JP5013913B2 - Method for forming photosensitive resin film for separating wall, photosensitive transfer material, substrate with separating wall, color filter, manufacturing method thereof, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a black matrix having good ink repellency and small variation in height, and to enable high-quality image display with suppressed display irregularities. <P>SOLUTION: A coating film formed by coating with a photosensitive resin composition containing an ink repellent is dried in a range that the flow rate of gas at a height of 0.5 cm from the film surface is made &le;0.5 m/s. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for forming a photosensitive resin film for a separating wall, a photosensitive transfer material, a substrate with a separating wall, a color filter, a manufacturing method thereof, 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 indispensable 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, it is possible to form a colored layer composed of three colored portions of R (red), G (green), and B (blue).
In addition, the pigment dispersion method is a method that 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 it. By repeating this step three times, it is possible to form a colored layer composed of three colored portions of R, G, and B.
The electrodeposition method is a method in which 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. By repeating three times, a colored layer composed of three colored portions of R, G, and B is obtained, and finally fired. In the printing method, a pigment is dispersed in a thermosetting resin, R, G, and B are separately applied by repeating printing three times, and then the resin is thermally cured to form a colored layer.

  These methods are common in that it is necessary to repeat the same process three times in order to form a red, green, and blue three-color pixel, resulting in high costs, and because the number of processes is large. There is also a problem that the yield tends to decrease.

In view of the above, 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 formed by an ink jet method has been studied. In this ink jet method, for example, liquids of R, G, and B colors are sequentially applied to concave portions surrounded by a black matrix that is a separation wall that partitions pixels to form colored regions (for example, pixels). The method using the ink jet method has an advantage that the manufacturing process is simple and the cost is low.
Further, the ink jet method is not limited to the manufacture of color filters, but can also be applied to the manufacture of other optical elements such as electroluminescent elements.

  In the ink jet 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 is hardened and stuck to a portion other than the predetermined region. For this reason, the separation wall such as a black matrix is required to have a property of repelling water or an organic solvent which is a coating liquid ejected by an ink jet method, so-called water repellency and oil repellency.

  In connection with water repellency and oil repellency, a photoresist composition containing a copolymer of a fluoroalkyl group-containing (meth) acrylate monomer and a silicone chain-containing ethylenically unsaturated monomer is disclosed, The addition of a copolymer in the range of 0.001 to 0.05 mass% with respect to the solid content of the photoresist composition is described (for example, see Patent Document 1).

Also, a coating composition containing a vinyl polymer obtained by polymerizing a monomer composition containing a vinyl monomer having a fluoroalkyl group, a photosensitive resin and an organic solvent, and having 4 to 6 carbon atoms. There are disclosures relating to a vinyl polymer obtained by polymerizing a monomer composition containing a vinyl monomer having a fluoroalkyl group, and a resist composition containing a photoreceptor (for example, Patent Documents 2 to 3). reference).
JP-A-9-54432 JP 2004-2733 A JP 2005-315984 A

  However, in the composition such as the above-described photoresist composition or coating composition, not only water repellency and oil repellency are insufficient when the coating film is formed, but also the film surface of the coating film due to ink repellency. Control becomes difficult, and fluctuations in the film are likely to occur in processes such as drying after coating. If the thickness of the film itself before pattern formation becomes non-uniform, the in-plane uniformity of the pattern formed from the film cannot be maintained, which hinders uniform pattern formation. Therefore, a color filter and a display device that can display a high-quality image without display unevenness cannot be obtained.

  The present invention has been made in view of the above, and when a separation wall such as a black matrix that partitions pixels constituting a pixel group is applied and formed in advance using a resin composition containing an ink repellent agent, Resistant for separation wall, which has good ink repellency that can prevent ink running, can form a separation film for separation wall formation with reduced film thickness fluctuation, and can obtain a separation wall with small height variation. Forming method of photosensitive resin film, photosensitive transfer material, and substrate with separation wall, color filter, and production thereof capable of preventing color mixing, color unevenness, etc. and suppressing display unevenness in a display image and displaying high-quality images An object is to provide a method and a display device, and to achieve the object.

  In the present invention, in order to form a separation wall having a uniform height, it is important to reduce the in-plane film thickness variation of the resin composition film before the pattern formation process by exposure, development, etc., In addition, in order to impart water repellency and ink repellency to the separation wall without performing fluorine plasma treatment, it has been found that it is effective to use a composition whose surface energy greatly increases before and after heating such as post-baking. Obtained based on this knowledge.

Specific means for achieving the above object are as follows.
<1> As an ink repellent agent , (a) a repeating unit having at least a fluorine atom in a side chain, (b) a repeating unit represented by the following structural formula (B), and (c) a carboxylic acid group in a side chain A coating step of coating a photosensitive resin composition containing a fluorine-containing compound containing a repeating unit, and a coating film formed by coating on the surface of the coating film with a wind speed of 0.1 m / s to 0.5 m / s And a drying step of drying at a flow rate of 0.1 m / s to 0.5 m / s at a flow rate of 0.5 cm / s at a height of 0.5 cm from the film surface. This is a method of forming a resin film.
<2> The method for forming a photosensitive resin film for a separating wall according to <1>, wherein a fluorine atom content in the ink repellent agent is 36 to 70% by mass .

In the structural formula (B), R ² represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. L ² represents a single bond or a divalent linking group, and M represents a repeating unit of polyethylene oxide. n represents 4-40. b represents the ratio (mass%) of the mass of the structural formula (B) in the total mass of the fluorine-containing compound.
< 3 > A photosensitive transfer material having a photosensitive resin layer formed on the temporary support by the method for forming a photosensitive resin film for a separating wall according to <1> or <2> .

<4> Exposing a substrate and a photosensitive resin layer formed by using the photosensitive resin film for a separating wall according to claim 1 or 2, or the photosensitive transfer material according to claim 3. And developed as an ink repellent agent ; (a) a repeating unit having at least a fluorine atom in a side chain; (b) a repeating unit represented by the structural formula (B); and (c) a carboxylic acid group. the containing a fluorine-containing compound containing a repeating unit having a side chain, a Hanarega a wall board having a resin Hanarega wall membrane plane thickness uniformity is within 5% ±, a.

< 5 > A photosensitive resin layer is formed on a substrate using the method for forming a photosensitive resin film for a separating wall according to <1> or <2> or the photosensitive transfer material according to < 3 >. A layer forming step to form, a separation wall forming step in which the formed photosensitive resin layer is exposed in a pattern through a mask and developed to form a separation wall; and a substrate partitioned by the separation wall A colored region forming step of forming a colored region by applying a colored liquid composition to the recesses by an inkjet method.
< 6 > A color filter produced by the method for producing a color filter according to < 5 >.
< 7 > A display device comprising the color filter according to < 6 >.

According to the present invention, when a separation wall such as a black matrix that partitions pixels constituting a pixel group is applied and formed using a resin composition containing an ink repellent agent in advance, it is possible to prevent ink from running up. It is possible to form a resin film for forming a separation wall that has ink repellency and suppresses film thickness fluctuations (preferably so that the in-plane uniformity of the coating film is within ± 5%). It is possible to provide a method for forming a photosensitive resin film for a separation wall and a photosensitive transfer material from which a separation wall with small variation can be obtained. Also,
According to the present invention, there are provided a substrate with a separating wall, a color filter, a manufacturing method thereof, and a display device that can prevent color mixing, color unevenness, and the like, and can perform high-quality image display while suppressing display unevenness in a display image. can do.

  Hereinafter, a method for forming a photosensitive resin film for a separation wall according to the present invention, a photosensitive transfer material using the same, a substrate with a separation wall, a color filter, a manufacturing method thereof, and a display device will be described in detail.

<Method for forming photosensitive resin film for separation wall>
The method for forming a photosensitive resin film for a separating wall according to the present invention is represented by (a) a repeating unit having at least a fluorine atom in a side chain as an ink repellent agent , and (b) a structural formula (B) shown below. A coating step of applying a photosensitive resin composition containing a fluorine-containing compound containing a repeating unit and a repeating unit having (c) a repeating unit having a carboxylic acid group in the side chain ; and a coating film formed by coating, Dry air is applied to the surface at a flow rate of 0.1 m / s or more and 0.5 m / s or less, and the gas flow rate at a height of 0.5 cm from the film surface is set to 0.1 m / s or more and 0.5 m / s or less. And a drying step for drying. Moreover, it can comprise by providing another process as needed.

-Application process-
In the coating step, as the ink repellent agent, (a) a repeating unit having at least a fluorine atom in the side chain, (b) a repeating unit represented by the structural formula (B) shown below, and (c) a carboxylic acid group in the side chain A photosensitive resin composition containing at least a fluorine-containing compound containing the repeating unit is applied.
When the separation wall is formed directly on the substrate, the separation wall is formed by transferring the layer made of the photosensitive resin composition onto the substrate as a permanent support or by the transfer method. In this case, it can be carried out on a temporary support constituting the photosensitive transfer material. Therefore, when forming the photosensitive resin layer using the photosensitive resin composition, the photosensitive transfer material of the present invention described later is used by using the photosensitive resin composition described later on at least one surface of the substrate. It can be formed by using. Details of the photosensitive resin composition and the photosensitive transfer material will be described later.

Application of the photosensitive resin composition is not particularly limited, but can be performed by a known application method such as slit application, bar application, curtain application, or the like.
In the case of coating on a desired substrate, after being subjected to a drying step described later, a photosensitive resin film (photosensitive resin layer) for a separation wall is directly formed on the substrate. Moreover, when apply | coating on a desired temporary support body, after using for the drying process mentioned later, the photosensitive resin film for image separation walls after drying is transcribe | transferred, and the photosensitive resin layer forms on a desired board | substrate. Is done. As in the latter case, when applying on a temporary support, generally, the application is performed using a long temporary support for the purpose of forming a roll-shaped transfer material. Is relatively fast. For this reason, in order to obtain a separation wall with reduced film thickness fluctuation (in-plane uniformity is good) and small height variation, it is necessary to consider not only the drying process described later, but also the amount of air entrained depending on the coating speed. .

In addition, when the photosensitive resin layer is transferred and formed on the substrate using the photosensitive transfer material, for example, it can be performed as follows. That is,
A photosensitive transfer material is prepared in which an oxygen blocking layer, a photosensitive resin layer, and a cover sheet for protecting the photosensitive resin layer are provided on the temporary support in order from the temporary support side. . First, after removing and removing the cover sheet, the exposed surface of the photosensitive resin layer is bonded onto a substrate which is a permanent support, and is 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 support layer is peeled between the temporary support and the oxygen barrier layer (or thermoplastic resin layer), and the temporary support is removed from the laminate, whereby the photosensitive resin layer is placed on the substrate. And a plastic resin layer).

~ Board etc. ~
In the present invention, as the substrate (permanent support), glass, ceramic, synthetic resin film or the like can be used. Particularly preferred are transparent substrates such as glass and synthetic resin films that are transparent and have good dimensional stability.
The details of the temporary support constituting the photosensitive resin transfer material will be described later.

-Photosensitive resin composition-
The photosensitive resin composition in the present invention comprises (a) a repeating unit having at least a fluorine atom in a side chain as at least an ink repellent agent , (b) a repeating unit represented by the following structural formula (B), and (c) It contains at least one fluorine-containing compound containing a repeating unit having a carboxylic acid group in the side chain , and if necessary, an initiator, a binder, an ethylenically unsaturated compound, a coloring material, and other additions It can be configured using an agent.

  Since the photosensitive resin composition includes an ink repellent agent, it is possible to improve water repellency and ink repellency on the surface of a pattern image formed using the photosensitive resin composition. And this photosensitive resin composition is applied to the method for forming a photosensitive resin film for a separation wall of the present invention, so that the film surface operation when a film is formed using a resin composition containing an ink repellent agent. Can be easily performed, and a coating film with high in-plane uniformity can be obtained while providing water repellency and ink repellency.

When the water contact angle is measured according to the method described in JIS R3257 due to the inclusion of the ink repellent agent, the water contact angle on the surface of the pattern image before the heat treatment is A °, and the condition of 240 ° C. for 50 minutes The water contact angle difference (B ° −A °) when the water contact angle on the surface of the pattern image is B ° after being heat-treated for 1 hour and allowed to cool for 1 hour is 20 ° or more. be able to. Details of the water contact angle will be described later.
In addition, a substrate on which the separation wall and the separation wall are formed while maintaining water repellency and ink repellency on the surface of the separation wall formed using the photosensitive resin composition by containing the ink repellent agent It is possible to maintain good adhesion with. Furthermore, when a colored liquid composition is applied to the concave portion surrounded by the separation wall to form a colored region to produce a color filter, it is possible to suppress the occurrence of color mixing and color unevenness.

1) Ink repellent agent The photosensitive resin composition of the present invention contains at least one ink repellent agent. The ink repellent agent is preferably a compound containing a silicon atom or a fluorine atom having a low affinity with a resin component such as a binder contained in a material constituting the separation wall such as a black matrix.

  Examples of the compound containing a silicon atom include those having as a main component a linear organic polysiloxane having a molecular weight of several thousand to several hundred thousand having the following repeating unit.

  In the repeating unit, n represents an integer of 2 or more, and each R independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or a phenyl group. Silicone rubber is obtained by sparsely cross-linking such a linear organic polysiloxane. Cross-linking agents used for cross-linking are acetoxy silane, ketoxime silane, alkoxy silane, amino silane, amide silane, alkenoxy silane, etc., which are used for so-called room temperature (low temperature) curable silicone rubber, and usually linear organic polysiloxane In combination with those having a terminal hydroxyl group, deacetic acid-type, deoxime-type, dealcohol-type, deamine-type, deamid-type and de-ketone-type silicone rubbers are obtained. In addition, a small amount of an organic tin compound or the like is added to the silicone rubber as a catalyst.

Preferred examples of the compound containing a fluorine atom include compounds containing a repeating unit having a fluorine atom. From the viewpoint of ink repellency, (a) a repeating unit having at least a fluorine atom in the side chain and (b) a polyether A fluorine-containing compound containing a repeating unit having a structure in the side chain and (c) a repeating unit having a carboxylic acid group in the side chain is preferable. In the present invention, as the ink repellent agent, (a) a repeating unit having at least a fluorine atom in the side chain, (b) a repeating unit represented by the following structural formula (B), and (c) a carboxylic acid group in the side chain A fluorine-containing compound containing the repeating unit.
Hereinafter, the fluorine-containing compound will be described in detail.

-(A) Repeating unit having at least fluorine atom in side chain-
The fluorine-containing compound in the present invention preferably contains (a) a repeating unit having at least a fluorine atom in the side chain. Thereby, water repellency and ink repellency can be provided. The repeating unit having at least a fluorine atom in the side chain is preferably a repeating unit having a fluorinated alkyl group having 4 to 8 carbon atoms, and the fluorinated alkyl group may be linear or branched. More preferably, the following structural formula (A) is mentioned.

In the structural formula (A), R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group and an ethyl group.
In the structural formula (A), a represents a mass ratio (mass%) of the structural formula (A) in the total mass of the fluorine-containing compound. A specific range of a will be described later.

In the structural formula (A), X ¹ represents an ether group, an ester group, an amide group, an arylene group, or a divalent heterocyclic residue.
The arylene group represented by X ¹ is preferably an arylene group having 6 to 20 carbon atoms, and examples thereof include phenylene, naphthylene, anthracenylene, and biphenylene, which may be o-, p-, or m-substituted. Among these, an arylene group having 6 to 12 carbon atoms is more preferable, and phenylene and biphenylene are particularly preferable.
As the heterocyclic residue represented by X ¹ , for example, a divalent heterocyclic residue derived from a 5-membered or 6-membered heterocyclic ring containing a nitrogen atom or an oxygen atom as a member of the ring is preferable. As specific examples, pyridine ring, pyrimidine ring, pyrazine ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring, isoxazole ring, pyrazole ring, imidazole ring, quinoline ring, thiadiazole ring and the like are preferable. A divalent heterocyclic residue derived from a pyridine ring, a thiadiazole ring, or the like is more preferable.
Among the above, X ¹ is preferably a linking group having the following linking group or the following structure.

Here, R ^X represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms in total, or an aryl group having 6 to 20 carbon atoms in total.
The alkyl group having a total carbon number of 1 to 12 represented by R ^X, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an unsubstituted alkyl group such as a dodecyl group, and an ether And a substituted alkyl group having a substituent such as a group, a thioether group, an ester group, an amide group, an amino group, a urethane group and a hydroxy group. Among them, an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, a butyl group, and an octyl group are more preferable.
The aryl group having a total carbon number of 6 to 20 represented by R ^X, for example, a phenyl group, a naphthyl group, methylphenyl group, methoxyphenyl group, nonyl phenyl group. Among them, an aryl group having 6 to 15 carbon atoms is preferable, and a phenyl group and a nonylphenyl group are more preferable.

In the structural formula (A), L ¹ is preferably the following linking group or a linking group having the following structure.

R ^Y represents a hydrogen atom or a methyl group.
n represents an integer of 2 to 20, preferably an integer of 4 to 12.
Y is more preferably a single bond, the following linking group, or a linking group having the following structure.

n represents an integer of 2 to 20, preferably an integer of 4 to 12.
R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.

  In the structural formula (A), Rf represents a group containing fluorine. Rf is preferably a fluorine-containing group having the following structure or a fluorine-containing group having a group having the following structure.

  m represents an integer of 1 to 20, and preferably represents an integer of 4 to 12.

Among the structural formulas (A), R ¹ is a hydrogen atom, X ¹ is an ester group, and L ¹ is the following linking group or a linking group having the following structure (R ^Y , n, and Y Is the same as described above, and the preferred embodiment is the same as above, and Rf is preferably a fluorine-containing group having the above structure or a fluorine-containing group having a group having the above structure.

-(B) Repeating unit having polyether structure in side chain-
The fluorine-containing compound in the present invention preferably further contains (b) a repeating unit having a polyether structure in the side chain. By including this repeating unit, the adhesiveness between the cured film formed of the photosensitive resin composition containing the fluorine-containing compound and the substrate can be improved. Examples of the polyether structure include polyethylene oxide, polypropylene oxide, polytetrahydrofuran and the like, and a plurality of these may be combined.

In the present invention, having the following structural formula (B).

In the structural formula (B), R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferably a hydrogen atom, a methyl group, and a hydroxymethyl group are represented.
In the structural formula (B), n is preferably 4 to 40, and more preferably 9 to 30. Furthermore, 12-24 are especially preferable.
In the structural formula (B), b represents the mass ratio (mass%) of the structural formula (B) in the total mass of the fluorine-containing compound. A specific range of b will be described later.

In the structural formula (B), L ² is preferably a single bond or a divalent linking group. The divalent linking group is more preferably a divalent linking group represented by the following structural formula. L ² in the structural formula (B) is more preferably a single bond.

  In the structural formula (B), M represents a repeating unit of polyethylene oxide, a repeating unit of polypropylene oxide, or a repeating unit of polytetrahydrofuran. Further, as M, a group having the following structure is more preferable.

R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. l represents an integer of 2 to 20, more preferably an integer of 4 to 12.
M is preferably an ethylene oxide chain represented by the above (a), and R ⁵ is preferably a hydrogen atom.

In the structural formula (B), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 15 and the alkyl group and the aryl group have a substituent even if they are unsubstituted. It may be.
Preferred examples of the alkyl group represented by R ⁴ include a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, an octadecyl group, and the like, and a methyl group and an octyl group are preferred.
Preferred examples of the aryl group represented by R ⁴ include a phenyl group, a methylphenyl group, a nonylphenyl group, and a methoxyphenyl group, and a phenyl group and a nonylphenyl group are preferred.

In the present invention, the repeating unit (b) having a polyether structure in the side chain is preferably end-capped from the viewpoint of ink repellency. Here, that the polyether structure is end-capped means that the end of the polyether structure in the repeating unit far from the main chain is an alkyl group or aryl group other than a hydroxy group. Specifically, for example, R ⁴ in the structural formula (B) means an alkyl group or an aryl group other than a hydrogen atom.
In the present invention, R ⁴ is more preferably a methyl group or a phenyl group.

Among the structural formulas (B), R ² is a hydrogen atom, a methyl group, or a hydroxymethyl group, L ² is a single bond, M is an ethylene oxide chain or the following group (R ⁵ is a hydrogen atom) 1 represents an integer of 2 to 20, and R ⁴ has an end-capped polyether structure in which an alkyl group or an aryl group other than a hydrogen atom is present, and n is 12 to 24. Repeating units are preferred.

  As a commercial item of the vinyl compound which has the said polyether structure, Nippon Oil & Fat Co., Ltd. product: Blemma-PME200, PME550, PME1000, 50POEP-800P, ALE800, PE1300, ANN1300, PSE-1300, PMEP-1200B041MA, PE350, PP800 Shin-Nakamura Chemical Co., Ltd .: NK Esters AM130G, M230G, M90G, M40G, AMP-60G, OC-18E, A-SAL-9E, A-CMP-5E, Kyoeisha Co., Ltd .: Light Ester 041MA Can be mentioned.

-(C) Repeating unit having a carboxylic acid group in the side chain-
The fluorine-containing compound in the present invention preferably further contains (c) a repeating unit having a carboxylic acid group in the side chain. The repeating unit having a carboxylic acid group in the side chain is not particularly limited and may be appropriately selected from known ones. For example, (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester , Fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone mono (Meth) acrylate etc. are mentioned. Any of those produced as appropriate and 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, a repeating unit represented by the following structural formula (C), (meth) acrylic acid, and the like are preferable in terms of excellent developability and low cost.

In the structural formula (C), R ⁶ represents a hydrogen atom or a methyl group.
Moreover, in structural formula (C), c represents the ratio (mass%) of the mass of structural formula (C) to the total mass of a fluorine-containing compound. A specific range of c will be described later.

When the fluorine-containing compound in the present invention contains the structural formula (A), the specific range of a in the structural formula (A) is preferably 40 to 85 mass%, more preferably 50 to 85 mass%, 50-80 mass% is the most preferable.
When the fluorine-containing compound in the present invention contains the structural formula (B), the specific range of b in the structural formula (B) is preferably 10 to 50 mass%, more preferably 15 to 50 mass%, 20-50 mass% is the most preferable.
When the fluorine-containing compound in the present invention contains the structural formula (C), the specific range of c in the structural formula (C) is preferably 0.1 to 50 mass%, more preferably 1 to 40 mass%. Preferably, 1-30 mass% is the most preferable.

  As fluorine atom content rate in a fluorine-containing compound, 36-70 mass% is preferable, More preferably, it is 36-65 mass%, and 36-60 mass% is the most preferable. When the fluorine atom content in the fluorine-containing compound is within the above range, the ink runs on the separation wall when the colored liquid composition is liquid-applied when forming a colored region (for example, colored pixels such as RGB), and Precipitation of the fluorine-containing compound during synthesis can be prevented, and the solubility of the fluorine-containing compound in the photosensitive resin composition can be further improved.

  As content in the photosensitive resin composition of a fluorine-containing compound, 0.01-30 mass% is preferable with respect to the total solid of a composition, More preferably, it is 0.05-20 mass%, Furthermore, Preferably it is 0.1-10 mass%. When the addition amount of the fluorine-containing compound is within the above range, it is possible to prevent the ink from running on the separation wall when the colored liquid composition is appropriately applied at the time of forming the colored region (for example, colored pixels such as RGB), and the substrate Adhesiveness and separation wall density can be obtained.

  As the ink repellent agent in the present invention, from the viewpoint of ink repellency, the repeating unit (a) is 50% by mass, the repeating unit (b) is 45% by mass, and (c) The repeating unit is preferably 5% by mass.

  The molecular weight of the fluorine-containing compound in the present invention is preferably 2000 to 30000, more preferably 3000 to 20000 in terms of polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC).

  Specific examples of the fluorine-containing compound according to the present invention [Exemplary compounds (1) to (26)] are shown below. However, the present invention is not limited to these. In addition, about the composition ratio (a, b, c) of each component, it can select within the range of the said preferable composition ratio.

2) Initiator The photosensitive resin composition in 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.

  A photopolymerization initiator is a compound capable of generating an active species that initiates polymerization of an ethylenically unsaturated compound described later upon irradiation (also referred to as exposure) of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. It can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.

  Examples of the photopolymerization initiator or photopolymerization initiator system include trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. Compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds, and the like.

  Specifically, a trihalomethyl group-substituted trihalomethyloxazole derivative or s-triazine derivative described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, A trihalomethyl group-containing compound such as the trihalomethyloxadiazole compound described in Japanese Patent No. 4221976;

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 ( Triazine compounds such as trichloromethyl) -s-triazine; 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 preferably, the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 2- (p-butoxystyryl) -5-trichloromethyl. -1,3,4-oxadiazole, and the triazine compound is 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl). -S-triazine, the acridine compound is 9-phenylacridine, the acetophenone compound is Michler's ketone, and the biimidazole compound is 2,2'-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

The said photoinitiator may be used independently and may use 2 or more types together.
The total amount of the initiator (particularly the photopolymerization initiator) in the resin composition is preferably 0.1 to 20% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content (mass) of the resin composition. When the total amount is within the above range, the resin composition can be efficiently photocured, and an image pattern can be obtained in which no omission or surface roughness occurs during development.

  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. As the hydrogen donor, the following mercaptan compounds, amine compounds and the like are preferable in 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-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 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.

3) Binder The photosensitive resin composition of the present invention can be suitably configured using at least one binder.
As the binder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. 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-59-53836. 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, etc. described in JP-A-59-71048. Can be mentioned. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group added to a polymer having a hydroxyl group can also be preferably used.

  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. These binder polymers having a polar group may be used alone, or may be used in the state of a composition used in combination with an ordinary film-forming polymer.

  As for content in the resin composition of a binder, 20-50 mass% is common with respect to the total solid of a resin composition, and 25-45 mass% is preferable.

4) 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 may 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.

Reaction of compounds having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate with diisocyanates 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 resin composition of an ethylenically unsaturated compound, 5-80 mass% is preferable with respect to the total solid (mass) of a resin composition, and 10-70 mass% is especially preferable. When the content of the ethylenically unsaturated compound is within the above range, it is possible to ensure the resistance to an alkali developer at the exposed portion of the composition, and to suppress the increase in tackiness when used as a resin composition, thereby making it easy to handle. Can keep.

5) Colorant The photosensitive resin composition of the present invention can be configured using at least one colorant.
Known colorants (dyes, pigments, etc.) can be used as the colorant. Specifically, pigments and dyes described in JP-A-2005-17716 [0038]-[0054] The pigments described in JP-A-2004-361447 [0068] to [0072] and the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

Organic pigments, inorganic pigments, dyes, and the like can be suitably used for the photosensitive resin composition of the present invention. In particular, when the photosensitive resin composition of the present invention is configured to form a light-shielding separation partition, carbon material (carbon black, etc.), metal oxide powder such as titanium oxide and iron oxide, metal sulfide powder, metal powder And a mixture of pigments such as red, blue, and green can be used. Among these, carbon black is preferable.
When using a pigment, it is preferable that it is uniformly dispersed in the photosensitive resin composition.

  As content in the resin composition of a coloring material, it is preferable that it is 30-70 mass% with respect to the total solid of a resin composition from a viewpoint of shortening development time, and is 40-60 mass%. It is more preferable, and it is still more preferable that it is 50-55 mass%.

  The pigment is preferably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing a pigment and a pigment dispersant in an organic solvent (or vehicle). The vehicle refers to a portion of the medium in which the 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, a roll mill, an atomizer described in “Encyclopedia of Pigments” (written by Asakura Kunizo, 1st edition, Asakura Shoten, 2000, page 438). Known dispersers such as a rider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, the material may be finely pulverized using frictional force by mechanical grinding described on page 310 of the same document.

  The particle diameter of the color material (pigment) is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm in terms of the number average particle diameter from the viewpoint of dispersion stability. The “particle diameter” refers to the diameter when the particle area determined from the electron micrograph image of the particle is represented by a circle having the same area, and the “number average particle diameter” refers to 100 particles. The average value obtained by obtaining the particle diameter and averaging.

  In addition to the components 1) to 5), 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, a solvent may be further used in addition to the above components. Examples of the solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, 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. .
Suitable 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 thermal polymerization inhibitors 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 ultraviolet absorber include compounds described in JP-A-5-72724, salicylates, benzophenones, benzotriazoles, cyanoacrylates, nickel chelates, hindered amines, and the like.

  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 Sebacate, 4-tert-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4 -Piperenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5 And triazin-2-yl] amino} -3-phenylcoumarin.

-Photosensitive transfer material-
The photosensitive transfer material of the present invention is formed by providing a photosensitive resin layer on a temporary support using the above-described method for forming a photosensitive resin film for a separation wall of the present invention. Accordingly, other layers such as a thermoplastic resin layer and a protective layer capable of blocking oxygen (hereinafter also referred to as “oxygen blocking layer”) can be provided between the temporary support and the photosensitive resin layer. . By using the photosensitive transfer material, the separation wall can be formed easily and at low cost.

  Specifically, on the temporary support, a photosensitive resin composition containing at least an ink repellent agent is applied in the application step, and in the drying step described later, the applied coating film is applied from the film surface. A photosensitive resin layer (photosensitive resin film for separation wall) is provided on the temporary support by drying at a gas flow rate of 0.5 m / s or less at a height of 0.5 cm.

  In the photosensitive transfer material of the present invention, when a photosensitive resin layer is provided using a resin composition containing an ink repellent agent, the use of the ink repellent agent makes smooth operation of the coating film surface difficult to obtain a uniform thickness. Although it is difficult, in the present invention, the photosensitive resin layer is formed by the above-described method for forming the photosensitive resin film for a separating wall of the present invention, so that the film thickness variation is maintained while having good ink repellency. A resin film for forming a separation wall with high uniformity in the film can be formed. Accordingly, it is possible to provide a color filter and a display device in which a separation wall (black matrix or the like) having a small height variation is obtained, and as a result, it is possible to display an image with display unevenness suppressed.

  When the oxygen blocking layer is used, the photosensitive resin layer is protected from the atmosphere by the oxygen blocking layer, so that it automatically becomes an oxygen-poor atmosphere. For this reason, there is no need to perform exposure under an inert gas or under reduced pressure, and there is an advantage that the current process can be used as it is and the sensitivity and hardness can be increased. As will be described later, the temporary support may be used as a “protective layer capable of blocking oxygen”. In this case, it is not necessary to provide an oxygen blocking layer, which contributes to a reduction in the number of steps.

  The photosensitive transfer material may be provided with a thermoplastic resin layer between the temporary support and the photosensitive resin layer, or in the case of having an oxygen barrier layer, between the temporary support and the oxygen barrier layer. The thermoplastic resin layer is a layer that has alkali solubility, includes a resin component having at least a substantial softening point of 80 ° C. or less, and has cushioning properties. By providing such a thermoplastic resin layer, good adhesion to a permanent support can be obtained.

  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 constituting the 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. As thickness of the said temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers. When the thickness is within the above range, the temporary support can be easily peeled so as not to be broken, and exposure with good resolution can be performed through the temporary support.
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 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 must be easily separated from the photosensitive resin 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.

-Drying process-
In the drying step, the coating film formed in the coating step is applied to the surface of the coating film with a drying wind at a wind speed of 0.1 m / s or more and 0.5 m / s or less, and the height from the film surface is 0. Drying is performed in a range where the gas flow rate at 0.5 cm is 0.1 m / s or more and 0.5 m / s or less. In this step, by drying the gas at a flow rate of 0.5 m / s or less, the film surface is manipulated by containing the ink repellent, specifically, convection of the coating liquid generated on the film surface with a slight external force, That is, it is effective in preventing the occurrence of film surface non-uniformity, and the in-plane uniformity of the coating film can be suppressed to within ± 5%. Accordingly, it is possible to form a separation wall (such as a black matrix) with little height variation. In other words, when the gas flow rate exceeds 0.5 m / s, the in-plane uniformity of the coating film exceeds ± 5%, and a separation wall having a uniform thickness cannot be stably formed.

The flow rate of the gas in the present invention is a flow rate measured at a position 0.5 cm away from the film surface of the coating film (the height from the film surface is 0.5 cm), using SYSTEM 6243 (manufactured by KANOMAX Co., Ltd.). The value to be measured.
The gas flow rate is 0.1 m / s to 0.5 m / s from the viewpoint of productivity such as drying time.

  The gas here refers to a gas that exists in the space where the coating film exists and touches the film surface. The flow rate of the gas is the speed of the flow generated by the movement of the gas existing near the membrane surface by evacuation or the like, and conversely, the gas (for example, dry air such as air) is applied to the membrane surface for drying from the outside. It may be the speed of the flow of gas that can be supplied.

Drying in this step may be performed by (1) supplying the supplied drying air so that it directly touches or does not touch the membrane surface, or (2) evacuating with or without maintaining the temperature. You may do it.
In the case of (1), the temperature, water content, and direction of the drying air can be selected as appropriate.
In the case of the above (2), it is preferable to vacuum so that the degree of vacuum is 10 ⁻³ Pa or less. When the degree of vacuum is 10 ⁻³ Pa or less, drying can be rapidly advanced while maintaining in-film uniformity. In the vacuum drying, in addition to the vacuum state, it may be heated and vacuum dried. The heating temperature can be 25-100 ° C. In the present invention, from the viewpoint of film thickness uniformity of the photosensitive resin film to be formed, it is preferable that the degree of vacuum is 10 ⁻⁴ Pa or less and the drying temperature is 30 to 80 ° C. for vacuum drying.

  The degree of vacuum can be measured with a general vacuum gauge. Specifically, a Pirani vacuum gauge or a diaphragm-type vacuum gauge (for example, a Baratron vacuum gauge manufactured by MK Japan Ltd.) Etc. can be measured.

<Substrate with separation wall>
The substrate with a separation wall of the present invention was formed using the substrate (preferably a transparent substrate) and the above-described method for forming the photosensitive resin film for the separation wall of the present invention or the photosensitive transfer material of the present invention. Formed by exposing and developing the photosensitive resin layer, and as an ink repellent agent , (a) a repeating unit having at least a fluorine atom in a side chain; and (b) a repeating unit represented by the structural formula (B); (c) those of the carboxylic acid group containing a fluorine-containing compound containing a repeating unit having a side chain, which is constituted by providing resin Hanarega wall membrane plane thickness uniformity is within 5% ±, the It is. The details of the ink repellent agent and the substrate are as described above, and the preferred embodiments are also the same.
Since the in-plane film thickness uniformity of the resin separating wall film is within ± 5%, the height of the separating wall (black matrix, etc.) is small. Color filters with high image quality can be obtained, and display unevenness when images are displayed can be prevented. The substrate with a separating wall of the present invention can be most suitably obtained by the method for forming a photosensitive resin film for a separating wall of the present invention described above.

<Color filter and manufacturing method thereof>
The method for producing a color filter of the present invention includes a photosensitive resin layer on a substrate using the above-described method for forming a photosensitive resin film for a separation wall of the present invention or the above-described photosensitive transfer material of the present invention. A layer forming step for forming a photosensitive resin layer, exposing the formed photosensitive resin layer in a pattern through a mask, and developing to form a separation wall; and a substrate partitioned by the separation wall And a colored region forming step of forming a colored region by applying a colored liquid composition to the recesses by an ink jet method.

-Layer formation process-
In the layer forming step, a photosensitive resin layer is formed on a substrate using the above-described method for forming a photosensitive resin film for a separation wall according to the present invention or the above-described photosensitive transfer material according to the present invention. Let it be the body. Details regarding the formation of the photosensitive resin layer are as described above.

-Separation wall formation process-
In the separation wall forming step, the photosensitive resin layer formed in the layer forming step is exposed in a pattern through a mask (exposure step), and further a development step is performed to form a separation wall.

  In the exposure step, the laminate obtained in the layer forming step and a desired photomask (for example, a quartz exposure mask) are removed from the photosensitive resin layer (removed surface after removal of the temporary support when a photosensitive transfer material is used). (Oxygen blocking layer surface)) and the photomask are arranged so as to face each other. For example, in a state where the photosensitive resin layer and the photomask stand vertically, the distance between the photomask surface and the photosensitive resin layer is appropriately set ( For example, 200 μm) is set and exposed.

The exposure can be performed using, for example, a proximity type exposure machine having an ultrahigh pressure mercury lamp (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), and the exposure amount may be appropriately selected (for example, 300 mJ / cm ² ).
Examples of the light source used for exposure include medium to ultra high pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

  The separation wall is preferably formed by exposing the photosensitive resin layer in an oxygen-poor atmosphere and then developing it in order to increase the photosensitivity, that is, the degree of curing. Here, under an oxygen-poor atmosphere means under an inert gas, under reduced pressure, and under a protective layer capable of blocking oxygen (hereinafter also referred to as “oxygen blocking layer”). is there.

“Under inert gas” means being exposed to a gas atmosphere such as an inert 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 preferable as the inert gas because of safety, availability, and cost.

  The term “under reduced pressure” refers to a state of 500 hPa or less, preferably 100 hPa or less.

Examples of the protective layer (oxygen blocking layer) capable of blocking oxygen include, for example, polyvinyl ether / maleic anhydride polymers and carboxyalkyl described in JP-A Nos. 46-2121 and 56-40824. Water-soluble salts of cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide Examples include polymers, water-soluble salts of the group consisting of various starches and the like, 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 based on the solid content of the alkali-soluble photosensitive resin layer. It is 1-50 mass%, More preferably, it is 10-40 mass%.

Various films can also be used for the oxygen barrier layer. For example, polyesters including PET, polyamides including nylon, and ethylene-vinyl acetate copolymers (EVAs) can be suitably used. These films may be stretched as necessary, and the thickness is suitably 5 to 300 μm, preferably 20 to 150 μm.
In particular, when the separation partition is formed using a photosensitive transfer material, the temporary support can be suitably used as a protective layer capable of blocking oxygen.

  When using the temporary support as an oxygen blocking layer, the temporary support is left (without peeling), and the temporary support and a desired photomask (for example, a quartz exposure mask) face each other. In a state where the laminated body and the photomask are set up vertically, the distance between the exposure mask surface and the temporary support is appropriately set (for example, 200 μm) and exposed.

The oxygen permeability coefficient of the protective layer (oxygen barrier layer) capable of blocking oxygen is preferably 2000 cm ³ / (m ² · day · atm) or less, but 100 cm ³ / (m ² · day · atm) or less. More preferably, it is 50 cm ³ / (m ² · day · atm) or less.
When the oxygen permeability is within the above range, photocuring proceeds favorably by blocking oxygen, and it is effective for forming the separation wall into a desired shape.

  Next, a development step is performed, and the exposed photosensitive resin layer is developed using a predetermined developer. Subsequently, a washing process is performed as necessary to obtain a pattern image (separated wall pattern). Prior to development, pure water is preferably sprayed with a shower nozzle or the like to uniformly wet the surface of the photosensitive resin layer or the oxygen blocking layer.

  As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but a solution obtained by adding a small amount of an organic solvent miscible with water may be used.

  Examples of the alkaline substance include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (for example, sodium bicarbonate, Potassium bicarbonate), alkali metal silicates (for example, sodium silicate, potassium silicate), alkali metal metasilicates (for example, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine Tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The dilute aqueous solution of the alkaline substance preferably has an alkaline substance concentration of 0.01 to 30% by mass, and preferably has a pH of 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 layer, methods such as rubbing with a rotating brush or 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, depending on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. When the development time is within the above range, the development progress of the non-cured portion (non-exposed portion in the case of negative type) is good, and the cured portion (exposed portion in the case of negative type) is not etched, This is effective in obtaining a well-shaped separation wall.
It is also possible to place a water washing step after the development processing.

~ Heat treatment process ~
By subjecting the pattern image (separation wall pattern) made of the photosensitive resin layer obtained in the development process to heat treatment (also referred to as baking treatment), a separation wall that is superior in water repellency and ink repellency can be obtained. .
In the heat treatment, the pattern image (separation wall pattern) formed by exposure and development is heated to be cured and the fluorine functional groups are arranged on the surface by heat. Can be exhibited more. In particular, it is effective when a fluorine-containing compound having the aforementioned repeating units (a) to (c) is used.

  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 can be appropriately selected depending on the baking temperature. For example, when the baking temperature is 240 ° C., 10 to 120 minutes is preferable, and 30 to 90 minutes is more preferable.

  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.

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.

The separation wall that can be produced by the method for forming a separation wall of the present invention preferably has a high optical density at 555 nm. In particular, when forming a black matrix constituting a color filter as a separating partition, an optical density of 2.5 or more is preferable from the viewpoint of providing a light shielding property and displaying a clearer and clearer multicolor image. 0.0 is more preferable, 2.5 to 6.0 is still more preferable, and 3.0 to 5.0 is particularly preferable.
Further, 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, a separation wall having a desired shape can be formed.

As for the width and height of the separation wall, the width (that is, the interval between the pixels when the color filter is formed) is preferably 15 to 100 μm, and the height (that is, from the substrate surface in the substrate normal direction). The distance to the top of the image 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-2006-154804 are also suitable in the present invention.

-Measurement of contact angle of separation wall-
Changes in the ink contact angle and water contact angle of the separation wall (for example, black matrix) before and after the heat treatment (baking treatment) are important. The contact angle measurement method here is a method in accordance with the JIS standard by the Japan Standards Association, specifically, “6. Still-drop method” in JIS R3257 “Wetting test method for substrate glass surface”. The described method applies.
More specifically, using a contact angle measuring device (contact angle meter CA-A manufactured by Kyowa Interface Science Co., Ltd.), ink droplets and water droplets having a size of 20 memories are produced, and ink droplets and water droplets are collected from the tip of the needle. The ink droplets and water droplets are formed by bringing them into contact with the upper surface of the partition wall formed in a pattern, and after standing for 10 seconds, the shapes of the ink droplets and water droplets are observed from the viewing hole of the contact angle meter. The contact angle θ is obtained. The term “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.

~ Contact angle value ~
When the water contact angle of the surface of the separation wall formed using the photosensitive resin composition is measured by the above method, the photosensitive resin composition has water contact with the surface of the separation wall pattern before heat treatment. When the angle is A °, the water contact angle on the surface of the separation wall after heating at 240 ° C. for 50 minutes and allowing to cool for 1 hour is B °, the contact angle difference (B ° −A °) is 20 ° or more. can do. 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 producing a color filter.

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 contacts the substrate (upper surface 4 in FIG. 1). The side surface of the separation wall refers to a surface other than the top surface of the separation wall among the exposed surfaces of the separation wall (side surface 5 in FIG. 1). Further, the concave portion on the substrate refers to a concave region that is surrounded by a separation wall and includes a separation wall side surface and a substrate surface on which the separation wall of the substrate is not formed (recess 3 in FIG. 1).

-Colored area formation process-
In the colored region forming step, a colored region is formed by applying a colored liquid composition to the recesses on the substrate defined by the separating wall formed in the separating wall forming step by an ink jet method. In this step, a colored liquid composition (preferably of two or more colors) is applied to a recess (colored region forming region) on the substrate partitioned by the separation wall, and a plurality of (preferably of two or more colors) is provided. Colored regions (for example, colored pixels such as red, green, blue, white, and purple) can be formed.

In the method for producing a color filter of the present invention, a colored liquid composition is applied onto a substrate having a partition wall (for example, a black matrix) using the above-described photosensitive composition for a color filter of the present invention, and a colored region is formed. As a result, it is possible to avoid color mixing due to ink running on the partition wall, etc., and to prevent separation of the partition wall and occurrence of chipped defects, etc., thus suppressing image failures such as color mixing, color unevenness, and white spots. Thus, a high-quality color filter can be produced.
Since the color filter of the present invention also includes a partition wall using the above-described photosensitive composition for a color filter of the present invention, there is no color unevenness, high color purity, and image failures such as white spots are suppressed. , Has vivid and clear display characteristics.

As an ink jet method, 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 a method in which ink is heated and ejected intermittently using its foaming Various methods can be employed.
The ink can be either 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 colored ink (for example, a colored resin composition described in paragraphs [0034] to [0063] of JP-A-2005-3861) used for application in the production of a known color filter, or JP-A-2004-2004 Known inks such as the color ink described in Japanese Patent No. 325736 and the ink described in Japanese Patent Application Laid-Open No. 2002-372613 can also be used.
In consideration of the steps after application, 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 ink jet 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 composition containing colorants, such as the pigment quoted by the said photosensitive composition, can be used as a suitable thing.

The color filter of the present invention is preferably a color filter in which colored regions (for example, pixels) are formed by discharging droplets of a colored liquid composition onto a substrate by an inkjet method, and at least RGB three-color inks are inkjet method. A color filter having at least three colored pixels ejected by the above is preferable.
The pattern shape of the color filter is not particularly limited, and may be a stripe shape that is a general black matrix shape, a lattice shape, or a delta array shape.

  The produced color filter may be provided with an overcoat layer on the entire surface in order to improve resistance. The overcoat layer can protect the colored region (for example, RGB pixels) and flatten the surface. However, it is preferably not provided from the viewpoint of increasing the number of steps.

  Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Among them, an acrylic resin composition is desirable because it is excellent in transparency in the visible light region, and the resin component of the curable composition constituting the color filter generally contains an acrylic resin as a main component and has excellent adhesion. Examples of the overcoat layer include those described in paragraphs [0018] to [0028] of JP-A No. 2003-287618, and “Optomer SS6699G” manufactured by JSR as a commercially available overcoat agent.

  In addition, a transparent electrode, an alignment film, or the like may be provided on the colored region (for example, RGB pixel) as necessary. A specific example of the transparent electrode is an ITO film. A specific example of the alignment film is polyimide.

<Display device>
The display device of the present invention is configured by providing the above-described color filter of the present invention. Since the color filter of the present invention is provided, display unevenness when an image is displayed can be suppressed, and a display image with good image quality can be obtained.

  The color filter obtained by the method for producing a color filter of the present invention can be 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, for example, “Electronic Display Device (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Device (written by Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year).

A liquid crystal display device is preferable as the display device provided with the color filter of the present invention. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Investigative Research Institute, Inc., 1994)”.
The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”. Especially, it is effective for a color TFT type 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.)”. Furthermore, the present invention can also be applied to a liquid crystal display device with a wide viewing angle, such as a horizontal 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 / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “2003 Current Status and Future Prospects of Liquid Crystal Related Markets (Volume 2)” , Fuji Chimera Research Institute, Ltd., published in 2003).

  As applications, it can be applied to applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile terminals such as mobile phones, digital cameras, car navigation systems, and the like.

  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. The molecular weight represents a weight-average molecular weight in terms of polystyrene by gel permeation chromatography (GPC), and “part” and “%” are based on mass unless otherwise specified.

Example 1
The above-described exemplary compound (1) of the fluorine-containing compound of the present invention was synthesized as follows. In addition, it is possible to synthesize the fluorine-containing compounds in the present invention other than the exemplified compounds synthesized here by a similar method.
In addition, the fluorine atom content rate in a fluorine-containing compound represents the fluorine amount estimated from structural formula.

-Synthesis of fluorine-containing compound (1)-
Under a nitrogen stream, 30 g of propylene glycol monomethyl ether acetate [MMPG-Ac, manufactured by Daicel Chemical Industries, Ltd.] was placed in a 300 ml three-necked flask equipped with a condenser, and the internal temperature was 70 ° C. in a water bath containing paraffin. Until heated. Further, 35 g of MMPG-Ac, 2.5 g of acrylic acid [AA, manufactured by Tokyo Chemical Industry Co., Ltd.], 25 g of 2- (perfluorohexyl) -ethyl acrylate [FAAC6, manufactured by NOK Co., Ltd.], and terminal methyl polyethylene oxide A solution in which 22.5 g of a monomer [PME1000, manufactured by NOF Corporation, 23 PEO repeats, terminal methyl group] and 0.70 g of lauryl mercaptan [LM, manufactured by Tokyo Chemical Industry Co., Ltd.] and MMPG are dissolved A solution in which 0.285 g of 2,2′-azobis (isovaleronitrile) [V65, manufactured by Wako Pure Chemical Industries, Ltd.] was dissolved in 10 g of Ac was dropped with a plunger pump over 2 hours. After completion of dropping, the mixture was stirred for 5 hours.

  As described above, 2- (perfluorohexyl) -ethyl acrylate [FAAC6], acrylic acid [AA], and polyethylene oxide monomer [PME1000] are copolymerized, and FAAC6 / AA / PME1000 = 50/5/45. A fluorine-containing compound (1) having a (mass ratio) was synthesized. The weight average molecular weight of the fluorine-containing compound (1) was 13,000, and the fluorine atom content in the fluorine-containing compound (1) was 36%.

-Preparation of photosensitive resin composition-
First, K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 below are weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes, Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'- in the amounts shown in Table 1 Bromophenyl] -s-triazine, surfactant 1, and fluorine-containing compound (1) are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and 150 r. At a temperature of 40 ° C. (± 2 ° C.). The photosensitive resin composition K1 was prepared by stirring for 30 minutes at pm.
In addition, the quantity of following Table 1 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-
An alkali-free glass substrate (hereinafter, also simply referred to as a glass substrate) was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The glass 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 prepared using a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Material K1 was applied. Then, it dried for 2 minutes with the drying apparatus of the temperature of 100 degreeC which made the dry air quantity in the apparatus 0.5 m / s, and obtained the photosensitive resin composition layer K1 with a film thickness of about 2.3 micrometers.
At this time, the amount of dry air in the apparatus was measured by using a system 6243 (manufactured by KANOMAX), an air volume having a height of 0.5 cm from the surface of the photosensitive resin composition layer K1.

Next, a glass substrate and a mask (quartz exposure mask having an image pattern) are applied to the photosensitive resin composition layer K1 by a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp. In a state of being vertically set, the distance between the mask surface and the photosensitive resin composition layer K1 was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in a nitrogen atmosphere.

Next, after pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin composition layer K1, a KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, Using 100-fold diluted FUJIFILM Electronics Materials Co., Ltd., shower development was performed at 23 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, after removing residues by spraying ultrapure water with an ultra-high pressure washing nozzle at a pressure of 9.8 MPa, post-exposure was performed at an exposure amount of 2000 mJ / cm ^{2 in} the atmosphere, and post-baking at 240 ° C. for 50 minutes. (Heating) treatment was performed to form a striped black matrix (separation wall) having an opening with a thickness of 2.0 μm, an optical density of 4.0, and a width of 100 μm, and a substrate with a black matrix was produced.

-Evaluation 1
(1) Evaluation of in-plane uniformity The thickness of the black matrix (separation wall) produced above was measured at five arbitrary points, and an average value Lav was calculated. Of the five thicknesses, the thickness Lm having the largest difference from the average value Lav was selected, the film thickness variation rate (%) was obtained from the following formula, and used as an index for evaluating the in-plane uniformity. The film thickness fluctuation rate is shown in Table 2 below.
Film thickness fluctuation rate (%) = Lm / Lav

-Fabrication of color filter-
(1) Preparation of Colored Ink Composition for Pixel Among the following components, a pigment, a polymer dispersant, and a solvent were first mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring this 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 pixel>
Pigment (CI Pigment Red 254) 5 parts Solsperse 24000 (manufactured by AVECIA; polymer dispersant) 1 part benzyl methacrylate / methacrylic acid (72/28 [molar ratio]) Random copolymer (molecular weight: 37,000, binder) 3 parts Epicote 154 (manufactured by Yuka Shell; novolak 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 Pixel Next, using the colored ink composition for each of the R, G, and B pixels, a region partitioned by the black matrix (separation wall) of the substrate with the black matrix obtained above. The ink composition is discharged into the inside (recessed part surrounded by the black matrix) using an ink jet recording apparatus until a desired density is obtained, and a color filter composed of R, G, and B patterns (colored pixels) is formed. 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.

-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.

-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-bisethoxycarbonylmethyl) amino-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 ・ ・ ・ 0.856 parts (Dainippon Ink & Chemicals, Inc .; surfactant) )
・ 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 ・ ・ ・ 14.9 parts (manufactured by IPS Japan Ltd., K) -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 2-
The following evaluation was performed about the separation wall and liquid crystal display device which were obtained from the above. The evaluation results are shown in Table 2 below.
(2) Water-repellent / ink-repellent property of image separation wall The photosensitive resin composition layer K1 formed in the same manner as described above is exposed by the same method as above except that no mask is 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 of the ink droplet after standing for 10 seconds after landing at 25 ° C. was determined.

(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 input is visually observed, and the occurrence 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 part was slightly uneven, it was within a practically acceptable range.
-D rank: The display part was uneven and the display image was slightly bad.
E rank: Strong unevenness was observed in the display part, and the display image was very bad.

(Examples 2 to 6)
In Example 1, the content of the fluorine-containing compound (1), the drying temperature, the drying time, the amount of drying air, and the drying method were changed as shown in Table 2 below. A substrate with a matrix (separation wall), a color filter, and a liquid crystal display device were produced, and the same evaluation was performed. The evaluation results are shown in Table 2 below.

( Reference Examples 1 to 3 )
In Example 1, the content of the fluorine-containing compound (1), the drying temperature, the drying time, the amount of drying air, and the drying method were changed as shown in Table 2 below, and “0. Except for drying the coating film at a vacuum degree shown in the following Table 2 instead of the vacuum drying oven DP-22 (manufactured by Yamato Co., Ltd.) In the same manner as in Example 1, a substrate with a black matrix (separation wall), a color filter, and a liquid crystal display device were produced, and the same evaluation was performed. The evaluation results are shown in Table 2 below.
The measurement of the degree of vacuum was carried out using a Baratron vacuum gauge manufactured by Nippon K.K.

(Comparative Examples 1-4)
In Example 1, the content of the fluorine-containing compound (1), the drying temperature, the drying time, the amount of drying air, and the drying method were changed as shown in Table 2 below. A substrate with a matrix (separation wall), a color filter, and a liquid crystal display device were produced, and the same evaluation was performed. The evaluation results are shown in Table 2 below.

(Example 10)
A non-alkali glass substrate (hereinafter also simply referred to as a 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. A ring solution (0.3% aqueous solution of N-β (aminoethyl) γ-aminopropyltrimethoxysilane, 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. . 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 following photosensitive transfer material K1 is overlaid so as to contact 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, a glass substrate and a mask (quartz exposure mask having an image pattern) are vertically set up 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 mask surface and the photosensitive resin composition layer was set to 200 μm, and pattern exposure was performed with 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. As a result, a black matrix (separation wall) having an optical density of 4.0 was obtained.

  Thereafter, a color filter and a liquid crystal display device were produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2 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 K1 prepared in Example 1 was applied on this intermediate layer. Then, it dried for 2 minutes with the drying apparatus of the temperature of 100 degreeC which made the dry air quantity 0.5 m / s, and laminated | stacked the photosensitive resin composition layer K1 of black (K) with a film thickness of about 2.3 micrometers.
At this time, the dry air volume was measured using a system 6243 (manufactured by KANOMAX) with an air volume of 0.5 cm from the surface of the photosensitive resin composition layer K1.

  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 K1 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 partsMethanol: 429 parts

As shown in Table 2, in the example, the in-plane uniformity of the formed film is high, the height variation of the formed black matrix is suppressed, and the in-plane uniformity is high (or within an allowable range). ) A color filter could be obtained. In the liquid crystal display device using this color filter, display unevenness when displaying an image is prevented, and a high-quality image can be obtained.
On the other hand, Comparative Example 1 containing no fluorine-containing compound as an ink repellent agent is not only inferior in ink repellency but also in-plane uniformity, and is a comparison in which drying was performed with a dry air flow exceeding 0.5 m / s. In Examples 2 and 3, the in-plane uniformity was poor and the black matrix height variation could not be suppressed. For this reason, when an image is displayed using a color filter and a liquid crystal display device, display unevenness deteriorates, and high-quality image display is difficult.

  In addition, although the said Example demonstrated centering on the case where a fluorine-containing compound (1) was used, when using the other fluorine-containing compound which can be used as an ink repellent agent in this invention, or combining 2 or more types. Even when it is used, the same effect as in the present embodiment can be exhibited, the in-plane uniformity can be improved in the same manner as described above, and display unevenness when an image is displayed can be suppressed.

It is sectional drawing of the color filter for demonstrating the upper surface of the image separation wall, a side surface, and the recessed part on a board | substrate.

Explanation of symbols

1 ... Image separation wall 2 ... Colored pixels (colored areas)
3 ... Concave 4 ... Separation wall upper surface 5 ... Separation wall side surface 6 ... Substrate

Claims (7)

As the ink repellent agent, (a) a repeating unit having at least a fluorine atom in the side chain, (b) a repeating unit represented by the following structural formula (B), and (c) a repeating unit having a carboxylic acid group in the side chain; An application step of applying a photosensitive resin composition containing a fluorine-containing compound containing,
The coating film thus formed is dried on the surface of the coating film with a wind speed of 0.1 m / s or more and 0.5 m / s or less, and the gas flow rate at a height of 0.5 cm from the film surface is reduced to 0. A drying step of drying at 1 m / s to 0.5 m / s;
A method for forming a photosensitive resin film for a separating wall.

[In Structural Formula (B), R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. L ² represents a single bond or a divalent linking group, and M represents a repeating unit of polyethylene oxide. n represents 4-40. b represents the ratio (mass%) of the mass of the structural formula (B) in the total mass of the fluorine-containing compound. ]   The method for forming a photosensitive resin film for a separating wall according to claim 1, wherein a fluorine atom content in the ink repellent agent is 36 to 70% by mass.   A photosensitive transfer material having a photosensitive resin layer formed by the method for forming a photosensitive resin film for a separating wall according to claim 1 on a temporary support. A substrate ,
It is formed by exposing and developing a photosensitive resin layer formed using the method for forming a photosensitive resin film for a separation wall according to claim 1 or claim 2 or the photosensitive transfer material according to claim 3. As the ink repellent agent , (a) a repeating unit having at least a fluorine atom in the side chain, (b) a repeating unit represented by the structural formula (B), and (c) a repeating unit having a carboxylic acid group in the side chain And a resin separation wall film having an in-plane film thickness uniformity within ± 5% ,
A substrate with a separation wall. A layer forming step of forming a photosensitive resin layer on a substrate using the method for forming a photosensitive resin film for a separation wall according to claim 1 or 2, or the photosensitive transfer material according to claim 3. ,
A separation wall forming step in which the formed photosensitive resin layer is exposed in a pattern through a mask and developed to form a separation wall;
A colored region forming step of forming a colored region by applying a colored liquid composition to the concave portion on the substrate partitioned by the separation wall by an inkjet method;
The manufacturing method of the color filter which has this.   A color filter produced by the method for producing a color filter according to claim 5.   A display device comprising the color filter according to claim 6.