JP2009058871A - Pixel barrier, color filter and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pixel barrier capable of forming a pixel without color mixing, void or the like positionally precisely; to provide a color filter having the pixel barrier; and to provide a liquid crystal display device comprising the color filter. <P>SOLUTION: The pixel barrier for separating a plurality of colored pixels formed by applying droplets of a colored liquid composition onto a substrate contains metal fine particles, has the upper surface with an ink-repellent property and has a height from the substrate of 1.0 μm or more. The color filter having the pixel barrier and the liquid crystal display device comprising the color filter are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a separation wall that contains metal fine particles and has ink repellency, a color filter having a separation wall, and a display device including the color filter.

  The color filter for a display device has a structure in which red, green, and blue dot images are arranged in a matrix on a substrate such as glass, and the boundary is divided by a separation wall such as a black matrix. As a manufacturing method of such a color filter, conventionally, a substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, and repeated exposure and development. Colored photosensitive resin liquid method (colored resist method) (see, for example, Patent Documents 1, 2, and 3), 4) A method of sequentially transferring an image formed on a temporary support onto a final or temporary support ( For example, see Patent Documents 4, 5 and 6.) 5) A colored layer is formed by coating a preliminarily colored photosensitive resin solution on a temporary support, and this photosensitive colored layer is formed directly on the substrate in sequence. A method of forming a multicolor image (transfer method) (for example, see Patent Document 7) by a method of repeating transfer, exposure and development by the number of colors is known. A method using an ink jet method (for example, see Patent Document 8) is also known.

Among these methods, although the color resist method can produce a color filter with high positional accuracy, it is not advantageous in terms of cost due to a large loss in application of the photosensitive layer resin solution. On the other hand, the ink-jet method has a problem that the position accuracy of the pixels is poor, although the loss of the resin liquid is small and advantageous in terms of cost. In order to overcome these problems, a color filter manufacturing method has been proposed in which a black matrix is formed by a colored resist method and an RGB pixel is manufactured by an ink jet method. In addition, bleeding, protrusion, color mixture with adjacent pixels, and white spots may occur. In order to prevent this, a method has been disclosed in which the black matrix and the ink have a repelling property or the ink wettability of the black matrix gap is increased (for example, Patent Documents 9 and 10). And 11).
In addition, a method of performing ink repellent treatment on a separation wall by plasma treatment is known (for example, see Patent Document 12).
JP-A-63-298304 JP-A 63-309916 Japanese Patent Laid-Open No. 1-152449 JP-A-61-99103 JP-A-61-233704 JP-A 61-279802 JP-A-61-99102 JP-A-8-227010 JP-A-6-347637 JP-A-7-35915 JP-A-10-142418 JP 2001-343518 A

  The present invention has been made in view of the above-described conventional problems, and is a separation wall capable of forming pixels without color mixing or whitening with high positional accuracy, a color filter having the separation wall, and this An object is to provide a display device including a color filter.

That is, the present invention
<1> A separation wall for separating a plurality of colored pixels formed by applying droplets of a colored liquid composition on a substrate, containing metal fine particles, and having an ink repellent upper surface A separation wall having a height of 1.0 μm or more from the substrate.

  <2> At least one of the metal fine particles is a metal fine particle containing one or more metals selected from the group consisting of Group 2 to Group 14 of the Periodic Table <1 It is a separation wall as described in>.

  <3> The separation wall according to <1> or <2>, wherein at least one of the metal fine particles is silver fine particles or silver-containing alloy fine particles.

  <4> Any one of <1> to <3>, wherein the ink repellent compound for expressing ink repellency on the upper surface is a fluorine-containing compound and / or a silicon-containing compound. This is the illustrated separation wall.

  <5> The separation wall according to <4>, wherein the fluorine-containing compound is a compound containing a perfluoroalkyl group having 4 to 10 carbon atoms.

  <6> The separation wall according to <4> or <5>, wherein the number of fluorine atoms / number of carbon atoms on the upper surface measured by ESCA is 0.10 or more.

  <7> The separation wall according to <4>, wherein the silicon-containing compound is silicone.

  <8> The separation wall according to <4> or <7>, wherein the number of silicon atoms / number of carbon atoms on the upper surface measured by ESCA is 0.10 or more.

  <9> A color filter having a substrate, a plurality of colored pixels formed by applying droplets of a colored liquid composition on the substrate, and a separation wall for separating the colored pixels, The color filter, wherein the image separation wall is the image separation wall according to any one of <1> to <8>.

  <10> The color filter according to <9>, wherein the application of the droplets is performed by an inkjet method.

  <11> A display device comprising the color filter according to <9> or <10>.

  According to the present invention, it is possible to provide a separation wall that can form a pixel having no color mixing or whitening with high positional accuracy, a color filter having the separation wall, and a display device including the color filter.

  Hereinafter, the separation wall, the color filter, and the display device of the present invention will be described in detail.

<Illustrated wall>
The separation wall of the present invention is a separation wall that separates a plurality of colored pixels formed by applying droplets of a colored liquid composition on a substrate, contains metal fine particles, and has an upper surface that is repellent. It has ink properties, and the height from the substrate is 1.0 μm or more.

  With the above-described configuration of the image separation wall, it is possible to obtain a image separation wall that can form pixels that are free of color mixing or whitening with high positional accuracy.

In the image separation wall of the present invention, the upper surface has ink repellency. If the upper surface of the image separation wall does not have ink repellency, ink mixing may occur, which is not preferable. In the present invention, the upper surface refers to a surface of the separation wall and an angle formed between a tangent to the surface and the substrate surface is 10 ° or less.
The ink repellency in the present invention is a property of repelling liquid (ink) applied to the gap between the image separation walls. The contact angle with ink is preferably 15 ° or more, more preferably 25 ° or more, and most preferably 30 ° or more. The contact angle in the present invention was defined as the angle between the separation wall and the droplet after 20 seconds after dropping ink having a particle size of 1.5 mm at 23 ° C. and 50% RH.
There is no particular upper limit for the ink contact angle as long as it is not ink-repellent in areas other than the desired location (such as the gap between the partition walls) (the contact angle is 180 ° or less). The contact angle is the ink contact angle of the partition after the ink repellent treatment is performed on the partition.

  The height of the separation wall of the present invention from the substrate is 1.0 μm or more, but if it is less than 1.0 μm, color mixing may occur, which is not preferable. The height of the separation wall of the present invention from the substrate is preferably 1.5 μm or more, and more preferably 2.0 μm or more.

-Metal fine particles-
The separation wall of the present invention contains fine metal particles as a colorant (dark color).
The metal constituting the metal fine particles in the present invention is not particularly limited, and any metal may be used. In addition, as the metal fine particles in the present invention, two or more kinds of metals may be used in combination, or may be used as an alloy.
The metal fine particles in the present invention may be composite fine particles of a metal or a metal and a metal compound.
In particular, as the types of metal fine particles preferably used in the present invention, the metal fine particles described in paragraph numbers [0038] to [0039] of JP-A-2006-251237 can be suitably used in the present invention.

At least one of the metal fine particles used for the separation wall of the present invention is a metal fine particle containing one or more metals selected from the group consisting of Groups 2 to 14 of the periodic table. preferable.
Among these, a preferable metal is at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or an alloy thereof, and more preferable metals are copper, silver, gold, platinum. , Tin and alloys thereof, and more preferably silver or an alloy containing silver.

  It is particularly preferable that at least one of the metal fine particles used for the separation wall of the present invention is silver fine particles or alloy fine particles containing silver.

The metal fine particles in the present invention can be obtained by reducing metal ions in the presence of a dispersion polymer described later.
Specifically, it is obtained by adding a metal salt-containing solution containing a metal and a reducing agent in the presence of a dispersion polymer, mixing them, and reducing metal ions.
The metal salt can be used without particular limitation, and examples thereof include metal salts such as chlorides, nitrates, nitrites, sulfates, ammonium salts, and acetates. Among these, particles are formed in the process of particle formation. From the viewpoint of not adsorbing, nitrates, nitrites and acetates are preferable, nitrates and acetates are more preferable, and nitrates are particularly preferable.

  The reducing agent is not particularly limited as long as it is usually used. For example, borohydride metal salts such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, beryllium aluminum hydride, magnesium magnesium hydride, calcium aluminum hydride, etc. Aluminum hydride salt; sodium sulfite, hydrazine compound, dextrin, hydroquinone, hydroxylamine, citric acid and its salt, succinic acid and its salt, ascorbic acid and its salt, etc .; diethylaminoethanol, ethanolamine, propanolamine, triethanolamine, Alkanolamines such as dimethylaminopropanol; propylamine, butylamine, dipropyleneamine, ethylenediamine, triethylenepentamine Any aliphatic amine; heterocyclic amines such as piperidine, pyrrolidine, N-methylpyrrolidine, morpholine; aromatic amines such as aniline, N-methylaniline, toluidine, anisidine, phenetidine; benzylamine, xylenediamine, N- Aralkylamine such as methylbenzylamine; etc., and from the viewpoint of shape control of the metal fine particles, among these, it is preferable to use one or more selected from sodium sulfite, hydroquinone, ascorbic acid or a salt thereof, A combination of sodium sulfite and hydroquinone, a combination of sodium sulfite and ascorbic acid is more preferable, and a combination of sodium sulfite and hydroquinone is more preferable.

  The metal salt / reducing agent equivalent ratio is preferably 0.2 to 5, more preferably 0.5 to 2, and particularly preferably 0.8 to 1.5.

  Examples of the dispersion polymer include thiol group-containing compounds, amino acids or derivatives thereof, peptide compounds, polysaccharides and natural polymers derived from polysaccharides, synthetic polymers, and polymers such as gels derived therefrom.

Examples of the polymers include gelatin, polyvinyl alcohol, methylcellulose, hydroxypropyl cellulose, polyalkyleneamine, partial alkyl esters of polyacrylic acid, polyvinylpyrrolidone, and polyvinylpyrrolidone copolymers, which are protective colloidal polymers. It is done.
For the polymer that can be used as the dispersion polymer, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.

In the method for producing fine metal particles of the present invention, the addition method of metal salt and reducing agent, the reaction temperature and the like are not particularly limited, and can be appropriately adjusted according to the intended fine metal particle composition to be prepared.
From the viewpoint of controlling the shape of the fine metal particles, the temperature during the reaction is preferably 60 ° C. or less, and more preferably 50 ° C. or less. The addition method is not particularly limited, but it is preferable to start the addition of metal ions earlier than the reducing agent. And it is preferable to stir from a viewpoint of forming a uniform system at the time of particle | grain formation, 200 rpm or more is preferable and the rotation speed is more preferable 400 rpm or more. Although there is no restriction | limiting in particular in pH at the time of particle | grain formation, It is preferable that pH before metal salt addition is 10 or more from a viewpoint of reducing a metal salt via a hydroxide.

-Composite fine particles-
The above-mentioned “composite fine particles of metal and metal compound” refers to particles obtained by combining a metal and a metal compound into one particle.
As the composite fine particles, metal compound fine particles, composite fine particles, and core shell type composite particles described in paragraphs [0040] to [0043] of JP-A-2006-251237 can be suitably used in the present invention. .

-Dispersion of fine metal particles-
The metal fine particles in the present invention are preferably dispersed in a metal fine particle dispersion. The presence state of the metal fine particles at the time of dispersion is not particularly limited, but the metal fine particles are preferably present in a stable dispersion state, for example, more preferably in a colloidal state.

  The separation wall of the present invention may contain any other organic pigment, inorganic pigment, dye or the like as long as it contains metal fine particles. Specific examples of these organic pigments, inorganic pigments, dyes, and the like include the pigments and dyes described in JP-A-2005-17716 [0038] to [0054], and JP-A-2004-361447 [0068]- The pigment described in [0072] and the colorant described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

  When the light-shielding property is required for the separating wall, a mixture of pigments such as red, blue, and green can be used in addition to the metal fine particles. Known colorants (dyes and pigments) can be used. When using a pigment among the known colorants, it is preferable that the pigment is uniformly dispersed in the separation wall.

Of the dark colored bodies, examples of black dark colored bodies include carbon black, titanium carbon, iron oxide, titanium oxide, graphite, and the like. Among these, carbon black is preferable.
The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle). The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion (binder) that binds to the pigment and hardens the coating film, and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used when dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, 438, Known dispersers such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, the material may be finely pulverized using frictional force by mechanical grinding described in Item 310.

The separation wall of the present invention is formed from the composition for the separation wall.
The separating wall composition preferably comprises at least a polymerization initiator and a polyfunctional monomer in addition to the dark color body. Further, if necessary, a known additive such as a plasticizer, a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, an adhesion promoter, and the like can be further contained. Further, the separating wall composition is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.

  As a method for curing the composition for the separation wall, a thermal initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are common, but it is preferable to use a photoinitiation system. Hereinafter, in the present invention, the photoinitiating composition for the separating wall is referred to as a photosensitive composition for the separating wall.

  The photopolymerization initiator used in the photosensitive composition for the separation wall is a polymerization of a polyfunctional monomer described later by irradiation (also referred to as exposure) of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Is a compound capable of generating an active species that initiates the reaction, and can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.

  For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

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

9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) ) Butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. Acridine compounds such as bis (9-acridinyl) alkane;

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

  Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and particularly selected from a trihalomethyl group-containing compound and an acridine compound. It is preferable to contain at least one kind. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.

  Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5 Trihalomethyl group-containing compounds such as trichloromethyl-1,3,4-oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole.

  The said photoinitiator may be used independently and may use 2 or more types together. The total amount of the photopolymerization initiator in the photosensitive composition for the separation wall is preferably 0.1 to 20% by mass of the total solid content (mass) of the photosensitive composition for the separation wall, and is preferably 0.5 to 10%. Mass% is particularly preferred. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.

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

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

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

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

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

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

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. The total amount of the hydrogen donor in the photosensitive composition for the separation wall is preferably 0.1 to 20% by mass, and preferably 0.5 to 10% by mass based on the total solid content (mass) of the photosensitive composition for the separation wall. % Is particularly preferred.

  As the polyfunctional monomer used in the photosensitive composition for the separating wall, the following compounds can be used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxy Ethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxy Nzenji (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide, and the like.

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

  As content in the photosensitive composition for separating walls of a polyfunctional monomer, 5-80 mass% is preferable with respect to the total solid (mass) of the photosensitive composition for separating walls, and 10-70 mass. % Is particularly preferred. When the content is less than 5% by mass, the resistance to the alkali developer at the exposed portion of the composition may be inferior. When the content exceeds 80% by mass, the photosensitive composition for the separation wall is obtained. The tackiness increases and the handleability may be poor.

Although the image separation wall of the present invention may be produced by any method, it is preferably formed by exposing the photoimageable composition for the image separation wall in a poor oxygen atmosphere and then developing it.
Under an oxygen-poor atmosphere when photocuring the photosensitive composition for a separating wall is one or more selected from an inert gas, a reduced pressure, and a protective layer capable of blocking oxygen. The details are as follows.

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

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

  Examples of the protective layer capable of blocking oxygen include, for example, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose described in JP-A Nos. 46-2121 and 56-40824. Water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches And a group of water-soluble salts thereof, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof.

  Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably the alkali-soluble resin layer solid content. It is 10-40 mass%.

  In addition, various films can be used as the layer capable of blocking oxygen. For example, polyesters such as PET, polyamides such as nylon, and ethylene-vinyl acetate copolymers (EVAs) are also preferably used. be able to. These films may be stretched as necessary, and the thickness is suitably 5 to 300 μm, preferably 20 to 150 μm. When the separation wall is produced using a transfer material, the temporary support described below can be suitably used as a layer capable of blocking oxygen.

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

On the substrate, when the photosensitive composition for the separation wall as described above is photopolymerized under the poor oxygen atmosphere as described above, exposure from the surface of the composition toward the substrate by absorption of the composition itself. As the amount decays, the result is more surface hardening. Furthermore, since it is under an oxygen-poor atmosphere, inhibition of polymerization on the surface of the composition is suppressed, and as a result, the surface is further cured.
Through the process of fixing the shape of the separation wall obtained in this way, the ink once deposited in the gap becomes difficult to get over the separation wall, and as a result, bleeding, protrusion, color mixing with adjacent pixels and white A good color filter can be obtained while preventing omission.

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

  The photosensitive transfer material may have a thermoplastic resin layer between the temporary support and the oxygen barrier layer as necessary. Such a thermoplastic resin layer is alkali-soluble and includes at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, good adhesion between the separation wall and the substrate can be exhibited.

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

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

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

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

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

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

(substrate)
As the substrate constituting the color filter (permanent support), that is, the substrate on which the separation wall is formed, a metallic support, a metal bonded support, glass, ceramic, synthetic resin film, or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

  Hereinafter, a case where a separation wall is formed using a photosensitive transfer material will be described. A photosensitive transfer material is prepared in which an oxygen-blocking layer, a separating wall photosensitive composition layer, and a cover sheet are provided on the separating wall photosensitive composition layer on a temporary support. First, the cover sheet is peeled and removed, and then the exposed surface of the separation wall photosensitive composition layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (laminate). As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to further increase the productivity.

Next, the temporary support is peeled from the oxygen barrier layer, and the temporary support is removed. Subsequently, in a state where a desired photomask (for example, quartz exposure mask) is vertically set above the removal surface after the temporary support is removed, an appropriate distance between the exposure mask surface and the oxygen blocking layer (for example, 200 μm) for exposure. Next, after the irradiation, development processing is performed using a predetermined processing solution to obtain a patterning image, and subsequently, washing treatment is performed as necessary to obtain a separation wall.
When the temporary support is used as a protective layer capable of blocking oxygen, a desired photomask (for example, a quartz exposure mask) is provided above the temporary support while leaving the temporary support (without peeling). In a state in which is vertically set, the distance between the exposure mask surface and the temporary support is appropriately set (for example, 200 μm) and exposed. Next, the temporary support is removed, and after irradiation, development processing is performed using a predetermined processing liquid to obtain a patterning image. Subsequently, if necessary, washing treatment is performed to obtain a separation wall.

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

  Prior to the development, it is preferable to spray the pure water with a shower nozzle or the like to uniformly wet the surface of the photosensitive composition layer for the separating wall. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water.

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

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

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

The upper surface of the separation wall of the present invention has ink repellency. In the present invention, it is preferable that an ink repellent treatment is performed on the separation wall so that the upper surface of the separation wall is in an ink repellent state (a state in which an ink repellent compound exists). Accordingly, when ink is applied between the separation walls by a method such as inkjet, it is possible to eliminate the inconvenience that the ink gets over the separation wall and mixes with the adjacent color.
The ink in the present invention is a liquid applied to the concave portion (pixel portion) of the separation wall after the separation wall is formed, and is not particularly limited. The ink is preferably made into a colored liquid composition by dispersing a pigment or incorporating a mechanism for curing with heat or curing with light.
The ink repellent compound in the present invention is a compound that, when present on the upper surface of the separation wall, has a property of repelling the ink, and there is no particular limitation. As the ink repellent compound, a fluorine-containing compound and / or a silicon-containing compound are preferable.
As the ink repellent treatment, there is a method of applying an ink repellent material on the upper surface of the separation wall, a method of newly providing an ink repellent layer, a method of imparting ink repellency by plasma treatment, and the metal fine particles and photopolymerization initiator. Examples thereof include a method of mixing an ink substance with a separation wall, a method of containing an ink repellent compound in an adjacent layer, and a method of exposing by exposure to an ink repellent compound solution having a polymerizable group.

Hereinafter, the ink repellent process will be described in detail.
(1) <Method of mixing an ink repellent substance with a separation wall>
As a means for preventing “color mixing”, there is a method of adding a fluorine-containing resin to the above-described photosensitive composition for a separation wall.
The fluororesin in the present invention has an Rf group (a) having a polyfluoroether structure represented by the following formula 1 and an acidic group (b), and an acid value of 1 to 300 mgKOH / g. Is preferred.

-(X-O) _n- Y ... Formula 1
In Formula 1, X is a C1-C10 divalent saturated hydrocarbon group or a C1-C10 fluorinated divalent saturated hydrocarbon group, and is the same for each unit surrounded by n Y represents a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or A fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is shown, and n is an integer of 2 to 50. However, the total number of fluorine atoms in Formula 1 is 2 or more.

As an aspect of X and Y in Formula 1, X is preferably an alkylene group that is fluorinated except for one hydrogen atom having 1 to 10 carbon atoms or a perfluorinated alkylene group that has 1 to 10 carbon atoms. Each of the units enclosed by n represents the same group or a different group, and Y represents a fluorinated alkyl group or a par group having 1 to 20 carbon atoms except for one hydrogen atom having 1 to 20 carbon atoms. The thing which shows the fluorinated alkyl group is mentioned.
As an embodiment of X and Y in Formula 1, more preferably, X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and represents the same group or a different group for each unit surrounded by n. , Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.
When the aspect of X and Y is as described above, the fluorine-containing resin exhibits good ink repellency.
In Formula 1, n represents an integer of 2 to 50. n is preferably from 2 to 30, and more preferably from 2 to 15. When n is 2 or more, the ink falling property is good. When n is 50 or less, the fluorine-containing resin is synthesized by copolymerization of a monomer having an Rf group (a), a monomer having an acidic group (b), and other monomers In addition, the compatibility of the monomers is improved.
Moreover, 2-50 are preferable and, as for the total number of the carbon atoms in Rf group (a) which consists of a polyfluoroether structure represented by Formula 1, 2-30 are more preferable. Within this range, the fluororesin exhibits good ink repellency, particularly organic repellency. In addition, when the fluororesin is synthesized by copolymerization with a monomer having an Rf group (a), a monomer having an acidic group (b), and another monomer, the compatibility of the monomer It becomes good.

Examples of _{X, -CF 2 -, - CF} 2 CF 2 -, - CF 2 CF 2 CF 2 -, - CF 2 CF (CF 3) -, - CF 2 CF 2 CF 2 CF 2 -, - _{CF 2 CF 2 CF (CF 3} ) -, and _{CF 2 CF (CF 3) CF} 2 - and the like.
Specific examples of _{Y, -CF 3, -CF 2 CF} 3, -CF 2 CHF 2, - (CF 2) 2 CF 3, - (CF 2) 3 CF 3, - (CF 2) 4 CF 3, _{- (CF 2) 5 CF 3} , - (CF 2) 6 CF 3, - (CF 2) 7 CF 3, - (CF 2) 8 CF 3, - (CF 2) 9 CF 3, (CF 2) 11 CF _3, and _- the like _{(CF 2)} 15 _{CF 3.}

  A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by Formula 1 includes the Rf group (a) represented by Formula 2.

_{-C p-1 F 2 (p} -1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 2
In Formula 2, p represents an integer of 2 or 3, and is the same for each unit surrounded by n, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

As Rf group represented by Formula 2 (a), the _{specific, -CF 2 O (CF 2 CF} 2 O) n-1 CF 3 (n is _{2~9), - CF (CF 3} ) O ( _{CF 2 CF (CF 3) O} ) n-1 C 6 F 13 (n is _{2~6), - CF (CF 3} ) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n 2 to 6) are preferable from the viewpoint of ease of synthesis.
The Rf groups (a) in the fluororesin may all be the same or different.
1-60 mass% is preferable and, as for content of the fluorine atom in a fluorine-containing resin, 5-40 mass% is more preferable. Within such a range, the fluorine-containing resin exhibits good ink repellency, and the developability of the photosensitive composition for the separating wall becomes good.

The fluorine-containing resin has an acidic group (b).
As the acidic group (b), at least one acidic group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group or a salt thereof is preferable.

  The fluorine-containing resin includes a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a), and a single unit based on a monomer having an ethylenic double bond and an acidic group (b). A copolymer containing a monomer unit and having an acid value of 1 to 300 mgKOH / g is preferable. Examples of the ethylenic double bond include a (meth) acryloyl group, a vinyl group, and an allyl group.

As a monomer having an ethylenic double bond and an Rf group (a),
CH ₂ = CR ¹ COOQ ² Rf, CH ₂ = CR ¹ OCOQ ¹ Rf, CH ₂ = CR ¹ OQ ¹ Rf, CH ₂ = CR ¹ CH ₂ OQ ¹ Rf, CH ₂ = CR ¹ COOQ ² NR ¹ SO ₂ Rf CH ₂ = CR ¹ COOQ ² NR ¹ CORf, CH ₂ = CR ¹ COOQ ² NR ¹ COOQ ² Rf, CH ₂ = CR ¹ COOQ ² OQ ¹ Rf, and the like. However, R ¹ represents a hydrogen atom or a methyl group, Q ¹ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and Q ² represents a divalent organic group having 1 to 6 carbon atoms. Q ¹ and Q ² may have a cyclic structure.

As specific examples of Q ¹ and Q ² ,
_{-CH 2 -, - CH 2 CH} 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3) -, - CH ₂ CH ₂ CH ₂ CH ₂ —, —CH (CH ₂ CH ₂ CH ₃ ) —, —CH ₂ (CH ₂ ) ₃ CH ₂ —, —CH (CH ₂ CH (CH ₃ ) ₂ ) —, —CH _{2 CH (OH) CH 2 -,} - CH 2 CH 2 NHCOOCH 2 -, - CH 2 CH (OH) CH 2 OCH 2 - and the like. Q ¹ may be a single bond.
From the viewpoint of ease of _{synthesis, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH (OH) CH 2 - is preferred.

Specific examples of the monomer having an ethylenic double bond and an Rf group (a) include the following.
_{CH 2 = CHCOOCH 2 CF 2 O} (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = CHCOOCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n _-1 C ₆ F ₁₃ (n is _{2~6), CH 2 = CHCOOCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is 2-6).

_{CH 2 = C (CH 3)} COOCH 2 CH 2 NHCOOCH 2 CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = C (} CH 3) COOCH 2 CH 2 NHCOOCH _{2 CF (CF 3) O (} CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is _{2~6), CH 2 = C (} CH 3) COOCH 2 CH 2 NHCOOCH 2 CF (CF 3 _{) O (CF 2 CF (CF} 3) O) n-1 C 6 F 13 (n is 2-6).

_{CH 2 = C (CH 3)} COOCH 2 CH (OH) CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = C (} CH 3) COOCH _{2 CH (OH) CH 2 OCH} 2 CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 6 F 13 (n is _{2~6), CH 2 = C (} CH 3) COOCH 2 _{CH (OH) CH 2 OCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is 2-6).

  The content of the monomer unit based on the monomer having an ethylenic double bond and an Rf group (a) in the fluororesin is preferably 1 to 95%, more preferably 5 to 80%, and more preferably 20 to 60%. % Is more preferable. Within such a range, the fluororesin exhibits good ink repellency, and the developability of the photosensitive composition for the separating wall becomes good.

  Examples of the monomer having an acidic group (b) include a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, a sulfonic acid group, and a monomer having a hydroxyl group.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These may be used alone or in combination of two or more.

  Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition, one or more hydrogen atoms of these benzene rings are an alkyl group such as a methyl group, an ethyl group or an n-butyl group, an alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group, a halogen atom or an alkyl group. Examples thereof include compounds in which one or more hydrogen atoms are substituted with a halogen atom, a haloalkyl group, a nitro group, a cyano group, or an amide group. These may be used alone or in combination of two or more.

  Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, and (meth) acrylic acid-2-sulfoethyl. , (Meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, or salts thereof. These may be used alone or in combination of two or more.

  Specific examples of the monomer having a hydroxyl group include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydro Shimechiru (meth) acrylamide, N, N-bis (hydroxymethyl), and the like.

Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _g H (where g is an integer of 1 to 100, the same shall apply hereinafter), CH ₂ = CHOC ₄ H ₈ O (C _{2 H 4 O) g H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) g H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) g H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _k H (where h is 0 or an integer from 1 to 100, k is an integer from 1 to 100, h + k is from 1 to 100. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 O) h (C 3 H 6 O) k H and the like. These may be used alone or in combination of two or more.

  The content of the monomer unit based on the monomer having an acidic group (b) in the fluororesin is preferably 0.1 to 40%, more preferably 0.5 to 30%, and 1 to 20%. Further preferred. Within such a range, the fluororesin exhibits good ink repellency, and the developability of the photosensitive composition for the separating wall becomes good.

  Monomer based on monomer unit based on monomer having fluorine-containing resin having ethylenic double bond and Rf group (a), and monomer having ethylenic double bond and acidic group (b) In the case of a copolymer having a body unit, it has a monomer unit based on a monomer having no Rf group (a) and acidic group (b) (hereinafter referred to as “other monomer”). You may do it.

  Other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides, aromatic Examples include vinyl compounds, chloroolefins, fluoroolefins, and conjugated dienes. These compounds may contain a functional group, and examples thereof include a hydroxyl group, a carbonyl group, an alkoxy group, and an amide group. Moreover, you may have group which has a polysiloxane structure. However, monomer units based on these other monomers do not have an Rf group (a) and an acidic group (b). These may be used alone or in combination of two or more. In particular, (meth) acrylic acid esters and (meth) acrylamides are preferable because they are excellent in the heat resistance of the coating film formed from the photosensitive composition for the separation wall.

  In the fluororesin, the proportion of monomer units based on other monomers is preferably 80% or less, and more preferably 70% or less. Within this range, the developability of the photosensitive composition for the separating wall is improved.

  The fluororesin in the present invention is a monomer unit based on a monomer having the above ethylenic double bond and Rf group (a), and a single unit having an ethylenic double bond and an acidic group (b). In addition to being obtained by synthesizing a copolymer containing monomer units based on a monomer, a compound having an Rf group (a) and / or a compound having an acidic group (b) in a polymer having a reactive site It can also be obtained by various modification methods to be reacted.

  As various modification methods for reacting a compound having an Rf group (a) with a polymer having a reactive site, for example, a monomer having an epoxy group is copolymerized in advance, and then an Rf group (a) and a carboxyl group are later included. Examples thereof include a method of reacting a compound and a method of previously copolymerizing an epoxy group-containing monomer and then reacting a compound having an Rf group (a) and a hydroxyl group.

  Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

Examples of the compound having an Rf group (a) and a carboxyl group include compounds represented by the following formula 3.
_{HOOC-C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 Equation 3
In Formula 3, p is an integer of 2 or 3, q is an integer of 1 to 20, and n is an integer of 2 to 50.

Examples of the compound having an Rf group (a) and a hydroxyl group include compounds represented by the following formula 4.
_{HOCH 2 -C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 Equation 4
In Formula 4, p represents an integer of 2 or 3, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

  Examples of various modification methods for reacting a polymer having a reactive site with a compound having an acidic group (b) include a method in which a monomer having a hydroxyl group is copolymerized in advance and then an acid anhydride is reacted. Moreover, the method of making the acid anhydride which has an ethylenic double bond copolymerize previously, and making the compound which has a hydroxyl group react later is mentioned.

  Specific examples of the monomer having a hydroxyl group include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydro Shimechiru (meth) acrylamide, N, N-bis (hydroxymethyl), and the like.

Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _g H (where g is an integer of 1 to 100, the same shall apply hereinafter), CH ₂ = CHOC ₄ H ₈ O (C _{2 H 4 O) g H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) g H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) g H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _k H (where h is 0 or an integer from 1 to 100, k is an integer from 1 to 100, h + k is from 1 to 100. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 O) h (C 3 H 6 O) k H and the like. These may be used alone or in combination of two or more.

  Specific examples of the acid anhydride include phthalic anhydride, 3-methylphthalic anhydride, trimellitic anhydride, and the like.

  Specific examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6 anhydride -Tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, etc. are mentioned.

  The compound having a hydroxyl group may be a compound having one or more hydroxyl groups. Specific examples of the monomer having a hydroxyl group shown above, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol and ethylene glycol; cellsolves such as 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol; 2- (2-ethoxyethoxy) ethanol; And carbitols such as (2-butoxyethoxy) ethanol. A compound having one hydroxyl group in the molecule is preferred. These may be used alone or in combination of two or more.

  The polymer having the reactive site, which is a fluorine-containing resin or a precursor of the fluorine-containing resin, is reacted by dissolving the monomer in a solvent together with a chain transfer agent as necessary and heating, and adding a polymerization initiator. It can be synthesized by the method.

  The acid value of the fluororesin is preferably 1 to 300 mgKOH / g, more preferably 5 to 200 mgKOH / g, and particularly preferably 10 to 150 mgKOH / g. Within this range, the developability of the photosensitive composition for the separating wall is improved. In addition, an acid value is the mass (unit mg) of potassium hydroxide required in order to neutralize 1 g of resin, and a unit is described in this specification as mgKOH / g.

  The number average molecular weight of the fluororesin is preferably 500 or more and less than 20000, and more preferably 2000 or more and less than 15000. Within this range, the developability of the photosensitive composition for the separating wall is good. The number average molecular weight is measured using polystyrene as a standard substance by gel permeation chromatography.

(Silicon-containing compound)
Examples of the silicon-containing compound that can be used in the present invention include silicon-based monomers having a Si—CH ₃ group or an —O—Si—CH ₃ group. Specifically a silicone acrylate or silicone methacrylate, the general formula _{(CH 3 O) n Si (} CH 3) 3-n -R 3 -O-CO-CR 4 = deli those represented by CH _2, R ³ is a linking group, R ⁴ is methyl or hydrogen, and n is an integer of 0 to 3. In addition, for example, silicone monomers described in paragraph No. [0025] of JP-A No. 2003-335984 can also be cited as suitable.

  The blending amount of the fluorine-containing resin and / or silicon-containing compound is preferably from 0.01 to 50%, more preferably from 0.1 to 30%, more preferably from 0.1 to 30%, based on the solid content in the photosensitive composition for the separation wall. 2 to 10% is particularly preferable. Within this range, the photosensitive composition for the separating wall exhibits good ink repellency and ink falling properties, and developability becomes good.

  In addition to the above, the ink repellent treatment can also be achieved by the method of mixing the water repellent material described in paragraphs 0007 to 0044 of JP-A-7-35915 with the separation wall.

(2) <Method of providing ink repellent layer>
As a means for preventing “color mixing”, there is a method of producing an ink repellent layer (partition wall) having ink repellency at a position matching the separation wall on the substrate on which the separation wall is formed.

  A silicone rubber layer is preferably used as the partition wall having ink repellency. The silicone rubber layer coated on the surface layer is required to have a repulsive effect on the solution and ink used for coloring, but is not limited to this, but the number of molecular weights having the following repeating units: The main component is one thousand to several hundred thousand linear organic polysiloxane.

  Here, n is an integer of 2 or more, and R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or a phenyl group. Silicone rubber can be obtained by sparsely cross-linking such a linear organic polysiloxane. Cross-linking agents are acetoxy silane, ketoxime silane, alkoxy silane, amino silane, amido silane, alkenoxy silane, etc., used for so-called room temperature (low temperature) curable silicone rubber, and the terminal is usually a hydroxyl group as a linear organic polysiloxane. In combination with these, a deacetic acid type, a deoxime type, a dealcohol type, a deamine type, a deamide type, and a deketone type silicone rubber are obtained. In addition, a small amount of an organic tin compound or the like is added to the silicone rubber as a catalyst. Various layers may be used as an adhesive layer between the photosensitive composition layer for the separating wall and the silicone rubber layer, and aminosilane compounds and organic titanate compounds are particularly preferable. Instead of providing an adhesive layer between the photosensitive composition layer for the separation wall and the silicone rubber layer, an adhesive component may be added to the silicone rubber layer. As this additional adhesive component, an aminosilane compound or an organic titanate compound can be used.

  Exposure for producing the partition wall is performed from the surface opposite to the surface on which the separation wall is provided, using the separation wall as a mask, and further, the incident UV light is scattered by diffusing the irradiated UV light. The resin is enlarged to act on the photosensitive resin so that the portion of the resin that is solubilized by photoreaction becomes larger on the surface side of the silicone rubber. After exposure in this manner, a partition wall having a silicone rubber surface layer can be prepared by developing with an n-heptane / ethanol mixture.

(3) <Method of imparting ink repellency by plasma treatment>
As means for preventing “color mixing”, there is a method of performing ink repellent treatment by plasma on a substrate on which a separation wall is formed.

As the gas containing at least fluorine atoms to be introduced in this step, one or more halogen gases selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ are used. It is preferable. In particular, C ₅ F ₈ (octafluorocyclopentene) has an ozone depletion ability of 0, and at the same time, has an atmospheric life (CF ₄ : 50,000 years, C ₄ F ₈ : 3200 years) as compared with conventional gases. It is very short with 98 years. Therefore, the global warming potential is 90 (100-year integrated value assuming CO ₂ = 2), which is very small (CF ₄ : 6500, C ₄ F ₈ : 8700) compared with conventional gases, and the ozone layer and the global environment It is extremely effective for protection and is desirable for use in the present invention.

Further, as the introduced gas, a gas such as oxygen, argon, or helium may be used in combination as necessary. In this step, when a mixed gas of at least one halogen gas selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ and O ₂ is used, It becomes possible to control the degree of ink repellency on the surface of the image separation wall processed in this step. However, in the mixed gas, the oxidation reaction mixture ratio by O ₂ exceeds 30% of O ₂ is dominant, because the ink repellency enhancing effect is prevented, also, O ₂ mixing ratio is more than 30% When the mixed gas is used, it is necessary to use the mixture ratio of O ₂ within 30% or less.

  In addition, plasma generation methods such as low frequency discharge, high frequency discharge, and microwave discharge can be used. Conditions such as pressure, gas flow rate, discharge frequency, and processing time during plasma processing are arbitrarily set. can do.

(4) <Method of applying an ink repellent material to the upper surface of the separation wall>
As a means for preventing “color mixing”, there is a method in which an ink-repellent material is applied to the entire surface of a substrate on which a separation wall is formed.
Materials having ink repellency include fluorine resin such as polytetrafluoroethylene, silicone rubber, perfluoroalkyl acrylate, hydrocarbon acrylate, methyl siloxane, etc., which are generally considered ink repellent materials, and have a contact angle with a colored liquid composition. If it is a thing of 50 degrees or more, it will not specifically limit.

  As a method for applying the ink repellent material, it is possible to select an optimum method for each material such as slit coat, spin coat, dip coat, roll coat, etc., as long as it does not affect the substrate, the separation wall, etc. is there.

Next, UVO ₃ treatment is performed through the separation wall from the side opposite to the surface on which the separation wall is provided on the substrate, and the ink repellent film on portions other than the separation wall is selectively removed or the parent ink. Treatment (the contact angle to the colorant is 30 ° or more before and after the treatment).

  If the ink repellent material can be removed or hydrophilized, the patterning method can be selected according to the material, such as laser ablation, plasma ashing, dry treatment such as corona discharge treatment, and wet treatment using alkali. Is possible. Further, if it is possible to pattern an ink repellent material on the image separation wall, a lift-off method or the like is also effective.

(5) <Method of incorporating an ink repellent compound in the adjacent layer>
As a means for preventing “color mixing”, a photosensitive transfer material (hereinafter referred to as a multilayer film for ink repellent treatment) comprising at least an adjacent layer and a photosensitive composition layer for a separating wall in this order on a temporary support. There is a method for forming the separation wall of the present invention. It is preferable to provide the thermoplastic resin layer between the temporary support and the adjacent layer from the viewpoint of improving the adhesion at the time of pressure bonding. By forming the separation wall using the multilayer film for ink repellent treatment, it is possible to impart ink repellency only to the upper surface of the separation wall.

  In the multilayer film for ink repellent treatment, a polymerizable group is used for the purpose of preventing mixing of components at the time of application of a plurality of application layers and storage after application, and for the purpose of performing ink repellent treatment on the surface of the separation wall. It is preferable to provide an adjacent layer containing the ink repellent compound. The adjacent layer is preferably water-based (25% or more of the solvent is water) from the viewpoint of coating with the photosensitive composition layer for the separating wall.

By coating the coating solution of the adjacent layer with a fluorine compound having a polymerizable group, the fluorine compound having a polymerizable group is concentrated at the air interface, and a photosensitive composition layer for a separation wall is formed thereon. It can form and can contain more fluorine compounds which have a polymeric group in the interface by the side of the photosensitive composition layer for image separation walls in this adjacent layer. With this polymerizable group-containing fluorine compound and the initiator in the release wall photosensitive composition layer, ink repellency can be imparted only to the upper surface of the release wall photosensitive composition layer (= release wall). it can.
The following are mentioned as a preferable fluorine compound which has a polymeric group.

<High molecular compound having fluorine atom, polymerizable unsaturated double bond and alkali-soluble group / water-soluble group>
The polymer compound having a fluorine atom and a polymerizable unsaturated double bond is preferably soluble in an alkaline aqueous solution. In this case, it is possible to remove the unreacted polymer compound in the development step, which is troublesome. It is possible to provide a process with few environmental compatibility. Furthermore, it is preferable to contain a water-soluble group in order to dissolve in the coating solution of the adjacent layer.
Such a polymer compound used in the present invention is a copolymer of a fluorine-containing monomer part and a double bond-containing part, and preferably further includes a hydrophilic monomer part.
The polymer compound can be synthesized as follows.

  As the synthesis method, first, an oil-repellent monomer such as a fluorine-containing monomer is used, and (a) a method of copolymerizing a fluorine-containing monomer, a hydrophilic monomer, and a monomer having an ethylene addition polymerizable unsaturated group in the side chain, b) a method in which a fluorine-containing monomer, a hydrophilic monomer and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like; (c) a hydrophilic functional group such as a carboxylic acid; And a method of reacting a fluorine polymer having a compound having an ethylene addition polymerizable unsaturated group. Among these, from the viewpoint of synthesis suitability, (a) a method of reacting a fluorine-containing monomer, a hydrophilic monomer, and a monomer having an ethylene addition polymerizable unsaturated group is particularly preferable.

When the radically polymerizable group-containing fluorine-containing polymer compound is synthesized by the method (a), examples of the monomer having an ethylene addition polymerizable unsaturated group to be copolymerized include an allyl group-containing monomer, specifically, , Allyl (meth) acrylate, and 2-allyloxyethyl methacrylate.
Examples of the monomer having a double bond precursor used in the method (b) include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate and 2- (2-bromo-2-methyl-1). -Oxopropoxy) ethyl methacrylate.
The method of “introducing a double bond by treatment with a base” will be described in more detail. A copolymer of a monomer having a fluorine-containing monomer, a hydrophilic monomer, and a double bond precursor by acting a base. From this, the deoxidation reaction is promoted to convert the double bond precursor into a double bond. Here, inorganic and organic bases can be used as the base, and organic bases are preferable. In particular, tertiary alkylamines such as triethylamine, diisopropylethylamine, diazabicycloundecene, diazabicyclononene, and the like are used. Can do.
Further, when the fluorine-containing polymer compound is synthesized by the method (c), the reaction is not performed by utilizing the reaction between a carboxyl group, an amino group or a salt thereof in the fluoropolymer and a functional group such as a hydroxyl group and an epoxy group. Examples of the monomer having an addition polymerizable unsaturated group used for introducing a saturated group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.
In general, as a monomer having an ethylene addition polymerizable unsaturated group, from the viewpoint of increasing the sensitivity of the ink repellent reaction, a monomer having a more reactive ethylene addition polymerizable unsaturated group or a longer chain monomer may be used. preferable.

The method for synthesizing the fluorine-containing polymer compound will be described in more detail.
(Fluorine-containing monomer)
The fluorine-containing monomer used as a raw material for the fluorine-containing polymer compound is at least one selected from the group consisting of the following general formulas (I), (II), (III), (IV) and (V) And fluorine-containing monomers.
CH ₂ = CR ¹ COOR ² R ^f (I)
Wherein, ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} is _{-C p H 2p -, - C} (C p H 2p + 1) H -, - CH 2 C (C p H 2p + 1) H- or -CH ₂ CH ₂ O-, the ^{_{R f -C n F 2n + 1}} , - (CF 2) n H, -C n F 2n + 1 -CF 3, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF 2 ) is a _{p OC m H 2m C i F} 2i H, -N (C p H 2p + 1) COC n F 2n + 1, -N (C p H 2p + 1) SO 2 C n F 2n + 1. However, p is 1-10, n is 1-16, m is 0-10, i is an integer of 0-16. ]

CF ₂ = CFOR ^g (II)
(Wherein R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
CH ₂ = CHR ^g (III)
(Wherein R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
^{_{CH 2 = CR 3 COOR 5 R}} j R 6 OCOCR 4 = CH 2 ··· (IV)
^Wherein, R 3, ^{R 4} is a hydrogen atom or a methyl ^group, R 5, ^{R 6} is _{-C q H 2q -, - C} (C q H 2q + 1) H -, - CH 2 C (C q H 2q + 1) H- or _-CH 2 _CH 2 O-, the ^{R j} is _-C t _{F 2t.} However, q is an integer of 1 to 10, and t is an integer of 1 to 16. ]
CH ₂ = CHR ⁷ COOCH ₂ (CH ₂ R ^k ) CHOCOCR ⁸ = CH ₂ (V)
^(Wherein, R 7, ^{R 8} represents a hydrogen atom or a methyl group, the ^{R k} is _-C y _{F 2y + 1.} However, y is 1 to 16 integer.)

Hereinafter, although the specific example of the fluorine-containing monomer which can be used for this invention is given, this invention is not restrict | limited to this.
Examples of the monomer represented by the general formula (I) include CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ CH _2. OCOC (CH ₃ ) ═CH ₂ , C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOC (CH ₃ ) = CH _{2, CF 3 (CF 2)} 4 CH (CH 3) OCOC (CH 3) = CH 2, CF 3 CH 2 OCH 2 CH 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH═CH ₂ , (CF ₃ ) ₂ CFO (CH ₂ ) ₅ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ OCH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , C ₂ F ₅ CON (C ₂ H _{5) CH 2 OCOCH = CH 2} , CF 3 (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, H (CF 2) 6 C (C 2 H 5) OCOC (CH 3 _{) = CH 2, H (CF} 2) 8 CH 2 OCOCH = CH 2, H (CF 2) 4 CH 2 OCOCH = CH 2, H (CF 2) CH 2 OCOC (CH 3) = CH 2, C _{3 (CF 2) 7 SO 2} N (CH 3) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 10 OCOCH = CH 2, _{C 2 F 5 SO 2 N (} C 2 H 5) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 4 OCOCH = CH 2, _{C 2 F 5 SO 2 N (} C 2 H 5) C (C 2 H 5) HCH 2 OCOCH = CH 2 and the like.

Examples of the fluoroalkylated olefin represented by the general formulas (II) and (III) include C ₃ F ₇ CH═CH ₂ , C ₄ F ₉ CH═CH ₂ , C ₁₀ F ₂₁ CH═CH ₂ , C such as _{3 F 7 OCF = CF 2,} C 7 F 15 OCF = CF 2 and _C 8 _F 17 OCF = CF ₂ and the like.

The monomer represented by the general formula (IV) and (V) for _{example, CH 2 = CHCOOCH 2 (CF} 2) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 CH (CH 2 C 8 F 17) OCOCH = CH _{2 and the} like can be mentioned.
From the viewpoint of increasing the ink repellency, it is preferable that the perfluoro group has a larger number of main chain carbon atoms. Six or more are particularly effective. _{Specifically, CF 3 (CF 2) 7} CH 2 CH 2 OCOCH = CH 2, C 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOC (CH ₃ ) ═CH ₂ , H (CF ₂ ) ₆ C (C ₂ H ₅ ) OCOC (CH ₃ ) ═CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCH═CH _2, CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF _{2 7 SO 2 N (CH 3)} (CH 2) 10 OCOCH = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 4 OCOCH = CH 2, C 10 F 21 CH = CH 2 C ₇ F ₁₅ OCF═CF ₂ and C ₈ F ₁₇ OCF═CF _{2 ,} CH ₂ ═CHCOOCH ₂ CH (CH ₂ C ₈ F ₁₇ ) OCOCH═CH _{2 and the} like.

Moreover, it is also preferable that the terminal of a perfluoro group is a fluorine atom. Specifically, as the monomer represented by the general formula (I), for example, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) _{4 CH 2 CH 2 OCOC (CH 3} ) = CH 2, C 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH _{2 OCOC (CH 3) = CH 2} , (CF 3) 2 CF (CF 2) 6 (CH 2) 3 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 10 (CH 2) 3 OCOC (CH _{) = CH 2, CF 3 (} CF 2) 4 CH (CH 3) OCOC (CH 3) = CH 2, CF 3 CH 2 OCH 2 CH 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) ₂ CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CFO (CH ₂ ) ₅ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ OCH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , C ₂ F ₅ CON ( _{C 2 H 5) CH 2 OCOCH} = CH 2, CF 3 (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, H (CF 2) 6 C (C 2 H 5) OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) ( C H ₂ ) ₁₀ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) ( _{CH 2) 4 OCOCH = CH 2} , C 2 F 5 SO 2 N (C 2 H 5) C (C 2 H 5) HCH 2 OCOCH = CH 2, C 3 F 7 CH = CH 2, C 4 F 9 CH ═CH ₂ , C ₁₀ F ₂₁ CH═CH ₂ , C ₃ F ₇ OCF═CF ₂ , C ₇ F ₁₅ OCF═CF ₂ , C ₈ F ₁₇ OCF═CF _{2 and the} like.

In addition, from the viewpoint of good compatibility with other components in the adjacent layer, it is also preferable to contain S, N, and the like. Specifically, C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ), C ₂ F ₅ CON (C ₂ H ₅ ) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₂ CON (CH ₃ ) CH (CH ₃ ) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC ( _{CH 3) = CH 2, CF} 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 10 OCOCH = CH 2, C 2 F 5 SO 2 N (C 2 H 5) CH 2 CH 2 OCOC ( CH ₃₎ = CH _{, CF 3 (CF 2) 7} SO 2 N (CH 3) (CH 2) 4 OCOCH = CH 2, C 2 F 5 SO 2 N (C 2 H 5) C (C 2 H 5) HCH 2 OCOCH = CH ₂ etc. are mentioned.

(Hydrophilic monomer)
As the hydrophilic monomer used when synthesizing the polymer compound having the oil-repellent and ink-repellent functional groups of the present invention and a polymerizable unsaturated double bond and capable of swelling in alkaline water or water, The following monomers can be mentioned.
The hydrophilic monomer useful in the present invention is a monomer having a positive charge such as ammonium or phosphonium, or a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group. In addition, monomers having a nonionic group such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, a cyano group, and an ethylene oxide group may be used. It can also be used.

In the present invention, specific examples of particularly useful hydrophilic monomers include the following monomers. For example, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt Vinyl sulfonic acid or its alkali metal salt and amine salt, styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and amine salt 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salts and amine salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or their salts, 2-dimethylaminoethyl (medium) ) Acrylate or its hydrohalide, 3-trimethylammoniumpropyl (meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) ) Ammonium chloride, etc. can be used. In addition, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) ) Acrylate is also useful.
Of these, nonionic ones are more preferable because they are less likely to be mixed with impurities into the liquid crystal layer. Specifically, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol A mono (meth) acrylate can be mentioned.

(Other monomers)
The polymer compound having a fluorine atom and a polymerizable unsaturated double bond of the present invention may be copolymerized with other monomers in addition to the fluorine atom and the polymerizable unsaturated double bond group. These monomers are used to increase the solvent solubility of the polymer compound of the present invention. Although it does not specifically limit as a monomer used for such a purpose, Acrylic acid ester, such as (meth) acrylic acid methyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid methoxyethyl ester, is used. be able to.
In addition, since the polymer compound having a fluorine atom and a polymerizable unsaturated double bond of the present invention has a lower Tg, ink repellency is more likely to proceed, so that such a monomer is copolymerized. Is also preferable. Alkyl (3 or more carbon atoms) acrylates can be used.

  Examples of the polymer compound having the fluorine atom and polymerizable unsaturated double bond in the side chain used in the present invention [Exemplary compounds (1) to (15)] are shown below. However, the present invention is not limited to these.

  The molecular weight (Mw) of the polymer compound having a fluorine atom and a polymerizable unsaturated double bond that can be used in the present invention is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 2,000 to 100,000. Most preferred is 2000 to 40,000. Within this molecular weight range, an excellent ink repellency effect and solubility in a solution can be achieved. If the molecular weight is less than 1000, it is difficult to achieve both ink repellency and solubility. If it is larger than 1,000,000, the solubility is poor, which is not preferable.

(6) <Method of exposure by immersion in an ink repellent compound solution having a polymerizable group>
As a means to prevent “color mixing”, the separation wall after pattern formation is brought into contact with an ink-repellent compound having a polymerizable group, and in the state of contact, the upper surface of the separation wall from the side on which the separation wall is formed There is a method of exposing. By exposure, the ink repellent compound having a polymerizable group can be fixed on the upper surface of the separation wall.

[Ink-repellent compound having a polymerizable group]
In this step, as the ink repellent compound to be brought into contact with the substrate on which the pattern is formed, any compound having a polymerizable group and an ink repellent functional group can be used. It may have any form such as a macromer or an oligomer.

  Examples of the polymerizable ink repellent compound that satisfies the above requirements include the aforementioned fluorine-containing monomers and the aforementioned silicon-containing compounds.

A method for fixing a polymerizable ink repellent compound such as a fluorine-containing monomer or a silicone-containing monomer on the upper surface of the separation wall will be described.
A polymerizable ink repellent compound may be brought into contact with the upper surface of the separation wall and exposed. At this time, it may be carried out in the so-called solvent-free state in which the polymerizable ink repellent compound is provided alone, but may be brought into contact as a composition containing another solvent or additive. From the viewpoint of handling properties, it may be diluted with a solvent in which such a polymerizable ink repellent compound is dissolved. Although there is no restriction | limiting in particular in the solvent used here, Methanol, acetone, methyl ethyl ketone, ethanol, propanol, etc. are preferable.
As a method for bringing the polymerizable ink repellent compound into contact with the upper surface of the separation wall, it is convenient to immerse the separation wall substrate after pattern formation in a liquid (solution) of the polymerizable ink repellent compound. In this case, it is preferable to clean the substrate after exposure.

In the separation wall of the present invention, the ink repellent compound is preferably a fluorine-containing compound and / or a silicon-containing compound.
When a fluorine-containing compound is used as the ink repellent compound, a compound containing a perfluoroalkyl group having 4 to 10 carbon atoms is preferably used as the fluorine-containing compound. In this case, the number of fluorine atoms / number of carbon atoms on the upper surface of the separation wall measured by ESCA is preferably 0.10 or more, and more preferably 0.30 or more.

  When using a silicon-containing compound as the ink repellent compound, it is preferable to use silicone as the silicon-containing compound. In this case, the number of silicon atoms / number of carbon atoms on the upper surface of the separation wall measured by ESCA is preferably 0.10 or more, and more preferably 0.30 or more.

  Among the ink repellent treatment methods (1) to (6) above, (1) and (5) from the viewpoint of “simplification of the process”, and (5) from the viewpoint of giving anisotropy to the ink repellency. However, (6) is preferable from the viewpoint of strong ink repellency.

<Color filter>
The color filter of the present invention includes a substrate, a plurality of colored pixels formed by applying droplets of a colored liquid composition on the substrate, and a separation wall of the present invention that separates the colored pixels. Have.
The method for producing the color filter of the present invention is not particularly limited, and the liquid droplets of the colored liquid composition for forming the RGB pixels are formed in the gaps in the separation wall formed in the development step. If it has the process to provide to, it will not specifically limit. As a method for imparting droplets of the colored liquid composition to the gap, a known method such as an ink jet method or a stripe Geyser coating method can be used, and the ink jet method is preferable in terms of cost.

  Further, the shape of the separation wall may be fixed before forming each pixel in this way, and the means is not particularly limited, and examples thereof include the following. That is, 1) re-exposure after development (sometimes referred to as post-exposure) 2) heat treatment after development, etc. The heat treatment here refers to heating a substrate having a separation wall in an electric furnace, a dryer or the like, or irradiating an infrared lamp.

Here, the exposure amount in the case of performing 1) above, 500 mJ / cm ² or more preferably 1000 mJ / cm ² or more, more preferably 3000 mJ / cm ² or more is most preferable. If it is 500 mJ / cm ² or less, the shape becomes round, and it is not preferable because the ink oozes out, color mixing, and pixel boundary disturbance easily occur. Although there is no upper limit to the exposure amount when performing re-exposure, it is preferable to set it to 10000 mJ / cm ² or less in that exposure takes too much time when the exposure amount is large. In the case of an oxygen-poor atmosphere, exposure can be performed with a lower exposure amount.
Similarly, the heating temperature in the case of 2) is 100 to 250 ° C., preferably about 120 to 240 ° C., and the heating time is about 10 to 20 minutes. When the temperature is lower than 100 ° C., there is a concern that the separation wall does not cure, and when it is higher than 250 ° C., there is a concern that the shape of the separation wall may be destroyed.

  Regarding the ink jet method used for forming each pixel, a known method such as a method of thermally curing ink, a method of photocuring, or a method of performing droplet ejection after forming a transparent image receiving layer on a substrate in advance is used. be able to.

  Preferably, after each pixel is formed, a heating step of performing a heat treatment (so-called baking treatment) is provided. That is, the substrate after pixel formation is heated in an electric furnace, a dryer or the like, or irradiated with an infrared lamp. The temperature and time of heating depend on the composition of the photosensitive composition for the separating wall and the thickness of the formed layer, but generally from about 120 ° C. to about 250 ° C. from the viewpoint of obtaining sufficient solvent resistance and strength. It is preferable to heat at about 10 minutes to about 120 minutes.

  The pattern shape of the color filter formed in this way is not particularly limited, and even with a general delta arrangement (FIG. 1A) as shown in FIG. 1 (B)).

The ink jet system used in the present invention includes a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and an ink is intermittently heated by using its foam. Various methods such as a method of injecting the ink can be employed.
The ink used can be oily or water-based. Moreover, the coloring material contained in the ink can use both dyes and pigments, and the use of pigments is more preferable from the viewpoint of durability. In addition, a coating-type colored ink (colored resin composition, for example, described in JP-A No. 2005-3861 [0034] to [0063]) or JP-A No. 10-195358 [0009] is used for producing a known color filter. ]-[0026] The inkjet composition as described above can also be used.
In consideration of the process after coloring, a component that is cured by heating or that is cured by energy rays such as ultraviolet rays can be added to the ink in the present invention. Various thermosetting resins are widely used as components that are cured by heating, and examples of components that are cured by energy rays include those obtained by adding a photoinitiator to an acrylate derivative or a methacrylate derivative. In particular, in view of heat resistance, those having a plurality of acryloyl groups and methacryloyl groups in the molecule are more preferable. These acrylate derivatives and methacrylate derivatives are preferably water-soluble, and even those that are sparingly soluble in water can be used after being emulsified.
In this case, a photosensitive composition for a separating wall containing a colorant such as a pigment can be suitably used.

  Further, as the ink that can be used in the present invention, a thermosetting ink for a color filter containing at least a binder and a bifunctional to trifunctional epoxy group-containing monomer can also be used as a suitable ink.

The color filter in the present invention is preferably a color filter in which pixels are formed by an inkjet method, and it is preferable to form three color filters by spraying RGB three color inks.
This color filter is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.

  After the color filter is manufactured, an overcoat layer may be provided on the entire surface to improve resistance. The overcoat layer can protect the pixels of the inks R, G, and B and can flatten the surface, but is preferably not provided from the viewpoint of increasing the number of steps.

Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters usually has an acrylic resin as the main component, so that the acrylic resin composition is excellent in adhesion. Things are desirable.
Examples of the overcoat layer include those described in paragraphs 0018 to 0028 of JP-A No. 2003-287618, and commercially available overcoat agents such as “Optomer SS6699G” manufactured by JSR.

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

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

  The display device of the present invention can be applied to applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile phones such as mobile phones, digital cameras, car navigation systems, and the like without particular limitations.

    The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

[Production method of pigment dispersion for separation wall]
<Preparation of silver fine particle dispersion (dispersion K-1)>
The following alkali-soluble polymer PO-1 was added to 1000 mL of water adjusted to pH 9.0 with a 1N NaOH solution so as to be 6.0 × 10 ⁻³ % (W / W) and stirred. Then, 50 mL of 1.0 mol / L silver nitrate aqueous solution was added over 30 seconds, and then 50 mL of 1.0 mol / L sodium sulfite aqueous solution and 25 mL of 1.0 mol / L hydroquinone aqueous solution were added over 30 seconds to obtain a silver fine particle solution. Got.
Nitric acid was added dropwise to the silver fine particle solution to adjust the pH to 4, and the silver fine particles were aggregated and settled.
The supernatant liquid of the above-mentioned silver fine particle liquid was removed, 750 mL of distilled water was added thereto, and allowed to stand for 120 minutes to remove the supernatant again. This was repeated 4 times.

Methyl ethyl ketone was added to the silver fine particles so that the amount of silver was 8% by mass, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a “Sonifer II type” ultrasonic homogenizer manufactured by Branson.
Then, 40 kHz ultrasonic waves were irradiated for 10 minutes with a “Model 2000bdc-h 40: 0.8 type ultrasonic homogenizer” manufactured by Branson to obtain a silver fine particle dispersion (dispersion K-1).
During the ultrasonic irradiation, the liquid was cooled by COOLNICS CTW400 manufactured by Yamato Scientific Co., Ltd. so that the liquid was maintained at 25 ° C.

<Preparation of silver tin alloy fine particle dispersion (dispersion K-2)>
In 1000 ml of pure water, 23.1 g of silver (I) acetate, 65.1 g of tin (II) acetate, 54 g of gluconic acid, 45 g of sodium pyrophosphate, 2 g of polyethylene glycol (molecular weight 3,000), and E735 (IS Japan ( Co., Ltd .; vinyl pyrrolidone / vinyl acetate copolymer) 5 g was dissolved to obtain solution 1. Separately, 36.1 g of hydroxyacetone was dissolved in 500 ml of pure water to obtain a solution 2.

While the solution 1 obtained above was vigorously stirred while maintaining at 25 ° C., the above solution 2 was added thereto over 2 minutes, and the stirring was continued gently for 6 hours. Then, the liquid mixture turned black, and metal particles having a silver-tin alloy part (hereinafter sometimes referred to as “silver-tin alloy part-containing particles”) were obtained. Subsequently, the silver tin alloy part containing particle | grains were disperse | distributed by operation of (A).
(A) Operation The liquid containing the metal particles was centrifuged to precipitate silver-tin alloy part-containing particles. Centrifugation is subdivided into a volume of 150 ml, and a rotational speed of 2,000 r. p. m. For 30 minutes. Then, the supernatant was discarded and the total liquid volume was made 150 ml. To this, 1350 ml of pure water was added and stirred for 15 minutes to re-disperse the silver-tin alloy part-containing particles. This operation (A) was repeated twice to remove soluble substances in the aqueous phase.

  Thereafter, the liquid was further centrifuged to precipitate silver tin alloy part-containing particles again. Centrifugation was performed under the same conditions as described above. After centrifuging, the supernatant was discarded as described above, the total liquid volume was made 150 ml, 850 ml of pure water and 500 ml of acetone were added thereto, and the mixture was further stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again.

Centrifugation was performed again in the same manner as described above to precipitate the silver-tin alloy part-containing particles. Then, the supernatant was discarded as described above to a liquid volume of 150 ml, and 150 ml of pure water and 1200 ml of acetone were added thereto, followed by further stirring for 15 minutes. Then, the silver tin alloy part-containing particles were dispersed again. Again, centrifugation was performed. The centrifugation conditions at this time are the same as described above except that the time is extended to 90 minutes. Thereafter, methyl ethyl ketone was added to the silver tin alloy fine particles so that the silver tin alloy was 8% by mass. This was dispersed for 6 hours using an Eiger mill (Eiger mill M-50 type (media: diameter 0.65 mm zirconia beads 130 g, manufactured by Eiger Japan Co., Ltd.)), and a dispersion of silver-tin alloy part-containing particles (dispersion K- 2) was obtained.
It was confirmed by X-ray scattering that the silver-tin alloy part-containing particles were a composite composed of an AgSn alloy (2θ = 39.5 °) and a Sn metal (2θ = 30.5 °). Here, the number in parentheses is the scattering angle of each (III) plane. As a result of observing the fine particle dispersion with a transmission electron microscope, the dispersion average particle size was about 40 nm in terms of number average particle size.

<Preparation of carbon black dispersion (dispersion K-3)>
In 80 cc of propylene glycol monomethyl ether acetate, 0.5 g of PO-2 below and a polymer (a random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000) were added and stirred for 30 minutes. Then, 13 g of carbon black (Nexex 35 manufactured by Degussa) was added while stirring, and stirred for 30 minutes to obtain a carbon black dispersion.

[Production Method of Separation Wall Composition (B-1)]
For the separation wall composition B-1, first, the dispersion K-1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 were weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 RPM for 10 minutes. Then, the amounts of methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) amino- described in Table 1 3-Bromophenyl] -s-triazine and Surfactant 1 are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at 150 RPM for 30 minutes at a temperature of 40 ° C. (± 2 ° C.). can get. In addition, the quantity of Table 1 is a mass part, and has the following composition in detail.

<Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

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

<Surfactant 1>
・ The following structure 1 30%

・ Methyl ethyl ketone 70%

[Production Method of Composition for Separation Wall (B-2)]
Separation wall composition B in the same manner as in [Production of separation wall composition (B-1)] except that dispersion K-2 is used instead of dispersion K-1 and the composition shown in Table 1 is used. -2 was obtained.

[Production Method of Composition for Separation Wall (B-3)]
Separation wall composition B in the same manner as in [Production of separation wall composition (B-1)] except that dispersion K-3 is used instead of dispersion K-1 and the composition shown in Table 1 is used. -3 was obtained.

[Example 1] (Transfer method)
[Production Method of Photosensitive Transfer Material K1]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an oxygen barrier layer coating solution having the following formulation P1 was applied and dried. Further, the separation wall composition B-1 was applied and dried. In this manner, a thermoplastic resin layer having a dry film thickness of 14.6 μm, an oxygen barrier layer having a dry film thickness of 1.6 μm, and a photosensitive for separating wall having a dry film thickness of 3.0 μm on the temporary support. Finally, a protective film (thickness 12 μm polypropylene film) was pressure-bonded.
In this way, a photosensitive transfer material in which the temporary support, the thermoplastic resin layer, the oxygen blocking layer, and the black (K) separation wall photosensitive composition layer were integrated was prepared, and the sample name was the photosensitive transfer material K1. It was.

<Coating liquid for thermoplastic resin layer: Formulation H1>
・ Methanol 11.1 parts ・ Propylene glycol monomethyl ether acetate 6.36 parts ・ Methyl ethyl ketone 52.4 parts ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.)
5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 1 part fluoropolymer _{(C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts of _{H (OCH (CH 3) CH} 2) 7 OCOCH = CH 2 55 parts of _{H (OCH 2 CH 2) 7} OCOCH = Copolymer with 5 parts of CH ₂ , average molecular weight 30,000, 30% solution of methyl ethyl ketone, manufactured by Dainippon Ink and Chemicals, Inc., trade name: Megafax F780F) 0.54 parts

<Coating liquid for oxygen barrier layer: prescription P1>
PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550) 32.2 partsPolyvinylpyrrolidone (APS Japan, K-30) 14.9 partsDistilled water 524 parts・ 429 parts of methanol

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

Next, development is performed with a 0.5% KOH aqueous solution to remove the unexposed portion of the photosensitive composition layer for the separation wall, the oxygen blocking layer, and the thermoplastic resin layer, and the black matrix pattern-like separation wall on the glass substrate. Got. Next, the entire surface was exposed with an exposure amount of 3100 mJ / cm ² from the surface side of the substrate where the separation wall was formed (post-exposure). Subsequently, heat treatment was performed at 220 ° C. for 10 minutes to obtain a separation wall having an optical density of 4.0.

Next, an ink repellent treatment was performed by the following method.
The fluorine-based monomer 2- (perfluorooctyl) -ethyl methacrylate (CHEMINOX FAMAC-8, manufactured by Unimatec) was dissolved in propanol to obtain a 5% solution.
The FAMAC-8 / propanol solution was dropped on the separation wall substrate and covered with a quartz plate from above to form a uniform liquid film. In this state, the entire surface was exposed with an exposure machine (USHIO INC.) Having an ultra-high pressure mercury lamp. The exposure amount was 3000 mJ / cm ² .
After the exposure, the quartz plate was removed, and the separation wall substrate was washed with propanol.
As a result, it was possible to form a separation wall having a fluorine compound only on the upper surface of the separation wall.

-Preparation of colored ink for pixel (colored liquid composition)-
Of the following components, first, a pigment, a polymer dispersant, and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels.
<Composition of colored ink composition for red pixel>
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (glycidyl methacrylate-styrene copolymer) 3 parts ・ First epoxy resin (novolak type epoxy resin) ,
Epicoat 154 manufactured by Yuka Shell Co., Ltd.) 2 parts, second epoxy resin (neopentyl glycol diglycidyl ether) 5 parts, curing agent (trimellitic acid) 4 parts, solvent: ethyl 3-ethoxypropionate 80 parts

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

  Next, using the color inks for R, G, and B pixels described above, an ink jet method is used in a region (a concave portion surrounded by a convex portion) partitioned by a separation wall of the color filter substrate obtained above. Was used to discharge the ink composition until the desired concentration was obtained, and a color filter composed of R, G, and B patterns was produced. The color filter after image coloring was baked in an oven at 230 ° C. for 30 minutes to completely cure the black matrix and each pixel.

In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap between the image separation walls, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found.
A transparent electrode made of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above by sputtering. Separately, a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively.
When the ITO resistance of this color filter was measured ("Loresta" manufactured by Mitsubishi Chemical Corporation; sheet resistance was measured by the four-probe method), it showed a very low value of 12Ω / □. This is presumably because the flatness of the black matrix surface was unexpectedly increased by using the present invention.

A photospacer was provided in a portion corresponding to the upper part of the separation wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
Then, after printing an epoxy resin sealant at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter and dropping the PVA mode liquid crystal and bonding it to the counter substrate The bonded substrate was heat treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

[Example 2]
A separation wall, a color filter, and a liquid crystal display device were obtained in the same manner as in Example 1 except that the separation wall composition B-2 was used instead of the separation wall composition B-1.

[Example 3]
A separation wall, a color filter, and a liquid crystal display device were obtained in the same manner as in Example 1 except that silicon-containing monomer FM0755 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of “CHEMINOX FAMAC-8”.

[Example 4] (Coating method)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle has the composition described in the above table. Image separation wall composition B-1 was applied. Subsequently, after a part of the solvent was dried by VCD (vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the EBR (edge bead remover) was unnecessary around the substrate. The coating solution was removed and prebaked at 120 ° C. for 3 minutes to obtain a photosensitive composition layer for a separating wall.
With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and the separation wall The distance from the photosensitive composition layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in a nitrogen atmosphere.

Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive composition layer for the separation wall, KOH developer (KOH, containing nonionic surfactant, trade name: CDK) −1, manufactured by Fuji Film Electronics Materials Co., Ltd.) 100 times diluted and shower-developed at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and post exposure was performed at an exposure amount of 1050 mJ / cm ^{2 in the} atmosphere to obtain an optical density of 4.0. A separation wall was obtained.
A color filter and a liquid crystal display device were obtained in the same manner as in Example 1 except that this separation wall was used.

[Comparative Example 1]
A separation wall, a color filter, and a liquid crystal display device were obtained in the same manner as in Example 1 except that the separation wall composition B-3 was used instead of the separation wall composition B-1.

[Comparative Example 2]
A separation wall, a color filter and a liquid crystal display device were obtained in the same manner as in Example 1 except that the ink repellent treatment using “CHEMINOX FAMAC-8” was not performed.

[Comparative Example 3]
A separation wall, a color filter, and a liquid crystal display device were obtained in the same manner as in Example 1 except that the dry film thickness of the photosensitive composition layer for the separation wall was 1.0 μm.

[Evaluation]
The following evaluation was performed using the separation wall, the color filter, and the liquid crystal display device obtained as described above. The obtained results are shown in Table 2.

[Evaluation of mixed colors and white spots]
The following evaluation was performed on 100 pixels of the obtained color filter. The evaluation of the color mixture was performed by 200 times observation with an optical microscope. The color mixture is the maximum landing position shift amount of the color filter in which color deviation or the ink remaining on the separation wall surface is not observed among the color filters drawn by shifting the shift amount x from the center of the pixel opening of the G head from 0 to 40 μm. Evaluated as a guideline.
The evaluation criteria for color mixing are as follows.
(Double-circle): The landing position deviation | shift amount in which the ink remainder is observed is 25 micrometers or more.
○: Landing position deviation amount at which ink residue is observed is 20 μm or more.
(Triangle | delta): The landing position shift | offset | difference amount in which the ink remainder is observed is 10 micrometers or more.
X: The amount of landing position deviation at which ink residue is observed is less than 5 μm.

The following evaluation was performed on 500 pixels of the obtained color filter. The evaluation of white spots was performed by 200 times observation with an optical microscope.
The evaluation criteria for white spots are as follows.
A: White spots are less than 5 places.
○: White spots are 5 or more and less than 10 places.
Δ: White spots are 10 or more and less than 50.
×: 50 or more white spots.

(Evaluation of display device)
The liquid crystal display device was evaluated by visual observation based on the following criteria.
<Evaluation criteria>
Good: Normal difficulty: Unevenness

(Detection of ink repellent compounds)
In each example / comparative example, a solid sample for measurement with a solid exposure at the same exposure as the pattern exposure was prepared, and the atomic ratio of the surface was ESCA (manufactured by ULVAC-PHI, PHI-5300, detection angle 45 °) Measured with In Example 3, (number of silicon atoms / number of carbon atoms) was measured, and (number of fluorine atoms / number of carbon atoms) was measured otherwise.

(Contact angle)
The contact angle can be measured with a contact angle meter DM300 manufactured by Kyowa Interface Science Co., Ltd. The measurement conditions are as described above.

(The height of the separation wall)
By using a contact-type surface roughness meter P-10 (manufactured by TENCOR), the height of the formed separation wall can be measured.

The color filter of the example had no color mixing. This is presumed to be an effect that the ink repellent compound is present on the upper surface of the separation wall (that is, the effect that the upper surface of the separation wall has ink repellency).
Further, a slight amount of ink was not observed, and the boundary between the RGB pixels was a very clear straight line (as in the mask).
The color filter of the comparative example had many mixed colors.

  According to the present invention, when forming each pixel, it is possible to prevent defects that cause defects such as bleeding and protrusion of each color ink, color mixture with adjacent pixels, and white spots, and a good color filter can be obtained.

FIG. 3 is a conceptual diagram showing a color filter pattern.

Claims (11)

A separation wall for separating a plurality of colored pixels formed by applying droplets of a colored liquid composition on a substrate,
A separation wall comprising metal fine particles, an upper surface having ink repellency, and a height from the substrate of 1.0 μm or more.   The at least one kind of the metal fine particles is a metal fine particle containing one or more metals selected from the group consisting of Group 2 to Group 14 of the Periodic Table. Painting wall.   The separation wall according to claim 1, wherein at least one of the metal fine particles is silver fine particles or alloy fine particles containing silver.   The separation wall according to any one of claims 1 to 3, wherein the ink repellent compound for expressing ink repellency on the upper surface is a fluorine-containing compound and / or a silicon-containing compound. .   The separation wall according to claim 4, wherein the fluorine-containing compound is a compound containing a perfluoroalkyl group having 4 to 10 carbon atoms.   6. The separation wall according to claim 4, wherein the number of fluorine atoms / number of carbon atoms on the upper surface measured by ESCA is 0.10 or more.   The separation wall according to claim 4, wherein the silicon-containing compound is silicone.   8. The separation wall according to claim 4, wherein the number of silicon atoms / number of carbon atoms on the upper surface measured by ESCA is 0.10 or more. A color filter having a substrate, a plurality of colored pixels formed by applying droplets of a colored liquid composition on the substrate, and a separation wall for separating the colored pixels,
The color filter according to claim 1, wherein the separation wall is the separation wall according to claim 1.   The color filter according to claim 9, wherein the application of the droplets is performed by an inkjet method.   A display device comprising the color filter according to claim 9.

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