KR20090123848A - Photosensitive resin composition, photosensitive transfer material, pixel barrier and method for forming the same, substrate with pixel barrier, color filter and method for producing the same, and display device - Google Patents

Abstract

Disclosed is a photosensitive resin composition which is suppressed in emission of a fluorine-containing compound component during a heat treatment. Also disclosed are a photosensitive transfer material, a pixel barrier using the photosensitive resin composition or the photosensitive transfer material, a method for forming such a pixel barrier, a substrate with pixel barrier, a color filter, a method for producing a color filter, and a display device. The photosensitive resin composition contains an initiator, an ethylenically unsaturated compound and a fluorine-containing compound. In this composition, the heat reduction rate of the fluorine-containing compound when it is kept at 150°C for 30 minutes is not more than 30% by mass.

Description

PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE TRANSFER MATERIAL, PIXEL BARRIER AND METHOD FOR FORMING THE SAME , SUBSTRATE WITH PIXEL BARRIER, COLOR FILTER AND METHOD FOR PRODUCING THE SAME, AND DISPLAY DEVICE}

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

In recent years, the demand for liquid crystal displays for PCs and liquid crystal color televisions tends to increase, and the demand for improved characteristics and cost reduction of color filters indispensable for such displays is increasing.

Conventionally, as a manufacturing method of a color filter, the dyeing method, the pigment dispersion method, the electrodeposition method, the printing method, etc. are performed.

For example, the dyeing method forms a water-soluble polymer material layer, which is a material for dyeing, on a transparent substrate, patterning it into a desired shape by a photolithography process, and then, the obtained pattern is immersed in a dye bath to obtain a colored pattern. By repeating this process three times, it is a method of forming the colored layer which consists of three coloring parts of R (red), G (green), and B (blue).

Moreover, the pigment dispersion method is actively performed recently, and the monochromatic pattern is obtained by forming the photosensitive resin layer which disperse | distributed the pigment on a transparent substrate, and patterning this. By repeating this process three times, it is a method of forming the colored layer which consists of three coloring parts of R, G, and B.

In the electrodeposition method, a transparent electrode is patterned on a transparent substrate, and the first color is electrodeposited by immersion in an electrodeposition coating solution containing pigment, resin, electrolysis solution, and the like. This process is repeated three times to form a colored layer consisting of three colored portions of R, G, and B, which is finally baked.

The printing method disperse | distributes a pigment in thermosetting resin, repeats printing three times, and apply | coats R, G, and B separately, and forms a colored layer by thermosetting resin.

All of these methods are common in that the same process needs to be repeated three times in order to form red, green, and blue tricolor pixels, resulting in high cost. Moreover, since there are many processes, there also exists a problem that a yield falls easily.

In order to overcome these, the color filter manufacturing method which forms a black matrix (pixel partition wall) by the pigment dispersion method and manufactures an RGB pixel by the inkjet method is examined recently. In this inkjet method, pixels of R, G, and B are sequentially provided to the recesses of the black matrix (pixel separation wall). The method using the inkjet method has the advantage that the manufacturing process is simple and low cost.

In addition, the inkjet method is not only limited to the production of color filters, but also applicable to the production of other optical devices such as electric luminescence devices.

In the inkjet method, it is necessary to suppress the occurrence of mixed color of the ink between adjacent pixel areas, and the phenomenon that the ITO solution or the metal solution solidifies and sticks to a portion other than the predetermined area. Therefore, the partition wall (pixel separation wall) is required to have a property of repelling water, an organic solvent, or the like, which is the ejection liquid of an inkjet, so-called water repellency, oil repellency.

A coating composition containing a vinyl polymer, a photosensitive resin, and an organic solvent obtained by polymerizing a monomer composition containing a vinyl monomer having a fluoroalkyl group as a resin for forming such a partition (pixel separation wall) is disclosed. A vinyl polymer is a polymer containing 0.1-5 mass% of fluorine atoms (for example, see Unexamined-Japanese-Patent No. 9-54432).

As a technique for imparting water repellency and oil repellency, for example, a vinyl monomer such as a vinyl polymer or hexafluoropropylene obtained by polymerizing a monomer composition containing a vinyl monomer having a fluoroalkyl group and three or more ester groups Copolymers of other vinyl monomers are disclosed (see Patent Document 1 and Patent Document 2, for example). Moreover, the resist composition containing the vinyl polymer obtained by superposing | polymerizing the monomer composition containing the vinyl monomer which has a C4-C6 fluoroalkyl group, and the photosensitive member is disclosed, The said vinyl polymer has a fluorine atom content rate of 7-. It is 35 mass% (for example, refer patent document 3).

Moreover, as a manufacturing method of the board | substrate with a black matrix containing ink repellent agent, the contact angle with respect to the coloring ink of the uppermost part of a black matrix is controlled to 30 degrees-60 degrees by controlling the thermosetting temperature and the thermosetting time of a black matrix. There exists a technique (for example, refer patent document 4).

On the other hand, the example of water-soluble photosensitive resin which added the tertiary amine to resin which has (alpha) -bromo acetic acid unit is disclosed (for example, refer patent document 5).

However, when forming a black matrix using the photosensitive resin composition in which ink repellent agent was added, black matrix containing a fluorine-containing compound is generally subjected to high temperature treatment such as baking treatment for ink repelling and curing after patterning. Therefore, ink is repelled to the glass surface, which is the pixel formation region surrounded by the black matrix, and when the ink for coloring pixel formation is applied, the glass repels the ink to form colored pixels of a desired quality, and thus color filters. There is problem that we cannot say.

Moreover, in the composition which consists of a compounding ratio of the copolymer of patent document 6, there existed a tendency for the water / oil repellency of the coating film formed by it to be insufficient. Moreover, in the vinyl polymer of patent document 3, there existed a tendency for the developing solution tolerance and the adhesiveness at the time of image development to be inadequate.

(Patent Document 1) Japanese Patent Application Laid-Open No. 2004-2733

(Patent Document 2) Japanese Patent Application Laid-Open No. 3-244604

(Patent Document 3) Japanese Unexamined Patent Publication No. 2005-315984

(Patent Document 4) Japanese Patent Application Laid-Open No. 2006-251433

(Patent Document 5) Japanese Patent Application Laid-Open No. 61-174202

(Patent Document 6) Japanese Patent Application Laid-Open No. 9-54432

The present invention, in certain embodiments, maintains the water repellency and ink repellency of the upper surface of the pattern image (exposed surface on the side opposite to the surface in contact with the substrate) when the pattern image (for example, the pixel separation wall) is used. It is an object of the present invention to provide a photosensitive resin composition in which adhesion between an image and a substrate on which the pattern image is formed can be maintained satisfactorily and release of a fluorine-containing compound component (containing a decomposition component) when heat treatment is suppressed. .

In addition, the present invention, in certain embodiments, maintains the 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 (e.g., the pixel separation wall). It is an object of the present invention to provide a photosensitive transfer material having a uniform photosensitive resin layer which can be maintained satisfactorily and the occurrence of repulsion (repelling) during coating is suppressed.

In addition, the present invention provides a method for forming a pixel separation wall in which a pixel partition wall that has ink repellency and suppresses bleeding of a given colored liquid can be formed while maintaining the wettability of a region to which the colored liquid is applied. And a pixel dividing wall formed by the forming method and a method of manufacturing the same.

In addition, the present invention, in certain embodiments, has an ink repellency and suppresses the bleeding of the colored liquid when the colored liquid is applied to the recesses between the pixel separation walls, and is a region to which the colored liquid is provided between the pixel separation walls. An object of the present invention is to provide a substrate having a pixel dividing wall whose wettability is maintained.

Moreover, this invention makes it a subject to provide the high quality color filter which suppressed the display stain at the time of mixed color, white spot, and image display in predetermined embodiment, and its manufacturing method.

Moreover, this invention makes it a subject to provide the display apparatus which can suppress a display stain and can display high quality image in predetermined embodiment.

According to the present invention, after forming a pattern such as a black matrix in advance using a resin composition containing ink repellent agent, the pattern is subjected to a high temperature treatment such as a baking treatment (for example, 150 ° C. or higher) and then contained in the pattern. A component derived from the fluorine-containing compound tends to come out of the system and adhere to the substrate surface to lower the wettability of the ink imparted to the substrate surface, but the specific fluorine-containing compound can suppress adhesion to the substrate surface after black matrix formation. It was achieved based on this knowledge.

Specific means for achieving the above object is as follows.

(1) The photosensitive resin composition which contains an initiator, an ethylenically unsaturated compound, and a fluorine-containing compound, and whose thermal reduction rate of the said fluorine-containing compound at 30 degreeC is hold | maintained for 30 minutes.

(2) Said fluorine-containing compound contains the repeating unit which has a fluorine atom in a side chain, and a main chain structure has an acryl linkage chain, The photosensitive resin composition as described in (1) characterized by the above-mentioned.

(3) Said fluorine-containing compound contains repeating unit which has a fluorine atom in a side chain, and repeating unit represented by following General formula (1), The photosensitive resin composition as described in (1) characterized by the above-mentioned.

In general formula (1), R <^1> represents a hydrogen atom or a C1-C5 alkyl group; R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an alkanoyl group of 2 to 5 carbon atoms; L ¹ represents a single bond or a divalent organic linking group; X represents a chlorine atom, bromine atom or iodine atom; Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group.

(4) The photosensitive resin composition as described in (3) characterized by the repeating unit which has the said fluorine atom in a side chain having three or more fluorine atoms.

(5) The photosensitive resin composition as described in (3) characterized by the repeating unit represented by the said General formula (1) being a repeating unit represented by following General formula (2).

In general formula (2), R <^1> represents a hydrogen atom or a C1-C5 alkyl group; R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an alkanoyl group of 2 to 5 carbon atoms; Z ¹ represents an ester group or an amide group; L ² represents a single bond or a divalent organic linking group; X represents a chlorine atom, bromine atom or iodine atom; Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group.

(6) The photosensitive resin composition as described in (3) characterized by the repeating unit represented by the said General formula (1) being a repeating unit represented by following General formula (3).

In general formula (3), R <^1> represents a hydrogen atom or a C1-C5 alkyl group; R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an alkanoyl group of 2 to 5 carbon atoms; Z ² represents a single bond, an arylene group, or a divalent heterocyclic moiety; X represents a chlorine atom, bromine atom or iodine atom; Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group.

(7) The photosensitive resin composition as described in (2) whose repeating unit which has the said fluorine atom in a side chain is a repeating unit which has a C4-C7 fluoroalkyl group.

(8) L1 in the said General formula (1) is a bivalent organic coupling group containing at least ¹ of an ester bond and an amide bond, The photosensitive resin composition as described in (3) characterized by the above-mentioned.

(9) The photosensitive resin composition according to (3), wherein L ¹ in General Formula (1) is a single bond, an arylene group, or a divalent heterocyclic moiety.

(10) Said fluorine-containing compound further has a repeating unit which has an acidic group, The photosensitive resin composition as described in (1) characterized by the above-mentioned.

(11) The photosensitive resin composition as described in (1) whose content with respect to the total solid mass of the said fluorine-containing compound is 0.1 mass%-10 mass%.

(12) The photosensitive transfer material which has a photosensitive resin layer using the photosensitive resin composition of (1) on a support body.

(13) Process of forming the photosensitive resin layer which forms the photosensitive resin layer using the photosensitive resin composition in any one of (1)-(11), or the photosensitive transfer material as described in (12),

Exposing the photosensitive resin layer,

Developing the exposed photosensitive resin layer, and

A method of forming a pixel separation wall comprising the step of heating a pattern image obtained by the above development.

(14) A pixel partition wall formed by the method for forming a pixel partition wall as described in (13).

(15) A substrate having a pixel dividing wall having a substrate and a pixel dividing wall formed on the substrate by the method for forming a pixel dividing wall according to (13).

(16) The pixel separation of the substrate surface on the side where the pixel separation wall of the substrate is formed when the water contact angle of the upper surface of the wall of the pixel separation wall is 60 ° or more when measured according to a known wettability test method of the surface of the substrate glass. The board | substrate with a pixel partition wall as described in (15) whose droplet diameter is 20 micrometers or more immediately after dripping the propylene glycol monomethyl ether monoacetate of the part in which the wall is not formed.

(17) The manufacturing method of the color filter including the process of providing a coloring liquid composition to the recessed part on the board | substrate partitioned by the pixel division wall of (14), and forming a colored area | region.

(18) The method for producing a color filter according to (17), wherein the applying of the colored liquid composition is performed by discharging droplets of the colored liquid composition by an inkjet method.

(19) A color filter produced by the method for producing a color filter according to (18).

(20) A display device provided with the color filter according to (19).

(Effects of the Invention)

According to the present invention, the pattern image and the pattern are maintained while maintaining the water repellency and ink repellency of the upper surface of the pattern image (exposed surface on the opposite side to the surface in contact with the substrate) when the pattern image (for example, the pixel separation wall) is used. The photosensitive resin composition which can maintain the adhesiveness of the board | substrate in which an image is formed favorably, and suppressed release of the fluorine-containing compound component (including a decomposition component) at the time of heat processing can be provided.

According to the present invention, it is possible to maintain good 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 transfer-formed pattern image (for example, the pixel separation wall). The photosensitive transfer material which has the uniform photosensitive resin layer by which generation | occurrence | production of repulsion (repelling) at the time of application | coating was suppressed can be provided.

According to the present invention, the pixel dividing wall which has ink repellency and suppresses the bleeding of the imparted colored liquid can be formed while maintaining the wettability of the region to which the colored liquid is impregnated, and by the forming method. The formed pixel dividing wall and its manufacturing method can be provided.

According to the present invention, it has ink repellency, suppresses the bleeding of the colored liquid when the colored liquid is applied to the recesses between the pixel partition walls, and maintains the wettability of the region to which the colored liquid between the pixel partition walls is applied. It is possible to provide a substrate having a pixel dividing wall.

According to the present invention, it is possible to provide a high quality color filter in which mixed color, white spots, and display stains in image display are suppressed, and a manufacturing method thereof.

According to the present invention, it is possible to provide a display device which can suppress display stains and enable high quality image display.

1 is a cross-sectional view of a color filter for explaining an upper surface of a pixel partition wall, a side surface of the pixel partition wall, a recess on a substrate, and the like in the present invention.

*** Brief description of symbols for the main parts of the drawings ***

1: pixel separation wall 2: colored pixel (colored area)

3: recess 4: upper surface of pixel dividing wall

5: pixel partition wall side 6: substrate

EMBODIMENT OF THE INVENTION Hereinafter, the photosensitive resin composition of this invention, the photosensitive transfer material using the same, the pixel partition wall, its formation method, the board | substrate with a pixel partition wall, a color filter, its manufacturing method, and a display apparatus are demonstrated in detail.

Photosensitive resin composition

The photosensitive resin composition of this invention contains an initiator, an ethylenically unsaturated compound, and a fluorine-containing compound at least, and is comprised so that the thermal reduction rate of the fluorine-containing compound at 30 degreeC may be suppressed to 30% or less.

Since the photosensitive resin composition of this invention contains a fluorine-containing compound so that the heat reduction rate at the time of holding at 150 degreeC for 30 minutes may be suppressed to 30% or less, it heats at high temperature (for example, 150 degreeC or more) after film formation, for example. Emission of the fluorine-containing component during the treatment is suppressed. For example, after the film is formed on the substrate and the pattern is formed, the film is formed on the non-formed surface when the heat treatment is performed in order to perform ink reking and thermosetting of the pattern. Adhesion of a fluorine-containing component can be prevented. From this, the liquid wettability in the region where the photosensitive resin composition is not formed can be maintained, and for example, in the case of producing a color filter, the pixel separation wall non-formed region (pixel of a substrate having pixel separation walls such as a black matrix) is formed. Repelling of the liquid at the time of forming a colored region (colored pixel such as RGB) by imparting a colored liquid composition (for example, applying ink droplets by an inkjet method) to a recessed part on a substrate separated by a separating wall) A color filter and a display device which can prevent the occurrence of white spots in the colored region and the occurrence of display stains when displaying images can be suppressed and high quality images can be obtained.

1) initiator

The photosensitive resin composition of this invention contains at least 1 sort (s) of initiator.

As a method of curing the photosensitive resin composition, a thermal clock using a thermal initiator and a photo-clock using a photoinitiator are generally used. However, in the present invention, it is preferable that the surface and cross-sectional shape of the pixel-divided wall after curing is tapered or rectangular. It is preferable to use a photo-clock as it is important.

A photoinitiator is a compound which can generate active species which initiates polymerization of an ethylenically unsaturated compound described later by irradiation (also referred to as exposure) of radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron ray, and X-ray. It can select suitably from a photoinitiator or a photoinitiator system.

As a photoinitiator or a photoinitiator type, For example, a trihalomethyl group containing compound, an acridine type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, a benzoin type compound, a benzophenone type compound, the (alpha)-dike Tone type compounds, a polynuclear quinone type compound, a xanthone type compound, a diazo type compound, etc. can be mentioned.

Specifically, the trihalomethyloxazole derivative or the s-triazine derivative substituted with the trihalomethyl group described in Japanese Patent Laid-Open No. 2001-117230, the trihalomethyl-s- described in the specification of US Pat. Trihalomethyl group-containing compounds such as triazine compounds and trihalomethyloxadiazole compounds described in US Patent No. 4212976;

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, Acridine-based compounds such as bis (9-acridinyl) alkanes such as 11-bis (9-acridinyl) undecane and 1,12-bis (9-acridinyl) dodecane;

6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2 , 4-bis (trichloromethyl) -s-triazine, 6- [4'- (N, N-bis (ethoxycarbonylmethyl) amino) -3'-phenyl] -2,4-bis (trichloro Triazine-based compounds such as rhomethyl) -s-triazine; 9,10-dimethylbenzophenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyl dimethyl 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-based compound, an acetophenone-based compound, a biimidazole-based compound, and a triazine-based compound is preferable from the viewpoint of sensitivity, and particularly, a trihalomethyl group-containing compound and It is preferable to contain at least 1 sort (s) chosen from an acridine type compound. Trihalomethyl group-containing compounds and acridine-based compounds are useful in terms of versatility and low cost.

Particularly preferably, the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole for the same reason as described above, and as the acridine-based compound, 9-phenylacridine and also 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 6- [4 '-(N, N-bis (ethoxycarbonylmethyl) amino) -3'-phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxysty Trihalomethyl group-containing compounds, such as aryl) -5-trichloromethyl-1,3,4-oxadiazole, and as the triazine-based compound, 6- [p- (N, N-bis (ethoxycarbonylmethyl); ) Amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 9-phenylacridine as the acridine compound, Michler's ketone as the acetophenone compound, Examples of the imidazole compound include 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

The said photoinitiator may be used independently and may use 2 or more types together.

As for the total amount of the initiator (especially photoinitiator) in the photosensitive resin composition, 0.1-20 mass% of the total solid (mass) of a resin composition is preferable, and 0.5-10 mass% is especially preferable. When the said total amount is in the said range, photocuring of a resin composition can be performed efficiently, and the image pattern which does not generate | occur | produce a fall and surface roughness at the time of image development can be obtained. By making the said total amount 0.1 mass% or more, the efficiency of photocuring of a composition can be improved and an exposure time can be shortened, and also by making it 20 mass% or less, the occurrence of the fall of the image pattern formed at the time of image development, and the roughness of a pattern surface can be prevented. It can be suppressed.

In addition, in this invention, the total solid (mass) of the photosensitive resin composition means all components except the solvent in a resin composition.

You may comprise the said photoinitiator using a hydrogen donor together. As the hydrogen donor, the following mercaptan-based compounds, amine-based compounds and the like are preferable in terms of improving the sensitivity. The "hydrogen donor" herein refers to a compound capable of donating hydrogen atoms to radicals generated from the photopolymerization initiator by exposure.

The mercaptan compound is a compound having a benzene ring or a heterocycle 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, "Mercaptan-based hydrogen donor"). In addition, the amine compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter, "Amine hydrogen donor"). In addition, these hydrogen donors may have a mercapto group and an amino group simultaneously.

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

One or more mercaptan-based hydrogen donors may be used alone or in combination of two or more, and the formed image is hardly eliminated from the permanent support upon development, and the strength and sensitivity may be improved. It is preferable to use in combination with one or more amine hydrogen donors.

Specific examples of the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4'- Bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzo Phenones and the like. More preferred combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone, in particular Preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

When the mercaptan-based hydrogen donor and the amine-based hydrogen donor are combined, the mass ratio (M: A) of the mercaptan-based hydrogen donor (M) and the amine-based hydrogen donor (A) is usually preferably 1: 1 to 1: 4. And 1: 1 to 1: 3 are more preferable. As 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) ethylenically unsaturated compounds

The photosensitive resin composition of this invention contains at least 1 sort (s) of an ethylenically unsaturated compound. As an ethylenically unsaturated compound, the following compound can be used individually or in combination with another monomer.

Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, and trimetholpropane tri (meth) ) Acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, polyoxyethylated trimetholpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenyl Benzene, 1,4-dihydroxybenzene di (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, trimellitic acid triallyl, lauryl (meth) acrylate, ( Meta) Arc The amide, xylene bis (meth) acrylamide and the like are listed.

Furthermore, the compound which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate, hexamethylene diisocyanate, toluene diisocyanate, The reactant with diisocyanate, such as xylene diisocyanate, can also be used.

Among these, especially preferred are pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate.

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 a resin composition, and 10-70 mass% is especially preferable. When content of an ethylenically unsaturated compound is in the said range, tolerance to the alkali developing solution in the exposure part of a composition can be ensured, the adhesiveness at the time of setting it as a resin composition can be suppressed, and handleability can be maintained.

3) fluorine-containing compounds

The photosensitive resin composition of this invention contains a fluorine atom as a fluorine-containing compound, and contains at least 1 sort (s) of the compound whose thermal reduction rate is 30 mass% or less. This fluorine-containing compound is a compound which has little fluorine-containing component emitted by heat processing (for example, 150 degreeC or more), and can impart the function of fluorine functional groups, such as water / oil repellency and surfactant.

Specifically, in the case where a pattern (e.g., pixel separation wall such as black matrix) is formed on the substrate by heat treatment after exposure and development, the surface of the pattern (e.g., pixel separation wall such as black matrix) It provides water repellency and oil repellency (including ink repellency) to the substrate, and conversely, adhesion of fluorine components to the unformed surface of the substrate pattern (e.g., pixel separation walls such as a black matrix) is suppressed. Wettability can be maintained (not water repellent).

In the present invention, wettability refers to the degree of wetness when a liquid flows on a plane, and is, for example, a concave portion surrounded by a pixel separation wall of a substrate on which a pixel separation wall such as a black matrix is formed (that is, a region to be a colored pixel). Refers to the degree of wetness of the ink droplets when the ink jet is applied to the droplets of the ink composition as the colored liquid composition. More specifically, the ink composition is one drop between the pixel dividing walls, and the diameter of the circle formed by the droplets is set as an index of wetness.

The thermal reduction rate refers to the mass reduction rate after heating with respect to before heating when the fluorine-containing compound is kept at 150 ° C for 30 minutes. In this invention, this thermal reduction rate is 30 mass% or less, Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less.

When the thermal reduction rate is within the above range, the remaining amount after heat treatment of the photosensitive resin composition can be ensured to impart good water repellency and oil repellency to the surface of the composition after heat treatment, for example, exposing, developing and thermosetting the photosensitive resin composition on a substrate. The wettability of the board | substrate exposure surface (for example, the recessed part on the board | substrate enclosed by the black matrix at the time of forming a black matrix on a board | substrate) at the time of forming a resin cured material can be maintained. From this, repelling when a liquid (including colored liquid compositions such as ink) is applied to the substrate exposed surface can be prevented.

As a fluorine-containing compound which contains a fluorine atom and whose thermal reduction rate is 30 mass% or less, it can select from the compound group containing the repeating unit which has a fluorine atom, and can provide water repellency and ink repellency. Among them, a compound selected from the group of compounds containing a repeating unit having a fluorine atom in the side chain and having a main chain structure of acryl linkage chain is difficult to come out of the composition system even under heat treatment (for example, at a high temperature of 150 ° C. or higher). desirable.

It is preferable that the repeating unit which has a fluorine atom in this invention is a repeating unit which has a side chain containing a fluorine atom. Moreover, it is preferable that the repeating unit which has a fluorine atom has three or more fluorine atoms. The side chain containing the fluorine atom preferably contains a fluoroalkyl group having 2 to 8 carbon atoms in total, and more preferably includes a fluoroalkyl group having 4 to 7 carbon atoms in total. When the total carbon number of the fluoroalkyl group is in the above range, the load on the environment can be reduced while maintaining the performance as a fluorine functional group. The fluoroalkyl group may be linear or branched.

It is preferable that the repeating unit which has a fluorine atom in this invention is a repeating unit represented with the following general formula (A).

In said general formula (A), R <^11> represents a hydrogen atom or a C1-C5 alkyl group. In the present invention, R ¹¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

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

As said alkylene group, a C1-C10 alkylene group is preferable, More preferably, it is a C1-C6 alkylene group. Specifically, methylene group, ethylene group, butylene group, heptylene group, hexylene group, dodecylene group, etc. are mentioned.

The arylene group is preferably an arylene group having 6 to 15 carbon atoms in total, and more preferably an arylene group having 6 to 10 carbon atoms in total. Specifically, a phenylene group, naphthylene group, anthracenylene group, biphenylene group, dialkylphenylene group, etc. are mentioned, These may be o-substituent, p-substituent, and / or m-substituent.

As said ester bond, a carboxylic acid ester bond, a sulfonic acid ester bond, a phosphate ester bond, etc. are preferable, and a carboxylic acid ester bond is more preferable.

As said amide bond, a carboxylic acid amide bond, a sulfonic acid amide bond, a phosphate amide bond, etc. are preferable, and a carboxylic acid amide bond is more preferable.

As said bivalent heterocyclic residue, the bivalent heterocyclic residue derived from the 5- or 6-membered ring which contains a nitrogen atom or an oxygen atom as a member of a ring, for example is preferable, and a pyridine ring, a pyrimidine ring, a pyrazine ring, thia Divalent heterocyclic residues derived from sol ring, benzothiazole ring, oxazole ring, benzoxazole ring, isoxoxazole ring, pyrazole ring, imidazole ring, quinoline ring or thiadiazole ring are more preferable, and pyridine ring or thiadiazole ring More preferred are divalent heterocyclic moieties derived from.

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

In formula, m shows the integer of 4-8, Preferably it is an integer of 4-7.

Although repeating units (a-1)-(a-34) are listed as a specific example of the repeating unit represented by general formula (A) below, this invention is not limited to these.

In addition, in the following specific example, R represents a hydrogen atom or a C1-C5 alkyl group.

As a repeating unit which has three or more fluorine atoms represented by general formula (A) in this invention, R <^11> is a hydrogen atom or a methyl group, and L <^11> is a carboxylic acid ester bond, an ether bond, an arylene group, and an alkylene group. A divalent organic linking group consisting of a single or a plurality of combinations selected from the group consisting of: Rf is preferably a C 4-7 perfluoroalkyl group (C ₄ F ₉ -C ₇ F ₁₅ ), R ¹¹ is A hydrogen atom, L ¹¹ is a divalent organic linking group consisting of a combination of a carboxylic ester bond and an alkylene group, and Rf is a C 4 to C 6 perfluoroalkyl group (C ₄ F _{9 to} C ₆ F ₁₃ ) More preferred.

As the repeating unit having the fluorine atom in the side chain, a repeating unit having a total of 2 to 12 carbon atoms, more preferably a total of 2 to 8 carbon atoms, and more preferably a total of 4 to 7 fluoroalkyl groups is preferable. Do. When the total carbon number of the fluoroalkyl group is in the above range, the load on the environment can be reduced while maintaining the performance as a fluorine functional group. The fluoroalkyl group may be linear or branched. The fluoroalkyl group may be linear or branched. More preferably, the following structural formula (A) is mentioned as a repeating unit which has the said fluorine atom in a side chain.

In said structural formula (A), R <^1> represents a hydrogen atom or a C1-C5 alkyl group.

In said structural formula (A), a shows the ratio (mass%) of the mass of the structural formula (A) to the total mass of a fluorine-containing compound.

In said structural formula (A), X <^1> represents an ether group, an ester group, an amide group, an arylene group, or a bivalent heterocyclic residue.

The arylene group represented by X ¹ is preferably an arylene group having 6 to 20 carbon atoms in total, and examples thereof include phenylene, naphthylene, anthracenylene and biphenylene, and these include o-substituents, p-substituents, and / or the like. Or m-substituents. Especially, a C6-C12 arylene group is more preferable, and phenylene and biphenylene are especially preferable.

As the heterocyclic moiety represented by X ¹ , for example, a divalent heterocyclic moiety derived from a 5- or 6-membered heterocycle containing a nitrogen atom or an oxygen atom as a member of the ring is preferable. As specific examples, pyridine ring, pyrimidine ring, pyrazine ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring, isoxazole ring, pyrazole ring, imidazole ring, quinoline ring, thiadiazole ring and the like are suitable, and pyridine The divalent heterocyclic residue derived from a ring, a thiadiazole ring, etc. is more preferable.

Among the above, as X ¹ , a linking group having a linking group having the following structure or at least one of the following structures is preferable.

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.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^X include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, and dodecyl group, and ether group, thioether group and ester. The substituted alkyl group which has substituents, such as group, an amide group, an amino group, a urethane group, and a hydroxyl group, is mentioned. Especially, an alkyl group with 1-8 total carbon atoms is preferable, and a methyl group, a butyl group, and an octyl group are more preferable.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^X include a phenyl group, a naphthyl group, a methylphenyl group, a methoxyphenyl group, and a nonylphenyl group. Especially, a C6-C15 aryl group is preferable and a phenyl group and a nonylphenyl group are more preferable.

As R <^X> , a methyl group, a butyl group, an octyl group, a phenyl group, and a nonylphenyl group are preferable from a water-repellent and oil-repellent performance viewpoint.

In said structural formula (A), as L <^1> , the coupling group which has at least one of the following groups or the following structures is preferable.

R ^Y represents a hydrogen atom or a methyl group.

n represents the integer of 2-20, Preferably the integer of 4-12 is represented.

Y is preferably a linking group having a single bond, a linking group having the following structure, or at least one of the following structures.

n represents the integer of 2-20, Preferably the integer of 4-12 is represented.

R <^3> represents a hydrogen atom or a C1-C5 alkyl group, and a hydrogen atom is preferable.

In said structural formula (A), Rf represents the group containing fluorine. In the present invention, Rf is preferably a fluoroalkyl group having 2 to 8 carbon atoms in total, and more preferably a fluoroalkyl group having 4 to 7 carbon atoms in total. Rf may be linear or branched. Rf is preferably a fluorine-containing group having a fluorine-containing group having the following structure or a group having the following structure.

m represents the integer of 1-20, Preferably it is 4-12, More preferably, the integer of 4-7 is shown.

In said structural formula (A), R <^1> is a hydrogen atom and X <^1>"the coupling group which has a coupling group of the said structure or at least 1 of the said structure (R <^X> is a methyl group, a butyl group, an octyl group, a phenyl group, or a nonylphenyl group) L ¹ is a linking group having the linking group of the above structure or at least one of the structures (R ³ is a hydrogen atom), and Rf is a fluorine-containing group having the above-mentioned structure or a group having the above-mentioned structure. Is preferable.

Fluorine containing the repeating unit which has a fluorine atom in a side chain, and the repeating unit represented by following General formula (1) in the said "compound which has a fluorine atom in a side chain, and a main chain structure has an acryl linkage chain." Containing compounds are preferred. In addition, the repeating unit which has a fluorine atom in a side chain is as above-mentioned, and its preferable form is also the same.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or 2 to 5 carbon atoms An alkanoyl group is shown.

As a C1-C5 alkyl group represented by said R <^1> , a methyl group, an ethyl group, a propyl group, etc. are mentioned, for example. It is preferable that R <^2> represents a hydrogen atom or a C1-C5 alkyl group, and a hydrogen atom, a methyl group, a phenyl group, a propyl group, and an acetyl group are mentioned as a preferable example. It is preferable that R ¹ and R ² each independently represent a hydrogen atom or a methyl group.

L ¹ represents a single bond or a divalent organic linking chain. As the divalent organic linking chain represented by L ¹ , an organic linking group consisting of a single organic linking group selected from the group consisting of an alkylene group, an arylene group, an ester linkage, an ether linkage, an amide linkage and a divalent heterocyclic residue or a combination thereof is preferable. .

In the present invention, L ¹ is preferably a divalent organic linking group containing an ester bond and / or an amide bond from the viewpoint of the polymerizability of the repeating unit, the solubility and the cost of the polymer. In addition, L ¹ is preferably a single bond, an arylene group or a divalent heterocyclic moiety from the viewpoint of the polymerizability of the repeating unit, the heat resistance and the cost of the polymer.

As an alkylene group in the bivalent organic coupling group represented by L <^1> , a C1-C10 alkylene group is preferable, More preferably, a C1-C6 alkylene group is preferable. Specifically, methylene group, ethylene group, butylene group, heptylene group, hexylene group, dodecylene group and the like are listed.

The arylene group in the divalent organic linking group represented by L ¹ is preferably an arylene group having 6 to 15 carbon atoms in total, and more preferably an arylene group having 6 to 10 carbon atoms in total. Specifically, a phenylene group, a naphthylene group, anthracenylene group, a biphenylene group, a dialkylphenylene group, etc. are mentioned, These may be o-substituent, p-substituent, and / or m-substituent.

As an ester group in the bivalent organic coupling group represented by L <^1> , a carboxylic acid ester group, a sulfonic acid ester group, a phosphate ester group, etc. are preferable, and a carboxylic acid ester group is more preferable.

As the amide group in the organic linking group represented by L ¹ , a carboxylic acid amide group, a sulfonic acid amide group, a phosphate amide group and the like are preferable, and a carboxylic acid amide group is more preferable.

As an ether group in the organic coupling group represented by L <^1> , an oxo ether group, a thioether group, etc. are preferable, and an oxo ether group is more preferable.

As the divalent heterocyclic moiety in the divalent organic linking group represented by L ¹ , for example, a divalent heterocyclic moiety derived from a 5- or 6-membered ring containing a nitrogen atom or an oxygen atom as a member of the ring is preferable. Bivalent heterocyclic residue derived from 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, etc. It is more preferable, and the bivalent heterocyclic residue derived from a pyridine ring and a thiadiazole ring is still more preferable.

In the general formula (1), X represents a chlorine atom, bromine atom or iodine atom. Especially, it is preferable that it is a chlorine atom or a bromine atom from the point of stability of the liquid crystal holding voltage, the suppression of color loss, and the availability when a color filter or a liquid crystal display element is comprised, and it is more preferable that it is a chlorine atom.

Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group.

The arylene group represented by Y is preferably an arylene group having 6 to 15 carbon atoms in total, and more preferably an arylene group having 6 to 10 carbon atoms in total. Specifically, a phenylene group, naphthylene group, anthracenylene group, biphenylene group, dialkylphenylene group, etc. are mentioned, These may be o-substituent, p-substituent, and / or m-substituent.

As the divalent heterocyclic moiety represented by Y, for example, a divalent heterocyclic moiety derived from a 5-membered or 6-membered ring containing a nitrogen atom or an oxygen atom as a member of the ring is preferable, and a pyridine ring, a pyrimidine ring and a pyra Divalent heterocyclic residues derived from a 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 or a thiadiazole ring are more preferable, and a pyridine ring or More preferred are bivalent heterocyclic moieties derived from thiadiazole rings.

In the above, Y is preferably a phenylene group, a naphthylene group or a carbonyl group.

As a commercial item of the compound which can form the repeating unit represented by the said General formula (1), SEIMI CHEMICAL Co., Ltd. Product: CMS-P series (brand name) is mentioned.

Although repeating units (h-1)-(h-37) are shown as a specific example of the repeating unit represented by General formula (1) below, this invention is not limited to these.

In addition, in the following specific example, R represents a hydrogen atom or a C1-C5 alkyl group.

As a repeating unit represented by the said General formula (1) in this invention, R <^1> is a hydrogen atom or a methyl group, R <^2> is a hydrogen atom, a methyl group, or a phenyl group, X is a chlorine atom or a bromine atom, and Y is C6 It is preferable that they are -10 arylene group or carbonyl group, L <^1> is a bivalent organic coupling group containing a single bond, an arylene group, a bivalent heterocyclic residue or ester bond, and / or an amide bond, R <^1> is a hydrogen atom, It is more preferable that R ² is a hydrogen atom, X is a chlorine atom, Y is a carbonyl group, and L ¹ is an ester bond.

Especially, the fluorine-containing compound containing the repeating unit which has a fluorine atom in a side chain, and the repeating unit represented by following General formula (2) is more preferable. In addition, the repeating unit which has a fluorine atom in a side chain is as above-mentioned, and its preferable form is also the same.

In the general formula (2), R ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or 2 to 5 carbon atoms An alkanoyl group is represented, X represents a chlorine atom, a bromine atom or an iodine atom, and Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group. R ^1, R ^2, X and Y are as defined R ^1, R ^2, X and Y in the general formula (1), as a preferred form.

In General Formula (2), Z ¹ represents an ester group or an amide group. As an ester group, a carboxylic acid ester group, a sulfonic acid ester group, a phosphate ester group, etc. are preferable, and a carboxylic acid ester group is more preferable. As an amide group, a carboxylic acid amide group, a sulfonic acid amide group, a phosphoric acid amide group, etc. are preferable, and a carboxylic acid amide group is more preferable.

As Z <^1> , a carboxylic ester group and a carboxylic acid amide group are the most preferable.

In addition, L ² represents a single bond or a divalent organic linking chain. The divalent organic linking chain represented by L ² is preferably an organic linking group consisting of a single organic linking group selected from the group consisting of an alkylene group, an arylene group and a divalent heterocyclic residue or a combination thereof. The alkylene group, arylene group, and bivalent heterocyclic residue here are synonymous with the alkylene group, arylene group, and bivalent heterocyclic residue in L <^1> of the said General formula (1), and its preferable form is also the same.

As L ² , a methylene group and an ethylene group are most preferable.

Furthermore, the fluorine-containing compound containing the repeating unit which has a fluorine atom in a side chain, and the repeating unit represented by following General formula (3) is more preferable. In addition, the repeating unit which has a fluorine atom in a side chain is as above-mentioned, and its preferable form is also the same.

In the general formula (3), R ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or 2 to 5 carbon atoms An alkanoyl group is represented, X represents a chlorine atom, a bromine atom or an iodine atom, and Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group. R ^1, R ^2, X and Y are as defined R ^1, R ^2, X and Y in the general formula (1), as a preferred form.

In General Formula (3), Z ² represents a single bond, an arylene group, or a heterocyclic moiety.

The arylene group represented by Z ² is preferably an arylene group having 6 to 15 carbon atoms in total, and more preferably an arylene group having 6 to 10 carbon atoms in total. Specifically, a phenylene group, a naphthylene group, anthracenylene group, a biphenylene group, a dialkylphenylene group, etc. are mentioned, These may be o-substituent, p-substituent, and / or m-substituent.

As the heterocyclic moiety represented by Z ² , for example, a divalent heterocyclic moiety derived from a 5-membered or 6-membered ring containing a nitrogen atom or an oxygen atom as a member of the ring is preferable, and a pyridine ring, a pyrimidine ring and a pyrazine ring And divalent heterocyclic moieties derived from 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, and a pyridine ring and a thia More preferred are divalent heterocyclic moieties derived from the diazole ring.

As Z <^{2>, a} single bond, a phenylene group, and a pyridine ring residue are the most preferable.

Among the above, the fluorine-containing compound in the present invention is a fluorine-containing compound comprising a repeating unit having a fluorine atom in the side chain and a repeating unit represented by the general formula (3) from the viewpoint of water repellency and oil repellency. In (3), it is particularly preferable when R ¹ is a hydrogen atom, R ² is a hydrogen atom, X is a chlorine atom, Y is a single bond, and Z ² is an oxycarbonyl group.

In addition, the fluorine-containing compound in this invention may also contain the repeating unit of a structure other than what is listed here in the range which does not impair heat resistance as needed. In general, fluorine-containing compounds having a repeating unit having a small molecular weight tend to be in a direction of decreasing heat resistance, and most of them are undesirable, and fluorine-containing compounds having a repeating unit having a high molecular weight are useful because they do not impair heat resistance. As a repeating unit with a large molecular weight, the repeating unit etc. which have a polyether structure in a side chain are mentioned, for example. As a repeating unit which has a polyether structure in a side chain, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, etc. are mentioned, These may be combined in multiple numbers.

More preferably, the following structural formula (B) is enumerated.

In said structural formula (B), R <_2> represents a hydrogen atom and a C1-C5 alkyl group. Preferably, a hydrogen atom, a methyl group, or a hydroxymethyl group is represented.

In said structural formula (B), 6-40 are preferable and, as for n, 9-30 are more preferable. 12-24 are especially preferable.

In the structural formula (B), L ₂ is preferably a single bond or a divalent linking group. As the divalent linking group, the following structural formulas are more preferable.

As L _{2, a} single bond is preferable.

In the structural formula (B), M represents a repeating unit of polyethylene oxide, a repeating unit of polypropylene oxide, and a repeating unit of polytetrahydrofuran. Moreover, as M, group which has the following structures is more preferable.

R <_5> represents a hydrogen atom and a C1-C5 alkyl group. l represents the integer of 2-20, More preferably, the integer of 4-12 is represented.

M is preferably an ethylene oxide chain, and R ₅ is preferably a hydrogen atom.

In said structural formula (B), R <_4> represents a hydrogen atom, a C1-C20 alkyl group, and 6-15 aryl group.

R <_4> represents a hydrogen atom, a C1-C20 alkyl group, 6-15 aryl group, and an alkyl group and an aryl group may have a substituent.

As an alkyl group of R <_4> , a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, and an octadecyl group are mentioned, A methyl group and an octyl group are more preferable.

As an aryl group of R <_4> , a phenyl group, a methylphenyl group, a nonylphenyl group, a methoxyphenyl group, etc. are mentioned, A phenyl group and a nonylphenyl group are more preferable.

R ₄ is preferably an alkyl group or an aryl group. These are called terminally sealed polyether structures, and this structure is most preferred. As R _{4, a} methyl group and a phenyl group are most preferred.

Commercially available vinyl compounds having the polyether structure include NOF CORPORATION products: Blemmer-PME200, PME550, PME1000, 50POEP-800P, ALE800, PE1300, ANE1300, PSE-1300, PMEP-1200B041MA, PE350, PP800, SHIN-NAKAMURA CHEMICAL Co ., Ltd. Products: NK ESTER AM130G, M230G, OC-18E, A-SAL-9E, A-CMP-5E, KYOEISHA CHEMICAL Co., Ltd. Product: LIGHT ESTER 041MA etc. (all are brand names) are listed.

Repeating Units Having Acidic Groups

As a fluorine-containing compound in this invention, it is preferable to further have a repeating unit which has an acidic group other than the repeating unit which has the said fluorine atom in a side chain, and the repeating unit represented by the said General formula (1).

It is preferable that the repeating unit which has the said acidic group has an acidic group in a side chain. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, a phosphinic acid group and a phosphoric acid group. It is preferable that the acidic group in this invention is a carboxyl group.

There is no restriction | limiting in particular as a monomer which can form the repeating unit which has a carboxyl group in a side chain, It can select from a well-known monomer suitably. As a known monomer, for example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, hydroxyl group And the addition reactants of monomers and cyclic acid anhydrides,? -Carboxy-polyhexanolactone mono (meth) acrylates, and the like. These may use suitably manufactured things and may use a commercial item.

As a monomer which has a hydroxyl group used for the monomer which has the said hydroxyl group, and the addition reaction product of cyclic acid anhydride, 2-hydroxyethyl (meth) acrylate etc. are mentioned, for example. As said cyclic acid anhydride, maleic anhydride, a phthalic anhydride, cyclohexane dicarboxylic anhydride, etc. are mentioned, for example.

As said commercial item, Toagosei Co., Ltd. Products: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, SHIN-NAKAMURA CHEMICAL Co., Ltd. Products: NK ESTER CB-1, NK ESTER CBX-1, KYOEISHA CHEMICAL Co., Ltd. Products: HOA-MP, HOA-MS, Osaka Organic Chemical Industry Ltd. Product: The BISCOAT # 2100 etc. (all are brand names) are mentioned. Among these, (meth) acrylic acid etc. are preferable at the point which is excellent in developability and low cost.

In addition to the repeating unit which has the said fluorine atom, and the repeating unit represented by the said General formula (1), the fluorine-containing compound in this invention may further have other repeating units other than the repeating unit which has the said acidic group. As a monomer which can form another repeating unit, what is necessary is just to be able to form a copolymer with the repeating unit which has the said fluorine atom, and the repeating unit represented by the said General formula (1), For example, (meth) acrylates and styrenes And vinyl alkanoates.

As said copolymerizable (meth) acrylates, C1-C50 alkyl methacrylate which may have a substituent, C6-C30 aryl (meth) acrylate which may have a substituent, Polyoxyalkyl of C2-C50 Phenylene (meth) acrylate is preferred. Moreover, C1-C40 alkyl (meth) acrylate and C10-C50 polyalkylene are more preferable, For example, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate , Butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, caprolactone modified (meth) acrylate, polyethylene oxide (meth) acrylate, polypropylene Oxide (meth) acrylates are preferable.

The copolymerizable styrenes are preferably those in which a vinyl group is substituted with a C6-C20 phenyl group, a vinyl group is substituted with a C10-C20 naphthyl group, and a vinyl group is substituted with a C14-C20 anthranyl group, and vinyl You may have substituents other than group. Furthermore, those in which a vinyl group is substituted with a C6-C10 phenyl group, a vinyl group is substituted with a C10-C15 naphthyl group, and a vinyl group is substituted with a C14-C18 anthranyl group are more preferable, for example, styrene , Butyl styrene, methoxy styrene, α-methyl styrene, vinyl naphthalene and vinyl anthracene are preferable.

As said vinyl alkanoate which can be copolymerized, a C4-C20 alkyl vinyl ester and a C1-C20 aryl vinyl ester are preferable. Moreover, a C4-C10 alkyl vinyl ester and a C1-C15 aryl vinyl ester are more preferable, For example, vinyl acetate, a vinyl butyrate, a vinyl dodecanoate, a vinyl benzoate, etc. are preferable.

As for content in the photosensitive resin composition of a fluorine-containing compound, 0.01-30 mass% is preferable with respect to the total solid of a resin composition, More preferably, it is 0.05 mass%-20 mass%, Most preferably, 0.1 mass% It is-10 mass%. When the content of the fluorine-containing compound is within the above range, better water repellency and ink repellency can be obtained, and adhesion to the region where the composition does not exist can be suppressed, and the substrate adhesion at the time of forming a film on the substrate can also be improved. For example, in the case of forming a pixel separation wall such as a black matrix by including a colorant such as a black pigment, it is possible to suppress the spreading of ink on the pixel separation wall when forming a colored region by applying droplets by the inkjet method. In addition, it is possible to prevent color mixing and to fabricate a pixel separation wall having high substrate adhesiveness and color density.

In the fluorine-containing compound of the present invention, the repeating units having fluorine atoms in the side chain are the repeating units (a-1), (a-2), (a-6), (a-9), and (a-10). Or (a-15), and the repeating unit represented by the general formula (1) includes the repeating units (h-1), (h-5), (h-10), (h-11), and (h-). 15) or (h-21), and the repeating unit having an acid group is preferably acrylic acid.

In the fluorine-containing compound of the present invention, the content of the repeating unit having a fluorine atom in the side chain is 30 to 70% by mass relative to the total weight of the fluorine-containing compound, and is represented by the general formula (1). It is preferable that content is 1-30 mass% with respect to the total weight of the said fluorine-containing compound, and content of the repeating unit which has an acidic group is 0-30 mass% with respect to the total weight of the said fluorine-containing compound.

Hereinafter, the specific example of the fluorine-containing compound which concerns on this invention is shown. However, the present invention is not limited to these. In addition, the composition ratio of each component can be selected from the range of the said preferable composition ratio.

4) Binder

The photosensitive resin composition of this invention can be suitably comprised using at least 1 sort (s) of binder other than the said component.

As a binder, the polymer which has polar groups, such as a carboxylic acid group and a carboxylic acid base, in a side chain is preferable. Examples include Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like described in Japanese Patent Application Laid-Open No. 59-71048; have. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be enumerated. Moreover, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.

Furthermore, as a particularly preferable example, the copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in the specification of US Pat. No. 4139391, or the multicomponent copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers is listed. can do. These binder polymers having polar groups may be used alone, or may be used in a state of a composition used in combination with an ordinary film-forming polymer.

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

5) color material

The photosensitive resin composition of this invention can be comprised using at least 1 sort (s) of a coloring material.

As a coloring material, well-known coloring agents (dye, pigment, etc.) can be used, Specifically, The pigment and dye of Unexamined-Japanese-Patent No. 2005-17716-[0054], and Unexamined-Japanese-Patent No. 2004-361447 [ The pigments described in 0068] to [0072], the colorants described in JP 2005-17521 A and [0080] to [0088] can be suitably used.

Organic pigments, inorganic pigments, dyes and the like can be suitably used for the photosensitive resin composition of the present invention. In particular, when the photosensitive resin composition of the present invention is formed for forming a light blocking pixel partition wall, a light blocking material such as a carbon material (carbon black or the like), metal oxide powder such as titanium oxide or iron tetraoxide, metal sulfide powder or metal powder, and Mixtures of pigments such as red, blue and green may be used. Especially, carbon black is preferable.

When using a pigment, it is preferable to disperse | distribute uniformly in the photosensitive resin composition.

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

It is preferable that a pigment is used as a dispersion liquid. This dispersion can be prepared by adding and dispersing the composition obtained by mixing a pigment and a pigment dispersant beforehand to an organic solvent (or vehicle). The vehicle refers to a part of a medium for dispersing a pigment when the paint is in a liquid state, and includes a part (binder) that is liquid and binds to the film to solidify the coating film, and a component (organic solvent) to dissolve and dilute it. There is no restriction | limiting in particular as a dispersing machine used when disperse | distributing a pigment, For example, the kneader, roll mill, art rider, super which are described in "the dictionary of pigments" (Asakura Kunizo, 1st edition, Asakura Shuppan, 2000, p. 438). Known dispersers such as mills, resolvers, homomixers, sand mills and the like are listed. Moreover, you may finely grind using frictional force by the mechanical grinding described on page 310 of the document.

The particle size of the color material (pigment) is preferably 0.001 to 0.1 µm, more preferably 0.01 to 0.08 µm in terms of number average particle diameter from the viewpoint of dispersion stability. In addition, "particle diameter" means the diameter when the particle area calculated | required from the electron microscope photograph image of particle is represented by this and the circle of the same area, and "number average particle diameter" means the particle diameter of 100 particle | grains, and calculated | required and averaged it. Say the mean.

6) Other

In the photosensitive resin composition, in addition to the components of the above 1) to 5), other solvents such as the following solvents, surfactants, thermal polymerization inhibitors, ultraviolet absorbers, and other additives such as the "adhesive aid" described in Japanese Patent Application Laid-open No. Hei 11-133600 You may add a component.

solvent

In the photosensitive resin composition in this invention, you may use a solvent further than the said component. Examples of the solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

Surfactants

In the photosensitive resin composition of this invention, it is preferable to contain a suitable surfactant in the said resin composition from a viewpoint which can be controlled by a uniform film thickness, and prevents coating unevenness effectively.

As surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a suitable thing.

Thermal polymerization inhibitor

It is preferable that the photosensitive resin composition in this invention 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 absorbers

The photosensitive resin composition in this invention can contain a ultraviolet absorber as needed. As a ultraviolet absorber, the compound of Unexamined-Japanese-Patent No. 5-72724, salicylate type, a benzophenone type, a benzotriazole type, a cyanoacrylate type, a nickel chelate type, a hindered amine type, etc. are mentioned.

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-diphenylacrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickeldibutyl dithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -sebacate , 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethyl piperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl- 4-piperidinyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- ( Diethylamino) -5-triazin-2-yl] amino} -3-phenylcoumarin It is listed.

Photosensitive transfer material

The photosensitive transfer material of this invention is formed by forming the photosensitive resin layer formed using the photosensitive resin composition of this invention mentioned above at least on a support body. By using the photosensitive transfer material, the pixel dividing wall can be formed easily and at low cost. In addition, other layers, such as a protective layer (henceforth an "oxygen barrier layer"), a thermoplastic resin layer, etc. which can block oxygen between a branch support and a photosensitive resin layer may be further formed as needed.

When an oxygen barrier layer is used, since the photosensitive resin layer is protected from the atmosphere by an oxygen barrier layer, the oxygen barrier layer is automatically placed in a poor oxygen atmosphere. Therefore, there is an advantage that high sensitivity and high hardness can be achieved by using the developing step as it is without having to perform exposure under inert gas or reduced pressure. As will be described later, the branch support may be used as a "protective layer capable of blocking oxygen", in which case it is not necessary to form an oxygen barrier layer, which contributes to the reduction in the number of steps. Details of the oxygen barrier layer will be described later.

In the photosensitive transfer material, a thermoplastic resin layer may be formed between the branch support and the photosensitive resin layer or between the branch support and the oxygen barrier layer in the case of having an oxygen barrier layer. The thermoplastic resin layer is a layer having alkali solubility, containing a resin component having at least a substantial softening point of 80 ° C. or less, and having cushioning properties. By forming such a thermoplastic resin layer, favorable adhesiveness with a permanent support body can be obtained.

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

At least one of the above-mentioned thermoplastic resins can be appropriately selected and used in the thermoplastic resin layer, and the "Plastic Performance Manual" is published in the Japan Plastics Industry Federation, the All-Japan Plastic Molding Industry Association, published by the Industrial Research Council, issued October 25, 1968. It is further possible to use a soluble in an aqueous alkali solution among organic polymers having a softening point of about 80 ° C. or less.

Moreover, also about the organic polymer material which has a softening point of 80 degreeC or more, by adding various plasticizers compatible with the said polymeric material in the organic polymer material, a substantial softening point can also be reduced to 80 degrees C or less, and can be used. In addition, various polymers, supercooled materials, adhesion improving agents or surfactants, and release agents may be added to these organic polymer materials in the range of substantially no softening point exceeding 80 ° C. for the purpose of adjusting the adhesion to the supporting member.

Specific examples of the preferred plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate and biphenyl diphenyl phosphate.

The branch members constituting the photosensitive transfer material are chemically and thermally stable and can be appropriately selected from those composed of flexible materials. 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 support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers. If this thickness is in the said range, it can peel easily without damaging a support, and exposure with a high resolution is performed also through a support.

Among the above specific examples, a biaxially stretched polyethylene terephthalate film is particularly preferable.

It is preferable to form a thin cover sheet on the photosensitive resin layer in order to protect it from contamination or damage during storage. The cover sheet may be made of the same or similar material as the supporting member, but must be easily separated from the photosensitive resin layer. As the cover sheet material, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable. Moreover, as for the thickness of a cover sheet, 4-40 micrometers is common, 5-30 micrometers is preferable, and 10-25 micrometers is especially preferable.

Board

In this invention, glass, a ceramic, a synthetic resin film, etc. can be used as a board | substrate (permanent support). Particularly preferred are glass or synthetic resin films which are transparent and have good dimensional stability.

Pixel divider and its formation method

The method of forming the pixel dividing wall of the present invention is a step of forming a photosensitive resin layer for forming the photosensitive resin layer by using the photosensitive resin composition of the present invention or the photosensitive transfer material of the present invention (at least on one side of the substrate), and formed. The process of exposing the photosensitive resin layer, the process of developing the exposed photosensitive resin layer, and the process of heat-processing which heat-processes the pattern image obtained by image development and which consist of the photosensitive resin layer are provided and comprised.

The pixel dividing wall in the present invention is to separate each pixel of two or more pixel groups (for example, pixel groups of different colors of color) formed by the method of forming the pixel dividing wall of the present invention. Although many are black (dark blue), it is not limited to black. As a coloring agent called deep color, organic substance (various pigment | dyes, carbon materials, such as a dye and a pigment) and an inorganic substance are preferable.

Further, the substrate having the pixel dividing wall of the present invention is formed by forming the pixel dividing wall on at least one surface of the substrate by the method of forming the pixel dividing wall of the present invention, and the pixel dividing wall of the present invention on the substrate and the substrate. And a pixel dividing wall formed by the method of forming a film.

Photosensitive resin layer forming process

The photosensitive resin layer forming step forms a photosensitive resin layer on at least one surface of the substrate, for example, by using the photosensitive resin composition having photosensitivity in the above-described resin composition of the present invention or by using the photosensitive transfer material of the present invention described above. do.

Although there is no limitation in particular as a method of forming the photosensitive resin layer using the photosensitive resin composition, For example, it can form by apply | coating the photosensitive resin composition on a board | substrate by well-known coating methods, such as slit coating. In addition, you may prebake after application as needed.

Although there is no limitation in particular as a method of forming the photosensitive resin layer using the photosensitive transfer material, For example, it can form as follows. In other words,

A photosensitive transfer material having a cover sheet for protecting an oxygen barrier layer, a photosensitive resin layer, and a photosensitive resin layer on the branch body is sequentially prepared from the side of the branch body. First, after peeling and removing a cover sheet, the surface of the exposed photosensitive resin layer is bonded on the board | substrate which is a permanent support body, and it laminates by heating, pressurizing through a laminator etc. (laminated body). As the laminator, any one suitably selected from conventionally known laminators, vacuum laminators, and the like can be used, and autocut laminators can also be used in order to increase productivity.

Next, the photosensitive resin layer can be transferred and formed on the substrate together with the oxygen blocking layer by peeling between the supporting member and the oxygen blocking layer to remove the supporting member from the laminate.

Exposure process and development process

In the exposure step, the removed surface (oxygen barrier layer surface) and the desired photomask (for example, a quartz exposure mask) are disposed to face each other, and the laminate and the photomask are placed vertically. The exposure is performed by appropriately setting the distance between the photomask surface and the photosensitive resin layer (for example, 200 µm).

Exposure is performed using the proxy meter type | mold exposure machine (for example, Hitachi High-Tech.Electronics Engineering Co., Ltd.) etc. which have an ultrahigh pressure mercury lamp, etc., and exposure amount is moderate (for example, 300mJ / cm <2>). ) It is good to choose.

As a light source used for exposure, medium pressure-ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. are mentioned.

In order to increase the photosensitivity, that is, the degree of curing, the pixel dividing wall is preferably formed by exposing the photosensitive resin layer under a poor oxygen atmosphere, and then developing it. Here, a poor oxygen atmosphere refers to what is under a protective layer (henceforth an "oxygen barrier layer") which can block oxygen under inert gas, under reduced pressure, and is as follows in detail.

Haran, the inert gas N _2, H _2, means that it is exposed to a gas atmosphere such as rare gas such as an inert gas and He, Ne, Ar, such as CO _2. Among them, the inert gas is preferably N _{2 because} of safety, availability and cost.

The said reduced pressure means the state of 500 hPa or less, Preferably it is 100 hPa or less.

The protective layer (oxygen barrier layer) capable of blocking oxygen is, for example, the polyvinyl ether / maleic anhydride polymer and carboxyalkyl cellulose described in Japanese Patent Application Laid-Open No. 46-2121 and Japanese Patent Publication No. 56-40824. Water-soluble salts, 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 , Water-soluble salts of the group consisting of various starches and the like, copolymers of styrene / maleic acid, maleate resins and combinations of two or more thereof. Among these, Especially preferably, it is a combination of polyvinyl alcohol and polyvinylpyrrolidone.

Moreover, it is preferable that polyvinyl alcohol has a saponification rate of 80% or more, and, as for content of polyvinylpyrrolidone, 1-75 mass% is preferable with respect to solid content of the alkali-soluble photosensitive resin layer, More preferably, 1-50 It is mass%, More preferably, it is 10-40 mass%.

In addition, various films can be used as the oxygen barrier layer. For example, polyesters including PET, polyamides including nylon, and ethylene-vinyl acetate copolymers (EVAs) can also be suitably used. These films may be stretched as needed, and thickness is 5-300 micrometers suitably, Preferably it is 20-150 micrometers.

In particular, when forming a pixel separation wall using a photosensitive transfer material, it is possible to suitably use a branch as a protective layer capable of blocking oxygen.

In the case of using the branch member as the oxygen barrier layer, the branch member is disposed so that the branch member and the desired photomask (for example, a quartz exposure mask) face each other without leaving the branch member. The exposure is performed by setting the distance between the exposure mask surface and the supporting member appropriately (for example, 200 µm) while the mask is upright.

The oxygen transmission coefficient of the protective layer (oxygen barrier layer) capable of blocking oxygen is preferably 2000 cm 3 / (m 2 · day · atm) or less, more preferably 100 cm 3 / (m 2 · day · atm) or less, most preferably Preferably it is 50 cm <3> / (m <2> * day * atm) or less.

When the oxygen transmittance is within the above range, photocuring proceeds satisfactorily by oxygen blocking, and it is also effective for forming the pixel separation wall into a desired shape.

Subsequently, a developing process is performed to develop the photosensitive resin layer after exposure using a predetermined developer. Subsequently, washing with water is performed as necessary to obtain a pattern image (pixel separation wall pattern). In addition, it is preferable that the surface of the photosensitive resin layer or the oxygen barrier layer can be uniformly wetted by spraying pure water with a shower nozzle or the like before development.

As a developing solution used for the developing treatment, a dilute aqueous solution of an alkaline substance is used, but a small amount of an organic solvent miscible with water may be added.

As said alkaline substance, alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (for example, sodium bicarbonate, hydrogen carbonate) Potassium), alkali metal silicates (e.g. sodium silicate, potassium silicate), alkali metal metasilicates (e.g. sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, mor Pauline, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, etc. are mentioned. As a density | concentration of alkaline substance, as for the lean aqueous solution of alkaline substance, 0.01-30 mass% is preferable, and pH is 8-14.

As said "an organic solvent miscible with water", for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monon-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 suitable. As for the density | concentration of the organic solvent miscible with water, 0.1-30 mass% is preferable.

Moreover, a well-known surfactant can also be added and 0.01-10 mass% is preferable for the density | concentration of the said surfactant.

The developing solution can also be used as a bath solution or a spray solution.

When the uncured portion of the photosensitive resin layer is removed, a method such as rubbing with a rotary brush or a wet sponge in the developer can be combined. As for the liquid temperature of a developing solution, normally the room temperature (20 degreeC) vicinity-40 degreeC is preferable. The developing time depends on the composition of the photosensitive resin layer, alkalinity and temperature of the developing solution, and the type and concentration of the organic solvent, but is usually about 10 seconds to 2 minutes. If the developing time is within the above range, the progress of development of the non-hardened portion (non-exposed portion in the case of negative type) is good, and the hardened portion (exposed portion in the case of negative type) is not etched. Valid.

It is also possible to add a washing step after the development treatment.

Heat treatment process

By heat-processing (also called baking process) of the pattern image (pixel partition wall pattern) which consists of the photosensitive resin layer obtained by the said image development process, the pixel partition wall excellent in water repellency and ink repellency can be obtained.

The heat treatment hardens by heating the pattern image (pixel partition wall pattern) formed by exposure and development, and further exhibits water repellency and ink repellency by the fluorine-containing compound because the fluorine functional groups are arranged on the surface by heat. .

As the 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 to be processed in a convection oven, a method to be processed one by one in a hot plate, a method to be processed by an infrared heater, and the like.

Moreover, baking temperature (heating temperature) is 150-280 degreeC normally, Preferably it is 180-250 degreeC. Although heating time can be suitably selected according to the said baking temperature, For example, when baking temperature is 240 degreeC, 10-120 minutes are preferable and 30-90 minutes are more preferable.

In addition, in the heat treatment step in the method of forming the pixel separation wall, uneven film reduction of the pixel separation wall pattern formed by the exposure and development steps is prevented, and precipitation of components such as UV absorbers included in the photosensitive resin layer is prevented. From the viewpoint of preventing the damage, post exposure may be performed before the heat treatment. If post-exposure is performed before the heat treatment, it is possible to effectively prevent swelling and defects of minute foreign matters mixed at the time of lamination.

Here, the post exposure will be briefly described.

As a light source used for post exposure, as long as it can irradiate light (for example, 365 nm and 405 nm) of the wavelength range which can harden | cure the photosensitive resin layer, it can select suitably and can use.

Specifically, ultra high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and the like are listed.

As an exposure amount, the exposure amount which supplements the said exposure may be sufficient, Usually, it is 50-5000mJ / cm <2>, Preferably it is 200-2000mJ / cm <2>, More preferably, it is 500-1000mJ / cm <2>.

It is preferable that the pixel separation wall which can be produced by the method for forming the pixel separation wall of the present invention has a high optical density at 555 nm. Particularly, when forming the black matrix constituting the color filter as the pixel separation wall, the optical density is preferably 2.5 or more, more preferably 2.5 to 10.0, from the viewpoint of providing a light-blocking property to display a clearer and clearer multicolor image. , 2.5 to 6.0 are more preferable, and 3.0 to 5.0 are particularly preferable.

In addition, since the photosensitive resin layer is preferably cured by a photo-opening clock, the optical concentration with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, as for the value, 2.0-10.0 are preferable, Furthermore, 2.5-6.0 are more preferable, 3.0-5.0 are especially preferable. If it is the said preferable range, the pixel division wall of a desired shape can be formed.

As for the width and height of the pixel dividing wall, the width (that is, the pixel and the pixel spacing when the color filter is formed) is preferably 15 to 100 µm, and the height (that is, the substrate surface in the substrate normal direction). To the apex of the pixel separation wall) is preferably 1.0 to 5.0 m.

As for the shape of the pixel separation wall, the shapes described in paragraphs [0054] to [0055] of JP-A-2006-154804 are also suitable in the present invention.

Further, the substrate having the pixel dividing wall of the present invention includes a substrate and an ink repellent agent, and when the water contact angle on the upper surface of the wall is measured based on the method described in the known wettability test method of the glass surface of the substrate, the separation of pixels of 60 ° or more. The droplet diameter immediately after dropping the propylene glycol monomethyl ether monoacetate of the part which has a wall and in which the pixel partition wall is not formed among the board | substrate surface on the side where the pixel partition wall of the said board | substrate was formed is comprised so that it may become 20 micrometers or more.

Conventionally, in the case of forming a pixel separation wall such as a black matrix having ink repellency by forming a film using an ink repellent agent-containing composition and adding heat treatment after exposure and development, the ink repellent component may be Although it is easy to reduce the liquid wettability by contaminating the exposed substrate surface out of the film system, in a substrate having the pixel dividing wall of the present invention, a pattern film including an ink repellent agent may be heat-treated for ink repelling and thermal curing. For example, the exposed substrate surface (non-film forming surface) is prevented from adhering to the fluorine-containing component even after the high temperature treatment of 150 ° C. or higher, and thus the wettability is maintained. Colored liquid composition in the pixel partition wall non-formation area | region (concave part on the board | substrate isolated by the pixel partition wall) of the board | substrate with which pixel partition walls, such as a matrix, were formed. It is possible to prevent the repelling of the liquid when applying (for example, dropping ink by an inkjet method) to form a colored region (colored pixel such as RGB), so that the occurrence of white spots in the colored region and image display By suppressing the generation of display stains, the color filter and the display device capable of high quality image display can be obtained.

Conventionally, since the ink repellent component deposited by heat treatment is not easy to be removed even after cleaning, it is easy to obtain a high quality color filter and display device easily by suppressing adhesion itself accompanying heat treatment as in the present invention.

The pixel separation wall in this invention is a resin hardened wall (for example, a black matrix) whose water contact angle of the upper surface of a wall after heat processing is 60 degrees or more, when measured based on the method as described in the well-known wettability test method of the substrate glass surface. And the like, and are formed by adding a heat treatment (for example, 150 ° C or higher) after film formation and patterning using a (photosensitive) resin composition containing an ink repellent agent in advance. The heat treatment is preferably performed mainly for the provision of thermosetting and ink repellency, and the range of 150 ° C to 250 ° C is suitably selected.

As mentioned above, the property which repels water and other solvents may be called ink repellency.

If the ink repellency is less than 60 °, the ink repellency on the surface of the pixel dividing wall becomes insufficient and liquid is applied to the substrate exposed portion (concave portion on the substrate surrounded by the black matrix) where the pixel dividing wall is not formed (for example, The mixed color at the time of applying droplets by the inkjet method to a colored liquid composition (for example, ink such as RGB) for forming the colored pixels constituting the color filter cannot be prevented.

The ink repellency is more preferably 70 ° or more from the viewpoint of preventing the spreading of the liquid onto the pixel dividing wall and preventing the mixing of the color.

The exposed surface of the substrate having the pixel dividing wall, on which the pixel dividing wall is not formed, is preferably high in wettability to liquid, in that the effect of the present invention is obtained. It has wettability such that the droplet diameter is 20 µm or more immediately after dropping one drop of propylene glycol monomethyl ether monoacetate onto the exposed surface.

When the droplet diameter is less than 20 µm, the degree of repelling of the dropped liquid is large, for example, by providing a colored liquid composition (for example, by applying ink droplets by an inkjet method) to color regions (color pixels such as RGB). When the substrate is to be formed, the substrate repels the ink to prevent the occurrence of white spots in the colored region and the generation of display stains when the image is displayed.

In the present invention, wettability refers to the degree of wetness when a liquid flows on a plane, and is, for example, a concave portion surrounded by a pixel separation wall of a substrate on which a pixel separation wall such as a black matrix is formed (that is, colored pixels). Refers to the degree of wetness of ink droplets when inkjet is applied to droplets of an ink composition that is a colored liquid composition. More specifically, a solvent and an ink composition are used as an index of the degree to which one drop is achieved between the pixel separation walls and the diameter of the circle formed by the droplets is wetted.

A droplet diameter is a value calculated | required by taking an optical photograph at arbitrary magnifications, and measuring the diameter and calculating an actual dimension from a magnification. When the solvent is applied, the fine droplets evaporate rapidly, so it is necessary to take a picture immediately after the shooting.

Measurement of contact angle of pixel dividing wall

It is important to change the ink contact angle and the water contact angle of the pixel separation wall (for example, the black matrix) before and after the heat treatment (baking treatment). The measuring method of the contact angle here is a method based on JIS standards by the Japan Standards Association, and specifically, "6. Test method for wettability of substrate glass surface" in JIS R3257. Static method "is applied.

More specifically, using a contact angle meter (contact angle meter CA-A (trade name) manufactured by Kyowa Interface Science Co., Ltd.), ink droplets and droplets of 20 memory sizes are made, and ink droplets and droplets are discharged from the needle tip. Ink droplets and water droplets are formed by contacting the surface of the pixel partition wall formed in a pattern shape. After 10 seconds of standing, the shapes of the ink droplets and water droplets are observed from the observation holes of the contact angle system, and the contact angle θ at 25 ° C. is obtained. . In addition, after the "heating process" here, after heating for 50 minutes at 240 degreeC, it means the thing after leaving to cool at room temperature for 1 hour and cooling.

Here, the upper surface of the pixel dividing wall will be described with reference to FIG. 1.

The upper surface of the pixel dividing wall means an exposed surface on the opposite side to the surface of the pixel dividing wall 1 that is in contact with the substrate 6 (upper surface 4 shown in FIG. 1).

In addition, the side surface of a pixel partition wall means the surface other than the said pixel partition wall upper surface among the surface of a pixel partition wall (side surface 5 shown in FIG. 1). In addition, the recessed part on a board | substrate means the recessed part which is enclosed by the pixel partition wall and consists of the board surface in which the pixel partition wall side surface and the pixel partition wall are not formed (recess part 3 shown in FIG. 1).

Contact angle

The photosensitive resin composition of this invention is a pattern image before performing heat processing, when the water contact angle of the upper surface of the pattern image (for example, pixel separation wall) formed using the said photosensitive resin composition was measured by the said method ( For example, the water contact angle of the upper surface of the pixel partition wall pattern before the heat treatment) is heated at A ° and 240 ° C. for 50 minutes, and left to cool for 1 hour to cool. When B is referred to as 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, most preferably 40 ° or more.

Moreover, 0-60 degrees are preferable from A viewpoint of improving the adhesiveness of a pixel partition wall and a board | substrate further, 0-55 degrees are more preferable, 0-50 degrees are especially preferable.

The 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 the color filter is produced.

Color filter and manufacturing method

The manufacturing method of the color filter of the present invention comprises the steps of preparing a substrate having a pixel dividing wall or a substrate having a pixel dividing wall manufactured by the method of manufacturing a substrate having a pixel dividing wall of the present invention. A colored liquid composition (preferably two or more colors) is given to the recesses (regions for forming colored areas) partitioned by the pixel separation wall of the substrate having a plurality of colored regions (preferably two or more colors) (for example, And colored pixels such as red, green, blue, white, purple, and the like).

In the manufacturing method of the color filter of this invention, since a coloring liquid composition is provided on the board | substrate which has the pixel partition wall (for example, black matrix) using the fluorine-containing compound of this invention mentioned above, a colored area | region is formed, Mixed color accompanying bleeding onto the pixel dividing wall and the like can be avoided, and repelling of the colored liquid composition in the recessed portion (region for forming colored regions) on the substrate partitioned by the pixel dividing wall can be prevented, and the pixel Since peeling of a separation wall, generation | occurrence | production of a crack defect, etc. are also suppressed, the high quality color filter by which the image defect by mixed color, a color stain, a white spot, etc. was suppressed can be manufactured.

Since the color filter of the present invention also has the pixel separation wall using the fluorine-containing compound of the present invention described above, image defects such as white spots are suppressed and have clear and distinct display characteristics.

It does not specifically limit as a method of providing a coloring liquid composition, Well-known methods, such as the coating method, such as an inkjet method, a slit coating method, and a stripe writing method, can be used suitably. The stripe substrate coating method is a method of forming stripe-shaped pixels by applying a droplet onto a substrate using a substrate having a thin droplet discharge hole.

Especially in this invention, the inkjet method can be used suitably.

Inkjet method

As the inkjet method, various methods such as a method of continuously spraying charged ink to control the electric field, a method of intermittently spraying ink using a piezoelectric element, a method of heating ink and intermittently spraying using the foaming thereof, and the like Can be adopted.

Ink can be used both oily and aqueous. Moreover, the coloring agent contained in the ink can be used together with a dye and a pigment, The use of a pigment is more preferable from a durable viewpoint. Moreover, the coloring ink (for example, the colored resin composition of Paragraph No. [0034]-[0063] of Unexamined-Japanese-Patent No. 2005-3861), and Unexamined Japan patent are used for the application | coating at the time of manufacture of a well-known color filter. Well-known inks, such as the coloring ink of 2004-325736, the ink of Unexamined-Japanese-Patent No. 2002-372613, can also be used.

To the ink used for the inkjet method, a component which is cured by heating or cured by energy rays such as ultraviolet rays can be added in consideration of the step after application. As the component cured by heating, various thermosetting resins are widely used, and examples of the component cured by energy radiation include those in which a photoreaction initiator is added to an acrylate derivative or a methacrylate derivative. In particular, in consideration of heat resistance, it is more preferable to have a plurality of acryloyl groups and methacryloyl groups in the molecule. These acrylate derivatives and methacrylate derivatives can be suitably used as water-soluble ones, and can be used by being emulsified even in poorly soluble in water.

In this case, the photosensitive resin composition which contained coloring agents, such as the pigment enumerated by the said photosensitive resin composition, can be used as a suitable thing.

It is preferable that the color filter of this invention is a color filter in which the droplet of a coloring liquid composition was discharged on the board | substrate by the inkjet method, and the colored area | region (for example, a pixel) was formed, and at least RGB tricolor ink was used for the inkjet method. The color filter which discharges by and has a coloring pixel of at least 3 colors is preferable.

The pattern shape of a color filter is not specifically limited, A stripe shape which is a general black matrix shape may be sufficient, and a grid shape and a delta arrangement shape may be sufficient as it.

In the produced color filter, an overcoat layer may be formed in the whole surface in order to improve tolerance. The overcoat layer can protect the colored region (for example, an RGB pixel) and can make the surface flat. However, it is preferable not to form an overcoat layer from a viewpoint that process number increases.

As resin (OC agent) which forms an overcoat layer, an acrylic resin composition, an epoxy resin composition, a polyimide resin composition, etc. are mentioned. Especially, since the resin component of the curable composition which comprises a color filter is excellent in transparency in a visible light region generally contains acrylic resin as a main component, and is excellent in adhesiveness, an acrylic resin composition is preferable. As an example of an overcoat layer, Paragraph No. 0018 of Unexamined-Japanese-Patent No. 2003-287618, "OPTOMER SS6699G" (brand name) of JSR product is mentioned as a commercial item made from an overcoat.

Moreover, you may form a transparent electrode, an orientation film, etc. on a coloring area | region (for example, RGB pixel) as needed. As an example of a transparent electrode, an ITO film is mentioned. Moreover, polyimide is mentioned as a specific example of an oriented film.

Display

The display device of the present invention is formed by forming the color filter of the present invention described above.

The color filter obtained by the manufacturing method of the color filter of this invention can be used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT (lead lanthanum zitconium titanate). It can also be used to use color cameras or other color filters.

As the display device, display devices such as a liquid crystal display device, a plasma display display device, an electroluminescence (EL) display device, a CRT (Cathode Ray Tube) display device, and the like are listed. For the definition of the display device and the explanation of each display device, for example, "Electronic display device (Akio Sasaki by Kogyo Chosakai Publishing, Inc. 1990)", "Display device (by Ibuki Sumiaki, Sangyo-tosho Publishing) Co., 1989).

As the display device formed by forming the color filter of the present invention, a liquid crystal display device is preferable. The liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo Chosakai Publishing, Inc., 1994)".

There is no restriction | limiting in particular in the liquid crystal display apparatus which can apply this invention, For example, it can apply to the liquid crystal display apparatus of various systems described in said "next-generation liquid crystal monitor technique." Especially, it is effective with respect to the liquid crystal display device of a color TFT system especially. A liquid crystal display device of a color TFT (Thin Film Transistor) system is described in, for example, a color TFT liquid crystal monitor (KYORITSU SHUPPAN Co., Ltd., issued in 1996). The present invention can also be applied to a liquid crystal display device having an enlarged viewing angle, such as a lateral electric field driving method such as IPS (In Plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment). These methods are described, for example, on page 43 of "EL, PDP, LCD display technology and the latest trends in the market" (TORAY RESEARCH CENTER, Inc., Research and Research Division, 2001).

In addition to the color filter, the liquid crystal display device is composed of 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 these members, for example, the '94 market for liquid crystal display peripheral materials and chemicals (Token Taro, CMC Publishing Co., Ltd., 1994), the present status and future prospects of the 2003 liquid crystal market (Submission) (Omote Ryokuki, Fuji Chimera Research Institute, 2003, etc.).

As a use, it can apply without a restriction | limiting in particular to the use of mobile telephone terminals, digital cameras, car navigation, etc., such as a television, a PC, a liquid crystal projector, a game machine, and a mobile telephone.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, molecular weight shows the polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC), and "part" and "%" are mass references | standards unless there is particular notice.

Synthesis Example

Below, the synthesis method of the compound (Hereinafter, it may be called a halide monomer) which can form the repeating unit represented by General formula (1) is shown.

Synthesis of Fluorine-Containing Compounds

Synthesis of Halide Monomer (1)

Into a 300 ml three-necked flask equipped with a dropping funnel, ethyl methyl ketone [MEK, Wako Pure Chemical Industries Ltd. Product] 50 g and hydroxyethyl acrylate [HEMA, TOKYO CHEMICAL INDUSTRY Co., Ltd.] Product] 26.1 g were added and cooled to an internal temperature of 5 ° C. in a water bath containing ice. Pyridine [Py, TOKYO CHEMICAL INDUSTRY Co., Ltd. Product] 16.2 g was added and stirred. Chloroacetyl chloride from the dropping funnel [CAC, Wako Pure Chemical Industries Ltd. Product] 22.6 g was added dropwise so that the flask internal temperature did not exceed 10 占 폚. The reaction was traced by NMR to confirm the disappearance of HEMA, and then stirred at room temperature for 2 hours. The reaction was added to 2 L of distilled water under stirring, followed by extraction with diethyl ether. The extracted organic layer was washed with sodium bicarbonate water and saturated brine, the organic layer was dried over magnesium sulfate, and insoluble matters were removed by filtration. The filtrate was concentrated and distilled under reduced pressure to obtain 35.4 g (yield: 86%) of a halide monomer (1).

Synthesis method of halide monomer (2)

In the synthesis method of the halide monomer (1), HEMA is hydroxyethyl acrylate [HEA, TOKYO CHEMICAL INDUSTRY Co., Ltd. Product], and the halide monomer (2) was synthesized according to the method for synthesizing the halide monomer (1). Yield 88%.

Synthesis method of halide monomer (3)

In the method for synthesizing the halide monomer (1), CAC is bromoacetyl bromide [BAB, TOKYO CHEMICAL INDUSTRY Co., Ltd. Halide monomer (3) was synthesized in accordance with the synthesis method of halide monomer (1), except that the product was changed to [product]. Yield 79%.

Synthesis method of halide monomer (4)

In the method for synthesizing halide monomer (1), HEMA is Aronix M152 [AX-M152, Toagosei Co., Ltd.]. Halide monomer (4) was synthesized according to the method for synthesizing halide monomer (1), except that the product was changed to [product]. Yield 88%.

Synthesis method of halide monomer (5)

In the method for synthesizing the halide monomer (1), HEMA is Aronix M154 [AX-M154, Toagosei Co., Ltd.]. Halide monomer (5) was synthesized in accordance with the synthesis method of halide monomer (1), except that the product was changed to [product]. Yield 87%.

Synthesis method of halide monomer (6)

In the method for synthesizing the halide monomer (1), the halide monomer (6) was synthesized according to the method for synthesizing the halide monomer (1) except that HEMA was changed to Blemmer PE200 [BL-PE200, manufactured by NOF CORPORATION]. Yield 90%.

Synthesis of Fluorine-Containing Compound (1)

Propylene glycol monomethyl ether acetate under nitrogen stream [MMPG-Ac, Daicel Chemical Industries, Ltd. Product] 25 g was placed in a 300 ml three-necked flask equipped with a cooling tube, and heated in a water bath containing paraffin until the internal temperature was 70 ° C. MMPG-Ac 40 g to acrylic acid [AA, TOKYO CHEMICAL INDUSTRY Co., Ltd. Product] 2.5 g and 2- (perfluorohexyl) -ethyl acrylate [FAAC6, product of NOK Corporation] 25 g and polyethylene glycol monomer [AM230G, SHIN-NAKAMURA CHEMICAL Co., Ltd.] Product] 17.5 g of the halide monomer (1) and 2-ethylhexyl mercaptopropionic acid [EHMP, TOKYO CHEMICAL INDUSTRY Co., Ltd.] Product] 2,2'-azobis (isovaleronitrile) in a solution of 0.88 g dissolved in 10 g MFGAc [trade name: V65, Wako Pure Chemical Industries Ltd. Product] A solution in which 0.334 g was dissolved was added dropwise over 2 hours with a plunger pump. After completion of the dropwise addition, the mixture was stirred for 5 hours, and disappearance of the remaining monomer was confirmed by ¹ H-NMR.

As described above, 2- (perfluorohexyl) -ethyl acrylate [FAAC6], acrylic acid [AA], polyethylene glycol monomer [AM230G], and halide monomer (1) are copolymerized to form a FAAC6 / AA / AM230G / halide monomer ( 1) = 50/5/35/10 (mass ratio) The fluorine-containing compound (1) was synthesize | combined. The weight average molecular weight was 1.6 million.

The synthesis | combination of the fluorine-containing resin which has a side chain which has six ester chains from the monomer which disappeared and has produced the high molecular weight component was confirmed.

Synthesis of Fluorine-Containing Compound (2)

According to the synthesis | combination of the said fluorine-containing compound (1), the fluorine-containing compound (2) was synthesize | combined. Each copolymerization component and composition ratio are as follows.

Fluorine-containing compound (2): FAAC6 / AA / AM230G = 50/5/45 (mass ratio)

Synthesis of Fluorine-Containing Compound (3)

According to the synthesis | combination of the said fluorine-containing compound (1), the fluorine-containing compound (3) was synthesize | combined. Each copolymerization component and composition ratio are as follows.

Fluorine-containing compound (3): FAMAC6 / MAA / M230G = 50/5/45 (mass ratio)

Synthesis of Fluorine-Containing Compounds (4) to (5)

According to the synthesis | combination of the said fluorine-containing compound (1), the synthesis | combination of fluorine-containing compounds (4)-(5) was performed. Each copolymerization component and composition ratio are as follows.

Fluorine-containing compound (4): R1420 / MAA / M230G = 50/5/45 (mass ratio)

Fluorine-containing compound (5): FAMAC6 / MAA / M90G = 50/5/45 (mass ratio)

Rating 1

(1) heat reduction rate

The thermal reduction rate was measured using fluorine-containing compounds (1)-(5) so that a composition might not be influenced by other components.

1g of the obtained fluorine-containing compound dried overnight in a vacuum oven was weighed, and the weight reduction rate after holding at 150 ° C. for 30 minutes using a thermogravimetric analyzer (trade name; DTG-60, manufactured by Shimadzu Corporation) was measured. Measurement results are shown in Table 3 below.

Synthesis method of fluorine-containing compound (6) to (18)

According to the synthesis example of the said fluorine-containing compound (1), the other fluorine-containing compounds (6)-(18) were synthesize | combined. Each copolymerization component and composition ratio are as follows.

Fluorine-containing compound (6) FAAC6 / AA / AM230G / halide monomer (2) = 50/5/43/2 (mass ratio)

Fluorine-containing compound (7) FAAC6 / AA / AM230G / halide monomer (2) = 50/5/40/5 (mass ratio)

Fluorine-containing compound (8) FAAC6 / AA / AM230G / halide monomer (2) = 40/5/35/20 (mass ratio)

Fluorine-containing compound (9) FAAC6 / AA / AM230G / halide monomer (2) = 30/5/55/10 (mass ratio)

Fluorine-containing compound (10) FAAC6 / AA / AM230G / halide monomer (2) = 50/5/35/10 (mass ratio)

Fluorine-containing compound (11) FAAC6 / AA / FA5 / halide monomer (2) = 40/5/45/10 (mass ratio)

Fluorine-containing compound (12) FAAC6 / AA / FA5 / CMS-P = 40/5/45/10 (mass ratio)

Fluorine-containing compound (13) FAAC6 / AA / AM230G / CMS-P = 40/5/45/10 (mass ratio)

Fluorine-containing compound (14) FAAC6 / AA / AM230G / halide monomer (3) = 50/5/35/10 (mass ratio)

Fluorine-containing compound (15) FAAC6 / AA / AM230G / halide monomer (4) = 50/5/35/10 (mass ratio)

Fluorine-containing compound (16) FAAC6 / AA / AM230G / halide monomer (5) = 50/5/35/10 (mass ratio)

Fluorine-containing compound (17) FAMAC6 / MAA / M230G / halide monomer (6) = 50/5/35/10 (mass ratio)

Fluorine-containing compound (18) FAAC6 / AM230G / halide monomer (2) = 50/40/10 (mass ratio)

Synthesis method of fluorine-containing compounds (19) to (20)

According to the synthesis example of the said fluorine-containing compound (1), the fluorine-containing compound (19)-(20) was synthesize | combined. Each copolymerization component and composition ratio are as follows.

Fluorine-containing compound (19) TFA / AA / AM130G / halide monomer (2) = 50/5/35/10 (mass ratio)

Fluorine-containing compound (20) FAAC6 / AA / V # 160 = 50/5/45 (mass ratio)

Propylene glycol monomethyl ether acetate was added and adjusted so that solid content concentration of each fluorine-containing compound synthesize | combined above might be 25%.

In addition, the symbol of each copolymerization component (monomer) which comprises the said fluorine-containing compound is as follows.

Fluorine-containing monomer

FAAC6; 2- (perfluorohexyl) -ethylacrylate [manufactured by NOK Corporation]

FAMAC6; 2- (perfluorohexyl) -ethyl methacrylate [manufactured by NOK Corporation]]

R1420; 2- (perfluorobutyl) -ethylacrylate [Daikin Industries, Ltd. product]

Other monomers

AA; Acrylic acid [TOKYO CHEMICAL INDUSTRY Co., Ltd. product]

MAA; Methacrylic acid [TOKYO CHEMICAL INDUSTRY Co., Ltd. product]

AM230G; Monomethyl acrylate of polyethylene glycol (23mers) [SHIN-NAKAMURA CHEMICAL Co., Ltd. product]

M230G; Monomethyl methacrylate of polyethylene glycol (23mers) [SHIN-NAKAMURA CHEMICAL Co., Ltd. product]

M90G; Monomethyl methacrylate of polyethylene glycol (9-mer) [SHIN-NAKAMURA CHEMICAL Co., Ltd. product]

The copolymerization component, copolymerization ratio, and mass average molecular weight in each of the fluorine-containing compounds (1) and (6) to (20) synthesized above are shown in Table 1 below. Furthermore, propylene glycol monomethyl ether acetate is added and adjusted so that solid content concentration of each fluorine-containing compound may be 25%.

Example 1

Preparation of the photosensitive resin composition

First, the K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 2 below were weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then, in the amounts shown in Table 2 Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA liquid, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'- The bromophenyl] -s-triazine, surfactant 1, and the fluorine-containing compound (1) obtained above were weighed and added in this order at a temperature of 25 ° C (± 2 ° C), and a temperature of 40 ° C (± 2 ° C). The photosensitive resin composition K1 was prepared by stirring at 150 rpm for 30 minutes at.

At this time, the ratio with respect to solid content mass in the photosensitive resin composition K1 of the fluorine-containing compound (1) was 5%. In addition, the quantity of Table 2 is a mass part, and has the following composition in detail.

K pigment dispersion 1

Carbon black (brand name: Nipex35, manufactured by Degussa) 13.1%

Dispersant 1 ... 0.65%

Polymer (benzyl methacrylate / methacrylic acid = random copolymer of 72/28 molar ratio, molecular weight 3.7 million) ... 6.72%

Propylene glycol monomethyl ether acetate 79.53%

Binder 2

Random copolymer of polymer (benzyl methacrylate / methacrylic acid (= 78/22 [molar ratio]), molecular weight 3.8 million)

Propylene glycol monomethyl ether acetate73%

DPHA liquid

Dipentaerythritol hexa acrylate (containing MEPP 500ppm of polymerization inhibitor, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)

Propylene glycol monomethyl ether acetate24%

Surfactant 1

30% of the following structures

Methyl ethyl ketone

Formation of pixel divider

After washing an alkali free glass substrate with a UV washing apparatus, it brush-cleaned using the washing | cleaning agent and ultrasonic cleaning was performed with the ultrapure water. This glass substrate was heat-processed at 120 degreeC for 3 minutes, and the surface state was stabilized.

After the heat processing, the glass substrate was cooled and temperature-controlled at 23 degreeC, and the said photosensitive resin composition K1 was apply | coated with the glass substrate coater (FAS Asia product, brand name: MH-1600) which has a slit-shaped nozzle. Subsequently, a part of the solvent was dried for 30 seconds with a vacuum dryer VCD (manufactured by Tokyo Oka Co., Ltd.) to remove fluidity of the coating layer, and then prebaked at 120 ° C. for 3 minutes to form a photosensitive resin composition layer having a thickness of 2.3 μm. K1 was formed (photosensitive resin layer formation process).

Next, using a proxy meter type exposure machine (manufactured by Hitachi High-Tech.Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask was placed vertically with a glass substrate and a mask (a quartz exposure mask having an image pattern). The distance between surface and the photosensitive resin composition layer K1 was set to 200 micrometers, and pattern exposure was performed by exposure amount 300mJ / cm <2> under nitrogen atmosphere (exposure process).

Next, pure water was sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin composition layer K1, and then diluted KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, manufactured by FUJIFILM Electronic Materials) by 100 times. As a result, shower development was performed at 23 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterned image (developing process). Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure cleaning nozzle to remove residue, and post exposure was performed at an exposure dose of 2000 mJ / cm 2 under air. Subsequently, the post-baking process was performed at 240 degreeC for 50 minutes (heat processing process), and the stripe-shaped black matrix (pixel partition wall) which has an opening of 2.0 micrometers in film thickness, 4.0 in optical density, and 100 micrometers width was obtained. Hereinafter, the glass substrate in which the black matrix was formed is called "the board | substrate with a pixel partition wall."

Evaluation 2

(2) wettability

The wettability was evaluated as follows about the obtained board | substrate with a pixel partition wall.

The recessed part surrounded by the pixel partition wall of the substrate having the pixel partition wall is used for the DIMATIX Inc. The inkjet head SE-128 of this product was used, and droplets of ink were beaten one by one under conditions of a driving voltage of 50 V and a driving frequency of 50 Hz. The size of the droplet at the time when 20 seconds passed from the deposit was measured by light microscope observation, and the average value of 10 points was calculated | required, and this was made into the droplet diameter. The case where the droplet diameter is 40 µm or more is preferable as the wettability maintained state.

The recessed part surrounded by the pixel partition wall of the substrate having the pixel partition wall is used for the DIMATIX Inc. Using the inkjet head SE-128 of the product, 1 drop of propylene glycol monomethyl ether monoacetate was applied under conditions of a driving voltage of 50 V and a driving frequency of 50 Hz. The size of the droplets immediately after deposition was measured by a photomicrograph to obtain an average value of 10 points, which was defined as the droplet diameter. The values are shown in Tables 3 and 4.

(3) Water repellency and ink repellency of the pixel separation wall

Ink repellency was evaluated about the obtained board | substrate with a pixel partition wall as follows.

The ion-exchanged water is made into a 20 memory size water sample using a contact angle meter (CA-A) manufactured by Kyowa Interface Science Co., Ltd., and the water sample is discharged from the needle tip to discharge the water sample. By contacting the edge portion, water droplets were formed on the edge portion of the pixel separation wall, the shape of the ink droplet was observed from the observation hole of the contact angle system, and the contact angle θ at 25 ° C. was obtained. The values are shown in Table 4 below.

In Examples 5 to 23 and Comparative Examples 3 to 4, the photosensitive resin composition layer K1 formed by the above-described method was exposed in the same manner as described above except that no mask was used, and then post-baking treatment (heating The operation to (processing process) was performed on the same conditions, and the test photosensitive resin composition layer was obtained. Then, the test photosensitive resin composition layer was left to cool at room temperature for 1 hour after the post-baking treatment, and then cooled, using a contact angle measuring instrument (contact angle meter manufactured by Kyowa Interface Science Co., Ltd., trade name: CA-A). Droplet of the coloring ink composition for R pixels on the test photosensitive resin composition layer by discharging the coloring ink composition for R pixels as a liquid sample (ink sample) having a size of 20 memory and contacting the test photosensitive resin composition layer. (Ink drops) were formed. And the shape of this ink droplet was observed from the observation hole of a contact angle system, and the ink contact angle (theta) ¹ of the ink droplet after 10 second standing from the deposit at 25 degreeC was calculated | required.

In addition, the water droplets were measured by changing the ink droplets of the contact angles into water droplets and measuring the water contact angles θ ² in the same order.

The value after postbaking was evaluated according to the following evaluation criteria as an index for evaluating water repellency and ink repellency. The allowable range is A rank and B rank. The evaluation results are shown in Tables 5 and 6 below.

Evaluation standard

A rank: Ink contact angle ≥50 °, water contact angle ≥100 °

B rank: Ink contact angle ≥40 °, water contact angle ≥90 °

C rank: Ink contact angle ≥35 °, water contact angle ≥80 °

D rank: Ink contact angle <35 °, water contact angle <80

(4) Substrate Adhesion of Pixel Separation Wall

Developing under the same development conditions except that three glass substrates having completed the exposure process under the same conditions in the above-described "formation of pixel separation walls" were prepared, and the development time was extended to 90 seconds, 100 seconds, and 110 seconds. The treatment was performed to evaluate the presence or absence of crack generation of the pixel dividing wall at each development time in accordance with the following evaluation criteria by visual inspection of 1000 pixels. The allowable range is A rank and B rank. The evaluation results are shown in Tables 5 and 6 below.

Evaluation standard

A rank: There was no pixel dividing wall crack at all.

-B rank: There were 1-2 pixel partition wall cracks.

C rank: There were 3 to 10 cracks in the pixel partition walls.

D rank: There were 11 or more pixel partition wall cracks.

Production of color filter

(1) Preparation of coloring ink composition for pixels

In the following composition, the pigment, the polymeric dispersing agent, and the solvent were mixed first, and the pigment dispersion liquid was obtained using three rolls and a bead mill. While stirring this pigment dispersion liquid sufficiently with a dissolver etc., the other material was added little by little, and the coloring ink composition for red (R) pixels was prepared.

Composition of coloring ink composition for red pixels

Pigment (C.I. pigment red 254)

Polymer Dispersant (trade name: SOLSPERSE 24000, AVECIA)

Random copolymer of benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) (molecular weight: 370,000, binder)

Novolak-type epoxy resin (trade name: EPICOAT 154, manufactured by Yuka-Shell Epoxy Co., Ltd.)

Neopentylglycol diglycidyl ether (epoxy resin)

Trimellitic acid (curing agent)

Ethyl 3-ethoxypropionate (solvent)

In addition, except using the same amount of C. I. pigment green 36 instead of C. I. pigment red 254 in the said composition, it is the same as the case of the coloring ink composition for R pixels, and it is the coloring ink composition for green (G) pixels. Prepared. In addition, except having used the same amount of C. I. Pigment Blue 15: 6 in place of C. I. Pigment Red 254 in the above composition, it was the same as in the case of the coloring ink composition for R pixels, and the coloring ink for blue (B) pixels. The composition was prepared.

(2) formation of colored pixels

Next, using the coloring ink composition for each pixel of said R, G, B, in the area partitioned by the pixel partition wall of the board | substrate with the pixel partition wall obtained above (concave part enclosed by the pixel partition wall) Using the inkjet recording apparatus, the ink composition was discharged until the desired density was obtained, thereby producing a color filter composed of R, G, and B patterns (colored pixels). Subsequently, this color filter was baked for 30 minutes in a 230 ° C. oven to obtain a color filter substrate in which the pixel separation wall and each pixel were completely cured.

Evaluation 3

(5) Mixed color and / or white spot of color filter

The obtained color filter substrate was visually observed with a 200-fold optical microscope from the side opposite to the side where the pixel of the color filter was formed, and the presence or absence of mixed color and / or white spot between the pixels was observed. Evaluation was performed by observing 1000 pixels and dividing it into the following ranks. The allowable range is A rank and B rank.

A rank: There was no mixed color and / or white spot.

Rank B: Mixed color and / or white spots were seen in 1-2 places around the periphery of the display.

C rank: 1 to 2 spots of mixed color and / or white spot were seen on the display unit.

D rank: More than two places of mixed color and / or white spots were shown on the display unit.

Manufacture of LCD

A transparent electrode of indium tin oxide (ITO) was further formed by sputtering on the R pixel, the G pixel and the B pixel of the color filter substrate obtained above, and the pixel separation wall. The resistance of this ITO was measured using a resistivity measuring device (trade name: Loresta, manufactured by Mitsubishi Chemical Corporation) using a four-probe method, and found to be 12 Ω / □, showing a very low value.

Formation of Columnar Spacer Patterns

The following coating liquid for photosensitive resin layers for spacer pattern formation was apply | coated on the ITO of the said color filter with the above-mentioned slit coater, and it dried, and formed photosensitive resin layer SP1.

Prescription SP1 of coating liquid for photosensitive resin layer

Methacrylic acid / allyl methacrylate copolymer (molar ratio = 20/80, molecular weight 40000; high molecular weight material) 108 parts

Dipentaerythritol hexaacrylate

Polymerizable monomer

2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine

Hydroquinone monomethyl ether

Victoria Pure Blue (brand name: BOHM, product of Hodogaya Chemical Co., Ltd.)

Surfactant (trade name: MEGAFAC F780F, Dainippon Ink & Chemicals Inc.); 0.856 parts

Methyl ethyl ketone

1-methoxy-2-propyl acetate

Methanol16.6 parts

Next, a proxy meter exposure was performed at 300 mJ / cm <2> with an ultrahigh pressure mercury lamp through a predetermined photomask. After exposure, 100 times dilution (pH = 11.8) of KOH developer [CDK-1 (brand name), FUJIFILM Corp. Product] was used to dissolve and remove the photosensitive resin layer of the unexposed part.

Subsequently, it baked for 30 minutes at 230 degreeC, and formed the columnar spacer pattern of diameter 16micrometer and average height 3.7micrometer in the part located in the upper part of the pixel separation wall on the ITO film | membrane on a glass substrate. An alignment film made of polyimide was further formed thereon.

Formation of projection for liquid crystal alignment

The coating liquid for photosensitive resin layers for protrusions was apply | coated on the ITO of the said color filter board | substrate with the above-mentioned slit coater, and it dried, and formed the photosensitive resin layer for protrusions. Next, the coating liquid for intermediate | middle layers which consists of following prescription P1 was apply | coated on the photosensitive resin layer for protrusions, and the intermediate | middle layer of 1.6 micrometers of dry film thicknesses was formed.

Prescription A of coating liquid for photosensitive resin layer for protrusion

Positive resist liquid

(CDK-1, FUJIFILM Electronic Materials, trade name: FH-2413F)

Methyl ethyl ketone

The surfactant 1 ... 0.04 parts

Prescription P1 of coating liquid for intermediate layers

PVA205 (polyvinyl alcohol, product of Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550)

Polyvinylpyrrolidone

(ISP, Japan product, brand name: FK-30)

Distilled water

Methanol

Next, the proxy meter exposure machine was arrange | positioned so that a photomask might be set to a distance of 100 micrometers from the surface of the photosensitive resin layer for protrusions, and the proxy meter exposure was carried out by 150 mJ / cm <2> of irradiation energy with the ultrahigh pressure mercury lamp through the said photomask. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying onto the substrate at 33 ° C. for 30 seconds with a shower developing device to develop and remove unnecessary portions (exposure portions) of the photosensitive resin layer for protrusions. Then, a projection made of a photosensitive resin layer patterned into a desired shape was formed on a portion located above the R, G, and B pixels on the ITO film of the color filter substrate. Subsequently, the color filter substrate in which the said projection was formed was baked at 240 degreeC for 50 minutes, and the orientation division protrusion which was 1.5 micrometers in height, and a longitudinal cross-sectional shape was semicircle was formed on the color filter substrate.

Moreover, the orientation division vertical orientation liquid crystal display element was produced by combining the drive side board | substrate and the liquid crystal material with respect to the obtained color filter substrate. Specifically, a TFT substrate having a TFT and a pixel electrode (conductive layer) arranged as a driving side substrate is prepared, and the TFT substrate and the color filter substrate obtained above are used as the surface and color of the side on which the pixel electrode and the like of the TFT substrate are formed. It arrange | positioned so that the surface of the side in which the orientation divider | protrusion process etc. of the filter board | substrate were formed may face, and provided the space | interval as much as a spacer and fixed. By encapsulating the liquid crystal material at this interval, a liquid crystal layer responsible for image display was formed to obtain a liquid crystal cell. The polarizing plate HLC2-2518 by Sanritz Corporation was attached to both surfaces of the liquid crystal cell obtained in this way. Subsequently, the backlight of the cold cathode tube was comprised, and this was arrange | positioned on the opposite side (back side) from the side in which the polarizing plate of the liquid crystal cell was formed, and it was set as the orientation division vertical alignment type liquid crystal display device.

Evaluation 4

(6) display stain of liquid crystal display device

About the liquid crystal display device produced above, the gray display at the time of inputting the test signal of gray was visually observed, and the presence or absence of generation | occurrence | production of a display stain was evaluated according to the following evaluation criteria.

Evaluation standard

A rank: There was no display stain at all, and a very good display image was obtained.

-B rank: Although the edge part of the glass substrate was slightly uneven, there was no influence to a display part, and the display image was favorable.

C rank: The stain was slightly seen on the display unit, but it was within the practically acceptable range.

D rank: A stain was seen on the display unit, and the display image was somewhat bad.

E rank: A strong stain was seen on the display unit, and the display image was very bad.

Example 2

Fabrication of Photosensitive Transfer Material K1

On the 75-micrometer-thick polyethylene terephthalate film support body (PET support body), the coating liquid for thermoplastic resin layers which consists of following formula H1 was apply | coated and dried using the slit-shaped nozzle, and the thermoplastic resin layer was formed. Next, the coating liquid for intermediate | middle layers which consists of following prescription P1 was apply | coated and dried on this thermoplastic resin layer, and the intermediate | middle layer was formed. Moreover, the photosensitive resin composition K1 prepared in Example 1 was apply | coated and dried, and the photosensitive resin layer was formed.

In this way, 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 layer having a dry film thickness of 2.3 μm were formed on the branch body, and finally, a protective film (thickness of 12 μm). Polypropylene film).

In this way, the photosensitive transfer material in which the support body, the thermoplastic resin layer, the intermediate | middle layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced, and the sample name was called photosensitive transfer material K1.

Prescription H1 of coating liquid for thermoplastic resin layers

Methanol11.1parts

Propylene glycol monomethyl ether acetate

Methyl ethyl ketone

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ° C.) · 5.83 copies

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 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.) 9.1 parts

The surfactant 1 ... 0.54 parts

Prescription P1 of coating liquid for intermediate layers

Polyvinyl alcohol (trade name: PVA-205, Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550)

Polyvinylpyrrolidone (trade name: K-30, ISP, Japan)

Distilled water

Methanol

The glass cleaner liquid which adjusted the alkali free glass substrate (henceforth simply a "glass substrate") to 25 degreeC was wash | cleaned with the rotating brush which has nylon hair, blowing for 20 second by a shower, and a silane coupling liquid (N after pure water shower cleaning). 0.3% aqueous solution of (beta) (aminoethyl) (gamma) -aminopropyl trimethoxysilane, brand name: KBM603 by Shin-Etsu Chemical Co., Ltd.) was blown by shower for 20 second, and the pure shower wash | cleaned. After the cleaning, the glass substrate was heated at 100 ° C. for 2 minutes with a substrate preheater.

The cover film is removed from the photosensitive transfer material K1 obtained above to the obtained glass substrate after the silane coupling treatment, and the photosensitive resin layer and the glass substrate after the silane coupling treatment exposed after the removal are subjected to the surface of the photosensitive resin layer and the surface of the glass substrate. Using a laminator (Hitachi Industries Co., Ltd., product name: Lamic II type), the glass substrate was laminated at a rubber roller temperature of 130 ° C. with a linear pressure of 100 N / cm and a conveyance speed of 2.2 m / min. Subsequently, the branched support of the polyethylene terephthalate was peeled off at the interface with the thermoplastic resin layer to remove the branched support. After peeling off the supporting member, the mask was placed in a vertical state with a substrate and a mask (a quartz exposure mask having an image pattern) vertically with a proxy meter type exposure machine (manufactured by Hitachi High-Tech.Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. The distance between a surface and the photosensitive resin layer was set to 200 micrometers, and pattern exposure was carried out with exposure amount 70mJ / cm <2>.

Subsequently, development was carried out with a KOH developer [100 times dilution (pH = 11.8) of CDK-1 (trade name, manufactured by FUJIFILM Corp.)], and the unexposed portion of the photosensitive resin layer, the intermediate layer below it, and the thermoplastic resin layer were removed to obtain glass. A black matrix pattern was formed on the substrate. Subsequently, in the air, the front surface of the substrate was post-exposed at 2000 mJ / cm 2 from the surface of the substrate with an aligner, and then post-baked at 240 ° C. for 50 minutes to obtain a pixel separation wall having an optical density of 4.0 (with a pixel separation wall). Board).

Next, similarly to Example 1, the color filter and the liquid crystal display device were produced, and the same evaluation as described in Example 1 was performed. The evaluation results are shown in Tables 3 and 4 below.

Example 3

In Example 2, except having changed the fluorine-containing compound (1) used for preparation of the photosensitive resin composition K1 into the fluorine-containing compound (2), it carried out similarly to Example 2, the board | substrate with a pixel partition wall, a color filter, and a liquid crystal The same evaluation was performed while producing a display device. The evaluation results are shown in Tables 3 and 4 below.

Example 4

In Example 2, except having changed the fluorine-containing compound (1) used for preparation of the photosensitive resin composition K1 into the fluorine-containing compound (3), it carried out similarly to Example 2, the board | substrate with a pixel partition wall, a color filter, and a liquid crystal The same evaluation was performed while producing a display device. The evaluation results are shown in Tables 3 and 4 below.

Comparative Example 1

In Example 2, except having changed the fluorine-containing compound (1) used for preparation of the photosensitive resin composition K1 into the fluorine-containing compound (4), it carried out similarly to Example 2, the board | substrate with a pixel partition wall, a color filter, and a liquid crystal The same evaluation was performed while producing a display device. The evaluation results are shown in Tables 3 and 4 below.

Comparative Example 2

In Example 2, except having changed the fluorine-containing compound (1) used for preparation of the photosensitive resin composition K1 into the fluorine-containing compound (5), it carried out similarly to Example 2, the board | substrate with a pixel partition wall, a color filter, and a liquid crystal The same evaluation was performed while producing a display device. The evaluation results are shown in Tables 3 and 4 below.

As shown in Tables 3 and 4 above, in the embodiment, while the black matrix has good ink repellency, the wettability of the coloring ink composition for pixels in the region forming the colored pixels between the black matrices can be maintained, High-quality image display with generation prevention and display spots suppressed was possible.

On the other hand, in the comparative example, the wettability with respect to the coloring ink composition for pixels was impaired, and generation | occurrence | production of the white spot and generation | occurrence | production of the display stain at the time of image display could not be prevented.

Example 5

In Example 1, the photosensitive resin composition K2 was prepared like Example 1 except having changed content of the fluorine-containing compound (1) from 5% to 1%, and manufacturing a color filter and a liquid crystal display device, In addition, the same evaluation was performed. The evaluation results are shown in Table 5 below.

Example 6

In Example 1, the photosensitive resin composition K3 was prepared like Example 1 except having changed content of the fluorine-containing compound (1) from 5% to 0.1%, and manufacturing a color filter and a liquid crystal display device, In addition, the same evaluation was performed. The evaluation results are shown in Table 5 below.

Examples 7-19

In Example 5, it carried out similarly to Example 2 except having changed the fluorine-containing compound (1) into the fluorine-containing compound (6)-(18) [fluorine-containing compound of this invention] of this invention obtained above. Resin compositions K4-K16 were prepared, the color filter and the liquid crystal display device were produced, and the same evaluation was performed. The evaluation results are shown in Table 5 below.

Comparative Example 3

In Example 5, the photosensitive resin composition K17 was prepared like Example 5 except having changed the fluorine-containing compound (1) into the said comparative fluorine-containing compound (19), and produced the color filter and the liquid crystal display device. In addition, the same evaluation was performed. The evaluation results are shown in Table 5 below.

Comparative Example 4

In Example 5, the photosensitive resin composition K18 was prepared like Example 5 except having changed the fluorine-containing compound (1) into the said comparative fluorine-containing compound (20), and produced the color filter and the liquid crystal display device. In addition, the same evaluation was performed. The evaluation results are shown in Table 5 below.

* Content in a table | surface shows mass ratio with respect to solid content.

As shown in Table 5, in the Examples, the water-repellent ink repellency on the pixel separation wall after the heat treatment was excellent, there was no color mixing and the substrate adhesion was good. In addition, the generation of display stains when the liquid crystal display device was produced and displayed was also effectively suppressed to obtain an image having excellent display characteristics.

On the other hand, in the comparative example, the water repellency and ink repellency on the pixel separation wall after heat processing deteriorated, the mixing prevention effect was inadequate, and the board | substrate adhesiveness also deteriorated. Therefore, in the liquid crystal display device, image display without the generation of display spots was difficult.

Example 20

After the glass cleaner liquid which adjusted the alkali free glass substrate (henceforth simply a "glass substrate") to 25 degreeC is blown for 20 second with a shower, it washes with the rotating brush which has a nylon hair, and after pure shower shower, a silane coupling liquid (N-β (aminoethyl) γ-aminopropyl trimethoxysilane 0.3% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was blown for 20 seconds by shower, and further washed by pure shower did. After washing, the glass substrate was heated at 100 ° C. for 2 minutes by a substrate preheater.

On the glass substrate after a silane coupling process, the cover film was removed from the following photosensitive transfer material K2, and the surface of the exposed photosensitive resin composition layer was overlapped with the surface of the said glass substrate, and a laminator (brand name: Lamic II type, Hitachi Industries Co., Ltd.) , Ltd.) was laminated at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm and a conveyance speed of 2.2 m / min. Subsequently, the PET branch body was peeled off and removed at the interface with a thermoplastic resin layer. After peeling off the branch, a glass substrate and a mask (a quartz exposure mask having an image pattern) were vertically oriented using a proxy meter type exposure machine (manufactured by Hitachi High-Tech.Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. In the standing state, the distance between the exposure mask surface and the photosensitive resin composition layer was set to 200 µm and pattern exposure was performed at an exposure dose of 70 mJ / cm 2.

Next, KOH developer [FUJIFILM Corp.]. 100 times dilution (pH = 11.8) of CDK-1 (brand name) of the product], and the unexposed part of the photosensitive resin composition layer, the intermediate | middle layer below it, and the thermoplastic resin layer were removed, and the pattern was formed on the glass substrate. Subsequently, the whole surface of the glass substrate was post-exposed at 2000mJ / cm <2> from the pattern formation surface side of a glass substrate with the aligner under air | atmosphere, and post-baking was performed at 240 degreeC for 50 minutes. As described above, a pixel separation wall (black matrix) having an optical density of 4.0 was obtained.

Then, similarly to Example 1, the color filter and the liquid crystal display device were produced, and the same evaluation as Example 1 was performed. The evaluation results are shown in Table 6 below.

Fabrication of Photosensitive Transfer Material K2

On the 75-micrometer-thick polyethylene terephthalate film (PET supporting body), the coating liquid for thermoplastic resin layers which consists of following formula H1 was apply | coated and dried using the slit-shaped nozzle, and the thermoplastic resin layer was formed. Next, the coating liquid for intermediate | middle layers which consists of following prescription P1 was apply-coated and dried on the formed thermoplastic resin layer, and the intermediate | middle layer (oxygen barrier film) was laminated | stacked. Moreover, the photosensitive resin composition K5 prepared in Example 8 was apply | coated and dried on this intermediate | middle layer, and the black (K) photosensitive resin composition layer K5 was laminated | stacked. At this time, the ratio with respect to solid content mass of the fluorine-containing compound (7) in the photosensitive resin composition K5 is 1.0%.

In this way, the thermoplastic resin layer with a dry film thickness of 14.6 micrometers, the intermediate | middle layer with a dry film thickness of 1.6 micrometers, and the photosensitive resin composition layer with a dry film thickness of 2.3 micrometers are laminated | stacked on the PET support body, and the surface of the photosensitive resin composition layer is carried out. The photosensitive transfer material K2 which integrated the support body / thermoplastic resin layer / intermediate | middle layer / photosensitive resin composition layer K2 was produced by crimping | bonding the protective film (12 micrometers polypropylene film thickness) further to the film.

Prescription H1 of coating liquid for thermoplastic resin layers

Methanol11.1parts

Propylene glycol monomethyl ether acetate

Methyl ethyl ketone

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ° C.) · 5.83 copies

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 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.) 9.1 parts

The surfactant 1 ... 0.54 parts

Prescription P1 of coating liquid for intermediate layers

Polyvinyl alcohol ... 32.2 parts (trade name: PVA205, Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550)

Polyvinylpyrrolidone

(ISP Japan product, brand name: K-30)

Distilled water

Methanol

Examples 21-23

In the preparation of the photosensitive transfer material of Example 20, instead of the photosensitive resin composition K2 containing the fluorine-containing compound (7), the fluorine-containing compounds (11), (13) and (15) in the present invention were included, respectively. Except having used photosensitive resin compositions K11, K13, and K15, photosensitive transfer materials K3 to 5 were produced in the same manner as in Example 20, and color filters and liquid crystal display devices were produced. In addition, evaluation similar to Example 1 was performed and the evaluation result is shown in following Table 6.

As shown in Table 6, in the Examples, the water-repellent ink repellency on the pixel separation wall after the heat treatment was excellent, there was no mixed color, and the substrate adhesion was also good. In addition, the generation of display stains when the liquid crystal display device was produced and displayed was also effectively suppressed to obtain an image having excellent display characteristics.

Claims (20)

A photosensitive resin composition comprising an initiator, an ethylenically unsaturated compound, and a fluorine-containing compound, wherein the thermal reduction rate of the fluorine-containing compound when held at 150 ° C. for 30 minutes is 30% by mass or less. The method of claim 1, The said fluorine-containing compound contains the repeating unit which has a fluorine atom in a side chain, and the main chain structure has an acryl connection chain, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The said fluorine-containing compound contains the repeating unit which has a fluorine atom in a side chain, and the repeating unit represented by following General formula (1), The photosensitive resin composition characterized by the above-mentioned.

[In General formula (1), R <^1> represents a hydrogen atom or a C1-C5 alkyl group; R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an alkanoyl group of 2 to 5 carbon atoms; L ¹ represents a single bond or a divalent organic linking group; X represents a chlorine atom, bromine atom or iodine atom; And Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group.] The method of claim 3, wherein The repeating unit having the fluorine atom in the side chain has three or more fluorine atoms. The method of claim 3, wherein The repeating unit represented by the said General formula (1) is a repeating unit represented by the following general formula (2), The photosensitive resin composition characterized by the above-mentioned.

[In General formula (2), R <^1> represents a hydrogen atom or a C1-C5 alkyl group; R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an alkanoyl group of 2 to 5 carbon atoms; Z ¹ represents an ester group or an amide group; L ² represents a single bond or a divalent organic linking group; X represents a chlorine atom, bromine atom or iodine atom; And Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group.] The method of claim 3, wherein The repeating unit represented by the said General formula (1) is a repeating unit represented by the following general formula (3), The photosensitive resin composition characterized by the above-mentioned.

[In General formula (3), R <^1> represents a hydrogen atom or a C1-C5 alkyl group; R ² represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an alkanoyl group of 2 to 5 carbon atoms; Z ² represents a single bond, an arylene group, or a divalent heterocyclic moiety; X represents a chlorine atom, bromine atom or iodine atom; And Y represents an arylene group, a divalent heterocyclic moiety, a carbonyl group or an oxycarbonyl group.] The method of claim 2, The said repeating unit which has a fluorine atom in a side chain is a repeating unit which has a C4-C7 fluoroalkyl group, The photosensitive resin composition characterized by the above-mentioned. The method of claim 3, wherein L <^1> in the said General formula (1) is a divalent organic coupling group containing 1 or more of an ester bond and an amide bond, The photosensitive resin composition characterized by the above-mentioned. The method of claim 3, wherein L <^1> in the said General formula (1) is a single bond, an arylene group, or a bivalent heterocyclic residue, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, Said fluorine-containing compound further has a repeating unit which has an acidic group, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, Content with respect to the total solid mass of the said fluorine-containing compound is 0.1 mass%-10 mass%, The photosensitive resin composition characterized by the above-mentioned. It has a photosensitive resin layer using the photosensitive resin composition of Claim 1 on a support body, The photosensitive transfer material characterized by the above-mentioned. Process of forming the photosensitive resin layer which forms the photosensitive resin layer using the photosensitive resin composition of any one of Claims 1-11, or the photosensitive transfer material of Claim 12; Exposing the photosensitive resin layer; Developing the exposed photosensitive resin layer; And And heating the pattern image obtained by the above development. A pixel partition wall formed by the method for forming a pixel partition wall according to claim 13. Board; And A substrate having a pixel separating wall, comprising a pixel separating wall formed on the substrate by the method for forming a pixel separating wall according to claim 13. The method of claim 15, When measured in accordance with the known wettability test method of the substrate glass surface, the water contact angle of the upper surface of the wall of the pixel separation wall is 60 ° or more, and the pixel separation wall is formed on the substrate surface on the side where the pixel separation wall of the substrate is formed. A substrate having a pixel separation wall, which has a droplet diameter of 20 µm or more immediately after dropping propylene glycol monomethyl ether monoacetate in an unused portion. A method of manufacturing a color filter, comprising: providing a colored liquid composition to a recessed portion on a substrate partitioned by the pixel dividing wall according to claim 14 to form a colored region. The method of claim 17, The provision of the said colored liquid composition is performed by ejecting the droplet of a colored liquid composition by the inkjet method, The manufacturing method of the color filter characterized by the above-mentioned. The color filter manufactured by the manufacturing method of the color filter of Claim 18. A display device comprising the color filter according to claim 19.

Images