JP2014177425A - Polymerizable fluorine-containing compound, curable composition, membrane, separation wall, antireflection film, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable fluorine-containing compound capable of forming color filter separation wall, that has high water and ink repellency property, has excellent heat resistance, has excellent adhesion with backing material, has excellent color mixing preventing property, and has less display unevenness when used in display device.SOLUTION: A polymerizable fluorine-containing compound is provided represented by the following formula (1), where Lrepresents a single bond or a coupling group of (p1+1) valence; Lrepresents a single bond or a coupling group of (p2+1) valence; Lrepresents a single bond or a coupling group of (p3+1) valence; Lrepresents a single bond or a coupling group of (p4+1) valence; Qto Qeach independently represents a group having polymerizable group; and p1 to p4 each independently represents an integer of 1 to 3.

Description

  The present invention relates to a polymerizable fluorine-containing compound, a curable composition, a film, a separation wall, an antireflection film, and a display device.

In recent years, the demand for liquid crystal displays for personal computers and liquid crystal color televisions has been increasing, and there has been an increasing demand for improved characteristics and cost reduction of color filters essential for such displays.
Conventionally, as a method for producing a color filter, a dyeing method, a pigment dispersion method, an electrodeposition method, a printing method, and the like have been carried out, and all of these methods are red (R), green (G), blue ( In order to form the three-color pixel B), it is necessary to repeat the same process three times, which is common in that the cost increases. In addition, since the number of processes is large, there is a problem that the yield is likely to decrease.

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

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

  In relation to the above, by using a fluorine-containing compound having a repeating unit having 7 or more fluorine atoms and a repeating unit having 3 or more ester groups, it is excellent in water repellency and ink repellency (oil repellency). It has been proposed to form a separation wall (see Patent Document 1).

  Patent Documents 2 and 3 describe polyfunctional polymerizable fluorine-containing compounds having a specific structure.

JP 2008-202006 A JP 2008-106036 A JP 2006-28280 A

  However, in the case where a film is formed on a substrate from a composition containing a fluorine-containing compound and other components such as a crosslinking agent, in order to ensure adhesion between the formed film and the substrate, There has been a demand to improve the compatibility with other components such as a crosslinking agent.

The object of the present invention is, for example, high water repellency and ink repellency, excellent heat resistance, excellent adhesion to a substrate, excellent color mixing prevention, and less display unevenness when used in a display device. An object of the present invention is to provide a polymerizable fluorine-containing compound capable of forming a separation wall of a color filter.
Another object of the present invention is to provide a curable composition containing the polymerizable fluorine-containing compound, a film obtained by curing the curable composition, a separation wall, an antireflection film, and a display device. There is.

  As a result of intensive studies to solve the above-described problems, the present inventors have found that the above-described problems can be solved and the object can be achieved by the following configuration, and the present invention has been completed.

[1]
A polymerizable fluorine-containing compound represented by the following general formula (I).

In general formula (I),
L ₁ represents a single bond or a (p1 + 1) -valent linking group.
L ₂ represents a single bond or a (p2 + 1) -valent linking group.
L ₃ represents a single bond or a (p3 + 1) -valent linking group.
L ₄ represents a single bond or a (p4 + 1) -valent linking group.
Q _{1 to} Q ₄ each independently represent a group having a polymerizable group.
p1 to p4 each independently represents an integer of 1 to 3.
[2]
The polymerizable fluorine-containing compound according to [1], wherein Q _{1 to} Q ₄ each independently represents an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an epoxy group.
[3]
The polymerizable fluorine-containing compound according to [1] or [2], wherein p1 to p4 each independently represents 2 or 3.
[4]
L _{1 to} L ₄ are each independently a linear, branched, or cyclic hydrocarbon group, an aromatic ring group, an oxygen atom, or a linking group obtained by combining these, [1] to [3] The polymerizable fluorine-containing compound according to any one of the above.
However, the hydrocarbon group and the aromatic ring group are an alkyl group, a fluorine atom, an alkyl group having a fluorine atom having 1 to 10 carbon atoms, or a group represented by —CF ₂ —O— (CF ₂ ) _m1 F. As a substituent. m1 represents an integer of 1 to 10.
[5]
The polymerization according to any one of [1] to [4], wherein L _{1 to} L ₄ are each independently a linking group represented by any one of the following general formulas (LL-1) to (LL-16). Fluorinated compounds.

In general formulas (LL-1) to (LL-16),
n represents the number of repeating units, and each independently represents an integer of 0 to 10.
Each R independently represents a hydrogen atom or an alkyl group.
* Represents a bond with a nitrogen atom, and ** represents a bond with Q _{1 to} Q ₄ .
[6]
[1] A curable composition comprising the polymerizable fluorine-containing compound according to any one of [5].
[7]
The curable composition according to [6], further comprising an initiator, a binder, and a compound having an ethylenically unsaturated double bond group.
[8]
The film | membrane obtained by hardening | curing the curable composition as described in [6] or [7].
[9]
A separation wall having the film according to [8].
[10]
The antireflection film which has a film | membrane as described in [8].
[11]
A display device comprising the separation wall according to [9] or the antireflection film according to [10].

  According to the present invention, for example, it has high water repellency and ink repellency, excellent adhesion to a base material, excellent color mixing prevention, little display unevenness when used in a display device, and separation of a color filter. A polymerizable fluorine-containing compound capable of forming an image wall can be provided. Further, according to the present invention, a treated substrate having a film formed from the surface modifier, a curable composition containing the polymerizable fluorine-containing compound, and a film obtained by curing the curable composition. A separation wall, an antireflection film, and a display device can be provided.

  The present invention will be described below. However, the present invention is not limited by the following description. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acryloyl group”, “(meth) acrylic acid” and the like.

<Polymerizable fluorine-containing compound>
The polymerizable fluorine-containing compound of the present invention is represented by the following general formula (I).
By using the polymerizable fluorine-containing compound of the present invention, a cured product having excellent adhesion to the substrate, high strength and excellent heat resistance can be obtained. The reason for this is not clear, but it is thought that the interaction between molecules becomes stronger due to the polarity generated by the presence of N atoms in addition to the C, H, and O atoms constituting the molecule.

In general formula (I),
L ₁ represents a single bond or a (p1 + 1) -valent linking group.
L ₂ represents a single bond or a (p2 + 1) -valent linking group.
L ₃ represents a single bond or a (p3 + 1) -valent linking group.
L ₄ represents a single bond or a (p4 + 1) -valent linking group.
Q _{1 to} Q ₄ each independently represent a group having a polymerizable group.
p1 to p4 each independently represents an integer of 1 to 3.

In the general formula (I), Q _{1 to} Q ₄ each independently represent a group having a polymerizable group.
Q _{1 to} Q ₄ each independently preferably represents an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an epoxy group, more preferably an acryloyl group, a methacryloyl group, a vinyl group, or an allyl group, and an acryloyl group. Or a methacryloyl group is more preferred.

L ₁ represents a single bond or a (p1 + 1) -valent linking group, L ₂ represents a single bond or a (p2 + 1) -valent linking group, L ₃ represents a single bond or a (p3 + 1) -valent linking group, and L ₄ Represents a single bond or a (p4 + 1) -valent linking group.

  p1 to p4 each independently represent an integer of 1 to 3, and 2 or 3 is preferable from the viewpoint of adhesion to the substrate.

L _{1 to} L ₄ are preferably each independently a linear, branched, or cyclic hydrocarbon group, an aromatic ring group, an oxygen atom, or a linking group obtained by combining these. However, the hydrocarbon group and the aromatic ring group are an alkyl group, a fluorine atom, an alkyl group having a fluorine atom having 1 to 10 carbon atoms, or a group represented by —CF ₂ —O— (CF ₂ ) _m1 F. As a substituent. m1 represents an integer of 1 to 10.
From the viewpoint of compatibility with other materials coexisting with ease of synthesis, m1 is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and still more preferably an integer of 1 to 4.
The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 4, from the viewpoint of ease of synthesis and compatibility with other materials coexisting.
The alkyl group having a fluorine atom having 1 to 10 carbon atoms is preferably a perfluoroalkyl group having 1 to 10 carbon atoms.

L _{1 to} L ₄ may be a single bond or a linking group represented by any of the following general formulas (LL-1) to (LL-16) from the viewpoint of availability of raw materials and ease of synthesis. More preferred.

In general formulas (LL-1) to (LL-16),
n represents the number of repeating units, and each independently represents an integer of 0 to 10.
Each R independently represents a hydrogen atom or an alkyl group.
* Represents a bond with a nitrogen atom, and ** represents a bond with Q _{1 to} Q ₄ .

From the viewpoint of the strength of the cured film, n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 3.
R is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

  Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited to these. The following specific examples are compounds in which R in the following general formula (I-1) is a group having each structure.

[Production Method of Compound Represented by General Formula (I)]
As a method for producing the compound represented by the general formula (I), an isocyanate compound having a polymerizable group as a substituent is reacted with the following compound (1) described in JP-A-2008-106036. Can be synthesized.

Although the isocyanate compound which has a polymeric group which can be used for this reaction in a substituent is not specifically limited, It is an aliphatic or aromatic isocyanate compound. As an isocyanate compound having a polymerizable group, for example, Karenz MOI, Karenz AOI, Karenz BEI (all manufactured by Showa Denko) or the like can be used.
The reaction solvent for this reaction is not particularly limited, but from the viewpoint of shortening the reaction time and the purity and yield of the reaction product, ethyl acetate, toluene, methylene chloride, chloroform, dimethylacetamide, dimethylformamide, acetonitrile, dimethylsulfoxide, tetrahydrofuran, Diethyl ether, N-methyl-2-methylpyrrolidone, propylene glycol 1-monomethyl ether 2-acetate and the like can be used.
Although the reaction temperature depends on the type of solvent used, the reaction temperature is preferably in the range of room temperature to 100 ° C. from the viewpoint of reaction acceleration and reaction product purity. In addition, it is preferable to use a reaction catalyst, an organic tin compound such as dibutyltin dilaurate, an organic zirconium compound such as zirconium tetraacetylacetonate, an organic titanium compound such as titanium diisopropoxybis (ethylacetoacetate), N, N- An amine compound such as dimethylcyclohexylamine and a salt thereof can be used. Furthermore, it is preferable to add a polymerization inhibitor such as hydroquinone monomethyl ether, benzoquinone, dibutylhydroxytoluene or the like in order to prevent the polymerizable group from causing a polymerization reaction during the reaction. These polymerization inhibitors may already be contained in commercially available isocyanate compounds used for the reaction. The extraction organic solvent used in the post-treatment of the reaction is not particularly limited, and ethyl acetate, toluene, diethyl ether, hexane and the like are used. An inorganic salt such as sodium chloride or an acid component such as hydrochloric acid or sulfuric acid may be added for the purpose of removing unreacted substances and improving the liquid separation property.

[Curable composition]
The curable composition of this invention is a curable composition containing the polymeric fluorine-containing compound represented by the said general formula (I). The polymerizable fluorine-containing compound represented by the general formula (I) can function as a crosslinking agent (curing accelerator).
The film obtained by curing the curable composition has high water repellency and ink repellency, excellent heat resistance, excellent adhesion to a substrate, excellent color mixing prevention, and used for a display device. In this case, it is possible to form a color filter separation wall with little display unevenness.

  The content of the polymerizable fluorine-containing compound represented by the general formula (I) in the curable composition is preferably 0.01 to 30% by mass with respect to the total solid content of the curable composition, and more Preferably it is 0.05-20 mass%, Most preferably, it is 0.1-10 mass%. When the content of the polymerizable fluorine-containing compound is within the above range, better water repellency and ink repellency can be obtained, and the adhesion of the substrate when a film is formed on the substrate can be improved. For example, when forming a separation partition such as a black matrix containing a colorant such as a black pigment, it is possible to suppress the ink from running on the separation wall when forming a colored region by applying droplets by the inkjet method. Color separation can be prevented, and a separation wall with high substrate adhesion and color density can be produced.

The curable composition of the curable composition may contain components other than the polymerizable fluorine-containing compound represented by the general formula (I).
It is preferable that the said curable composition contains the compound which has an initiator, a binder, and an ethylenically unsaturated double bond group.
Since the polymerizable fluorine-containing compound of the present invention is highly compatible with other components (particularly, a compound having an ethylenically unsaturated double bond group that functions as a cross-linking agent), the above curable composition is used as a substrate. When a film is formed thereon, the adhesion between the film and the substrate is high.

  Hereinafter, each component other than the polymerizable fluorine-containing compound will be described in detail.

[Initiator]
The curable composition of this invention can be set as the structure which has photosensitivity by using at least 1 sort (s) of an initiator.
As a method for curing the curable composition, a thermal initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are generally used, but in the present invention, the shape of the separation wall after curing is described later. Therefore, it is preferable to use a photoinitiating system.

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

Examples of the photopolymerization initiator or photopolymerization initiator system include trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. Compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds, and the like.
Specific examples of preferable initiators are the same as those described in JP-A-2008-202006, [0062] to [0066].

The said photoinitiator may be used independently and may use 2 or more types together.
The total amount of the initiator (particularly the photopolymerization initiator) in the curable composition is preferably 0.1 to 20% by mass, and particularly preferably 0.5 to 10% by mass, based on the total solid content (mass) of the curable composition. preferable. When the total amount is within the above range, photocuring of the curable composition can be efficiently performed, and an image pattern free from omission or surface roughness can be obtained during development.

  In the present invention, the total solid content (mass) of the curable composition means all components excluding the solvent in the curable composition.

The photopolymerization initiator may be configured using a hydrogen donor in combination. As the hydrogen donor, a mercaptan compound, an amine compound, or the like is preferable because 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 hydrogen donor can be used alone or in admixture of two or more, and the formed image is less likely to fall off from the permanent support during development, and can be improved in strength and sensitivity. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors.
Specific examples of mercaptan compounds, amine compounds, and combinations thereof are the same as those described in JP-A-2008-202006, [0070] to [0074].

  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 curable resin composition is preferably from 0.1 to 20 mass%, particularly preferably from 0.5 to 10 mass%, based on the total solid content (mass) of the curable resin composition.

[binder]
The curable composition of this invention can be comprised suitably using at least 1 sort (s) of a binder.
As the binder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, etc. described in JP-A-59-71048. Can be mentioned. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group added to a polymer having a hydroxyl group can also be preferably used.

  Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. These binder polymers having a polar group may be used alone, or may be used in the state of a composition used in combination with an ordinary film-forming polymer.

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

[Ethylenically unsaturated compound]
The curable composition of this invention can be set as the structure which has photosensitivity by using at least 1 sort (s) of an ethylenically unsaturated compound. A compound having a plurality of ethylenically unsaturated bond groups can function as a crosslinking agent (curing accelerator). As the ethylenically unsaturated compound, the following compounds may be used alone or in combination with other monomers.

  Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxy Ethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxy Nzenji (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide, and the like.

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

  As content in the curable composition of an ethylenically unsaturated compound, 5-80 mass% is preferable with respect to the total solid (mass) of a curable composition, and 10-70 mass% is especially preferable. When the content of the ethylenically unsaturated compound is within the above range, it is possible to ensure the resistance to an alkaline developer at the exposed portion of the composition, and to handle it while suppressing an increase in tackiness when used as a curable composition. Can keep sex.

[Color material]
The curable resin composition of this invention can be comprised using at least 1 sort (s) of a coloring material.
Known colorants (dyes, pigments, etc.) can be used as the colorant. Specifically, pigments and dyes described in JP-A-2005-17716 [0038]-[0054] The pigments described in JP-A-2004-361447 [0068] to [0072] and the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

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

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

  The pigment is preferably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing a pigment and a pigment dispersant in an organic solvent (or vehicle). The vehicle refers to a portion of the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, a kneader, a roll mill, an atomizer described in “Encyclopedia of Pigments” (written by Asakura Kunizo, 1st edition, Asakura Shoten, 2000, page 438). Known dispersers such as a rider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, the material may be finely pulverized using frictional force by mechanical grinding described on page 310 of the same document.

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

[Others]
In addition to the above components, the curable composition includes the following solvents, surfactants, thermal polymerization inhibitors, ultraviolet absorbers, and the like, and “adhesion aids” and other additions described in JP-A-11-133600 Other components such as an agent may be added.

[solvent]
In the curable composition of the present invention, a solvent may be further used in addition to the above components. Examples of the solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

[Surfactant]
In the curable composition of the present invention, it is preferable to contain an appropriate surfactant in the resin composition from the viewpoint of being able to control the film thickness to be uniform and effectively preventing coating unevenness.
Suitable surfactants include those disclosed in JP2003-337424A and JP11-133600A.

[Thermal polymerization inhibitor]
The curable composition in the present invention preferably contains a thermal polymerization inhibitor.
Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

[Ultraviolet absorber]
The curable composition in the present invention may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include compounds described in JP-A-5-72724, salicylate series, benzophenone series, benzotriazole series, cyanoacrylate series, nickel chelate series, hindered amine series, and the like.
Specific examples of the ultraviolet absorber are the same as those described in [0093] of JP-A-2008-202006.

A film obtained by curing the curable composition is preferably used for a separation wall of a color filter as described above. Moreover, the film | membrane obtained by hardening | curing the said curable composition can also be used as an anti-reflective layer, apply | coats the said curable composition on a transparent support body, and hardens | cures to form a film | membrane. It can also be a prevention film.
The polymerizable fluorine-containing compound, curable composition, and film of the present invention can also be used for applications other than those described above, such as optical fibers, optical waveguides, lens materials, volume holograms, hologram memory materials, and coating materials. , Nanoimprint monomers, surface modifiers, industrial tube materials, seal materials, solid polymer fuel cell electrolyte membranes, and the like.

[Transparent support]
In the present invention, glass, ceramic, synthetic resin film, etc. can be used as the transparent support (substrate). Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

<Illustrated wall>
The method for forming the separation wall of the present invention is the same as that described in [0104] to [0127] of JP-A-2008-202006.

Regarding the width and height of the separation wall, the width (that is, the distance between the pixels when the color filter is formed) is preferably 15 to 100 μm, and the height (that is, the separation from the substrate surface in the substrate normal direction). The distance to the top of the wall is preferably 1.0 to 5.0 μm.
As the shape of the separation wall, the shapes described in [0054] to [0055] of JP-A No. 2006-154804 are also suitable in the present invention.

<Display device>
The display device of the present invention has the separation wall or the antireflection film of the present invention.
Examples of the display device include display devices such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention should not be construed as being limited thereto. In addition, molecular weight represents the weight average molecular weight of polystyrene conversion by gel permeation chromatography (GPC), and “part” and “%” are based on mass unless otherwise specified.

<Synthesis Example 1>
Synthesis of Exemplary Compound (HMM-1) Synthesis was performed according to the following synthesis scheme.

25 mL of ethyl acetate and 0.02 g of dibutyltin dilaurate were added to 5 g of the compound (1) described in JP-A-2008-106036. To this solution, 8.97 g of Karenz BEI (manufactured by Showa Denko KK) was added dropwise, and 5 mL of ethyl acetate was added. After stirring for 2 hours at room temperature, the mixture was heated to 60 ° C. and stirred for 13 hours. After adding 3.05 g of 2-dimethylaminoethanol and stirring at 60 ° C. for 1.5 hours, the mixture was allowed to cool and extracted and separated by adding 60 mL of ethyl acetate, 9 mL of concentrated hydrochloric acid and 60 mL of 10 wt% sodium chloride aqueous solution. . After discarding the aqueous layer, 9 mL of concentrated hydrochloric acid and 60 mL of 10 wt% sodium chloride aqueous solution were added to perform extraction and liquid separation operations. After discarding the aqueous layer, extraction and liquid separation operations were performed by adding 120 mL of 25 wt% sodium chloride aqueous solution. After discarding the aqueous layer, extraction and liquid separation operations were performed by adding 90 mL of a 7.5 wt% aqueous sodium bicarbonate solution and 30 mL of a 25 wt% aqueous sodium chloride solution. After discarding the aqueous layer, the organic layer was washed twice with 120 mL of a 25 wt% aqueous sodium chloride solution, magnesium sulfate was added, and the mixture was allowed to stand at room temperature for 30 minutes. After removing magnesium sulfate by filtration, 10.95 mg of hydroquinone monomethyl ether was added, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography to obtain 4.86 g of exemplary compound (HMM-1).
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.30 (s, 12H), 4.26 (s, 16H), 4.62 (t, J = 13.8 Hz, 8H), 5.95 (dd, J = 1.7 Hz, 10.2 Hz, 8H), 6.15 (dd, J = 10.2 Hz, 17.1 Hz, 8H), 6.34 (dd, J = 1.7 Hz, 17.1 Hz, 8H), 7 .83 (s, 4H). ¹⁹ F NMR (282 MHz, CDCl ₃ ) δ-122.78, −85.41, −66.06.

  Based on the synthesis method similar to the above, the exemplified compounds (HMM-3), (HMM-4), (HMM-7), (HMM-8), (HMM-9), (HMM-10), (HMM) -12) was synthesized.

Example 101
-Preparation of photosensitive resin composition K1-
K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 below are respectively weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes. Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, curing accelerator [DPHA solution and compound HMM-1 of the present invention (25% 2-butanone solution)], 2,4-bis (trichloromethyl) -6-6 [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine and surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.). A photosensitive resin composition K1 was prepared by stirring at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).
At this time, the ratio of HMM-1 to the solid content mass in the photosensitive resin composition K1 was 5%. In addition, the amount described in Table 1 is parts by mass, and each component described in Table 1 has the following composition in detail.

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

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

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

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

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

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

-Formation of colored regions-
(1) Preparation of Colored Ink Composition for Pixel Among the following compositions, first, a pigment, a polymer dispersant, and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels.

(Composition of colored ink composition for red pixel)
・ Pigment (CI Pigment Red 254) ・ ・ ・ ・ 5 parts ・ Solsperse 24000 (manufactured by AVECIA; polymer dispersant) ・ ・ ・ ・ 1 part ・ Benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio] ]) Random copolymer (molecular weight: 37,000, binder) ... 3 parts Epicoat 154 (manufactured by Yuka Shell; novolak epoxy resin) ... 2 parts Neopentyl glycol di Glycidyl ether (epoxy resin) ··· 5 parts · Trimellitic acid (curing agent) ··· 4 parts · Ethyl 3-ethoxypropionate (solvent) · · · 80 parts

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

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

-Formation of conductive film 1-
A transparent electrode of ITO (Indium Tin Oxide) is further sputtered at 250 ° C. (deposition temperature; 250 ° C., no annealing) on the R pixel, G pixel, B pixel and separation wall of the color filter obtained above. Formed. “Sputtering temperature” shown in Table 2 is a deposition temperature.
When the resistance of this ITO was measured (sheet resistance was measured by a four-point probe method using “Loresta” manufactured by Mitsubishi Chemical Corporation), it was 80Ω / □ (Ω / sq.).

-Color mixing evaluation of color filter substrate-
The obtained color filter substrate was evaluated as follows. The evaluation results are shown in Table 2 below.
Visual observation was performed with a 200 × optical microscope from the side opposite to the side where the pixels of the color filter were formed, and the presence or absence of color mixing between the pixels was observed. The evaluation was performed by observing 1000 pixels and dividing them into the following ranks. The allowable ranges are A rank and B rank.

(Evaluation criteria)
-Rank A: There was no color mixing.
-B rank: The color mixture was 1-2 places.
-C rank: The color mixture was 3-10 places.
-D rank: The color mixture was 11 or more places.

<Production of liquid crystal display device>
-Formation of columnar spacer pattern-
The following photosensitive resin layer coating solution for forming a spacer pattern was applied onto the ITO of the color filter by a slit coater similar to the above, and dried to form a photosensitive resin layer SP1.

-Formulation SP1- of coating liquid for photosensitive resin layer
・ Methacrylic acid / allyl methacrylate copolymer (molar ratio = 20/80, weight average molecular weight 40000; high molecular weight substance) 108 parts dipentaerythritol hexaacrylate 64.7 parts Polymerizable monomer)
2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine ... 6.24 parts hydroquinone Monomethyl ether: 0.0336 parts ・ Victoria Pure Blue BOHM (manufactured by Hodogaya Chemical Co., Ltd.) ・ ・ ・ ・ 0.874 parts ・ Megafac F780F (manufactured by Dainippon Ink & Chemicals, Inc .; surfactant)
・ ・ ・ ・ 0.856 parts ・ Methyl ethyl ketone ・ ・ ・ ・ ・ ・ 328 parts ・ 1-methoxy-2-propyl acetate ・ ・ ・ ・ ・ ・ 475 parts ・ Methanol ・ 16.6 parts

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

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

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

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

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

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

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

[Evaluation criteria]
Rank A: ink contact angle ≧ 50 °, water contact angle ≧ 100 °
Rank B: Ink contact angle ≧ 40 °, water contact angle ≧ 90 °
C rank: ink contact angle ≧ 35 °, water contact angle ≧ 80 °
D rank: ink contact angle <35 °, water contact angle <80

(2) Substrate adhesion of separation wall Prepare three glass substrates that have completed the exposure process under the same conditions in the above-mentioned "Formation of separation wall", and increase the development time to 90 seconds, 130 seconds, and 180 seconds. Except for the above processing, development was performed under the same development conditions, and the presence or absence of chipping of the separation wall at each development time was evaluated according to the following evaluation criteria by visual observation for 1000 pixels. The allowable ranges are A rank and B rank. The evaluation results are shown in Table 2 below.

[Evaluation criteria]
-Rank A: No separation wall was missing.
-B rank: The image separation wall chip was 1-2 places.
-C rank: The image separation wall chip was 3-10 places.
-D rank: There were 11 or more image separation wall defects.

(3) Display unevenness of liquid crystal display device For the liquid crystal display device produced above, the gray display when a gray test signal is input is visually observed, and the occurrence of display unevenness is evaluated according to the following evaluation criteria. did.

[Evaluation criteria]
A rank: There was no display unevenness and a very good display image was obtained.
Rank B: Although the edge of the glass substrate was slightly uneven, there was no effect on the display part and the display image was good.
-C rank: Although the display part was slightly uneven, it was within a practically acceptable range.
-D rank: The display part was uneven.

[Examples 102 to 108, 114]
In Example 101, the compound HMM-1 of the present invention was converted to the compound of the present invention (HMM-3, HMM-4, HMM-7, HMM-8, HMM-9, HMM-10, HMM-12, HMM-18). ), A photosensitive resin composition K1 was prepared in the same manner as in Example 101, a color filter substrate and a liquid crystal display device were produced, and the same evaluation was performed. The evaluation results are shown in Table 2 below.

[Comparative Example 101]
In Example 101, a photosensitive resin composition K1 was prepared in the same manner as in Example 101 except that DPHA solution was added in place of compound HMM-1 of the present invention (3.0 parts of 25% propylene glycol monomethyl ether acetate solution). Were prepared, and a color filter substrate and a liquid crystal display device were produced, and the same evaluation was performed.

[Examples 109 and 110]
In Example 101, as shown in Table 2, instead of DPHA solution, pentaerythritol tetraacrylate (trade name A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) solution (76% propylene glycol monomethyl ether acetate solution was added in 5. 4 parts) or ethoxylated glycerin triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name A-GLY-9E) solution (5.4 parts of 76% propylene glycol monomethyl ether acetate solution) was added. Except for the above, a photosensitive resin composition K1 was prepared in the same manner as in Example 101 to prepare a color filter substrate and a liquid crystal display device, and the same evaluation was performed. The evaluation results are shown in Table 2 below.

[Comparative Examples 102-104]
In Example 101, instead of the compound HMM-1 of the present invention, pentaerythritol tetraacrylate (trade name A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) solution (25% propylene glycol monomethyl ether acetate solution in 3.0%) Part), ethoxylated glycerin triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name A-GLY-9E) (3.0 parts of 25% propylene glycol monomethyl ether acetate solution), 2, 2, 3, From 3,4,4,5,5-octafluoro-1,6-hexanediacrylate (hereinafter referred to as OFHDA, manufactured by SynQuest Laboratories, Inc.) solution (3.0 parts of 25% propylene glycol monomethyl ether acetate solution) The selected ingredients are shown in Table 2, respectively. Except for adding in the same manner as in Example 101 to prepare the photosensitive resin composition K1, a color filter substrate, thereby manufacturing a liquid crystal display device was evaluated in the same manner. The evaluation results are shown in Table 2 below.

[Comparative Example 105]
In Example 101, instead of the compound HMM-1 of the present invention, the fluorine-containing compound (1) described in JP-A-2008-202006 (3.0 parts of a 25% propylene glycol monomethyl ether acetate solution) [In Table 1, A photosensitive resin composition K1 was prepared in the same manner as in Example 101 except that “F-containing compound (1)” was added, and a color filter substrate and a liquid crystal display device were produced, and the same evaluation was performed. It was. The evaluation results are shown in Table 2 below.

[Examples 111 to 113, Comparative Examples 106 to 108]
In Examples 101, 102, and 105 and Comparative Examples 101, 102, and 104, except that the sputtering temperature of the ITO transparent electrode was changed from 250 ° C. to 280 ° C. (deposition temperature: 280 ° C., no annealing) when the liquid crystal display device was produced. In the same manner as in Examples 101, 102, and 105 and Comparative Examples 101, 102, and 104, a liquid crystal display device was manufactured and the same evaluation was performed. The evaluation results are shown in Table 2 below.

[Comparative Example 109]
In Example 101, instead of the compound HMM-1 of the present invention, a fluorine-containing polymerizable compound (Z-1) having the following structure (3.0 parts of a 25% propylene glycol monomethyl ether acetate solution) [In Table 1, A photosensitive resin composition K1 was prepared in the same manner as in Example 101 except that “denoted as Z-1” was added, and a color filter substrate and a liquid crystal display device were produced, and the same evaluation was performed. In addition, the compound (Z-1) can be obtained from SynQuest Laboratories, Inc. It is a manufactured compound.
The evaluation results are shown in Table 2 below.

[Comparative Example 110]
In Example 101, instead of the compound HMM-1 of the present invention, a fluorine-containing polymerizable compound (Z-2) having the following structure (3.0 parts of a 25% propylene glycol monomethyl ether acetate solution) [In Table 1, A photosensitive resin composition K1 was prepared in the same manner as in Example 101 except that “Z-2” was added, and a color filter substrate and a liquid crystal display device were produced, and the same evaluation was performed. The evaluation results are shown in Table 2 below.

-Synthesis of fluorinated polymerizable compound (Z-2)-
The fluorine-containing polymerizable compound (Z-2) was obtained as follows.
1,4-bis (5 ′, 6′-epoxyhexyl) perfluorobutane (6.2 g), acrylic acid (4.2 g), tetraethylammonium bromide (0.1 g), tert -Butylcatechol (0.01 g) was charged and stirred at 95 ° C for 4 hours. The reaction solution was cooled to room temperature, diluted with 50 mL of methylene chloride, and washed with water. After removing the solvent, 100 mL of dimethylacetamide was added, and acrylic acid chloride (7.2 g) was added dropwise under ice cooling. After completion of the dropwise addition, the mixture was heated to 50 ° C. and stirred for 2 hours, and then the solvent was removed and the residue was purified by a silica gel column to obtain a compound (Z-2) having the following structure.

[Comparative Example 111]
In Example 101, instead of the compound HMM-1 of the present invention, a fluorine-containing polymerizable compound (Z-3) having the following structure (3.0 parts of a 25% propylene glycol monomethyl ether acetate solution) [in Table 1, A photosensitive resin composition K1 was prepared in the same manner as in Example 101 except that “denoted as“ Z-3 ”” was added, and a color filter substrate and a liquid crystal display device were prepared, and the same evaluation was performed. The evaluation results are shown in Table 2 below.

-Synthesis of fluorinated polymerizable compound (Z-3)-
The fluorine-containing polymerizable compound (Z-3) was obtained as follows.
A compound (Z-3) having the following structure was obtained by the same operation as in Example 2 of JP-A-11-80312.

  In the structure of the compound (Z-3), a and b each independently represent an integer of 1 to 50.

  In Table 2, the numerical value shown in the “amount” of the “compound of the present invention” in the “curing accelerator” represents the mass ratio [%] of the specific compound in the entire curing accelerator.

As shown in Table 2, in the examples, the water and ink repellency on the separation wall after the heat treatment was excellent, no color mixing occurred, and the substrate adhesion was good. In addition, the occurrence of display unevenness when a liquid crystal display device was produced and displayed was effectively suppressed, and an image having excellent display characteristics was obtained.
On the other hand, Comparative Examples 101 to 103 are particularly inferior in the color mixture evaluation, which is considered to be derived from insufficient ink repellency. In Comparative Example 4, the substrate adhesion is particularly inferior, but this is probably because a dense cross-linked structure is not formed, and the separation wall is not sufficiently formed. In Comparative Example 105, the adhesion to the substrate is particularly inferior, but this is due to inhomogeneous formation such as phase separation between DPHA, which is a curing accelerator, and a fluorine compound, resulting in insufficient separation wall formation. This is probably because of this. Further, from the results of Examples 111 to 113 and Comparative Examples 106 to 108, it is understood that the separation wall of the present invention is excellent in heat resistance.

Example 201
An alkali-free glass substrate (hereinafter, simply referred to as “glass substrate”) was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower. Coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and further washed with a pure water shower. did. After cleaning, the glass substrate was heated at 100 ° C. for 2 minutes by a substrate preheating device.

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

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

  Thereafter, a color filter substrate and a liquid crystal display device were produced in the same manner as in Example 101 except that the conductive film was formed by the method “Formation of conductive film 2” described later, and evaluation similar to that in Example 101 was performed. It was. The evaluation results are shown in Table 3 below.

-Formation of conductive film 2-
The glass substrate on which the color filter obtained from the above is formed is put in a sputtering apparatus, and ITO (Indium) is further formed on the R pixel, G pixel, and B pixel of the color filter and the separation wall.
A transparent electrode of Tin Oxide) was formed by sputtering (deposition temperature: 100 ° C., annealing temperature: 250 ° C.) at 250 ° C.
The details of “sputtering at 250 ° C.” in the formation 2 of the conductive film are as follows.

ITO (Indium Tin Oxide) was vacuum-deposited on the entire surface of the R, G, and B pixels and the separation wall at 100 ° C., and then annealed at 250 ° C. for 90 minutes to crystallize the ITO transparent electrode. Formed. The “sputtering temperature” shown in Table 3 is an annealing temperature.
When the resistance of this ITO was measured (sheet resistance was measured by the four-probe method using “Loresta” manufactured by Mitsubishi Chemical Corporation), it was 80Ω / □.

<Preparation of photosensitive transfer material K1>
On a polyethylene terephthalate film (PET temporary support) having a thickness of 75 μm, using a slit nozzle, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried to form a thermoplastic resin layer. Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation P1 was applied and dried to laminate an intermediate layer (oxygen barrier film). Further, on this intermediate layer, the photosensitive resin composition K1 prepared in Example 1 was applied and dried to laminate a black (K) photosensitive resin composition layer K1. At this time, the ratio with respect to solid content mass of the compound HMM-1 of this invention in the photosensitive resin composition K1 is 5%.
Thus, a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a photosensitive resin having a dry film thickness of 2.3 μm on the PET temporary support. A temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin composition is laminated by laminating the composition layer and further pressure-bonding a protective film (thickness 12 μm polypropylene film) to the surface of the photosensitive resin composition layer. A photosensitive transfer material K1 integrated with the layer K1 was produced.

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

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

[Examples 202 to 204, 211]
In Example 201, except that the compound HMM-1 of the present invention was replaced with the specific compound of the present invention (HMM-3, HMM-7, HMM-8, HMM-18), A photosensitive resin composition K1 was prepared to produce a photosensitive transfer material K1, and a color filter substrate and a liquid crystal display device were further produced. Further, the same evaluation as in Example 101 was performed, and the evaluation results are shown in Table 3 below.

[Comparative Example 201]
In Example 201, a photosensitive resin composition K1 was prepared in the same manner as in Example 201 except that DPHA solution was added in place of compound HMM-1 of the present invention (3.0 parts of 25% propylene glycol monomethyl ether acetate solution). The photosensitive transfer material K1 was prepared, and further, a color filter substrate and a liquid crystal display device were prepared, and the same evaluation was performed. The evaluation results are shown in Table 3 below.

Example 205
In Example 204, the liquid crystal display device was manufactured in the same manner as in Example 204 except that the sputtering temperature of the ITO transparent electrode was changed from 250 ° C. to 280 ° C. (deposition temperature: 100 ° C., annealing temperature: 280 ° C.). A display device was fabricated and the same evaluation was performed. The evaluation results are shown in Table 3 below.

[Comparative Example 202]
In Example 201, instead of the compound HMM-1 of the present invention, a fluorine-containing compound (1) described in JP-A-2008-202006 (3.0 parts of a 25% propylene glycol monomethyl ether acetate solution) was added, and liquid crystal A liquid crystal display device was produced in the same manner as in Example 201 except that the sputtering temperature of the ITO transparent electrode was changed from 250 ° C. to 2800 ° C. (deposition temperature: 100 ° C., annealing temperature: 280 ° C.) at the time of producing the display device. The same evaluation was performed. The evaluation results are shown in Table 3 below.

Example 206
In Example 205, a photosensitive resin composition K1 was prepared in the same manner as in Example 205 except that Compound HMM-1 of the present invention was added instead of DPHA solution (5.4 parts of 76% 2-propanone solution). A color filter substrate and a liquid crystal display device were prepared, and the same evaluation was performed.

Example 207
In Example 205, the DPHA solution was added in an amount of 0.64 parts, and the addition of 4.8 parts of the compound HMM-1 (76% 2-propanone solution) of the present invention was performed in the same manner as in Example 205. A photosensitive resin composition K1 was prepared, and a color filter substrate and a liquid crystal display device were prepared, and the same evaluation was performed.

Example 208
In Example 205, the amount of DPHA solution added was 3.2 parts, and 2.2 parts of compound HMM-1 (76% 2-propanone solution) of the present invention was added in the same manner as in Example 205, A photosensitive resin composition K1 was prepared, and a color filter substrate and a liquid crystal display device were prepared, and the same evaluation was performed.

Example 209
In Example 205, the DPHA solution was added in an amount of 3.8 parts, and 1.6 parts of the compound HMM-1 (76% 2-propanone solution) of the present invention was added in the same manner as in Example 205. The photosensitive resin composition K1 was prepared, a color filter and a liquid crystal display device were prepared, and the same evaluation was performed.

Example 210
In Example 205, the addition amount of the compound HMM-1 (25% 2-propanone solution) DPHA solution of the present invention was 1.9 parts, and 1.1 parts of DPHA solution (25% propylene glycol monomethyl ether acetate solution) was added. Except for the addition, a photosensitive resin composition K1 was prepared in the same manner as in Example 205, a color filter substrate and a liquid crystal display device were prepared, and the same evaluation was performed.

  In Table 3, the numerical value shown in the “amount” of the “compound of the present invention” in the “curing accelerator” represents the mass ratio [%] of the specific compound in the entire curing accelerator.

  As shown in Table 3, in the examples, the water and ink repellency on the partition walls after the heat treatment was excellent, no color mixing occurred, and the substrate adhesion was good. In addition, the occurrence of display unevenness when a liquid crystal display device was produced and displayed was effectively suppressed, and an image having excellent display characteristics was obtained. On the other hand, the comparative example 201 is particularly inferior in color mixture evaluation, which is considered to be derived from insufficient ink repellency. Moreover, it can be seen from the results of Example 205 and Comparative Example 202 that the separation wall of the present invention is excellent in heat resistance.

Claims (11)

A polymerizable fluorine-containing compound represented by the following general formula (I).

In general formula (I),
L ₁ represents a single bond or a (p1 + 1) -valent linking group.
L ₂ represents a single bond or a (p2 + 1) -valent linking group.
L ₃ represents a single bond or a (p3 + 1) -valent linking group.
L ₄ represents a single bond or a (p4 + 1) -valent linking group.
Q _{1 to} Q ₄ each independently represent a group having a polymerizable group.
p1 to p4 each independently represents an integer of 1 to 3. The polymerizable fluorine-containing compound according to claim 1, wherein Q _{1 to} Q ₄ each independently represents an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an epoxy group.   The polymerizable fluorine-containing compound according to claim 1 or 2, wherein p1 to p4 each independently represents 2 or 3. L _{1 to} L ₄ are each independently a linear, branched, or cyclic hydrocarbon group, an aromatic ring group, an oxygen atom, or a linking group obtained by combining them. 2. The polymerizable fluorine-containing compound according to item 1.
However, the hydrocarbon group and the aromatic ring group are an alkyl group, a fluorine atom, an alkyl group having a fluorine atom having 1 to 10 carbon atoms, or a group represented by —CF ₂ —O— (CF ₂ ) _m1 F. As a substituent. m1 represents an integer of 1 to 10. The polymerization according to any one of claims 1 to 4, wherein L _{1 to} L ₄ are each independently a linking group represented by any one of the following general formulas (LL-1) to (LL-16). Fluorinated compounds.

In general formulas (LL-1) to (LL-16),
n represents the number of repeating units, and each independently represents an integer of 0 to 10.
Each R independently represents a hydrogen atom or an alkyl group.
* Represents a bond with a nitrogen atom, and ** represents a bond with Q _{1 to} Q ₄ .   A curable composition comprising the polymerizable fluorine-containing compound according to claim 1.   Furthermore, the curable composition of Claim 6 containing the compound which has an initiator, a binder, and an ethylenically unsaturated double bond group.   The film | membrane obtained by hardening | curing the curable composition of Claim 6 or 7.   A separation wall having the film according to claim 8.   An antireflection film having the film according to claim 8.   A display device comprising the separation wall according to claim 9 or the antireflection film according to claim 10.