JP2008033229A - Photosensitive resin composition, photosensitive transfer material, partition wall and method for producing the same, color filter and method for manufacturing the same, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of keeping good adhesion between a pattern image (e.g., a partition wall) formed therefrom and a substrate on which the pattern image is formed, while keeping the water- and ink-shedding properties of an upper surface of the pattern image (an exposed surface opposite to a surface being in contact with the substrate). <P>SOLUTION: The photosensitive resin composition is characterized in that when a water contact angle of an upper surface of a pattern image formed using the photosensitive resin composition is measured in conformity to a method described in JIS R3257, a contact angle difference B°-A° is ≥20°, wherein A° is a water contact angle of the upper surface of the pattern image before heat treatment, and B° is a water contact angle of the upper surface of the pattern image after heating at 240°C for 50 min and standing to cool for 1 h. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a photosensitive transfer material, a separation wall and a manufacturing method thereof, a color filter and 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 essential for such displays.
Conventionally, as a method for producing a color filter, a dyeing method, a pigment dispersion method, an electrodeposition method, a printing method, and the like have been performed.
For example, in the dyeing method, a water-soluble polymer material layer, which is a dyeing material, is formed on a transparent substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To obtain a colored pattern. By repeating this step three times, a colored layer comprising three colored portions of R (red), G (green), and B (blue) is formed.
In addition, the pigment dispersion method has been actively performed in recent years, and a monochromatic pattern is obtained by forming a photosensitive resin layer in which a pigment is dispersed on a transparent substrate and patterning the same. By repeating this process three times, a colored layer composed of colored portions of R, G, and B is formed.

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

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

  In the 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 clumps and sticks to portions other than the predetermined region. Therefore, the partition wall (separation wall) is required to have a property of repelling water or an organic solvent which is an ink-jet coating liquid, so-called water and oil repellency.

  Patent Document 1 discloses a photoresist composition containing a copolymer of a fluoroalkyl group-containing (meth) acrylate monomer and a silicone chain-containing ethylenically unsaturated monomer, and the copolymer Is added in an amount of 0.001 to 0.05 mass% with respect to the solid content of the photoresist composition.

  Patent Document 2 discloses 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. The vinyl polymer is a polymer containing 0.1 to 5% by mass of fluorine atoms, and the ratio of the vinyl polymer to the total mass of the vinyl polymer and the photosensitive resin. Is 0.25 to 2.0 mass%.

  Patent Document 3 discloses a resist composition containing a vinyl polymer obtained by polymerizing a monomer composition containing a vinyl monomer having a C 4-6 fluoroalkyl group, and a photoreceptor. The vinyl polymer has a fluorine atom content of 7 to 35% by mass, and the ratio of the fluorine-containing resin to the total solid content of the composition is 0.1 to 30% by mass. Furthermore, there is no description about the end-capped polyether structure as a copolymerization component.

However, the coating film formed from the composition consisting of the blending ratio of the copolymer described in Patent Document 1 and the composition consisting of the blending ratio of the vinyl polymer described in Patent Document 2 is insufficient in water and oil repellency. To do.
Furthermore, the vinyl polymer described in Patent Document 3 lacks developer resistance and adhesion during development.

JP-A-9-54432 JP 2004-2733 A JP 2005-315984 A

The present invention has been made in view of the above-mentioned conventional problems. When a pattern image (for example, a separation wall) is used, the upper surface of the pattern image (exposed surface opposite to the surface in contact with the substrate) has water repellency and The objective is to provide a photosensitive resin composition capable of maintaining good adhesion between the pattern image and the substrate on which the pattern image is formed while maintaining ink repellency. Let it be an issue.
In addition, the present invention maintains adhesion between the pattern image and the substrate on which the pattern image is formed while maintaining the water repellency and ink repellency of the upper surface of the transferred pattern image (for example, a separation wall). An object of the present invention is to provide a photosensitive transfer material having a uniform photosensitive resin layer that can be kept in good condition and suppressed generation of repelling at the time of application, and to achieve the object. .
Furthermore, the present invention provides a separation wall that is excellent in water repellency and ink repellency on the top surface, prevents ink from running on the separation wall when ink is suitable, and has good adhesion to the substrate. To provide a separation wall manufacturing method capable of easily forming an image wall, to provide a high-quality color filter in which the occurrence of color mixing and color unevenness is suppressed, a simple manufacturing method thereof, and display unevenness An object of the present invention is to provide a display device capable of displaying a high-quality image in which the occurrence of the above is suppressed, and to achieve the object.

As a result of intensive studies, the present inventors have found that it is effective to use a composition that greatly increases the surface energy before and after post-baking in order to impart ink repellency to the upper and side surfaces of the separation wall without fluorine plasma treatment. I found out. Specifically, the inventors have found that by using a composition using a specific fluorine-containing compound, the above-mentioned problems can be solved without fluorine plasma treatment, and a high-quality color filter can be produced, and the present invention has been completed.
That is, specific means for solving the above problems are as follows.

<1> A photosensitive resin composition, which is subjected to heat treatment when the water contact angle on the upper surface of a pattern image formed using the photosensitive resin composition is measured according to the method described in JIS R3257. When the water contact angle on the upper surface of the previous pattern image is A °, heat treatment at 240 ° C. for 50 minutes, and the water contact angle on the upper surface of the pattern image after allowing to cool for 1 hour is B °, the contact angle difference B ° −A The photosensitive resin composition is characterized in that the angle is 20 ° or more.

<2> A photosensitive resin composition containing at least 1) an initiator, 2) a binder, 3) an ethylenically unsaturated compound, 4) a coloring material, and 5) a fluorine-containing compound, wherein the fluorine-containing compound is: A photosensitive resin composition comprising a repeating unit having at least a fluorine atom in a side chain, wherein a fluorine atom content in the fluorine-containing compound is from 36 to 70% by mass.

<3> The <2> characterized in that the fluorine-containing compound includes (a) a repeating unit having at least a fluorine atom in a side chain and (b) a repeating unit having a polyether structure in a side chain. It is the photosensitive resin composition of description.
<4> The fluorine-containing compound has (a) a repeating unit having at least a fluorine atom in the side chain, (b) a repeating unit having a polyether structure in the side chain, and (c) a carboxylic acid group in the side chain. It is a photosensitive resin composition as described in <2> or <3> characterized by including a repeating unit.
<5> The photosensitive resin composition according to <3> or <4>, wherein the repeating unit (b) having a polyether structure in a side chain has an end-capped polyether structure. is there.

<6> A photosensitive transfer material having a photosensitive resin layer comprising the photosensitive resin composition according to any one of <1> to <5> on a temporary support.
<7> A photosensitive resin layer on at least one surface of the substrate using the photosensitive resin composition according to any one of <1> to <5> or the photosensitive transfer material according to <6>. Forming a photosensitive resin layer,
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer;
A heat treatment step of heat-treating a pattern image formed of the photosensitive resin layer obtained by the development;
It is a manufacturing method of the separation wall characterized by having at least.
<8> A separation wall formed by the method for producing a separation wall according to <7>.

<9> A method for producing a color filter, wherein the separation wall according to <8> partitions the substrate, and a colored liquid composition is applied to the recessed portion on the partitioned substrate.
<10> The method for applying a colored liquid composition according to <9> is a pixel forming method in which droplets of the colored liquid composition are applied by an inkjet method to form a pixel. It is a manufacturing method.
<11> A color filter manufactured by the method for manufacturing a color filter according to <9> or <10>.
<12> A display device having the color filter according to <11>.

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

Hereinafter, the present invention will be described in detail.
≪Photosensitive resin composition≫
The photosensitive resin composition of the present invention is a photosensitive resin composition containing at least 1) an initiator, 2) a binder, 3) an ethylenically unsaturated compound, 4) a coloring material, and 5) a fluorine-containing compound. The fluorine-containing compound is a photosensitive resin composition comprising a repeating unit having at least a fluorine atom in a side chain, and the fluorine atom content in the fluorine-containing compound is 36 to 70% by mass. .
Since the photosensitive resin composition of the present invention is configured as described above, the water contact angle on the upper surface of the pattern image formed using the photosensitive resin composition is measured according to the method described in JIS R3257. Then, the water contact angle on the upper surface of the pattern image before the heat treatment is A °, 240 ° C. for 50 minutes, and the water contact angle on the upper surface of the pattern image after cooling for 1 hour is B °. The contact angle difference B ° -A ° can be 20 ° or more.
As a result, while maintaining the water repellency and ink repellency of the upper surface of the separation wall formed using the photosensitive resin composition, adhesion between the separation wall and the substrate on which the separation wall is formed is improved. Can keep good. Furthermore, by producing a color filter using the separation wall, it is possible to suppress the occurrence of color mixing and color unevenness.
Details of the water contact angle will be described later.

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

  Specifically, a 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 preferable as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (4-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferable. Further, 6- [4- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 6- [4 ′-(N, N— Bis (ethoxycarbonylmethyl) amino) -3'-bromophenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4 Trihalomethyl group-containing compounds such as oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetra Eniru 1,2' is a bi-imidazole.

The said photoinitiator may be used independently and may use 2 or more types together. As a total amount in the photosensitive resin composition of the said photoinitiator, 0.1-20 mass% of the total solid (mass) of the photosensitive resin composition is preferable, and 0.5-10 mass% is especially preferable. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.
In the present invention, the total solid content (mass) of the photosensitive resin composition means all components excluding the solvent in the photosensitive resin composition.

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

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

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

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

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

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

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

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

3) Ethylenically unsaturated compound The photosensitive resin composition of the present invention contains at least one 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.

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

  As content in the photosensitive resin composition of an ethylenically unsaturated compound, 5-80 mass% is preferable with respect to the total solid (mass) of the photosensitive resin composition, and 10-70 mass% is especially preferable. When the content is less than 5% by mass, the resistance to an alkali developer at the exposed portion of the composition may be inferior, and when it exceeds 80% by mass, the tackiness when a photosensitive resin composition is obtained. It may increase and may be inferior in handleability.

4) Coloring material The photosensitive resin composition of the present invention contains at least one coloring material.
Specific examples of the color material used in the present invention include pigments and dyes described in JP-A-2005-17716 [0038] to [0054], and JP-A-2004-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

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

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

5) Fluorine-containing compound The photosensitive resin composition of the present invention contains at least one fluorine-containing compound.
-(A) Repeating unit having at least fluorine atom in side chain-
The fluorine-containing compound in the present invention includes (a) a repeating unit having at least a fluorine atom in a side chain. The repeating unit having at least a fluorine atom in the side chain is preferably a fluorinated alkyl group having 4 to 8 carbon atoms, and 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.
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 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.
The heterocyclic residue represented by X _1, for example, 5-membered ring, or a 6-membered ring is preferred containing a nitrogen atom or an oxygen atom as a member of the ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a thiazole ring, A benzothiazole ring, an oxazole ring, a benzoxazole ring, an isoxazole ring, a pyrazole ring, an imidazole ring, a quinoline ring, a thiadiazole ring, and the like are preferable, and a pyridine ring and a thiadiazole ring are 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.
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. R ₃ is preferably a hydrogen atom.

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

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

-(B) Repeating unit having polyether structure in side chain-
The fluorine-containing compound in the present invention may further contain (b) a repeating unit having a polyether structure in the side chain. Examples of the repeating unit having a polyether structure in the side chain include polyethylene oxide, polypropylene oxide, and polytetrahydrofuran, and a plurality of these may be combined.
More preferably, structural formula (B) is mentioned below.

In the structural formula (B), R ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferably, it represents a hydrogen atom, a methyl group or a hydroxymethyl group.
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 above structural formula (B), b represents the ratio (% by mass) of the 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 following structural formula is more preferable as the divalent linking group.

L ₂ is preferably a single bond.

  In the above structural formula (B), M represents a polyethylene oxide repeating unit, a polypropylene oxide repeating unit, and a polytetrahydrofuran repeating unit. 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, 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 carbon atoms.
R ₄ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and the alkyl group and aryl group may have a substituent.
Preferred examples of the alkyl group for R ₄ include a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, and an octadecyl group, and a methyl group and an octyl group are preferred.
Preferred examples of the aryl group for 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 preferable.
R ₄ is preferably an alkyl group or an aryl group. These are called end-capped polyether structures, and this structure is most preferred. R ₄ is more preferably a methyl group or a phenyl group.

  As a commercial item of the vinyl compound which has the said polyether structure, Nippon Oil & Fats Co., Ltd. product: BLEMMER PME200, PME550, PME1000, 50POEP-800P, ALE800, PE1300, ENE1300, PSE-1300, PMEP-1200B041MA, PE350, PP800, New 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 It is done.

-(C) Repeating unit having a carboxylic acid group in the side chain-
Moreover, the fluorine-containing compound in the present invention may further contain (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. As these, those produced as appropriate may be used, or commercially available products may be used.

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

  As said commercial item, Toa Gosei Chemical Industry Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shin-Nakamura Chemical Co., Ltd .: NK Ester CB-1, NK ester CBX-1, manufactured by Kyoeisha Oil Chemical Co., Ltd .: HOA-MP, HOA-MS, manufactured by Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100, and the like. Among these, 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.

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

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

  The fluorine atom content in the fluorine-containing compound is essentially 36 to 70% by mass, more preferably 36 to 65% by mass, and most preferably 36 to 60% by mass. When the fluorine atom content in the fluorine-containing compound is lower than 36% by mass, there is a concern that ink may run on the separation wall when ink is applied for forming the pixel portion. In some cases, the fluorine-containing compound may be precipitated during the synthesis or it may be difficult to dissolve the resin in the composition.

  The amount of the fluorine-containing compound added is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass with respect to the total solid content in the photosensitive resin composition. 10% by mass is most preferred. When the addition amount of the fluorine-containing compound is lower than 0.01% by mass with respect to the solid content of the photosensitive resin, there is a concern that ink may run on the separation wall when ink is applied for forming the pixel portion. When the content is higher than mass%, the coating adhesion and the separation wall concentration are lowered, and the desired separation wall may not be produced.

  Specific examples of the fluorine-containing compound according to the present invention [Exemplary compounds (1) to (36)] 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.

  In addition to the components 1) to 5) described above, the following solvents, surfactants, thermal polymerization inhibitors, ultraviolet absorbers and the like can be added to the photosensitive resin composition. In addition, “adhesion aid” described in JP-A-11-133600, other additives, and the like can be contained.

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

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

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

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

≪Isolated wall and its manufacturing method≫
The image separation wall according to the present invention is formed from the photosensitive resin composition. The image separation wall separates two or more pixel groups and is generally black (dark color) in many cases, but is not limited to black. The dark colored product is preferably an organic material (various dyes such as dyes and pigments).
The image separation wall is preferably formed by exposing the photosensitive resin composition to an oxygen-poor atmosphere and then developing the photosensitive resin composition.
Under an oxygen-poor atmosphere when photo-curing such a photosensitive resin composition refers to an inert gas, a reduced pressure, and a protective layer that can block oxygen, and these are described in detail below. is there.

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

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

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

The oxygen permeability coefficient of the protective layer capable of blocking oxygen produced in this way is preferably 2000 cm ³ / (m ² · day · atm) or less, but 100 cm ³ / (m ² · day · atm) or less. Is more preferably 50 cm ³ / (m ² · day · atm) or less.
When the oxygen permeability is higher than 2000 cm ³ / (m ² · day · atm), oxygen cannot be effectively blocked, and it may be difficult to make the separation wall into a desired shape.

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

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

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

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

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

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

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

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

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

<Method for manufacturing separation wall>
The method for producing a separation wall according to the present invention is characterized in that the photosensitive resin composition or the photosensitive transfer material is used on at least one surface of the substrate (hereinafter also simply referred to as “on the substrate”). A photosensitive resin layer forming step for forming a resin layer; an exposure step for exposing the photosensitive resin layer; a developing step for developing the exposed photosensitive resin layer; and a photosensitive resin obtained by the development. A heat treatment step of heat-treating a pattern image formed of layers.

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

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

(Exposure process and development process)
In the exposure step, the removal surface (oxygen blocking layer surface) after removal of the temporary support of the laminate is arranged so that a desired photomask (for example, a quartz exposure mask) faces each other, and the laminate and the photomask are arranged. In the state of being set up vertically, the exposure mask surface and the distance between the oxygen blocking layer are appropriately set (for example, 200 μm) and exposed.
Subsequently, after the irradiation, development processing is performed using a predetermined processing solution (development process), and then, if necessary, washing treatment is performed to obtain a pattern image (separated wall pattern).

  When the temporary support is used as a protective layer capable of blocking oxygen, the temporary support and a desired photomask (for example, a quartz exposure mask) are left with the temporary support remaining (without peeling). 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. Next, the temporary support is removed, and after irradiation, development processing is performed using a predetermined processing solution, followed by washing with water as necessary to obtain a pattern image (separation wall pattern).

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

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

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

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

(Heat treatment process)
The image separation wall of the present invention can be obtained by subjecting a pattern image (image separation wall pattern) made of the photosensitive resin layer obtained by the development step to heat treatment (also referred to as baking treatment).
In the heat treatment, a pattern image (separation wall pattern) formed by exposure and development is heated and cured.

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

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

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

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

<Illustrated wall>
The separation wall of the present invention can be manufactured by the above manufacturing method.
The separation wall of the present invention preferably has a high optical density at 555 nm, more preferably 2.5 or more, more preferably 2.5 to 10.0, and 2.5 to 6.0. Is more preferable, and 3.0 to 5.0 is particularly preferable. Further, since the photosensitive resin composition layer is preferably cured by a photoinitiating system, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is preferably 2.0 to 10.0, more preferably 2.5 to 6.0, and particularly preferably 3.0 to 5.0. If it is in the preferred range, the shape of the separation wall can be as desired.
The width and height of the separation wall of the present invention formed as described above are preferably 15 to 100 μm in width (that is, the interval between pixels when a color filter is formed). The height (that is, the distance from the substrate to the top of the separation wall) is preferably 1.0 to 5.0 μm.
As the shape of the separation wall, the shapes described in paragraph numbers [0054] to [0055] of JP-A No. 2006-154804 are also suitable in the present invention.

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

Here, the upper surface of the pattern image will be described with reference to FIG.
The upper surface of the separation wall refers to the exposed surface on the opposite side of the surface of the separation wall that is in contact with the substrate (upper surface 4 shown in FIG. 1).
The side surface of the separation wall refers to the surface of the separation wall other than the top surface of the separation wall (side surface 5 shown in FIG. 1). Further, the concave portion on the substrate refers to a concave portion composed of a separation wall side surface and a separation wall non-forming surface on the substrate (the concave portion 3 shown in FIG. 1).

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

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

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

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

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

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

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

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

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

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

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

≪Synthesis example of fluorine-containing compound≫
Of the exemplified compounds of the fluorine-containing compound in the present invention, a synthesis example will be shown by taking a specific fluorine-containing compound as an example. In addition, it is possible to synthesize the fluorine-containing compounds according to the present invention other than the exemplified compounds by the same method.
Unless otherwise specified, the numerical values are expressed in parts by mass and mass%. The molecular weight is a polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography (GPC), and the fluorine atom content in the fluorine-containing compound represents the amount of fluorine assumed from the structural formula.

<Synthesis example of fluorine-containing compound (1)>
Under a nitrogen stream, 30 g of propylene glycol monomethyl ether acetate (MMPG-Ac, manufactured by Daicel Corporation) was placed in a 300 ml three-necked flask equipped with a cooling tube and heated to 70 ° C. in a water bath containing paraffin. To this, 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 monomer [PME1000, manufactured by NOF Corporation, PEO repeat number (23) terminal Me] 22.5 g and lauryl mercaptan [LM, manufactured by Tokyo Chemical Industry Co., Ltd.] 0.70 g, and MMPG- 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 added dropwise over 2 hours with a plunger pump. 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 was 13,000. The fluorine atom content in the fluorine-containing compound (1) was 36% by mass.
The fluorine-containing compound (1) is a compound belonging to the above-described exemplary compound (1).

<Synthesis example of fluorine-containing compound (2), (3), (8), (9)>
According to the synthesis example of the fluorine-containing compound (1), the fluorine-containing compound (2) FAAC6 / AA / PME1000 = 65/5/25 (mass ratio), the fluorine-containing compound (3) FAAC6 / AA / PME1000 = 80/5 / 15 (mass ratio), fluorine-containing compound (8) FAAC6 / AA / PME1000 = 36/5/59 (mass ratio), fluorine-containing compound (9) FAAC6 / AA / PME1000 = 90/5/5 (mass ratio) Synthesis was performed. The fluorine atom content in each copolymer component and fluorine-containing compound (2), (3), (8), (9) is as shown in Table 1.
However, regarding the fluorine-containing compound (9), since the solubility of the resin was insufficient, it was deposited at the time of synthesis and could not be evaluated.
The fluorine-containing compounds (2) and (3) are compounds belonging to the above-described exemplary compound (1). Although the said fluorine-containing compound (8), (9) has a structure similar to exemplary compound (1), since a fluorine atom content rate is outside the range of 36-70 mass%, the above-mentioned exemplary compound (1) Does not belong to.

<Synthesis example of fluorine-containing compound (4)>
In the synthesis example of the fluorine-containing compound (1), terminal methylpolyethylene oxide monomer [PME1000, manufactured by NOF Corporation, PEO repeat number (23) terminal Me] was determined by Bremer ANE 1300, PEO manufactured by NOF Corporation. Fluorine-containing compound (4) FAAC6 / AA according to the synthesis example of fluorine-containing compound (1) except that the number of repetitions (30) was changed to terminal nonyl Ph and other components were changed to the addition amounts shown in Table 1. / ANE1300 = 50/5/45 (mass ratio) was synthesized.
In addition, a fluorine-containing compound (4) is a compound which belongs to the above-mentioned exemplary compound (21).

<Synthesis example of fluorine-containing compound (5)>
In the synthesis example of the fluorine-containing compound (1), terminal methyl polyethylene oxide monomer [PME1000, manufactured by NOF Corporation, PEO repeat number (23) terminal Me] was changed to NK-ester M90G manufactured by Shin-Nakamura Chemical Co., Ltd. , Fluorine-containing compound (5) FAAC6 according to the synthesis example of fluorine-containing compound (1) except that the number of repetitions of PEO (9) is changed to terminal Me and other components are changed to the addition amounts shown in Table 1. / AA / M90G = 50/5/45 (mass ratio) was synthesized.
In addition, a fluorine-containing compound (5) is a compound which belongs to the above-mentioned exemplary compound (2).

<Synthesis example of fluorine-containing compound (6)>
In the synthesis example of the fluorine-containing compound (1), except that 2.5 g of acrylic acid [AA, manufactured by Tokyo Chemical Industry Co., Ltd.] is not added, the fluorine-containing compound ( 6) Synthesis of FAAC6 / PME1000 = 50/50 (mass ratio) was performed.
In addition, a fluorine-containing compound (6) is a compound which belongs to the above-mentioned exemplary compound (25).

<Synthesis example of fluorine-containing compound (7)>
In the synthesis example of the fluorine-containing compound (1), the terminal methyl polyethylene oxide monomer [PME1000, manufactured by NOF Corporation, PEO repeat number (23) terminal Me] was changed to that of Bremer PE350, PEO manufactured by NOF Corporation. Fluorine-containing compound (7) FAAC6 / AA / According to the synthesis example of fluorine-containing compound (1) except that the number of repetitions (8) was changed to terminal H and other components were changed to the addition amounts shown in Table 1. The synthesis of PE350 = 50/5/45 (mass ratio) was performed.
In addition, a fluorine-containing compound (7) is a compound which belongs to the above-mentioned exemplary compound (36).

<Synthesis example of fluorine-containing compound (10)>
In the synthesis example of the fluorine-containing compound (1), 2- (perfluorohexyl) -ethyl acrylate [FAAC6, manufactured by NOK Co., Ltd.] was converted to 3- (perfluorohexyl) -2-hydroxy-propyl acrylate [R1633, Daikin Kogyo Co., Ltd.], terminal methyl polyethylene oxide monomer [PME1000, manufactured by NOF Corporation, PEO repeat number (23) terminal Me], NK ester AM230G manufactured by Shin-Nakamura Chemical Co., Ltd. Synthesis of fluorine-containing compound (10) R1633 / AA / AM230G = 50/5/45 (mass ratio) according to the synthesis example of fluorine-containing compound (1) except that the number of PEO repeats (23) is changed to terminal methyl. Went.
In addition, a fluorine-containing compound (10) is a compound which belongs to the above-mentioned exemplary compound (27).

<Synthesis example of fluorine-containing compound (11)>
In the synthesis example of the fluorine-containing compound (1), terminal methylpolyethylene oxide monomer [PME1000, manufactured by NOF Corporation, PEO repeat number (23) terminal Me] was changed to NK ester AM130G manufactured by Shin-Nakamura Chemical Co., Ltd. , Fluorine-containing compound (11) FAAC6 according to the synthesis example of fluorine-containing compound (1) except that the number of repeating PEO (13) is changed to terminal methyl and other components are changed to the addition amounts shown in Table 2. / AA / AM130G = 65/5/30 (mass ratio) was synthesized.
In addition, a fluorine-containing compound (11) is a compound which belongs to the above-mentioned exemplary compound (15).

<Synthesis example of fluorine-containing compound (12)>
In the synthesis example of the fluorine-containing compound (1), the terminal methyl polyethylene oxide monomer [PME1000, manufactured by NOF Corporation, PEO repeat number (23) terminal Me] is changed to NK ester AM230G manufactured by Shin-Nakamura Chemical Co., Ltd. , Fluorine-containing compound (12) FAAC6 according to the synthesis example of fluorine-containing compound (1) except that the number of PEO repeats (23) was changed to terminal methyl and other components were changed to the addition amounts shown in Table 2. / AA / AM230G = 50/5/45 (mass ratio) was synthesized.
In addition, a fluorine-containing compound (12) is a compound which belongs to the above-mentioned exemplary compound (16).

<Synthesis example of fluorine-containing compound (13)>
In the synthesis example of the fluorine-containing compound (1), the terminal methyl polyethylene oxide monomer [PME1000, manufactured by NOF Corporation, PEO repeat number (23) terminal Me] is changed to NK ester AM230G manufactured by Shin-Nakamura Chemical Co., Ltd. The compound M-1 (2- (perfluorohexyl) -ethyl acrylate [FAAC6, manufactured by NOK Co., Ltd.]) synthesized according to the following synthesis example Fluorinated compound (13) according to the synthesis example of the fluorinated compound (1) except that it was changed to fluorohexyl) -ethyloxycarbamoyl-ethyl acrylate) and other components were changed to the addition amounts shown in Table 2. Synthesis of M-1 / AA / AM230G = 50/5/45 (mass ratio) was performed.
In addition, a fluorine-containing compound (13) is a compound which belongs to the above-mentioned exemplary compound (33).

~ Synthesis Example of Compound M-1 ~
Under a nitrogen stream, 150 g of dehydrated tetrahydrofuran (anhydTHF, manufactured by Kanto Chemical Co., Ltd.), 182.1 g of perfluorohexylethanol (FA6, manufactured by NOK Co., Ltd.), and acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko Co., Ltd.) It was put into a 1000 ml three-necked flask equipped with a dropping funnel and a condenser tube containing 70.6 g, and immersed in an ice-cooled water bath. AOI was dropped from the dropping funnel so that the internal temperature was 5 ° C. or lower. After dropping, the temperature was raised to room temperature and stirred for 1 hour. After stirring, the reaction was completed by heating at 50 ° C. for 4 hours. The reaction mixture was partitioned with diethyl ether / distilled water, washed with saturated brine, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, and 100 mg of 2,5-di-t-octylhydroquinone was added to the filtrate collected by filtration and concentrated under reduced pressure to obtain a crude product of compound M-1. This was purified by silica gel column chromatography with hexane / ethyl acetate 20/1 to obtain 234 g (93%) of Compound M-1.

  Table 1 and Table 2 show the fluorine atom content in each copolymer component and fluorine-containing compounds (1) to (13) synthesized above. Further, propylene glycol monomethyl ether acetate is added and adjusted so that the solid content concentration of each fluorine-containing compound is 25%.

(Explanation of symbols in Table 1 and Table 2)
PME1000: Bremer PME1000, PEO repeat number (23) Terminal Me [manufactured by NOF Corporation]
AA: Acrylic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
FAAC6: 2- (perfluorohexyl) -ethyl acrylate [manufactured by NOK Corporation]
M90G: NK-ester M90G, PEO repeat number (9) Terminal Me [manufactured by Shin-Nakamura Chemical Co., Ltd.]
ANE1300: Bremer ANE1300, PEO repeat number (30) Terminal nonyl Ph [manufactured by NOF Corporation]
PE350: Bremer PE350, PEO repeat number (8) Terminal H [manufactured by NOF Corporation]
R1633: 3- (perfluorohexyl) -2-hydroxy-propyl acrylate [manufactured by Daikin Industries, Ltd.]
M-1: 2- (perfluorohexyl) -ethyloxycarbamoyl-ethyl acrylate [synthetic product according to the above synthesis example]
AM130G: NK-ester AM130G, PEO repeat number (13) Terminal Me [manufactured by Shin-Nakamura Chemical Co., Ltd.]
AM230G: NK-ester AM230G, PEO repeat number (23) Terminal Me [manufactured by Shin-Nakamura Chemical Co., Ltd.]
V65: 2,2′-azobis (isovaleronitrile) [manufactured by Wako Pure Chemical Industries, Ltd.]
・ LM: Lauryl mercaptan [manufactured by Tokyo Chemical Industry Co., Ltd.]
MMPG-Ac: Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation)

<< Preparation of photosensitive resin composition >>
The photosensitive resin composition K1 was first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 3, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 RPM for 10 minutes, and then Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bis (ethoxycarbonylmethyl) amino) -3 in the amounts shown in Table 3 '-Bromophenyl] -s-triazine, surfactant 1, and fluorine-containing compound (1) are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.), and 150 RPM30 at a temperature of 40 ° C. (± 2 ° C.). Obtained by stirring for a minute. In addition, the quantity of Table 3 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nexex 35 manufactured by Degussa) ... 13.1%
・ 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>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, 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%

[Example 1]
≪Formation of separation wall≫
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle has the composition described in the above table. Photosensitive resin composition K1 was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum dryer, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a photosensitive film thickness of 2.3 μm. A resin composition layer K1 was obtained.
With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and photosensitive resin The distance between the composition layers K1 was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in a nitrogen atmosphere.

Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin composition layer K1, and then a KOH developer (KOH, containing a nonionic surfactant, product name: CDK-1). , Manufactured by Fuji Film Electronics Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, followed by post-exposure at an exposure amount of 2000 mJ / cm ^{2 in} the atmosphere, followed by 240 ° C. for 50 minutes. Post-baking (heat treatment) was performed to obtain a striped separation wall (substrate with a separation wall) having an opening having a thickness of 2.0 μm, an optical density of 4.0, and a width of 100 μm.

≪Preparation of color filter≫
<Preparation of colored ink composition for pixels>
Among the following components, first, a pigment, a polymer dispersant, and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels.

(Composition of colored ink composition for red pixel)
-Pigment (CI Pigment Red 254)-5 parts-Polymer dispersing agent (Solsperse 24000 manufactured by AVECIA)-1 part-Binder (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random combination) Polymer, molecular weight 37,000) ... 3 parts, first epoxy resin (Novolac type epoxy resin, Epicoat 154 manufactured by Yuka Shell) ... 2 parts, second epoxy resin (neopentyl glycol diglycidyl ether) ) ... 5 parts ・ Curing agent (trimellitic acid) ・ ・ ・ 4 parts ・ Solvent: Ethyl 3-ethoxypropionate ・ ・ ・ 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 the red pixel colored ink composition except that the same amount of pigment green 36 was used.
Further, 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 the red pixel colored ink composition except that the same amount of CI Pigment Blue 15: 6 was used.

  Next, in the region separated by the separation wall of the substrate with the separation wall obtained above using the colored ink composition for R, G, and B pixels described above (concave part surrounded by the convex part) Further, an ink composition was discharged using an ink jet recording apparatus until a desired concentration was obtained, and a color filter composed of R, G, and B patterns was produced. The color filter after image coloring was baked in an oven at 230 ° C. for 30 minutes to completely cure the separation wall and each pixel, thereby obtaining a color filter substrate.

The color filter thus obtained was evaluated as follows.
(Evaluation of color mixing of color filters)
The obtained color filter was visually observed with a 200-fold optical microscope from the side opposite to the side on which the pixels were formed to check for color mixing between the pixels. 1000 pixels were observed and divided into the following ranks. The results are shown in Table 10. Allowed are those of A rank, B rank and C rank.
Rank A: No color mixing B Rank: Color mixing 1-2 places C Rank: Color mixing 3-10 places D Rank: Color mixing 11 places or more

≪Production of liquid crystal display device≫
A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and separation wall of the color filter substrate obtained above.

  When the ITO resistance of this color filter was measured ("Loresta" manufactured by Mitsubishi Chemical Corporation; sheet resistance was measured by the four-probe method), it showed a very low value of 12Ω / □.

<Formation of columnar spacer pattern>
The following coating SP1 for the photosensitive resin layer coating solution for spacers was applied onto the ITO of the color filter by the same slit coater as described 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, weight average molecular weight 40000; polymer substance) 108 parts dipentaerythritol hexaacrylate (polymerizable monomer) 64.7 parts 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bis (ethoxycarbonylmethyl) 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, MegaFuck F780F (Dainippon Ink Chemical Co., Ltd .; surfactant) 856 parts · 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 Photo 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 protrusions for dividing liquid crystal alignment>
Prescription A of 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 having a dry film thickness of 1.6 μm was provided on the protrusion photosensitive resin layer using an intermediate layer coating solution of the following formulation P1.

(Coating liquid for photosensitive resin layer for protrusions: prescription A)
・ 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

(Coating liquid for intermediate layer: prescription P1)
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts · Polyvinylpyrrolidone (manufactured by ASP Japan, K-30 14.9 parts · 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 located on the ITO film and above the R, G, and B pixels. Next, the color filter substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes to form alignment splitting protrusions having a height of 1.5 μm and a vertical cross-sectional shape on the color filter substrate. did it.

  Further, an alignment-divided vertical alignment type liquid crystal display element was produced by combining the drive side substrate and the liquid crystal material with the color filter substrate obtained above. That is, a TFT substrate in which TFTs and pixel electrodes (conductive layers) are arrayed is prepared as a drive side substrate, the surface of the TFT substrate on which the pixel electrodes and the like are provided, and the color filter obtained from the above. The substrate was arranged so as to face the surface on the side where the alignment dividing projections were formed, and fixed with a gap formed by the spacers formed above. A liquid crystal material was sealed in the gap to provide a liquid crystal layer for image display. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed and arranged on the side that would be the back side of the liquid crystal cell provided with the polarizing plate, thereby obtaining an alignment-divided vertical alignment type liquid crystal display device.

≪Measurement and evaluation≫
<Parent wall separation / hydrophobicity evaluation>
Except that the photosensitive resin composition layer K1 produced in the same manner as in Example 1 above is exposed without using a mask, the exposure is performed in the same manner as in Example 1, and then under the same conditions until post-exposure. A photosensitive resin composition layer for testing was obtained. The red (R) pixel ink prepared in Example 1 was contact angle measuring device (contact angle meter (CA-A) manufactured by Kyowa Interface Science Co., Ltd.) with respect to the obtained photosensitive resin composition layer for testing. A photosensitive resin composition for testing is prepared by making a liquid sample (ink sample) having a size of 20 memories, taking out the ink sample from the tip of the needle, and bringing it into contact with the photosensitive resin composition layer for testing. Red (R) pixel ink droplets were formed on the physical layer, the shape of the ink droplets was observed from the viewing hole of the contact angle meter, and the contact angle θ at 25 ° C. was determined. The ink contact angle after standing for 10 seconds was 10 °. Thereafter, the test photosensitive resin composition layer was post-baked under the same conditions as in Example 1, and the contact angle of the red (R) pixel ink was measured again. As a result, the contact angle was improved to 37 °. Further, the ink droplet for the contact angle measurement was changed to a water droplet, and the water contact angle before and after baking was measured in the same procedure. As a result, it was 48 ° before baking and 92 ° after baking.

<Evaluation of adhesion between separation wall and substrate>
The same development except that three substrates prepared up to the pattern exposure process under the same conditions as the above-mentioned separation wall formation were prepared and the development time was increased to 90 seconds, 100 seconds, and 110 seconds. The film was processed under the conditions, and the chipping of the separation wall at each development time was visually evaluated as follows for 1000 pixels. In addition, what is permitted is A rank, B rank, and C rank.
(Evaluation criteria)
No separation wall chipping ・ ・ ・ A rank 1 to 2 separation wall chippings ・ ・ ・ B rank 3 to 10 separation wall chipping ・ ・ ・ C rank 11 or more separation wall chippings ・ ・・ D rank

<Evaluation of liquid crystal display device>
The liquid crystal display device produced in Example 1 was evaluated as follows.
For each liquid crystal display device, the gray display when a gray test signal was input was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria. Table 10 shows the evaluation results.
(Evaluation criteria 1)
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)

[Example 2]
≪Method for producing photosensitive transfer material K1≫
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, the photosensitive resin composition K1 was applied and dried. 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 composition layer having a dry film thickness of 2.3 μm on the temporary support. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded.
In this way, a photosensitive transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the photosensitive resin composition layer of black (K) are integrated is prepared, and the sample name is the photosensitive transfer material. It was set as K1.

<Coating liquid for thermoplastic resin layer: Formulation H1>
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

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

≪Formation of separation wall≫
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water by shower. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.
On the obtained silane coupling treated glass substrate, the cover film is removed from the photosensitive transfer material K1 produced by the above production method, and the surface of the photosensitive resin composition layer exposed after the removal and the silane coupling treated glass are removed. The substrate was superposed so that it was in contact with the surface of the substrate, and the substrate was heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)). The laminate was laminated with a transfer speed of 2.2 m / min. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support. After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the photosensitive resin composition layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, development is performed with a KOH developer (100-fold diluted solution of CDK-1 (trade name) (pH = 11.8), manufactured by Fuji Photo Film Co., Ltd.), and an unexposed portion of the photosensitive resin composition layer. The intermediate layer and the thermoplastic resin layer thereunder were removed to obtain a black matrix pattern-like separation wall on the glass substrate. Subsequently, the whole surface of the substrate was post-exposed at 2000 mJ / cm ² from the surface of the substrate with an aligner in the atmosphere, followed by post-baking at 240 ° C. for 50 minutes to obtain a separation wall having an optical density of 4.0. .
Next, a color filter and a liquid crystal display device were produced in the same manner as in Example 1, and the results of evaluation similar to that described in Example 1 are shown in Table 10.

[Example 3]
In the photosensitive resin composition K1, the photosensitive resin composition K2 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (2). Table 10 shows the results of producing the photosensitive transfer material K2 by the described method, performing the same procedure as in Example 2, and performing the same evaluation.

[Example 4]
In the photosensitive resin composition K1, the photosensitive resin composition K3 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (3). Table 10 shows the results of producing a photosensitive transfer material K3 by the described method, performing the same procedure as in Example 2, and performing the same evaluation.

[Example 5]
In the photosensitive resin composition K1, the photosensitive resin composition K4 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (4). Table 10 shows the results of producing a photosensitive transfer material K4 by the described method, performing the same procedure as in Example 2, and performing the same evaluation.

[Example 6]
In the photosensitive resin composition K1, the photosensitive resin composition K5 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (5). The photosensitive transfer material K5 was prepared by the method described, and the results of the same procedure and the same evaluation as in Example 2 are shown in Table 10.

[Example 7]
In the photosensitive resin composition K1, the photosensitive resin composition K6 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (6). The photosensitive transfer material K6 was prepared by the method described, and the results of the same procedure and the same evaluation as in Example 2 are shown in Table 10.

[Example 8]
In the photosensitive resin composition K1, the photosensitive resin composition K7 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (7). Table 10 shows the results of producing a photosensitive transfer material K7 by the described method, performing the same procedure as in Example 2, and performing the same evaluation.

[Example 9]
Photosensitive transfer by the method described in Example 2 using the photosensitive resin composition K8 prepared in the same procedure except that the composition of the photosensitive resin composition K1 in Example 1 was changed as shown in the table below. Table 10 shows the result of producing the material K8 and performing the same procedure and the same evaluation as in Example 2.

[Example 10]
Photosensitive transfer by the method described in Example 2 using the photosensitive resin composition K9 prepared in the same procedure except that the composition of the photosensitive resin composition K1 in Example 1 was changed as shown in the table below. Table 10 shows the results of manufacturing the material K9, performing the same procedure as in Example 2, and performing the same evaluation.

[Example 11]
Photosensitive transfer by the method described in Example 2 using the photosensitive resin composition K10 prepared in the same procedure except that the composition of the photosensitive resin composition K1 in Example 1 was changed as shown in the table below. Table 10 shows the results of manufacturing the material K10, performing the same procedure as in Example 2, and performing the same evaluation.

[Example 12]
Photosensitive transfer by the method described in Example 2 using the photosensitive resin composition K11 produced in the same procedure except that the composition of the photosensitive resin composition K1 in Example 1 was changed as shown in the table below. Table 10 shows the results of manufacturing the material K11, performing the same procedure as in Example 2, and performing the same evaluation.

[Example 13]
In Example 1, a color filter and a liquid crystal display device were produced in the same manner as in Example 1 except that the color ink composition for RGB pixels was changed to the color ink composition 2 for RGB pixels described below. Table 10 shows the same procedure and the results of the same evaluation.

-Preparation of pigment dispersion-
Brominated phthalocyanine green (CI Pigment Green 36, trade name: Rionol Green 6YK, manufactured by Toyo Ink Manufacturing Co., Ltd.) with a dispersant (dispersant 1 above) and a solvent (1,3-butanediol diacetate) 1,3-BGDA) is blended as shown in Table 8 below, and after premixing, zirconia beads having a diameter of 0.65 mm are filled with a motor mill M-50 (manufactured by Eiger Japan) at a filling rate of 80. %, And dispersed for 25 hours at a peripheral speed of 9 m / s to prepare a pigment dispersion for G (G1). In the G pigment dispersion (G1), except that the pigment and other components were blended as shown in Table 8, the same as the G pigment dispersion (G1), the G pigment dispersion (G2) and the R pigment Dispersions (R1) and (R2) and pigment dispersions for B (B1) and (B2) were prepared. The number average particle size of the pigment dispersion was measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

Next, as shown in the following Table 9, the solvent, the monomer and the surfactant component were mixed and stirred at 25 ° C. for 30 minutes. After confirming that there was no insoluble matter, a monomer solution was prepared.
Next, while stirring the pigment dispersion liquid for G (G1) and the pigment dispersion liquid for G (G2), the monomer liquid is slowly added and stirred at 25 ° C. for 30 minutes. 1) was prepared.
Similarly, each color ink (B-1, R-1) was adjusted.

Details of the materials used are shown.
・ C. I. P. R. 254 (Brand name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.)
・ C. I. P. R. 177 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.)
・ C. I. P. Y. 150 (Brand name: Bayplast Yellow 5GN 01, manufactured by Bayer Corporation)
・ C. I. P. B. 15: 6 (trade name: Rionol Blue ES, manufactured by Toyo Ink Manufacturing Co., Ltd.)
・ C. I. P. V. 23 (Product name: Hostaperm Violet RL-NF, manufactured by Clariant Japan Co., Ltd.)
1,3-BGDA (1,3-butanediol diacetate; boiling point 232 ° C.)
・ DPHA (Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA), (solid content: 100%)
Surfactant 2: Structure 1 (100% solid content) shown in the surfactant 1 column

[Example 14]
In the photosensitive resin composition K1, the photosensitive resin composition K12 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (10). A photosensitive transfer material K12 was prepared by the method described, and the results of the same procedure and the same evaluation as in Example 2 are shown in Table 10.

[Example 15]
In the photosensitive resin composition K1, the photosensitive resin composition K13 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (11). A photosensitive transfer material K13 was prepared by the method described, and the results of the same procedure and the same evaluation as in Example 2 are shown in Table 10.

[Example 16]
In the photosensitive resin composition K1, the photosensitive resin composition K14 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (12). A photosensitive transfer material K14 was prepared by the method described, and the results of the same procedure and the same evaluation as in Example 2 are shown in Table 10.

[Example 17]
In the photosensitive resin composition K1, the photosensitive resin composition K15 produced in the same procedure was used except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (13). The photosensitive transfer material K15 was produced by the method described, and the results of the same procedure and the same evaluation as in Example 2 are shown in Table 10.

[Comparative Example 1]
Table 10 shows the results of the same procedure and the same evaluation as in Example 1 except that the fluorine-containing compound (1) to be added was changed to the fluorine-containing compound (8) in the photosensitive resin composition K1. Show.

[Comparative Example 2]
With respect to the fluorine-containing compound (9), since the solubility of the resin was insufficient, it was deposited at the time of synthesis and could not be evaluated.

As shown in Table 10, when a separation wall, a color filter, and a liquid crystal display device were produced using the photosensitive resin composition of the present invention (Examples 1 to 17), between the separation wall and the substrate. Adhesion was good (or within an allowable range), and color mixing and display unevenness were suppressed.
On the other hand, when a separation wall, a color filter, and a liquid crystal display device were produced using the photosensitive resin composition having a fluorine atom content of 26% by mass in the fluorine-containing compound (Comparative Example 1), the separation was performed. The adhesion between the wall and the substrate, color mixing, and display unevenness deteriorated and exceeded the allowable range.

  In addition, although the said Example centered on the case where each of said fluorine-containing compound (1)-(7), (10)-(13) was used as a fluorine-containing compound, it was included in the scope of the present invention. Among the fluorine-containing compounds, when other fluorine-containing compounds are used or when two or more kinds are used in combination, the same effect as in this example can be exhibited, and similarly, the separation wall-substrate Color mixing and display unevenness can be suppressed while maintaining good adhesion.

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

Explanation of symbols

1... Separation wall 2... Colored pixel (colored area)
3... Recessed portion 4... Separation wall upper surface 5... Separation wall side surface 6.

Claims (12)

  A photosensitive resin composition, wherein the water contact angle on the upper surface of a pattern image formed using the photosensitive resin composition is measured in accordance with the method described in JIS R3257, before the heat treatment is performed. When the water contact angle on the upper surface of the image is heat treated at A ° and 240 ° C. for 50 minutes and the water contact angle on the upper surface of the pattern image after cooling for 1 hour is B °, the contact angle difference B ° −A ° is A photosensitive resin composition having an angle of 20 ° or more.   A photosensitive resin composition comprising at least 1) an initiator, 2) a binder, 3) an ethylenically unsaturated compound, 4) a colorant, and 5) a fluorine-containing compound, wherein the fluorine-containing compound is at least a fluorine atom A photosensitive resin composition comprising a repeating unit having a side chain and a fluorine atom content in the fluorine-containing compound of 36 to 70% by mass.   The photosensitive compound according to claim 2, wherein the fluorine-containing compound contains (a) a repeating unit having at least a fluorine atom in a side chain and (b) a repeating unit having a polyether structure in a side chain. Resin composition.   The fluorine-containing compound is (a) a repeating unit having at least a fluorine atom in the side chain, (b) a repeating unit having a polyether structure in the side chain, and (c) a repeating unit having a carboxylic acid group in the side chain. The photosensitive resin composition of Claim 2 or 3 characterized by the above-mentioned.   The photosensitive resin composition according to claim 3 or 4, wherein the repeating unit (b) having a polyether structure in a side chain has a terminal-capped polyether structure.   The photosensitive transfer material which has the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-5 on a temporary support body. Photosensitivity which forms the photosensitive resin layer in the at least one surface of a board | substrate using the photosensitive resin composition of any one of Claims 1-5, or the photosensitive transfer material of Claim 6. A resin layer forming step;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer;
A heat treatment step of heat-treating a pattern image formed of the photosensitive resin layer obtained by the development;
A method for producing a separation wall, comprising:   A separation wall formed by the method for producing a separation wall according to claim 7.   9. A method for producing a color filter, wherein the separation wall according to claim 8 partitions the substrate, and the colored liquid composition is applied to the recesses on the partitioned substrate.   10. A method for producing a color filter, wherein the method for applying a colored liquid composition according to claim 9 is a pixel forming method for forming pixels by applying droplets of the colored liquid composition by an ink jet method.   The color filter manufactured by the manufacturing method of the color filter of Claim 9 or 10.   A display device comprising the color filter according to claim 11.

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