JP2007292961A - Microcapsule containing fluorine composition and composition for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine composition with which the immobilization and patterning of a fluorine compound in a raw material having the fluorine compound can be easily performed, and a composition for a color filter. <P>SOLUTION: The fluorine compound of the microcapsule containing fluorine composition including the fluorine compound includes at least one of an organic functional group selected from the group consisting of an acidic group, a basic group, a cyclic ether group, a polymerizable vinyl group, a hydroxyl group, and a thiol group, and the composition for the color filter includes the microcapsule-containing fluorine composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a microcapsule-containing fluorine-based composition and a color filter composition.

  Conventionally, it consists of a wall film mainly made of natural and synthetic polymers and a content called core material (nuclear material), and the diameter is in the micrometer range (usually in the millimeter to nanometer range) Microcapsules, which are minute containers in the field of Microcapsules are widely used in various fields because they have a function of protecting the core substance from the external environment and a function of adjusting the speed at which the core substance is released to the outside. In particular, those using the function of protecting the core substance from the external environment include pressure-sensitive copying paper, pressure measurement sheets, pressure-sensitive adhesives, liquid crystal display materials, etc., and the release rate of the core substance to the external environment Examples of those utilizing the function of regulating the above include sustained-release pharmaceuticals, sustained-release agricultural chemicals, etc., and those utilizing both of these functions simultaneously include artificial cells and artificial organs.

  And as a manufacturing method of such a microcapsule, various manufacturing methods are employ | adopted ["Microcapsule-its function and application" (Publisher: Japan Standards Association, issued on March 20, 1991) Etc.]. Specifically, (1) interfacial deposition methods using the deposition of wall material on the core material interface [for example, phase separation, submerged drying, solution dispersion cooling, spray drying, pan coating, Medium suspension coating method (Wurster method, powder bed method, etc.), and (2) interfacial reaction method that forms a film using reaction at the interface [for example, interfacial polymerization method, in situ polymerization method, submerged curing Covering method (orifice method), interface reaction method (inorganic chemical reaction method, etc.) are employed.

On the other hand, fluorine-based compounds are widely used as a transparent material, a low friction material, and a water / oil repellent material, from a plastic optical fiber to an outer wall coding of a house.
Generally, for fluorine processing, it is necessary to dissolve and disperse a fluorine-containing material in the material, but it is difficult to process this fluorine-based compound so that it exists in the material. Furthermore, patterning as a material having the above functions has been difficult.
In response to this problem, by encapsulating the fluorine compound in a microcapsule, the composition in the material and the fluorine compound can coexist without being in contact with each other, and can be easily introduced into the material. Are known.

For the microcapsules encapsulating the fluorine-based compound, a method of introducing into a polyester fiber (for example, see Patent Document 1), the surface of an abrasive tool (for example, see Patent Document 2), the inside of a polishing cloth (for example, There is known a method that can maintain low friction by being present in a lapping tool (for example, see Patent Document 4).
In addition, a technique has been proposed in which microcapsules encapsulating a fluorosurfactant are present on the surface of polyester (see, for example, Patent Document 5).

  However, since the fluorine compound contained in these microcapsules is a perfluoro (poly) ether compound and not a fluorine oil having a functional group capable of reacting with other compounds, the released fluorine It was not possible to immobilize and further pattern the system compound. The inability to immobilize and pattern such a fluorinated compound closes the way of use of immobilizing the function of the fluorinated compound.

  In recent years, as a method for manufacturing a color filter, a manufacturing method in which a black matrix is formed in advance by a pigment dispersion method and then RGB colored pixels are formed by an inkjet method has been studied.

  In this method using the inkjet method, pixels can be formed by sequentially applying colored inks of R, G, and B colors to the recesses surrounded by the black matrix, which can simplify the manufacturing process and reduce costs. There is an advantage that can be achieved.

However, as problems peculiar to the production of an optical element by the ink jet method, there are concerns about “white spots”, “ink protrusion”, “color mixing”, and the like. “Extruding ink” refers to a black matrix that is a partition when ink is applied to an exposed portion (region where pixels are to be formed) surrounded by a black matrix provided as a partition to form a colored region. Is a phenomenon in which the ink overflows and “mixed color” is a phenomenon in which the overflowed ink is mixed between adjacent colored regions.
If ink overflows or mixes when applying ink by the inkjet method, it may cause display defects such as color unevenness in the produced color filter or reduction in contrast of the displayed image. .

  For this reason, various techniques for preventing ink protrusion and color mixing have been studied in the past. For example, a method of patterning a water- and oil-repellent silicone rubber layer to form a partition wall for preventing color mixing (for example, patents) Document 6) and a method of forming a silicone rubber layer on a black matrix serving as a light shielding layer and using it as a partition wall for preventing color mixing (for example, see Patent Documents 7 to 8) have been proposed.

In addition, a color filter is disclosed in which a resin layer containing a fluorine-containing compound or the like is laminated on a light shielding layer provided on a transparent substrate constituting the color filter (see, for example, Patent Document 9).
JP 62-104978 A JP 2000-79666 A JP 2001-162515 A JP 2002-28848 A JP-A-1-320161 JP 4-123005 A JP-A-5-241011 JP-A-5-241012 Japanese Patent Laid-Open No. 7-35916

The present invention has been made in view of the above-described conventional problems, and an object thereof is to achieve the following object. That is,
An object of the present invention is to provide a fluorine-based composition and a color filter composition that can easily fix and pattern a fluorine-based compound in a material having a fluorine-based compound.

In the present invention, the fluorine compound contained in the microcapsule is a fluorine oil having a functional group capable of reacting with another compound, particularly a radical polymerizable group, so that the fluorine compound in a desired material can be obtained. It has been found that the compound can be immobilized and patterned. That is, the present invention
<1> In a fluorine-containing composition containing microcapsules enclosing a fluorine-containing compound,
The micro compound containing at least one organic functional group selected from the group consisting of an acidic group, a basic group, a cyclic ether group, a polymerizable vinyl group, a hydroxyl group, and a thiol group. It is a capsule-containing fluorine-based composition.

<2> The microcapsule-containing fluorine-based composition according to <1>, wherein the organic functional group is a polymerizable vinyl group.

<3> The number average particle diameter of the microcapsule is 0.01 to 10.0 μm, and the mass ratio of the capsule wall of the microcapsule to the fluorine compound is 1/10 to 10/1. The microcapsule-containing fluorine-based composition according to <1> or <2>.

<4> The capsule wall of the microcapsule is formed by any one of an interfacial polymerization method, an in situ polymerization method, a coacervation method, a submerged curing coating method, and a submerged drying method. The microcapsule-containing fluorine-based composition according to any one of <1> to <3>.

<5> The microcapsule-containing fluorine-based composition according to any one of <1> to <4>, wherein the capsule wall forming material of the microcapsule is a compound containing a urethane urea bond.

<6> A color filter composition comprising the microcapsule-containing fluorine-based composition according to any one of <1> to <5>.

  ADVANTAGE OF THE INVENTION According to this invention, the fluorine-type composition and composition for color filters which can perform fixation of a fluorine-type compound in the raw material which has a fluorine-type compound, and patterning easily can be provided.

The fluorine-based composition of the present invention is a fluorine-based composition containing microcapsules enclosing a fluorine-based compound, wherein the fluorine-based compound is an acidic group, a basic group, a cyclic ether group, a polymerizable vinyl group, a hydroxyl group, And at least one organic functional group selected from the group consisting of thiol groups.
The fluorine-based composition of the present invention is fixed and patterned by reacting an organic functional group of the fluorine-based compound with another compound when the fluorine-based compound encapsulated in the microcapsule is released. Can do.
Below, the component of the fluorine-type composition of this invention is demonstrated.

[Fluorine compounds]
Below, a fluorine-type compound is explained in full detail.
In the present invention, the fluorine-based compound contains at least one organic functional group selected from the group consisting of acidic groups, basic groups, cyclic ether groups, polymerizable vinyl groups, hydroxyl groups, and thiol groups. Among these organic functional groups, an acidic group, a basic group, and a polymerizable vinyl group are preferable, and a polymerizable vinyl group is most preferable.

As the acidic group, a carboxyl group, a phosphoric acid group, a boric acid group, a sulfonic acid group, and a sulfinic acid group are preferable, and a carboxyl group is more preferable.
Specific compounds are shown below, but are not limited thereto.

  As the basic group, an amino group, an imino group, an anilino group, and a nitrogen-containing heterocyclic group are preferable, and among them, an amino group and a nitrogen-containing heterocyclic group are particularly preferable.

As the cyclic ether group, an oxirane group, an oxetane group and a tetrahydrofuran group are preferable, and among them, an oxetane group is particularly preferable.
Specific compounds are shown below, but are not limited thereto.

  The polymerizable vinyl group is more preferably a methacryloyl group, an acryloyl group, a styryl group, a vinyl ether group, or a vinyl ester group.

  Further preferred examples of the fluorine-based compound according to the present invention include the compound represented by the structural formula (1) below, but the present invention is not limited thereto.

In the structural formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Among them, an alkyl group having 1 to 3 carbon atoms is particularly preferable. A methyl group is preferable, and a methyl group is particularly preferable.
Among these, as R ¹ , a hydrogen atom or a methyl group is particularly preferable.

In the above structural formula (1), X represents a divalent linking group containing at least one of an ether bond, an ester bond, an amide bond, —NR ^X CO—, an arylene group, and a heterocyclic residue. R ^X represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^x include, for example, an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, and an ether. And a substituted alkyl group having a substituent such as a group, a thioether group, an ester group, an amide group, an amino group, a urethane group and a hydroxy group. Among them, an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, a butyl group, and an octyl group are preferable.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^x include a phenyl group, a naphthyl group, a methylphenyl group, a methoxyphenyl group, and a nonylphenyl group. Among them, an aryl group having 6 to 15 carbon atoms is preferable, and a phenyl group and a nonylphenyl group are preferable.

Among the above, R ^x is preferably a methyl group, a phenyl group, or a nonylphenyl group.

  Among these, the divalent linking group represented by X is preferably a group having the following group or the following structure.

In the structural formula (1), L ¹ represents a single bond or an organic linking group including at least one of an alkylene group, an arylene group, an ether bond, and an ester bond.
Among these, L ¹ is preferably a group having the following group or the following structure.

Here, R ² represents a hydrogen atom or a methyl group. Y represents a single bond, an alkylene group, or an arylene group. Z represents a group represented by the following Z-1 to Z-8 or a group having a structure represented by the following Z-1 to Z-8.

  In the structural formula (1), Rf represents a substituent containing fluorine. As the group containing fluorine, the following fluorine-containing groups or fluorine-containing groups having the following structures are suitable.

  Here, l represents an integer of 2 to 20, more preferably an integer of 4 to 12. m represents an integer of 1 to 20, and more preferably an integer of 4 to 12. n represents an integer of 2 to 20, more preferably an integer of 4 to 12.

Among the above, R ¹ is a hydrogen atom, a methyl group, X is an ester bond, L ¹ is a single bond, or L-1 and Y; a combination of single bonds, L-7 and Y single bond Combination, combination of L-3 and Y single bond, combination of L-4 and Y single bond, combination of L-8, Y single bond and Z-1, wherein Rf is -C ₈ F ₁₇ or -C ₆ aspect is a F ₁₃ are particularly preferred.

  Hereinafter, specific examples [Exemplary compounds a to q] of the fluorine-based compound according to the present invention are shown. However, the present invention is not limited to these.

[Microcapsule]
The above fluorine compound is encapsulated in microcapsules. The microcapsules will be described below.

  The capsule wall-forming material will be described in detail in the method for forming microcapsules described later, but is preferably a compound containing a urethane urea bond.

Below, the microcapsule-containing fluorine-based composition of the present invention will be described in detail through a method for forming microcapsules. In addition, the microcapsule-containing fluorine-based composition of the present invention is contained as it is when the components added in the following microcapsule formation method are not particularly removed.
The capsule wall of the microcapsule is preferably formed by any one of an interfacial polymerization method, an in situ polymerization method, a coacervation method, a submerged curing coating method, and a submerged drying method.
In particular, it is preferably applied to a phase separation method, a submerged drying method, an interfacial polymerization method, an in situ polymerization method, or a submerged curing coating method. Therefore, it is preferable in terms of easy control.

-Interfacial polymerization method-
The interfacial polymerization method is a method in which a polymer film formed by an interfacial polymerization reaction between a hydrophobic monomer and a hydrophilic monomer is used as a coating wall, and a core substance solution or dispersion is used as a W / O or O / W type. In this method, the monomer (A) is dispersed in the emulsifying system, and the monomer (A) is collected at the interface, and the monomer (B) and the monomer (A) are reacted at the interface in the next step.

  The reactant forming the polymer film is added inside the oil droplet and / or outside the oil droplet. Specific examples of the polymer film include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, and the like. Among these, polyurethane, polyurea, polyurethane urea, polyamide, polyester, and polycarbonate are preferable, polyurethane, polyurea, and polyurethane urea are more preferable, and polyurethane urea is particularly preferable.

  For example, when polyurea is used as a capsule wall material, polyisocyanates such as diisocyanate, triisocyanate, tetraisocyanate, and polyisocyanate prepolymer, polyamines such as diamine, triamine, and tetraamine, two or more amino acids A microcapsule wall can be easily formed by reacting a prepolymer having a group, piperazine or a derivative thereof, a polyol, or the like with the interfacial polymerization method in the aqueous phase.

  In addition, for example, a composite wall made of polyurea and polyamide or a composite wall made of polyurethane and polyamide is made of, for example, polyisocyanate and a second substance that reacts therewith to form a capsule wall (for example, acid chloride, polyamine, or polyol). It can be prepared by mixing in a water-soluble polymer aqueous solution (aqueous phase) or an oily medium to be encapsulated (oil phase), emulsifying and dispersing them, and then heating. Details of the method for producing the composite wall comprising polyurea and polyamide are described in JP-A-58-66948.

  As the polyisocyanate compound, a compound having a trifunctional or higher isocyanate group is preferable, but a bifunctional isocyanate compound may be used in combination. Specifically, diisocyanates such as xylene diisocyanate and hydrogenated products thereof, hexamethylene diisocyanate, tolylene diisocyanate and hydrogenated products thereof, isophorone diisocyanate and the like, and dimers thereof. Alternatively, in addition to a trimer (burette or isocyanurate), a polyfunctional adduct of a polyol such as trimethylolpropane and a bifunctional isocyanate such as xylylene diisocyanate, a polyol such as trimethylolpropane and a xylylene Examples thereof include a compound in which a high molecular weight compound such as polyether having active hydrogen such as polyethylene oxide is introduced into an adduct with a bifunctional isocyanate such as range isocyanate, and a formalin condensate of benzene isocyanate. The compounds described in JP-A-62-212190, JP-A-4-26189, JP-A-5-317694, and Japanese Patent Application No. 8-268721 are preferable.

  The polyisocyanate is preferably added so that the average particle size of the microcapsules is 0.3 to 12 μm and the thickness of the capsule wall is 0.01 to 0.3 μm. The dispersed particle size is generally about 0.2 to 10 μm.

  The number average particle size of the microcapsules is preferably from 0.01 to 10.0 μm, more preferably from 0.01 to 4.0 μm, from the viewpoint of coating stability and light transmittance, and more preferably 0.05 μm. -1.0 micrometer is further more preferable.

  Specific examples of polyols and / or polyamines that react with the polyisocyanate and are added to the aqueous phase and / or the oil phase as one of the components of the microcapsule wall include propylene glycol, glycerin, trimethylolpropane, Examples include ethanolamine, sorbitol, hexamethylenediamine, and tetramethylenepentamine. When a polyol is added, a polyurethane wall is formed. In the above reaction, it is preferable to keep the reaction temperature high or to add an appropriate polymerization catalyst from the viewpoint of increasing the reaction rate. Polyisocyanates, polyols, reaction catalysts, polyamines for forming a part of the wall agent, etc. are well known in the book (Polyurethane Handbook, Nikkan Kogyo Shimbun (1987) edited by Keiji Iwata).

  In addition, a metal-containing dye, a charge control agent such as nigrosine, or any other additive can be added to the microcapsule wall as necessary. These additives can be included in the wall of the capsule at the time of wall formation or at any time. Further, a monomer such as a vinyl monomer may be graft-polymerized in order to adjust the chargeability of the capsule wall surface as necessary.

  Furthermore, a plasticizer suitable for the polymer used as the wall material can be used to make the wall of the microcapsule excellent in material permeability even under a lower temperature and rich in color development. The plasticizer preferably has a melting point of 50 ° C. or higher, and more preferably has a melting point of 120 ° C. or lower. Among these, those that are solid at room temperature can be suitably selected and used. For example, when the wall material is made of polyurea or polyurethane, a hydroxy compound, a carbamic acid ester compound, an aromatic alkoxy compound, an organic sulfonamide compound, an aliphatic amide compound, an arylamide compound, or the like is preferably used.

  In preparing the oil phase, the hydrophobic organic solvent used for dissolving the fluorine compound and forming the core of the microcapsule is preferably an organic solvent having a boiling point of 100 to 300 ° C. Specifically, in addition to esters, dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene, dimethylbiphenyl, diisopropylbiphenyl, diisobutylbiphenyl, 1-methyl-1-dimethylphenyl-2-phenylmethane, 1-ethyl-1-dimethylphenyl -1-phenylmethane, 1-propyl-1-dimethylphenyl-1-phenylmethane, triallylmethane (eg, tritoluylmethane, toluyldiphenylmethane), terphenyl compound (eg, terphenyl), alkyl compound, alkylated diphenyl ether (For example, propyl diphenyl ether), hydrogenated terphenyl (for example, hexahydroterphenyl), diphenyl ether, and the like. Among these, it is particularly preferable to use esters from the viewpoint of emulsion stability of the emulsion dispersion.

  Examples of the esters include phosphate esters such as triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, cresyl phenyl phosphate; dibutyl phthalate, 2-ethylhexyl phthalate, ethyl phthalate, Phthalic acid esters such as octyl phthalate and butyl benzyl phthalate; Dioctyl tetrahydrophthalate; Benzoic acid esters such as ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate and benzyl benzoate; Ethyl abietic acid, abietic acid Abietic acid esters such as benzyl; dioctyl adipate; isodecyl succinate; dioctyl azelate; oxalic acid esters such as dibutyl oxalate and dipentyl oxalate; diethyl malonate; dimethyl maleate, diethyl maleate, di maleate Maleic acid esters such as chill; Tributyl citrate; Sorbic acid esters such as methyl sorbate, ethyl sorbate, and butyl sorbate; Sebacic acid esters such as dibutyl sebacate and dioctyl sebacate; Formic acid monoesters and diesters, butyric acid monoester And ethylene glycol esters such as diester, lauric acid monoester and diester, palmitic acid monoester and diester, stearic acid monoester and diester, oleic acid monoester and diester; triacetin; diethyl carbonate; diphenyl carbonate; ethylene carbonate; propylene carbonate And boric acid esters such as tributyl borate and tripentyl borate.

  Among these, in particular, when tricresyl phosphate is used alone or in combination, the stability of the emulsion is most favorable, which is preferable. It is also possible to use the above oils in combination with other oils.

  On the other hand, an aqueous solution in which a water-soluble polymer is dissolved as a protective colloid is used for the aqueous phase to be used, and after the oil phase is added thereto, emulsification and dispersion are performed by means such as a homogenizer. It acts as a dispersion medium that makes the aqueous solution emulsified and dispersed stable. Here, in order to more uniformly emulsify and disperse and stabilize, a surfactant may be added to at least one of the oil phase and the aqueous phase. A known emulsifying surfactant can be used as the surfactant. 0.1-5% is preferable with respect to the mass of an oil phase, and, as for the addition amount of surfactant, 0.5-2% is more preferable.

  As the surfactant to be contained in the aqueous phase, an anionic or nonionic surfactant that does not cause precipitation or aggregation by acting with the protective colloid can be suitably selected and used. Preferable surfactants include, for example, sodium alkylbenzene sulfonate, sodium alkyl sulfate, dioctyl sulfosuccinate sodium salt, polyalkylene glycol (for example, polyoxyethylene nonyl phenyl ether) and the like.

  For emulsification, means used for usual fine particle emulsification such as high-speed stirring, ultrasonic dispersion, etc., for example, a homogenizer, a manton gory, an ultraphase, and an oil phase containing the above components and an aqueous phase containing a protective colloid and a surfactant. It can be easily carried out using a known emulsifying device such as a sonic disperser, a dissolver, a teddy mill or the like. After emulsification, the emulsion is preferably heated to 30 to 70 ° C. in order to promote the capsule wall formation reaction. Further, during the reaction, in order to prevent aggregation between the capsules, it is preferable to add water to reduce the collision probability between the capsules or perform sufficient stirring.

  Further, a dispersion for preventing aggregation may be added again during the reaction. Generation of carbon dioxide gas is observed as the polymerization reaction proceeds, and the end of the generation can be regarded as an approximate end point of the capsule wall formation reaction. Usually, the target microcapsule can be obtained by reacting for several hours.

  The water-soluble polymer contained as the protective colloid can be appropriately selected from known anionic polymers, nonionic polymers, and amphoteric polymers, and has a solubility in water at the temperature to be emulsified. A water-soluble polymer of 5% or more is preferable, and specific examples thereof include polyvinyl alcohol or a modified product thereof, polyacrylic acid amide or a derivative thereof, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, ethylene -Maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, vinyl acetate-acrylic acid copolymer, cellulose derivatives such as carboxymethylcellulose, methylcellulose, casein, gelatin, Starch derivatives, arabic gum, sodium alginate Etc. The. Among these, polyvinyl alcohol, gelatin, and cellulose derivatives are particularly preferable.

  Moreover, 0.02-0.6 are preferable and, as for the mixing ratio (oil phase mass / aqueous phase mass) with respect to the water phase of an oil phase, 0.1-0.4 are more preferable. When the mixing ratio is in the range of 0.02 to 0.6, an appropriate viscosity can be maintained, the production suitability is excellent, and the coating solution stability is excellent.

  Further, the mass ratio of the capsule wall to the fluorine compound is preferably 1/10 to 10/1, more preferably 1/10 to 5/1, more preferably 1/10 to 10/1, in view of the stability of the capsule shape. More preferably, it is 2/1.

-In situ polymerization method-
Encapsulation by a general in-situ polymerization method is performed by supplying raw material monomers, initiators, and the like of the resin for the outer shell from either the inner phase or the outer phase of the dispersed phase, and forming the outer shell by polymerization to obtain an encapsulated product. (Takanori Kondo, Naozumi Koishi “Microcapsule”, 1987, Sankyo Publishing Co., Ltd.)
That is, the in situ polymerization method sets the polymerization conditions such that the polymer formed in the surface layer of the core material uniformly surrounds the surface layer of the core material, and the monomer or This is a method of microencapsulation by supplying a polymerization catalyst.

~ Coacervation method ~
In the coacervation method, an oily component, which is a capsule core substance substantially insoluble in water, is dispersed in an aqueous solution containing the polyvinyl alcohol as a membrane material, and an electrolyte is added. A capsule is produced (described in JP-A-62-2440).

-Submerged curing coating method-
In-liquid curing coating method is to form the wall film by dispersing the material of the wall film constituting the microcapsule in a polymer solution in advance and preparing this solution in the desired shape and curing the polymer. Is the method.

~ Drying method in liquid ~
The in-liquid drying method is a dispersion in which a core substance (core solution or solid) is dispersed in a solvent in which a polymer material to be a wall film constituting a microcapsule is dissolved, and this is further used as the solvent. And then, the first solvent is gradually removed to precipitate the polymer at the interface of the core material.

  The microcapsule-containing fluorine-based composition of the present invention described above is heated to release the fluorine-based compound from the microcapsules when the function of the fluorine-based compound is exhibited. Heating can be performed using an oven, electron beam irradiation, laser irradiation, a heat exchange medium (heated water vapor, organic matter, flame gas, etc.), or a contact heating method in which a heater is brought into direct / indirect contact. As temperature in that case, it can be set as the temperature of about 50-250 degreeC, for example.

<Color filter composition>
The composition for a color filter of the present invention is characterized by containing the aforementioned microcapsule-containing fluorine-based composition of the present invention.
The color filter composition of the present invention can be suitably used for imparting water repellency (ink repellency) to the partition wall in the method for producing a color filter using the ink jet method as described above. That is, in the past, when the fluorine-based compound was used as it was, it could not be applied satisfactorily due to the repelling at the time of application, but in the color filter composition of the present invention, the fluorine-based compound is encapsulated in the microcapsule, By using it in that state, it can be applied satisfactorily. Moreover, water repellency can be imparted by releasing the fluorine-based compound from the microcapsule after coating. Furthermore, since the fluorine compound has an organic functional group capable of reacting with other compounds, the fluorine compound can be immobilized in patterning exposure after the fluorine compound is released from the microcapsules.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Note that “%” means “mass%” unless otherwise specified.

[Example 1]
(Preparation of microcapsule solution J1)
10.0 g of perfluorooctylethyl methacrylate (FAMAC, manufactured by Unimatec Co., Ltd.) was added to 21.2 g of ethyl acetate and dissolved. To this, 13.92 g of capsule wall material (Takenate D110N, Takeda Pharmaceutical Co., Ltd.) was added and mixed.
This solution was added to an aqueous phase mixed with 55.2 g of a 5.85 mass% polyvinyl alcohol aqueous solution (MP103, manufactured by Kuraray Co., Ltd.), and then rotated using an ace homogenizer (manufactured by Nippon Seiki Co., Ltd.). Emulsification was performed at 14000 rpm for 10 minutes. To the obtained emulsion, 93.60 g of water and 0.57 g of tetraethylenepentamine were further added, followed by an encapsulation reaction at 60 ° C. for 4 hours and 30 minutes, and a microcapsule coating solution having an average particle size of 0.21 μm ( A solid concentration of 23%) was prepared.

<Formation of capsule coating film>
Next, a capsule coating film was formed, and the coated surface and water repellency by heating were evaluated.
10.0 g of the microcapsule liquid J1 and 21 g of 0.58 mass% aqueous PVA205 were mixed at room temperature to obtain a uniform capsule coating liquid (microcapsule-containing fluorine-based composition).
Coating obtained by coating this capsule coating solution on a transparent glass substrate (Corning Corporation: 7059 material) having a thickness of 1.1 mm so as to have a film thickness of about 10 microns using a conventional bar coating method. After passing the membrane through a decompression chamber set to a pressure 196 to 882 Pa lower than the atmospheric pressure, in the subsequent first drying zone, the dry bulb temperature is 40 to 60 ° C., the dew point is 0 ° C., and the membrane surface wind speed is 5 m / sec or less. After initial drying with wind, the membrane surface temperature was adjusted to 18-23 ° C. with a dry bulb temperature of 23-45 ° C., a relative humidity of 20-70% RH, and a membrane surface wind speed of 15-25 m / sec. It was dried and the surface shape of the coated surface was confirmed. The evaluation results are shown in Table 1.

<Evaluation rank>
A The surface of the coated surface was good, and no cloudiness or aggregation was observed.
B Although white turbidity / aggregation was observed only slightly, the surface condition was good and there was no problem.
C Surface roughness or repelling occurred, and no coating film was obtained.

The obtained coating film was heated in a 120 ° C. oven and the contact angle was measured to evaluate water repellency. The evaluation results are shown in Table 1.
<Evaluation rank>
A The contact angle of water on the surface was 100 ° or more, indicating high water repellency.
The contact angle of water on the surface B was 60 ° to 100 °, indicating sufficient water repellency.
C The contact angle of water on the surface was less than 60 ° C. and showed no water repellency.

<Black pattern evaluation>
A black resist (manufactured by Fuji Hunt: CK2000) containing a black pigment and a photosensitive resin as a main component on a transparent glass substrate (Corning: 7059 material) having a thickness of 1.1 mm, and a conventional spin coating method. It was applied using a heat treatment called pre-baking and pre-dried.
Thereafter, the glass substrate holding the capsule coating film was attached so that the capsule film side was adhered to the black resist, and heated at 120 ° C. for 5 minutes to release a fluorine compound.

Next, a black pattern was formed by using a photomask to irradiate the entire surface with a light amount of 300 mJ / cm ² using ultraviolet light having a main wavelength of 365 nm and developing it. And in order to improve the adhesive strength of a resist and a glass substrate, the heat processing called post-baking were performed, and the black pattern with a thickness of 0.6 micrometer by which the surface was fluorinated was formed.
The resulting black pattern was heated in a 120 ° C. oven and the contact angle was measured to evaluate water repellency. The evaluation results are shown in Table 1.
<Evaluation rank>
A The contact angle of water on the surface was 100 ° or more, indicating high water repellency.
The contact angle of water on the surface B was 60 ° to 100 °, indicating sufficient water repellency.
C The contact angle of water on the surface was less than 60 ° C. and showed no water repellency.

[Example 2]
A microcapsule solution was prepared by the following preparation method, a capsule coating film was formed using the microcapsule solution, and the coated surface state and water repellency by heating were evaluated.
(Preparation of microcapsule solution J2)
In the preparation of the microcapsule liquid J1 of Example 1, perfluorooctylethyl methacrylate (FAMAC, manufactured by Unimatec Co., Ltd.) was changed to perfluorooctylethyl acrylate (FAAC, manufactured by Unimatec Co., Ltd.), According to the preparation method of the microcapsule solution J1, microcapsule solution J2 was prepared, and a capsule coating solution (solid content concentration 23%) having an average particle size of 0.20 μm was prepared.

  Using the obtained capsule coating solution, a capsule coating film was formed in the same manner as in Example 1, and the surface repellency, water repellency and black pattern water repellency were evaluated. The results are shown in Table 1.

[Example 3]
A microcapsule solution was prepared by the following preparation method, a capsule coating film was formed using the microcapsule solution, and the coated surface state and water repellency by heating were evaluated.
(Preparation of microcapsule solution J3)
In the preparation of the microcapsule solution J1 of Example 1, the capsule material (Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd.) was changed to 5.57 g and tetraethylenepentamine 0.23 g. According to the preparation method, a microcapsule liquid J3 was prepared, and a capsule coating liquid (solid content concentration 21%) having an average particle diameter of 0.22 μm was prepared.

  Using the obtained capsule coating liquid, a capsule coating film was formed in the same manner as in Example 1, and the surface repellency, water repellency and black pattern water repellency were evaluated. The results are shown in Table 1.

[Example 4]
A microcapsule solution was prepared by the following preparation method, a capsule coating film was formed using the microcapsule solution, and the coated surface state and water repellency by heating were evaluated.
(Preparation of microcapsule solution J4)
In the preparation of the microcapsule liquid J1 of Example 1, the capsule material (Takenate D110N, Takeda Pharmaceutical Co., Ltd.) was changed to 1.65 g, and tetraethylenepentamine was changed to 0.07 g. According to the preparation method of J1, microcapsule liquid J4 was prepared, and a capsule coating liquid (solid content concentration 23%) having an average particle diameter of 0.21 μm was prepared.
Using the obtained capsule coating liquid, a capsule coating film was formed in the same manner as in Example 1, and the surface repellency, water repellency and black pattern water repellency were evaluated. The results are shown in Table 1.

[Example 5]
A microcapsule solution was prepared by the following preparation method, a capsule coating film was formed using the microcapsule solution, and the coated surface state and water repellency by heating were evaluated.
(Preparation of microcapsule solution J5)
In the preparation of the microcapsule liquid J1 of Example 1, except that the rotation speed of the homogenizer was changed to 7000 rpm, a microcapsule liquid J5 was prepared according to the preparation method of the microcapsule J1, and a capsule coating liquid having an average particle size of 0.56 μm (Solid content concentration 25%) was prepared.
Using the obtained capsule coating liquid, a capsule coating film was formed in the same manner as in Example 1, and the surface repellency, water repellency and black pattern water repellency were evaluated. The results are shown in Table 1.

[Example 6]
A microcapsule solution was prepared by the following preparation method, a capsule coating film was formed using the microcapsule solution, and the coated surface state and water repellency by heating were evaluated.
(Preparation of microcapsule J6)
A microcapsule was used except that the capsule wall material (Takenate D110N, Takeda Pharmaceutical Co., Ltd.) was changed to a capsule wall material (Takenate D140N, Takeda Pharmaceutical Co., Ltd.) in the preparation of the microcapsule J4 of Example 4. According to the preparation method of J4, microcapsule liquid J6 was prepared, and a capsule coating liquid (solid content concentration 22%) having an average particle diameter of 0.23 μm was prepared.
Using the obtained capsule coating liquid, a capsule coating film was formed in the same manner as in Example 1, and the surface repellency, water repellency and black pattern water repellency were evaluated. The results are shown in Table 1.

[Comparative Example 1]
A microcapsule solution was prepared by the following preparation method, a capsule coating film was formed using the microcapsule solution, and the coated surface state and water repellency by heating were evaluated.
(Preparation of microcapsule solution H1)
In the preparation of the microcapsule liquid J1 of Example 1, perfluorooctylethyl methacrylate (FAMAC, manufactured by Unimatec) was changed to a fluorinated oil (perfluoropolyether compound, PTFE, manufactured by 3M). Prepared a microcapsule liquid H1 according to the method for preparing the microcapsule liquid J1, and prepared a capsule coating liquid (solid content concentration 24%) having an average particle size of 0.32 μm.
Using the obtained capsule coating liquid, a capsule coating film was formed in the same manner as in Example 1, and the surface repellency, water repellency and black pattern water repellency were evaluated. The results are shown in Table 1.

[Comparative Example 2]
(Preparation of microcapsule solution H2)
In the preparation of the microcapsule liquid J1 of Example 1, in order to increase the capsule particle size to 10 μm or more, when the rotation speed of the homogenizer was lowered to 2000 rpm, aggregation occurred during the encapsulation reaction, and microcapsules could not be obtained. .

[Comparative Example 3]
<Preparation of capsule coating film H4>
An attempt was made to form a capsule coating film in the same manner as in Example 1, except that the microcapsule liquid J1 of Example 1 was changed to a fluorinated oil (perfluoropolyether compound, PTFE, manufactured by 3M Corporation). . However, repelling occurred and a coating film was not obtained.

  From Table 1, in Examples 1 to 6, good results were obtained in the preparation of the microcapsule solution, the capsule coating film, and the black pattern. In contrast, Comparative Example 1 using a perfluoropolyether compound as the fluorine-based compound was able to form a capsule coating film, but was inferior in water repellency. In Comparative Example 2 in which the particle size of the microcapsules was set to 10 μm or more, the microcapsules themselves could not be formed. Further, in Comparative Example 3 in which a microcapsule was not formed and a perfluoropolyether compound was used as it was, a coating film could not be formed and practicality was not recognized.

Claims (6)

In the fluorine-based composition containing the microcapsules encapsulating the fluorine-based compound,
The micro compound containing at least one organic functional group selected from the group consisting of an acidic group, a basic group, a cyclic ether group, a polymerizable vinyl group, a hydroxyl group, and a thiol group. Capsule-containing fluorine-based composition.   The microcapsule-containing fluorine-based composition according to claim 1, wherein the organic functional group is a polymerizable vinyl group.   The number average particle diameter of the microcapsules is 0.01 to 10.0 μm, and the mass ratio of the capsule wall of the microcapsules to the fluorine-based compound is 1/10 to 10/1. Or the microcapsule-containing fluorine-based composition according to 2;   The capsule wall of the microcapsule is formed by any one of an interfacial polymerization method, an in situ polymerization method, a coacervation method, a submerged curing coating method, and a submerged drying method. 4. The microcapsule-containing fluorine-based composition according to any one of items 1 to 3.   The microcapsule-containing fluorine-based composition according to any one of claims 1 to 4, wherein the capsule wall-forming material of the microcapsule is a compound containing a urethane urea bond.   A color filter composition comprising the microcapsule-containing fluorine-based composition according to any one of claims 1 to 5.