfer material having a uniform photosensitive resin layer that can maintain good properties and suppress the occurrence of repelling during application.
Furthermore, according to the present invention, the separation wall is excellent in water repellency and ink repellency on the upper surface, prevents the ink from running on the separation wall at the time of ink hitting, and provides a separation wall with good adhesion to the substrate. To provide a method for producing a separation wall capable of easily forming the separation wall, and to provide a high-quality color filter in which the occurrence of mixed colors, white spots, color unevenness, etc. is suppressed, and a simple production method thereof. In addition, it is possible to provide a display device capable of displaying a high-quality image in which the occurrence of display unevenness is suppressed.

The present invention will be described in detail below.
<Resin composition>
The resin composition of the present invention comprises (a) at least one fluorine-containing compound having a repeating unit having 3 or more fluorine atoms and (b) a repeating unit represented by the following general formula (B). It is characterized by including at least. When the fluorine-containing compound has the above-described configuration, when a pattern image (for example, a separation wall) is formed on a substrate using the resin composition of the present invention containing the fluorine-containing compound, the upper surface of the pattern image It is possible to maintain good adhesion between the pattern image and the substrate while maintaining the water repellency and ink repellency (exposed surface opposite to the surface in contact with the substrate).

In General Formula (B), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²² R ²¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or An alkanoyl group having 2 to 5 carbon atoms; a single bond L ²¹ represents a single bond or a divalent organic linking group; X represents a chlorine atom, a bromine atom or an iodine atom; Y represents an arylene group; Represents a ring residue or a carbonyl group.

[Fluorine-containing compounds]
The fluorine-containing compound in the present invention has (a) at least one repeating unit having three or more fluorine atoms and (b) at least one repeating unit represented by the general formula (B). It is characterized by that.
The fluorine-containing compound preferably further includes (c) at least one repeating unit having an acidic group. Thereby, the developability of the photosensitive resin layer formed using the photosensitive resin composition containing the said fluorine-containing compound can be improved more.

(A) Repeating unit having 3 or more fluorine atoms The repeating unit having 3 or more fluorine atoms in the present invention is preferably a repeating unit having a side chain containing 3 or more fluorine atoms. The side chain containing three or more fluorine atoms preferably contains a fluoroalkyl group having 2 to 8 carbon atoms in total, more preferably a fluoroalkyl group having 4 to 7 carbon atoms in total. When the total number of carbon atoms of the fluoroalkyl group is within the above range, the load on the environment can be reduced while maintaining the performance as a fluorine functional group. The fluoroalkyl group may be linear or branched.
In the present invention, the repeating unit (a) having 3 or more fluorine atoms is preferably a repeating unit represented by the following general formula (A).

In the general formula (A), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the present invention, R ¹¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the general formula (A), L ¹¹ represents a single bond or a divalent organic linking group. In the present invention, L ¹¹ is preferably a divalent organic linking group. The organic linking group is preferably an organic linking group consisting of a single organic linking group selected from the group consisting of an alkylene group, an arylene group, an ester bond, an amide bond and a divalent heterocyclic residue, or a combination thereof. .

  As said alkylene group, a C1-C10 alkylene group is preferable, More preferably, it is a C1-C6 alkylene group. Specific examples include a methylene group, an ethylene group, a butylene group, a heptylene group, a hexylene group, and a dodecylene group.

  The arylene group is preferably an arylene group having 6 to 15 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Specific examples include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, and a dialkylphenylene group, and these may be o-, p-, and m-substituted.

As the ester bond, a carboxylic acid ester bond, a sulfonic acid ester bond, a phosphoric acid ester bond and the like are preferable, and a carboxylic acid ester bond is more preferable.
As the amide bond, a carboxylic acid amide bond, a sulfonic acid amide bond, a phosphoric acid amide bond and the like are preferable, and a carboxylic acid amide bond is more preferable.

  The divalent heterocyclic residue is preferably, for example, a 5-membered ring containing a nitrogen atom or an oxygen atom as a ring member, or a divalent heterocyclic residue derived from a 6-membered ring, such as a pyridine ring or pyrimidine. A divalent heterocyclic residue derived from a ring, a pyrazine ring, a thiazole ring, a benzothiazole ring, an oxazole ring, a benzoxazole ring, an isoxazole ring, a pyrazole ring, an imidazole ring, a quinoline ring, a thiadiazole ring, or the like; More preferred are divalent heterocyclic residues derived from a ring or a thiadiazole ring.

  In the general formula (A), Rf represents a fluoroalkyl group having 3 or more fluorine atoms. Rf in the present invention is preferably a fluoroalkyl group having 2 to 8 carbon atoms, and more preferably a fluoroalkyl group having 4 to 7 carbon atoms. Rf may be linear or branched. More preferably, it is a fluoroalkyl group represented by any one of the following general formulas (A-1) to (A-3).

In formula, m represents the integer of 4-8, Preferably it is an integer of 4-7.
The repeating units (a-1) to (a-34) are listed below as specific examples of the repeating unit represented by the general formula (A), but the present invention is not limited thereto.
In the following specific examples, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

As the repeating unit having three or more fluorine atoms represented by formula (A) in the present invention, R ¹¹ is a hydrogen atom or a methyl group, and L ¹¹ is a carboxylic acid ester bond, an ether bond, an arylene group, and A divalent organic linking group consisting of a single or a plurality of combinations selected from the group consisting of alkylene groups, wherein Rf is a C _{4 to} C 7 perfluoroalkyl group (C ₄ F _{9 to} C ₇ F ₁₅ ). R ¹¹ is a hydrogen atom, L ¹¹ is a divalent organic linking group comprising a combination of a carboxylic ester bond and an alkylene group, and Rf is a C 4 to C 6 carbon atom. It is more preferably a fluoroalkyl group (C ₄ F _{9 to} C ₆ F ₁₃ ).

(B) Repeating unit represented by general formula (B) The fluorine-containing compound in the present invention includes a repeating unit represented by the following general formula (B).
By including this repeating unit, the surface of the photosensitive resin layer formed on the substrate using the photosensitive resin composition containing the fluorine-containing compound has water / ink repellency, suppression of color mixing / color loss, to the substrate. Better adhesion.

In the general formula (B), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ²¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R ²² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms or an alkanoyl group having 2 to 5 carbon atoms, and is a hydrogen atom, a methyl group, a phenyl group or an acetyl group. Preferably there is.
X represents a chlorine atom, a bromine atom or an iodine atom. Among these, a chlorine atom or a bromine atom is preferable and a chlorine atom is more preferable in terms of stability of liquid crystal holding voltage, suppression of color loss, and availability.

  Y represents an arylene group, a divalent heterocyclic residue or a carbonyl group. Preferred examples of the arylene group and divalent heterocyclic residue include those similar to the arylene group and divalent heterocyclic residue in formula (A). In the present invention, Y is preferably a phenylene group, a naphthylene group or a carbonyl group.

In the general formula (B), L ²¹ represents a single bond or a divalent organic linking group. The divalent organic linking group represented by L ²¹ is a single organic linking group selected from the group consisting of an alkylene group, an arylene group, an ester bond, an ether bond, an amide bond, and a divalent heterocyclic residue, or those In the present invention, L ²¹ is preferably a divalent group containing an ester bond and / or an amide bond from the viewpoint of polymerizability of repeating units, polymer solubility and cost. An organic linking group is preferred. L ²¹ is also preferably a single bond, an arylene group or a divalent heterocyclic residue from the viewpoint of polymerizability of repeating units, heat resistance of the polymer and cost.

The alkylene group in the divalent organic linking group represented by L ²¹ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. Specific examples include a methylene group, an ethylene group, a butylene group, a heptylene group, a hexylene group, and a dodecylene group.

The arylene group in the divalent organic linking group represented by L ²¹ is preferably an arylene group having 6 to 15 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Specific examples include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, and a dialkylphenylene group, and these may be o-, p-, and m-substituted.

The ester group in the divalent organic linking group represented by L ²¹ is preferably a carboxylic acid ester group, a sulfonic acid ester group, or a phosphoric acid ester group, and more preferably a carboxylic acid ester group.
The amide group in the organic linking group represented by L ²¹ is preferably a carboxylic acid amide group, a sulfonic acid amide group, a phosphoric acid amide group, and more preferably a carboxylic acid amide group.
The ether group in the organic linking group represented by L ²¹ is preferably an oxoether group, a thioether group, and more preferably an oxoether group.

As the divalent heterocyclic residue in the divalent organic linking group represented by L ²¹ , for example, a 5-valent ring containing a nitrogen atom or an oxygen atom as a member of the ring, or a divalent derived from a 6-membered ring And preferably derived from a pyridine ring, pyrimidine ring, pyrazine ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring, isoxazole ring, pyrazole ring, imidazole ring, quinoline ring, thiadiazole ring, etc. A divalent heterocyclic residue is more preferable, and a divalent heterocyclic residue derived from a pyridine ring or a thiadiazole ring is more preferable.

Examples of commercially available vinyl compounds that can form the repeating unit represented by the general formula (B) include CMS-P series manufactured by Seimi Chemical Co., Ltd.
Hereinafter, as specific examples of the repeating unit represented by the general formula (B), repeating units (h-1) to (h-37) are shown, but the present invention is not limited thereto.
In the following specific examples, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

As the repeating unit represented by the general formula (B) in the present invention, R ²¹ is a hydrogen atom or a methyl group, R ²² is a hydrogen atom, a methyl group or a phenyl group, and X is a chlorine atom or 2 which is a bromine atom, Y is an arylene group or carbonyl group having 6 to 10 carbon atoms, and L ²¹ contains a single bond, an arylene group, a divalent heterocyclic residue or an ester bond and / or an amide bond. A valent organic linking group,
More preferably, R ²¹ is a hydrogen atom, R ²² is a hydrogen atom, X is a chlorine atom, Y is a carbonyl group, and L ²¹ is an ester bond.

(C) Repeating unit having acidic group Examples of the fluorine-containing compound in the present invention include (a) a repeating unit having three or more fluorine atoms, and (b) a repeating unit represented by the above general formula (B). In addition, it is preferable to further have (c) a repeating unit having an acidic group.
The repeating unit having an acidic group preferably has an acidic group in the side chain. Examples of the acidic group include a carboxy 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 carboxy group.

  There is no restriction | limiting in particular as a monomer which can form the repeating unit which has a carboxy group in a side chain, It can select suitably from well-known monomers. Known monomers include, for example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid Examples thereof include dimer, addition reaction product of a monomer having a hydroxyl group and a cyclic acid anhydride, and ω-carboxy-polyhexanolactone mono (meth) acrylate. As these, those produced as appropriate may be used, or commercially available products may be used.

  Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

  As said commercial item, Toa Gosei Chemical Industry Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shin-Nakamura Chemical Co., Ltd .: NK Ester CB-1, NK ester CBX-1, manufactured by Kyoeisha Oil Chemical Co., Ltd .: HOA-MP, HOA-MS, manufactured by Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100, and the like. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

  The fluorine-containing compound in the present invention may further have another repeating unit other than the repeating unit (c) in addition to the repeating units (a) and (b). The monomer that can form other repeating units may be any monomer that can form a copolymer with the repeating units (a) and (b), such as (meth) acrylates, styrenes, vinyl alkanoates. And the like.

  Examples of the copolymerizable (meth) acrylates include optionally substituted alkyl methacrylate having 1 to 50 carbon atoms, optionally substituted aryl having 6 to 30 carbon atoms (meta ) Acrylate and polyoxyalkylene (meth) having 2 to 50 carbon atoms are preferred. More preferably, an alkyl (meth) acrylate having 1 to 40 carbon atoms and a polyalkylene having 10 to 50 carbon atoms are preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, caprolactone-modified (meth) acrylate, polyethylene oxide (meth) acrylate, polypropylene oxide (meth) acrylate and the like are preferable.

  Examples of the copolymerizable styrenes include those having a vinyl group substituted for a phenyl group having 6 to 20 carbon atoms, those having a vinyl group substituted for a naphthyl group having 10 to 20 carbon atoms, and vinyl having a 14 to 20 anthranyl group having carbon atoms. What substituted the group is preferable and may have substituents other than a vinyl group. More preferably, a vinyl group substituted on a phenyl group having 6 to 10 carbon atoms, a vinyl group substituted on a naphthyl group having 10 to 15 carbon atoms, or a vinyl group substituted on an anthranyl group having 14 to 18 carbon atoms For example, styrene, butyl styrene, methoxy styrene, α-methyl styrene, vinyl naphthalene, and vinyl anthracene are preferable.

  As the copolymerizable vinyl alkanoates, alkyl vinyl esters having 4 to 20 carbon atoms and aryl vinyl esters having 9 to 20 carbon atoms are preferable. More preferably, an alkyl vinyl ester having 4 to 10 carbon atoms and an aryl vinyl ester having 9 to 15 carbon atoms are preferable. For example, vinyl acetate, vinyl butyrate, vinyl dodecanoate, vinyl benzoate and the like are preferable.

  The content of the repeating unit (a) having 3 or more fluorine atoms in the fluorine-containing compound in the present invention is preferably 20 to 85% by mass, more preferably 40 to 85% by mass, and most preferably 50 to 80% by mass. preferable.

  Moreover, 20-80 mass% is preferable in the content of the repeating unit represented by (b) said general formula (B) in the fluorine-containing compound in this invention, 20-75 mass% is more preferable, 40- 70% by mass is most preferred.

  When the fluorine-containing compound of the present invention includes (c) a repeating unit having an acidic group, the content is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and 1 to 30% by mass. Is most preferred.

  The molecular weight of the fluorine-containing compound of the present invention (mass average molecular weight in terms of polystyrene by gel permeation chromatography (GPC)) is preferably 1,000 to 40,000 from the viewpoint of ink repellency and compatibility with the resin composition. 2,000 to 20,000 is more preferable.

  Moreover, 0.01-30 mass% is preferable with respect to the total solid of the photosensitive resin composition, and, as for content of the said fluorine-containing compound in the photosensitive resin composition of this invention, More preferably, it is 0.05-20. It is mass%, and 0.1-10 mass% is the most preferable. When the content of the fluorine-containing compound is 0.01% by mass or more, it is possible to effectively suppress the occurrence of ink running on the separation wall when ink is applied for forming the pixel portion. Moreover, by being 30 mass% or less, application | coating adhesiveness and a separation wall density | concentration can be improved, and preparation of the desired separation wall becomes easier.

  As the fluorine-containing compound in the present invention, (a) the repeating unit having 3 or more fluorine atoms is the repeating unit (a-1), (a-2), (a-6), (a-9), (a-10) or (a-15), wherein (b) the repeating unit represented by the general formula (B) is the repeating unit (h-1), (h-5), (h- 10), (h-11), (h-15) or (h-21), and (c) the repeating unit having an acidic group is preferably acrylic acid.

  Moreover, as a fluorine-containing compound in this invention, content of the repeating unit which has (a) 3 or more fluorine atoms is 30-70 mass%, (b) It represents with the said General formula (B) The content of the repeating unit is preferably 1 to 30% by mass, and (c) the content of the repeating unit having an acidic group is preferably 0 to 30% by mass.

  Specific examples of the fluorine-containing compound according to the present invention are shown below. However, the present invention is not limited to these. In addition, about the composition ratio of each component, it can select in the range of the said preferable composition ratio.

  The fluorine-containing compound in the present invention includes (a) a monomer capable of forming a repeating unit having 3 or more fluorine atoms, (b) a monomer capable of forming a repeating unit represented by the general formula (B), and Depending on the above, (c) a monomer capable of forming a repeating unit having an acidic group and / or other monomer may be mixed at a desired mixing ratio and polymerized by a known method.

  The resin composition of this invention containing the said fluorine-containing compound should just contain the said fluorine-containing compound, and may further contain the other well-known component. Examples of other known components include a solvent, a surfactant, a thermal polymerization inhibitor, and an ultraviolet absorber described later.

  In addition to the above fluorine-containing compound, the resin composition of the present invention may be configured to be photosensitive using at least 1) an initiator, 2) a binder, and 3) an ethylenically unsaturated compound. it can. Hereinafter, the resin composition of the present invention having photosensitivity may be referred to as “photosensitive resin composition”.

1) Initiator The photosensitive resin composition of this invention can be comprised using at least 1 sort (s) of an initiator.
As a method for curing the photosensitive resin composition, a heat initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are generally used. In the present invention, a separation wall after curing will be described later. Since it is important to use a shape, it is preferable to use a photoinitiating system. The photopolymerization initiator used here generates an active species that initiates polymerization of a polyfunctional monomer, which will be described later, upon irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray (also referred to as exposure). It is a compound to be obtained and can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.
For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

  Specifically, a trihalomethyloxazole derivative or s-triazine derivative substituted with a trihalomethyl group described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, Trihalomethyl group-containing compounds such as the trihalomethyloxadiazole compounds described in US Pat. No. 4,221,976;

9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-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) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. Acridine compounds such as bis (9-acridinyl) alkane;

6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis ( Triazines such as trichloromethyl) -s-triazine, 6- [4 ′-(N, N-bis (ethoxycarbonylmethyl) amino) -3′-phenyl] -2,4-bis (trichloromethyl) -s-triazine Other compounds: 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2'-bis (2,4-dichlorophenyl)- 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole And the like.

Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and particularly selected from a trihalomethyl group-containing compound and an acridine compound. It is preferable to contain at least one kind. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.
Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 6- [4 ′-(N, N— Bis (ethoxycarbonylmethyl) amino) -3'-phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxa Trihalomethyl group-containing compounds such as diazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrapheny 1,2' is a bi-imidazole.

The said photoinitiator may be used independently and may use 2 or more types together. As a total amount in the photosensitive resin composition of the said photoinitiator, 0.1-20 mass% of the total solid (mass) of the photosensitive resin composition is preferable, and 0.5-10 mass% is especially preferable. When the total amount is 0.1% by mass or more, the photocuring efficiency of the composition can be increased and the exposure time can be shortened. When the total amount is 20% by mass or less, it is formed during development. Occurrence of missing image patterns and roughness of the pattern surface can be suppressed.
In the present invention, the total solid content (mass) of the photosensitive resin composition means all components excluding the solvent in the photosensitive resin composition.

  The photopolymerization initiator may be configured using a hydrogen donor in combination. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. The “hydrogen donor” herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.

  The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-based hydrogen donor). The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, and more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , Referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

  Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2. , 5-dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

  Specific examples of the amine-based hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl. Examples include -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like. Of these, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferable.

  The hydrogen donor can be used alone or in admixture of two or more, and the formed image is less likely to fall off from the permanent support during development, and can be improved in strength and sensitivity. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors.

  Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzobenzone. Thiazole / 4,4′-bis (diethylamino) benzophenone.

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. As a total amount in the photosensitive resin composition of the said hydrogen donor, 0.1-20 mass% of the total solid (mass) of the photosensitive resin composition is preferable, and 0.5-10 mass% is especially preferable.

2) Binder The photosensitive resin composition of this invention can be comprised using at least 1 sort (s) of a binder.
The binder in the present invention is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. The binder polymer having these polar groups may be used alone, or may be used in the state of a composition used in combination with a normal film-forming polymer, and contained in the total solid content of the photosensitive resin composition. The amount is generally 20 to 50% by mass, and preferably 25 to 45% by mass.

3) Ethylenically unsaturated compound The photosensitive resin composition of this invention can be comprised using at least 1 sort (s) of an ethylenically unsaturated compound.
As the ethylenically unsaturated compound, the following compounds can be used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxy Ethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxy Nzenji (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide, and the like.

Moreover, reaction of a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate with a diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate and xylene diisocyanate. Things can also be used.
Of these, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.

  As content in the photosensitive resin composition of an ethylenically unsaturated compound, 5-80 mass% is preferable with respect to the total solid (mass) of the photosensitive resin composition, and 10-70 mass% is especially preferable. By setting the content to 5% by mass or more, it is possible to further improve the resistance to the alkaline developer at the exposed portion of the composition. Moreover, by setting it as 80 mass% or less, the increase in tackiness when it is set as the photosensitive resin composition is suppressed, and the handleability is further improved.

4) Colorant The (photosensitive) resin composition of the present invention may contain at least one colorant. By containing a color material, the (photosensitive) resin composition of the present invention can be suitably used for, for example, production of a color filter.
Specific examples of the color material used in the present invention include pigments and dyes described in JP-A-2005-17716 [0038] to [0054], and JP-A-2004-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

In the photosensitive resin composition of the present invention, organic pigments, inorganic pigments, dyes, and the like can be suitably used. When the light-shielding property is required for the separation wall, carbon black, titanium oxide, three-tetraoxide. In addition to light-shielding agents such as metal oxide powder such as iron, metal sulfide powder, and metal powder, a mixture of pigments such as red, blue, and green can be used, and among these, carbon black is preferable. Known colorants (dyes and pigments) can be used. When using a pigment among the known colorants, it is preferable that the pigment is uniformly dispersed in the photosensitive resin composition.
The ratio of the coloring material in the total solid content of the photosensitive resin composition is preferably 30 to 70% by mass and more preferably 40 to 60% by mass from the viewpoint of sufficiently shortening the development time. More preferably, it is 50-55 mass%.

The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle). The vehicle refers to a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, a kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, page 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.
The color material (pigment) used in the present invention preferably has a number average particle size of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. The “particle size” here means the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle size” is the above-mentioned particle size for many particles, This 100 average value is said.

  In addition to the components 1) to 3) and the fluorine-containing compound, the following solvent, surfactant, thermal polymerization inhibitor, ultraviolet absorber, and the like can be added to the photosensitive resin composition. In addition, “adhesion aid” described in JP-A-11-133600, other additives, and the like can be contained.

-Solvent-
In the photosensitive resin composition in the present invention, an organic solvent may be further used in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

-Surfactant-
In the photosensitive resin composition of the present invention, it is preferable to contain an appropriate surfactant in the photosensitive resin composition from the viewpoint of being able to control to a uniform film thickness and effectively preventing coating unevenness. .
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.

-Thermal polymerization inhibitor-
The photosensitive resin composition in the present invention preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

-UV absorber-
The photosensitive resin composition in the present invention may contain an ultraviolet absorber as necessary. Examples of the UV absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds, etc., in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like.

<Separation wall and its formation method>
The image separation wall according to the present invention is formed from the photosensitive resin composition. The image separation wall separates two or more pixel groups and is generally black (dark color) in many cases, but is not limited to black. The dark colored product is preferably an organic substance (various dyes such as dyes and pigments, carbon materials) and an inorganic substance (various dark metals such as black metal and salts thereof).

-Method of forming separation wall-
In the method for forming a separation wall according to the present invention, the photosensitive resin composition or the photosensitive transfer material described below is used on at least one surface of a substrate described later (hereinafter also simply referred to as “on the substrate”). A photosensitive resin layer forming step for forming a photosensitive resin layer, an exposure step for exposing the photosensitive resin layer, and development for developing a pattern image on the substrate by developing the exposed photosensitive resin layer And at least a heat treatment step for heat-treating the pattern image.

(Photosensitive resin layer forming step)
In the photosensitive resin layer forming step, a photosensitive resin layer is formed on at least one surface of the substrate using the above-described photosensitive resin composition or using a photosensitive transfer material described later.
The method for forming the photosensitive resin layer using the photosensitive resin composition is not particularly limited. For example, the photosensitive resin composition is applied onto the substrate by a known coating method such as slit coating. Can be formed. As needed, you may pre-bake after application | coating.
The method for forming the photosensitive resin layer using the photosensitive transfer material is not particularly limited, and for example, it can be formed as follows.

A photosensitive transfer material in which an oxygen blocking layer, a photosensitive resin layer, and a cover sheet is provided on the photosensitive resin layer is prepared on a temporary support. First, after removing and removing the cover sheet, the exposed surface of the photosensitive resin layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (laminate). As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to further increase the productivity.
Next, the photosensitive resin layer and the oxygen blocking layer can be formed in this order on the substrate by peeling between the temporary support and the oxygen blocking layer and removing the temporary support from the laminate.

  Since the photosensitive resin layer is preferably cured by a photoinitiating system, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is preferably 2.0 to 10.0, more preferably 2.5 to 6.0, and particularly preferably 3.0 to 5.0. If it is in the preferred range, the shape of the separation wall can be as desired.

-Photosensitive transfer material-
In order to realize such a separation wall easily and at low cost, a layer made of at least the above-mentioned photosensitive resin composition (hereinafter referred to as “photosensitive resin layer” or “photosensitive resin composition layer”) on a temporary support. There is a technique of using a photosensitive transfer material having the above. Further, a protective layer capable of blocking oxygen (hereinafter sometimes referred to as “oxygen blocking layer”) may be provided between the temporary support and the photosensitive resin composition layer as necessary. When the material is used, since the photosensitive resin composition layer is protected by the oxygen blocking layer, it automatically becomes an oxygen-poor atmosphere. Therefore, it is not necessary to perform the exposure process under an inert gas or under reduced pressure, and there is an advantage that the current process can be used as it is. The material constituting the photosensitive resin composition layer in the photosensitive transfer material is as described above. The material constituting the oxygen barrier layer will be described later.
Further, the temporary support may be used as “a protective layer capable of blocking oxygen”. In this case, it is not necessary to provide the oxygen barrier layer, and the number of steps can be reduced.

  The photosensitive transfer material may be heated between the temporary support and the photosensitive resin composition layer as necessary (between the temporary support and the oxygen barrier layer when the oxygen barrier layer is provided). You may have a plastic resin layer. Such a thermoplastic resin layer is alkali-soluble and includes at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, good adhesion to the permanent support can be exhibited.

  Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.

  For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.

  In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.

  Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl phosphate.

The temporary support in the above photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyester, or a laminate thereof is preferable. The thickness of the temporary support is suitably 5 to 300 μm, preferably 20 to 150 μm. If the thickness is less than 5 μm, the temporary support tends to be easily broken when peeled off, and if the exposure is performed via the temporary support, the resolution tends to be lowered if the thickness exceeds 300 μm.
Among the above specific examples, a biaxially stretched polyethylene terephthalate film is particularly preferable.

  A thin cover sheet is preferably provided on the photosensitive resin composition layer in order to protect it from contamination and damage during storage. The cover sheet may be made of the same or similar material as the temporary support, but it should be easily separated from the photosensitive resin composition layer. As the cover sheet material, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable. The thickness of the cover sheet is generally 4 to 40 μm, preferably 5 to 30 μm, particularly preferably 10 to 25 μm.

-Board-
In the present invention, as the substrate (permanent support), glass, ceramic, synthetic resin film or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

(Exposure process and development process)
In the exposure process, the removal surface (oxygen blocking layer surface) after removal of the temporary support of the laminate is arranged so that a desired photomask (for example, quartz exposure mask) faces each other, for example, the laminate and the photomask. Can be exposed by setting the distance between the mask surface and the oxygen blocking layer as appropriate (for example, 200 μm).

The image separation wall is preferably formed by exposing the photosensitive resin composition to an oxygen-poor atmosphere and then developing the photosensitive resin composition.
Under an oxygen-poor atmosphere when photo-curing such a photosensitive resin composition refers to an inert gas, a reduced pressure, and a protective layer that can block oxygen, and these are described in detail below. is there.

The inert gas refers to a general gas such as N ₂ , H ₂ or CO ₂ or a rare gas such as He, Ne or Ar. Among these, N ₂ is preferably used because of safety, availability, and cost.

  Under reduced pressure refers to a state of 500 hPa or less, preferably 100 hPa or less.

Examples of the protective layer capable of blocking oxygen include, for example, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose described in JP-A Nos. 46-2121 and 56-40824. Water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches And a group of water-soluble salts thereof, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably the alkali-soluble resin layer solid content. It is 10-40 mass%.
In addition, various films can be used as the layer capable of blocking oxygen. For example, polyesters such as PET, polyamides such as nylon, and ethylene-vinyl acetate copolymers (EVAs) are also preferably used. be able to. These films may be stretched as necessary, and the thickness is suitably 5 to 300 μm, preferably 20 to 150 μm. When the separation wall is produced using a transfer material, the temporary support described below can be suitably used as a layer capable of blocking oxygen.

The oxygen permeability coefficient of the protective layer capable of blocking oxygen produced in this way is preferably 2000 cm ³ / (m ² · day · atm) or less, but 100 cm ³ / (m ² · day · atm) or less. Is more preferably 50 cm ³ / (m ² · day · atm) or less.
When the oxygen permeability is higher than 2000 cm ³ / (m ² · day · atm), oxygen cannot be effectively blocked, and it may be difficult to make the separation wall into a desired shape.
Subsequently, after the irradiation, development processing is performed using a predetermined processing solution (development process), and then, if necessary, washing treatment is performed to obtain a pattern image (separated wall pattern).

  When the photosensitive transfer material is used and the temporary support is used as a protective layer capable of blocking oxygen, the temporary support and the desired photomask are left with the temporary support remaining (without peeling). (For example, a quartz exposure mask) is arranged so as to face each other, and the distance between the mask surface and the temporary support is appropriately set (for example, 200 μm) in a state where the stacked body and the photomask are set up vertically. , Expose. Next, the temporary support is removed, and after irradiation, development processing is performed using a predetermined processing solution, followed by washing with water as necessary to obtain a pattern image (separation wall pattern).

The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount may be appropriately selected (for example, 300 mJ / cm ² ). it can.
After the irradiation, development processing is performed using a predetermined processing solution. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water. Examples of the light source used for the light irradiation include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like.
Prior to the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the photosensitive resin composition layer or the oxygen barrier layer. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water.

  Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate). , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Examples include morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone 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, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin composition layer, methods such as rubbing with a rotating brush or a wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature (20 ° C.) to 40 ° C. The development time is usually about 10 seconds to 2 minutes, although depending on the composition of the photosensitive resin composition layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If the length is too short, the development of the non-cured portion (non-exposed portion in the case of the negative type) may be insufficient, and at the same time, the absorbance of the ultraviolet rays may be insufficient. May also be etched. In either case, it is difficult to make the separation wall shape suitable. It is also possible to put a water washing step after the development processing. In this developing step, the separating wall shape is formed as described above.

(Heat treatment process)
The image separation wall of the present invention can be obtained by subjecting a pattern image (image separation wall pattern) made of the photosensitive resin layer obtained by the development step to heat treatment (also referred to as baking treatment).
The heat treatment heats and cures the pattern image (separation wall pattern) formed by exposure and development, and since the fluorine functional groups are arranged on the surface by heat, the water repellency and ink repellency by the fluorine-containing compound is more effective. Can be demonstrated.

  As a heat treatment method, various conventionally known methods can be used. That is, for example, a method of storing a plurality of substrates in a cassette and processing them with a convection oven, a method of processing one by one with a hot plate, a method of processing with an infrared heater, and the like.

  Moreover, as baking temperature (heating temperature), it is 150-280 degreeC normally, Preferably it is 180-250 degreeC. The heating time varies depending on the baking temperature. When the baking temperature is 240 ° C., the heating time is preferably 10 to 120 minutes, and more preferably 30 to 90 minutes.

  Further, in the heat treatment step in the method for forming the separation wall, the separation wall pattern formed by the exposure and development steps can be prevented from uneven film loss, UV absorbers contained in the photosensitive resin layer, etc. From the viewpoint of preventing the deposition of these components, post-exposure may be performed before the heat treatment. When post-exposure is performed before the heat treatment, it is possible to effectively prevent the minute foreign matter swelled during lamination from causing defects.

(Post exposure)
Here, the post-exposure will be briefly described.
As the light source used for the post-exposure, any light source capable of irradiating light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm) can be appropriately selected and used.
Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
The exposure may be an exposure to compensate for the exposure, is usually in the 50 to 5000 mJ / cm ^2, preferably not 200~2000mJ / cm ^2, more preferably a 500~1000mJ / cm ^2.

-Separation wall-
The separation wall of the present invention can be formed by the above forming method.
The separation wall of the present invention preferably has a high optical density at 555 nm, more preferably 2.5 or more, more preferably 2.5 to 10.0, and 2.5 to 6.0. Is more preferable, and 3.0 to 5.0 is particularly preferable.
The width and height of the separation wall of the present invention formed as described above are preferably 15 to 100 μm in width (that is, the interval between pixels when a color filter is formed). The height (that is, the distance from the substrate to the top of the separation wall) is preferably 1.0 to 5.0 μm.
As the shape of the separation wall, the shapes described in paragraph numbers [0054] to [0055] of JP-A No. 2006-154804 are also suitable in the present invention.

(Measurement of contact angle on the upper surface of the pattern image)
In the present invention, the water contact angle change of pattern images (for example, separation walls) before and after heat treatment (also referred to as baking treatment) is important. The contact angle measurement method here is a method compliant with the JIS standard by the Japan Standards Association, and specifically, “6. Still-drop method” in JIS R3257 “Test method for wettability of substrate glass surface”. It is the method described in the above. More specifically, using a contact angle measuring device (contact angle meter (CA-A) manufactured by Kyowa Interface Science Co., Ltd.) By contacting the upper surface of the image, water droplets were formed on the upper surface of the pattern image, and after standing for 10 seconds, the shape of the water droplets was observed from the viewing hole of the contact angle meter, and the contact angle θ at 25 ° C. was determined. Further, “after heat treatment” as used herein refers to after heating at 240 ° C. for 50 minutes and then allowing to cool at room temperature for 1 hour.

Here, the upper surface of the separation wall will be described with reference to FIG.
The upper surface of the separation wall refers to the exposed surface on the opposite side of the surface of the separation wall that is in contact with the substrate (upper surface 4 shown in FIG. 1).
The side surface of the separation wall refers to the surface of the separation wall other than the top surface of the separation wall (side surface 5 shown in FIG. 1). Further, the concave portion on the substrate refers to a concave portion that is surrounded by a separation wall and includes a side surface of the separation wall and a substrate surface on which the separation wall is not formed (recess portion 3 shown in FIG. 1).

(Contact angle value)
The photosensitive resin composition of the present invention is a case where the water contact angle on the upper surface of a pattern image (for example, a separation wall) formed using the photosensitive resin composition is measured by the above method, and the heat treatment Pattern image (for example, separation wall before heating) The water contact angle on the upper surface of the pattern image (for example, separation wall pattern before heat treatment) is heated at A ° and 240 ° C. for 50 minutes and allowed to cool for 1 hour. ) When the water contact angle on the upper surface is B °, the contact angle difference B ° −A ° needs to be 20 ° or more.
The contact angle difference B ° −A ° is more preferably 30 ° or more, and most preferably 40 ° or more.

A ° is preferably 0 to 60 °, more preferably 0 to 55 °, and particularly preferably 0 to 50 ° from the viewpoint of further improving the adhesion between the separation wall and the substrate.
B ° is preferably 65 ° to 180 °, more preferably 80 ° to 180 °, and particularly preferably 90 ° to 180 ° from the viewpoint of more effectively suppressing color mixing when a color filter is produced.

<Color filter and manufacturing method thereof>
The color filter manufacturing method of the present invention uses a substrate having the separation wall, and a colored liquid (preferably of two or more colors) in a recess (pixel formation region) on the substrate partitioned by the separation wall. A composition is applied to form a colored pixel group composed of colored pixels (preferably two or more colors) (for example, red, green, blue, white, purple, etc.). The method for applying the colored photosensitive resin composition is not particularly limited, and a known method such as an ink-jet method, a slit coating method, or a trypgicer coating method can be used as appropriate. It is preferable to use an inkjet method. The stripe Geyser coating method is a method of forming stripe-like pixels by applying droplets onto a substrate using a Geyser having fine droplet ejection holes.

-Inkjet system-
As an ink jet system used in the present invention, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and an ink is intermittently heated by using its foaming. Various methods such as a method of injecting the liquid can be employed.
The ink used may be oily or water-based. Further, the colorant contained in the ink can be used for both dyes and pigments, and the use of pigments is more preferable from the viewpoint of durability. In addition, a coating-type colored ink (colored resin composition, for example, described in JP-A-2005-3861 [0034] to [0063]) or JP-A-2004-325736, which is used for producing a known color filter. Also known inks such as those described in JP-A-2002-372613 may be used.
In consideration of a process after coloring, a component that is cured by heating or that is cured by energy rays such as ultraviolet rays can be added to the ink used in the inkjet method. Various thermosetting resins are widely used as components that are cured by heating, and examples of components that are cured by energy rays include those obtained by adding a photoinitiator to an acrylate derivative or a methacrylate derivative. In particular, in view of heat resistance, those having a plurality of acryloyl groups and methacryloyl groups in the molecule are more preferable. These acrylate derivatives and methacrylate derivatives are preferably water-soluble, and even those that are sparingly soluble in water can be used after being emulsified.
In this case, the photosensitive resin composition containing a colorant such as a pigment described in the above-described photosensitive resin composition can be preferably used.

  The color filter in the present invention is preferably a color filter in which pixels are formed by an inkjet method, and it is preferable that at least three color filters are formed by spraying at least RGB three color inks. The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix shape such as a stripe shape, a lattice shape, or a delta arrangement. May be.

(Overcoat layer)
After the color filter is manufactured, an overcoat layer may be provided on the entire surface to improve resistance. The overcoat layer can protect the colored pixels of the inks R, G, and B and can flatten the surface, but it is preferably not provided from the viewpoint of increasing the number of steps.
Examples of the resin (OC agent) forming the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually mainly composed of an acrylic resin, so that the acrylic resin composition is excellent in adhesion. Things are desirable.
Examples of the overcoat layer include those described in JP-A No. 2003-287618, paragraphs 0018 to 0028, and commercially available overcoat agents such as “Optomer SS6699G” manufactured by JSR.

  A transparent electrode, an alignment film, and the like may be provided on the colored pixel layer as necessary. Specific examples of the transparent electrode include, for example, ITO. A specific example of the alignment film is polyimide.

<Display device>
The color filter obtained by the above method is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.
Examples of the display device include display devices such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).
Of the display devices provided with the color filter of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

  In addition, as a target use, it can apply without a restriction | limiting in particular to uses, such as portable terminals, such as a television system, a personal computer, a liquid crystal projector, a game machine, a mobile phone, a digital camera, and a car navigation system.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis example>
Below, the synthesis | combining method of the vinyl compound (henceforth a halide monomer) which can form the repeating unit represented by (b) general formula (B) is shown.
<Synthesis Method of 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.] The internal temperature was cooled to 5 ° C. with an ice bath. To this, 16.2 g of pyridine [Py, manufactured by Tokyo Chemical Industry Co., Ltd.] was added and stirred. 22.6 g of chloroacetyl chloride [CAC, manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise from the dropping funnel so that the temperature inside the flask did not exceed 10 ° C. The reaction was monitored by NMR, and disappearance of HEMA was confirmed, followed by stirring 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 layered water and saturated brine, the organic layer was dried over magnesium sulfate, and insolubles were removed by filtration. The obtained filtrate was concentrated and distilled under reduced pressure to obtain 35.4 g (yield: 86%) of the halide monomer (1).

<Method for synthesizing halide monomer (2)>
In the synthesis method of the halide monomer (1), the halide monomer (2) was synthesized according to the synthesis method of the halide monomer (1) except that HEMA was changed to hydroxyethyl acrylate [HEA, manufactured by Tokyo Chemical Industry Co., Ltd.]. . Yield 88%.

<Method for synthesizing halide monomer (3)>
In the method for synthesizing the halide monomer (1), the halide monomer (3) was synthesized according to the method for synthesizing the halide monomer (1) except that CAC was changed to bromoacetyl bromide [BAB, manufactured by Tokyo Chemical Industry Co., Ltd.]. . Yield 79%.

<Synthesis Method of Halide Monomer (4)>
In the method for synthesizing the halide monomer (1), the halide monomer (4) was synthesized according to the method for synthesizing the halide monomer (1) except that HEMA was changed to Aronix M152 (AX-M152, manufactured by Toagosei Co., Ltd.). . Yield 88%.

<Method for synthesizing halide monomer (5)>
In the method for synthesizing the halide monomer (1), the halide monomer (5) was synthesized according to the method for synthesizing the halide monomer (1) except that HEMA was changed to Aronix M154 (AX-M154, manufactured by Toagosei Co., Ltd.). . Yield 87%.

<Synthesis Method of Halide Monomer (6)>
In the method for synthesizing the halide monomer (1), the halide monomer (6) was synthesized according to the method for synthesizing the halide monomer (1) except that HEMA was changed to Bremer PE200 [BL-PE200, manufactured by NOF Corporation]. . Yield 90%.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, the molecular weight of a fluorine-containing compound represents the mass mean molecular weight of polystyrene conversion by gel permeation chromatography (GPC).

<Method for synthesizing fluorine-containing compound (1)>
In a nitrogen stream, 25 g of propylene glycol monomethyl ether acetate [MMPG-Ac, manufactured by Daicel Chemical Industries, Ltd.] is placed in a 300 ml three-necked flask equipped with a condenser, and the internal temperature is 70 ° C. in a water bath containing paraffin. Until heated. To this, 40 g of MMPG-Ac, 2.5 g of methacrylic acid [MAA, manufactured by Tokyo Chemical Industry Co., Ltd.], 25 g of 2- (perfluorohexyl) -ethyl methacrylate [FAMAC6, manufactured by NOK Corporation], and polyethylene glycol monomer [M90G , Shin-Nakamura Chemical Co., Ltd.] 17.5 g, the above halide monomer (1) 5.0 g, and 2-ethylhexyl mercaptopropionic acid [EHMP, Tokyo Chemical Industry Co., Ltd.] 0.88 g A solution in which 0.334 g of 2,2′-azobis (isovaleronitrile) [V65, manufactured by Wako Pure Chemical Industries, Ltd.] was dissolved in 10 g of MMPG-Ac was added dropwise over 2 hours with a plunger pump. After completion of dropping, the mixture was stirred for 5 hours, and disappearance of the residual monomer was confirmed by ¹ H-NMR.
As described above, (a) 2- (perfluorohexyl) -ethyl methacrylate [FAMAC6], which is a fluorine-containing monomer capable of forming a repeating unit having 3 or more fluorine atoms, and (c) a repeating group having an acidic group Methacrylic acid [MAA] which is a monomer having an acidic group capable of forming a unit, polyethylene glycol monomer [M90G] which is a monomer which can form another repeating unit, and (b) the general formula (B). The fluorine-containing compound (1) of FAMAC6 / MAA / M90G / (1) = 50/5/35/10 (mass ratio) was synthesized by copolymerizing with a halide monomer (1) capable of forming a repeating unit. . The mass average molecular weight was 16,000.
The synthesis of a fluororesin having side chains having six ester chains was confirmed from the disappearance of the monomers and the generation of high molecular weight components.

<Method for synthesizing fluorine-containing compounds (2) to (14)>
According to the synthesis example of the fluorine-containing compound (1), other fluorine-containing compounds (2) to (14) were synthesized. The respective copolymerization components and composition ratios are as follows.
Fluorine-containing compound (2) FAAC6 / AA / AM230G / halide monomer (2) = 50/5/43/2 (mass ratio)
Fluorine-containing compound (3) FAAC6 / AA / AM230G / halide monomer (2) = 50/5/40/5 (mass ratio)
Fluorine-containing compound (4) FAAC6 / AA / AM230G / halide monomer (2) = 40/5/35/20 (mass ratio)
Fluorine-containing compound (5) FAAC6 / AA / AM230G / halide monomer (2) = 30/5/55/10 (mass ratio)
Fluorine-containing compound (6) FAAC6 / AA / AM230G / halide monomer (2) = 50/5/35/10 (mass ratio)
Fluorine-containing compound (7) FAAC6 / AA / FA5 / halide monomer (2) = 40/5/45/10 (mass ratio)
Fluorine-containing compound (8) FAAC6 / AA / FA5 / CMS-P = 40/5/45/10 (mass ratio)
Fluorine-containing compound (9) FAAC6 / AA / AM230G / CMS-P = 40/5/45/10 (mass ratio)
Fluorine-containing compound (10) FAAC6 / AA / AM230G / halide monomer (3) = 50/5/35/10 (mass ratio)
Fluorine-containing compound (11) FAAC6 / AA / AM230G / halide monomer (4) = 50/5/35/10 (mass ratio)
Fluorine-containing compound (12) FAAC6 / AA / AM230G / halide monomer (5) = 50/5/35/10 (mass ratio)
Fluorine-containing compound (13) FAMAC6 / MAA / M230G / halide monomer (6) = 50/5/35/10 (mass ratio)
Fluorine-containing compound (14) FAAC6 / AM230G / halide monomer (2) = 50/40/10 (mass ratio)

<Method for synthesizing fluorine-containing compounds (15) to (16)>
According to the synthesis example of the fluorine-containing compound (1), the fluorine-containing compounds (15) to (16) were synthesized. The respective copolymerization components and composition ratios are as follows.
Fluorine-containing compound (15) TFA / AA / AM130G / halide monomer (2) = 50/5/35/10 (mass ratio)
Fluorine-containing compound (16) FAAC6 / AA / V # 160 = 50/5/45 (mass ratio)

In the above synthesis examples, the abbreviations of the fluorine-containing monomer and other monomers are as follows.
<Fluorine-containing monomer>
FAAC6; 2- (perfluorohexyl) -ethyl acrylate [manufactured by NOK Corporation]
FAMAC6; 2- (perfluorohexyl) -ethyl methacrylate [manufactured by NOK Corporation]
R1420; 2- (perfluorobutyl) -ethyl acrylate [manufactured by Daikin Industries, Ltd.]
<Halide monomer>
CMS-P; chloromethylstyrene [manufactured by Seimi Chemical Co., Ltd.]
<Other monomers>
AA: Acrylic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
MAA; methacrylic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
TFA: trifluoroethyl acrylate [manufactured by Tokyo Chemical Industry Co., Ltd.]
AM130G; monomethyl acrylate of polyethylene glycol (13-mer) [manufactured by Shin-Nakamura Chemical Co., Ltd.]
M90G: Monomethyl methacrylate of polyethylene glycol (9-mer) [manufactured by Shin-Nakamura Chemical Co., Ltd.]
AM230G: Polyethylene glycol (23-mer) monomethyl acrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.]
FA5: monoethyl acrylate of polycaprolactone (pentamer) [manufactured by Daicel Chemical Industries, Ltd.]
V # 160; benzyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd.]

  Regarding each of the fluorine-containing compounds (1) to (16) synthesized above, 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 is added and adjusted so that the solid content concentration of each fluorine-containing compound is 25%.

(Example 1)
-Preparation of photosensitive resin composition-
First, K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 2 below are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then listed in Table 2. Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-diethoxycarbonylmethylamino) -3'-bromophenyl]- s-Triazine, surfactant 1, and fluorine-containing compound (1) obtained above are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and adjusted to 150 rpm at a temperature of 40 ° C. (± 2 ° C.). The mixture was stirred for 30 minutes to prepare a photosensitive resin composition K1.
At this time, the ratio of the fluorine-containing compound (1) to the solid content mass in the photosensitive resin composition K1 was 5%. In addition, the quantity of Table 2 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nexex 35 manufactured by Degussa) ... 13.1%
・ The following dispersant 1 ... 0.65%
-Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000) ... 6.72%
・ Propylene glycol monomethyl ether acetate: 79.53%

<Binder 2>
・ Random copolymer of polymer (benzyl methacrylate / methacrylic acid (= 78/22 [molar ratio]), molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

<DPHA solution>
-Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%

<Surfactant 1>
・ The following structure 1 ・ ・ ・ 30%
・ Methyl ethyl ketone 70%

-Formation of separation wall-
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the glass substrate and adjusting the temperature to 23 ° C., the photosensitive resin composition was coated with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. K1 was applied. Subsequently, a portion of the solvent was dried with a VCD (vacuum drying apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to give a film thickness of 2.3 μm. Photosensitive resin composition layer K1 was obtained (photosensitive resin layer forming step).
Next, with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, The distance between the photosensitive resin composition layers K1 was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in a nitrogen atmosphere (exposure process).

Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin composition layer K1, and then a KOH developer (KOH, containing a nonionic surfactant, product name: CDK-1). , Manufactured by FUJIFILM Electronics Materials Co., Ltd.) was diluted 100 times, and shower development was performed at 23 ° C. for 80 seconds with a flat nozzle pressure of 0.04 MPa to obtain a patterning image (development process). Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and post-exposure was performed at an exposure amount of 2000 mJ / cm ^{2 in the} atmosphere. Subsequently, post-baking is performed at 240 ° C. for 50 minutes (heat treatment step), and striped separation walls having a film thickness of 2.0 μm, an optical density of 4.0, and a width of 100 μm (a substrate with a separation wall) )
The substrate adhesion of the separation wall and the water / ink repellency of the separation wall will be described later.

-Fabrication of color filter-
(1) Preparation of Colored Ink Composition for Pixel Among the following compositions, first, a pigment, a polymer dispersant, and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels.
<Composition of colored ink composition for red (R) pixel>
Pigment (CI Pigment Red 254) 5 parts Solsperse 24000 (manufactured by Nihon Lubrizol; polymer dispersant) 1 part Benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio] ]) Random copolymer (molecular weight: 37,000, binder) 3 parts Epicoat 154 (manufactured by Yuka Shell; Novolac epoxy resin) 2 parts Neopentyl glycol diglycidyl ether (Epoxy resin) ··· 5 parts · Trimellitic acid (curing agent) · · · 4 parts · Ethyl 3-ethoxypropionate (solvent) · · · 80 parts

  Further, C.I. I. Pigment Red 254 instead of C.I. I. A green (G) pixel colored ink composition was prepared in the same manner as in the R pixel colored ink composition except that the same amount of Pigment Green 36 was used. In the above composition, C.I. I. Pigment Red 254 instead of C.I. I. A blue (B) pixel colored ink composition was prepared in the same manner as in the R pixel colored ink composition except that the same amount of Pigment Blue 15: 6 was used.

(2) Formation of Colored Pixels Next, using the colored ink composition for each of the R, G, and B pixels, the region (separated by the separation wall of the substrate with the separation wall obtained above). The ink composition was discharged into the concave portion surrounded by the image wall using an ink jet recording apparatus until a desired density was obtained, and a color filter composed of R, G, and B patterns (colored pixels) was produced. . Subsequently, this color filter was baked in an oven at 230 ° C. for 30 minutes to obtain a color filter substrate in which both the separation wall and each pixel were completely cured.

-Color mixing evaluation of color filters-
The obtained color filter substrate was evaluated as follows. The evaluation results are shown in Table 3 below.
Visual observation was performed with a 200 × optical microscope from the side opposite to the side where the pixels of the color filter were formed, and the presence or absence of color mixing between the pixels was observed. The evaluation was performed by observing 1000 pixels and dividing them into the following ranks. The allowable ranges are A rank and B rank.
-Rank A: There was no color mixing.
-B rank: The color mixture was 1-2 places.
-C rank: The color mixture was 3-10 places.
-D rank: The color mixture was 11 or more places.

-Production of liquid crystal display device-
A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel, and separation wall of the color filter substrate obtained above. When the resistance of this ITO was measured (sheet resistance was measured by a four-probe method using a “Loresta” manufactured by Mitsubishi Chemical Corporation), it was 12Ω / □, indicating a very low value.

-Formation of columnar spacer pattern-
The following photosensitive resin layer coating solution for forming a spacer pattern was applied onto the ITO of the color filter by a slit coater similar to the above, and dried to form a photosensitive resin layer SP1.
<Prescription SP1 of coating solution for photosensitive resin layer>
・ Methacrylic acid / allyl methacrylate copolymer (molar ratio = 20/80, molecular weight 40000; high molecular weight substance) 108 parts ・ Dipentaerythritol hexaacrylate 64.7 parts (polymerizable monomer)
2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine ... 6.24 parts hydroquinone monomethyl ether・ ・ ・ 0.0336 parts ・ Victoria Pure Blue BOHM (Hodogaya Chemical Co., Ltd.) ・ ・ ・ 0.874 parts ・ Megafac F780F (Dainippon Ink Chemical Co., Ltd .; surfactant) ・ ・ ・ 0.856 Methyl ethyl ketone 328 parts 1-methoxy-2-propyl acetate 475 parts Methanol 16.6 parts

Next, proximity exposure was performed at 300 mJ / cm ² with an ultrahigh pressure mercury lamp through a predetermined photomask. After the exposure, the unexposed portion of the photosensitive resin layer was dissolved and removed using a KOH developer [CDK-1 (trade name) 100-fold diluted solution (pH = 11.8), manufactured by Fuji Film Co., Ltd.].
Subsequently, baking was performed at 230 ° C. for 30 minutes, and a columnar spacer pattern having a diameter of 16 μm and an average height of 3.7 μm was formed on a portion located on the upper part of the separation wall on the ITO film on the glass substrate. An alignment film made of polyimide was further provided thereon.

-Formation of liquid crystal alignment split projections-
The following coating liquid for photosensitive resin layer for protrusions was applied onto the ITO of the color filter substrate by a slit coater similar to the above, and dried to form a photosensitive resin layer for protrusions. Next, an intermediate layer coating solution was applied from the following formulation P1 on the protrusion photosensitive resin layer to provide an intermediate layer having a dry film thickness of 1.6 μm.

<Prescription A of coating liquid for photosensitive resin layer for protrusion>
-Positive resist solution 53.3 parts (FH-2413F, manufactured by FUJIFILM Electronics Materials Co., Ltd.)
-Methyl ethyl ketone-46.7 parts-Surfactant 1-0.04 parts

<Prescription P1 of coating solution for intermediate layer>
PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550)... 32.2 parts Polyvinylpyrrolidone. -30)
・ Distilled water: 524 parts ・ Methanol: 429 parts

Next, a proximity exposure machine is arranged so that the photomask is at a distance of 100 μm from the surface of the photosensitive resin layer for protrusions, and the proximity exposure is performed through the photomask with an irradiation energy of 150 mJ / cm ² by an ultrahigh pressure mercury lamp. did. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying on the substrate at 33 ° C. for 30 seconds with a shower type developing device, and unnecessary portions (exposed portions) of the photosensitive resin layer for protrusion were developed and removed. . As a result, a protrusion made of a photosensitive resin layer patterned in a desired shape was formed on a portion of the color filter substrate on the ITO film located above the R, G, and B pixels. Next, the color filter substrate on which the protrusions were formed was baked at 240 ° C. for 50 minutes to form alignment dividing protrusions having a height of 1.5 μm and a vertical cross-sectional shape on the color filter substrate.

  Further, an alignment-divided vertical alignment type liquid crystal display element was manufactured by combining the obtained color filter substrate with a driving side substrate and a liquid crystal material. Specifically, a TFT substrate on which TFTs and pixel electrodes (conductive layers) are arrayed is prepared as a driving side substrate, and the TFT substrate pixel electrode and the like are provided on the TFT substrate and the color filter substrate obtained from the above. The surface on the side and the surface on the side of the color filter substrate on which the alignment dividing projections and the like are formed are arranged to face each other, and are fixed with a gap corresponding to the spacer. A liquid crystal layer responsible for image display was provided by enclosing a liquid crystal material in the gap to obtain a liquid crystal cell. A polarizing plate HLC2-2518 manufactured by Sanlitz Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed, and this was disposed on the side (back side) opposite to the side where the polarizing plate of the liquid crystal cell was provided, thereby obtaining an alignment-divided vertical alignment type liquid crystal display device.

-Evaluation-
(1) Water-repellent / ink-repellent property of separation wall The photosensitive resin composition layer K1 formed in the same manner as described above is exposed by the same method as described above except that a mask is not used, and then post-baked ( The operation up to the heat treatment step) was performed under the same conditions to obtain a photosensitive resin composition layer for testing. And after leaving this photosensitive resin composition layer for a test to cool at room temperature for 1 hour after the post-baking treatment, using a contact angle measuring device (contact angle meter CA-A manufactured by Kyowa Interface Science Co., Ltd.) The colored ink composition for R pixel is taken out from the needle tip as a liquid sample (ink sample) having a size of 20 memories, and is brought into contact with the photosensitive resin composition layer for testing. A droplet (ink droplet) of a colored ink composition for an R pixel was formed on. Then, the shape of the ink droplet was observed from the viewing hole of the contact angle meter, and the ink contact angle θ ⁰ of the ink droplet after standing for 10 seconds after landing at 25 ° C. was determined.
Thereafter, the test photosensitive resin composition layer was post-baked under the same conditions as described above, and ink droplets of the R pixel colored ink composition were again formed in the same manner, and the ink contact angle θ ¹ was measured. did.
Further, the ink droplet whose contact angle was measured was changed to a water droplet, and the water contact angle θ ² before post-baking and the water contact angle θ ³ after post-baking were measured in the same procedure.
The value after post-baking was used as an index for evaluating water repellency and ink repellency, and evaluated according to the following evaluation criteria. The allowable ranges are A rank and B rank. The evaluation results are shown in Table 3 below.
<Evaluation criteria>
Rank A: ink contact angle ≧ 50 °, water contact angle ≧ 100 °
Rank B: Ink contact angle ≧ 40 °, water contact angle ≧ 90 °
C rank: ink contact angle ≧ 35 °, water contact angle ≧ 80 °
D rank: ink contact angle <35 °, water contact angle <80

(2) Substrate Adhesion of Separation Wall Prepare three glass substrates that have been subjected to the exposure process under the same conditions in “Formation of Separation Wall”, and increase the development time to 90 seconds, 100 seconds, and 110 seconds. Except for the above processing, development was performed under the same development conditions, and the presence or absence of chipping of the separation wall at each development time was evaluated according to the following evaluation criteria by visual observation for 1000 pixels. The allowable ranges are A rank and B rank. The evaluation results are shown in Table 3 below.
<Evaluation criteria>
-Rank A: No separation wall was missing.
-B rank: The image separation wall chip was 1-2 places.
-C rank: The image separation wall chip was 3-10 places.
-D rank: There were 11 or more image separation wall defects.

(3) Display unevenness of liquid crystal display device For the liquid crystal display device produced above, the gray display when a gray test signal is inputted is visually observed, and the presence or absence of display unevenness is evaluated according to the following evaluation criteria. did.
<Evaluation criteria>
A rank: There was no display unevenness and a very good display image was obtained.
Rank B: Although the edge of the glass substrate was slightly uneven, there was no effect on the display part and the display image was good.
-C rank: Although the display portion was slightly uneven, it was within a practically acceptable range.
-D rank: The display part was uneven.

(Example 2)
A photosensitive resin composition K2 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, and a color filter and a liquid crystal display device were prepared. And the same evaluation was performed. The evaluation results are shown in Table 3 below.

(Example 3)
A photosensitive resin composition K3 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 0.1% in Example 1, and a color filter, liquid crystal A display device was fabricated and the same evaluation was performed. The evaluation results are shown in Table 3 below.

(Examples 4 to 16)
Example 2 was the same as Example 2 except that the fluorine-containing compound (1) was replaced with the fluorine-containing compounds (2) to (14) of the present invention obtained above (the fluorine-containing compound of the present invention). Photosensitive resin compositions K4 to K16 were prepared to produce color filters and liquid crystal display devices, and the same evaluation was performed. The evaluation results are shown in Table 3 below.

(Comparative Example 1)
In Example 2, a photosensitive resin composition K17 was prepared in the same manner as in Example 2 except that the fluorine-containing compound (1) was replaced with the comparative fluorine-containing compound (15), and a color filter, A liquid crystal display device was produced and the same evaluation was performed. The evaluation results are shown in Table 3 below.

(Comparative Example 2)
In Example 2, a photosensitive resin composition K18 was prepared in the same manner as in Example 2 except that the fluorine-containing compound (1) was replaced with the comparative fluorine-containing compound (16), and a color filter, A liquid crystal display device was produced and the same evaluation was performed. The evaluation results are shown in Table 3 below.

As shown in Table 3, in the examples, the water and ink repellency on the partition walls after the heat treatment was excellent, no color mixing occurred, and the substrate adhesion was good. In addition, the occurrence of display unevenness when a liquid crystal display device was produced and displayed was effectively suppressed, and an image having excellent display characteristics was obtained.
On the other hand, the comparative example was inferior in water and ink repellency on the partition wall after the heat treatment, had insufficient color mixing prevention effect, and inferior in substrate adhesion. For this reason, it has been difficult for the liquid crystal display device to display an image without display unevenness.

(Example 17)
An alkali-free glass substrate (hereinafter, simply referred to as “glass substrate”) was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower. Coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and further washed with a pure water shower. did. After cleaning, the glass substrate was heated at 100 ° C. for 2 minutes by a substrate preheating device.

On the glass substrate after the silane coupling treatment, the surface of the photosensitive resin composition layer exposed by removing the cover film from the photosensitive transfer material K1 described below is superposed so as to be in contact with the surface of the glass substrate, and a laminator ( Using a Lamic II type (manufactured by Hitachi Industries, Ltd.), lamination was performed at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min. Subsequently, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer. After peeling off the temporary support, the glass substrate and the mask (quartz exposure mask having an image pattern) are set up vertically using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. Then, the distance between the exposure mask surface and the photosensitive resin composition layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Subsequently, development was performed with a KOH developer (100-fold diluted solution (pH = 11.8) of CDK-1 (trade name) manufactured by FUJIFILM Corporation), and unexposed portions of the photosensitive resin composition layer and The underlying intermediate layer and the thermoplastic resin layer were removed, and a pattern was formed on the glass substrate. Subsequently, the entire surface of the glass substrate was post-exposed at 2000 mJ / cm ² from the pattern forming surface side of the glass substrate with an aligner in the atmosphere, and post-baked at 240 ° C. for 50 minutes. Thus, a separation wall (black matrix) having an optical density of 4.0 was obtained.

  Thereafter, in the same manner as in Example 1, a color filter and a liquid crystal display device were produced, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 4 below.

<Preparation of photosensitive transfer material K1>
On a polyethylene terephthalate film (PET temporary support) having a thickness of 75 μm, using a slit nozzle, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried to form a thermoplastic resin layer. Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation P1 was applied and dried to laminate an intermediate layer (oxygen barrier film). Further, the photosensitive resin composition K5 prepared in Example 5 was applied on the intermediate layer and dried to laminate a black (K) photosensitive resin composition layer K5. At this time, the ratio with respect to solid content mass of the fluorine-containing compound (3) in the photosensitive resin composition K5 is 1.0%.
Thus, 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 on the PET temporary support. A temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin composition is laminated by laminating the composition layer and further pressure-bonding a protective film (thickness 12 μm polypropylene film) to the surface of the photosensitive resin composition layer. A photosensitive transfer material K1 integrated with the layer K2 was produced.

(Prescription H1 of coating solution for thermoplastic resin layer)
Methanol: 11.1 parts Propylene glycol monomethyl ether acetate: 6.36 parts Methyl ethyl ketone: 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (co-polymer) Polymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.) 5.83 parts Styrene / acrylic acid copolymer (copolymerization) Composition ratio (molar ratio) = 63/37, average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (Shin Nakamura) Chemical Industry Co., Ltd.) ... 9.1 parts-Surfactant 1 ... 0.54 parts

(Prescription P1 of coating solution for intermediate layer)
-PVA205 ... 32.2 parts (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
Polyvinylpyrrolidone: 14.9 parts (APS Japan, K-30)
・ Distilled water: 524 parts ・ Methanol: 429 parts

(Examples 18 to 20)
In the production of the photosensitive transfer material of Example 17, photosensitive materials each containing the fluorine-containing compounds (7), (9) and (11) in the present invention instead of the photosensitive resin composition K2 containing the fluorine-containing compound (3). Photosensitive transfer materials K2 to 4 were prepared in the same manner as in Example 17 except that the photosensitive resin compositions K9, K11, and K13 were used, and further, a color filter and a liquid crystal display device were manufactured. Further, the same evaluation as in Example 1 was performed, and the evaluation results are shown in Table 4 below.

  As shown in Table 4, in the examples, the water and ink repellency on the separation wall after the heat treatment was excellent, no color mixing occurred, and the substrate adhesion was good. In addition, the occurrence of display unevenness when a liquid crystal display device was produced and displayed was effectively suppressed, and an image having excellent display characteristics was obtained.

In the present invention, it is a cross-sectional view of a color filter for explaining a separation wall upper surface, a separation wall side surface, a concave portion on a substrate, and the like.

Explanation of symbols

1 ... image separation wall 2 ... colored pixels (colored areas)
3... Recessed portion 4... Separation wall upper surface 5... Separation wall side surface 6.

Claims (15)

(A) A resin composition comprising a fluorine-containing compound having a repeating unit having three or more fluorine atoms and (b) a repeating unit represented by the following general formula (B).

In General Formula (B), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 2 carbon atoms. -5 represents an alkanoyl group, L ²¹ represents a single bond or a divalent organic linking group, X represents a chlorine atom, a bromine atom or an iodine atom, Y represents an arylene group, a divalent heterocyclic residue or a carbonyl group Represents a group.   The resin composition according to claim 1, wherein the repeating unit (a) having 3 or more fluorine atoms is a repeating unit having a fluoroalkyl group having 4 to 7 carbon atoms. The resin composition according to claim 1 or 2, wherein L ²¹ in the general formula (B) is a divalent organic linking group containing an ester bond and / or an amide bond. L ²¹ in the said general formula (B) is a single bond, an arylene group, or a bivalent heterocyclic residue, The resin composition of Claim 1 or Claim 2 characterized by the above-mentioned.   The said fluorine-containing compound further has a repeating unit which has (c) acidic group, The resin composition of any one of Claims 1-4 characterized by the above-mentioned.   The resin composition according to any one of claims 1 to 5, further comprising 1) an initiator, 2) a binder, and 3) an ethylenically unsaturated compound, and having photosensitivity. object.   Content of the said fluorine-containing compound in solid content is 0.1 mass%-10 mass%, The resin composition of any one of Claims 1-6 characterized by the above-mentioned.   It is used for preparation of a color filter, The resin composition of any one of Claims 1-7 characterized by the above-mentioned.   The photosensitive transfer material which has the photosensitive resin layer which consists of a resin composition of any one of Claims 6-8 on a temporary support body. Photosensitivity which forms the photosensitive resin layer in the at least one surface of a board | substrate using the resin composition of any one of Claims 6-8, or the photosensitive transfer material of Claim 9. A functional resin layer forming step;
An exposure step of exposing the photosensitive resin layer;
A developing step of developing the exposed photosensitive resin layer to form a pattern image on the substrate;
A heat treatment step of heat-treating the pattern image;
A separation wall having at least   A separation wall formed by the method for forming a separation wall according to claim 10.   The manufacturing method of the color filter which has the process of providing a colored liquid composition to the recessed part on the board | substrate divided by the separation wall of Claim 11.   The step of applying the colored liquid composition is a colored region forming step of forming a colored region by applying a droplet of the colored liquid composition by an inkjet method. Production method.   A color filter manufactured by the method for manufacturing a color filter according to claim 12.   A display device comprising the color filter according to claim 14.

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