JP5531495B2 - Color resist composition, color filter, and liquid crystal display device - Google Patents

Description

  The present invention relates to a color resist composition excellent in coatability and developability, a color filter using the same, and a liquid crystal display device.

  The color filter used in the color liquid crystal display device is generally a basic in which each pixel of red (R), green (G), and blue (B) and a black matrix (BM) are formed between them for the purpose of improving display contrast. It has a configuration. In the production of a color filter, a color resist composition is generally applied on a glass substrate by a coating method such as spin coating or slit coating, and after drying, exposed using a mask and then developed to form a colored pattern. If the coating smoothness is not good and the film thickness is uneven, or if there is application unevenness, repellency, etc., pixel color unevenness occurs. When a color liquid crystal display device is manufactured using a color filter having such color unevenness, there arises a problem that color unevenness occurs in an image obtained on the display. That is, the surface of these R, G, B pixels and BM in the color filter is required to have high smoothness. For this purpose, when the color resist composition is applied, it has a uniform film thickness and uneven coating. It is necessary to apply the coating so as not to cause repelling and color unevenness.

  In recent years, the amount of polymerizable compounds has decreased with the increase in the content of pigments used in color resists due to the increase in brightness and definition of color filters. It has become. In addition, the concentration of the alkaline developer is increased as a shortening of the manufacturing process time associated with the improvement in productivity, and the coating surface of the exposed portion that remains is more likely to be eroded. Therefore, there is a demand for a material that is resistant to an alkaline developer and that can form a pattern with high accuracy after exposure and development.

  Furthermore, after development with the developer, unexposed areas are washed away by rinsing, but the resin and contaminants in the unexposed areas present in the cleaning liquid adhere to the cured coating surface of the colored pattern in the exposed areas. There is also a defect called “stain”, and this water stain prevention is one of the required characteristics of developability.

  In order to prevent color unevenness due to coating unevenness, repelling, etc., a method of using a fluorosurfactant has been proposed, and in order to improve its effect, the constituent components of the copolymer used for the surfactant have been improved. (For example, refer to Patent Documents 1 to 4.) Although the water repellent effect of these fluorosurfactants can be expected to be resistant to alkali developer (alkali resistance) and prevent water stains, these fluorosurfactants are actually used as a component of color resist compositions. When used, the effect of preventing alkali resistance and water spots was insufficient.

  Therefore, there is a demand for a color resist composition that can form a colored pattern with high accuracy and does not cause water spots by having a high color unevenness prevention effect and alkali resistance that can prevent erosion of the coating film surface by an alkali developer. Yes.

JP-A-10-230154 JP-A-10-309455 JP 2002-139830 A JP 2004-109179 A

  The problem to be solved by the present invention is a color resist that can prevent color unevenness due to coating unevenness, repelling, etc., and can form a colored pattern with high accuracy by having alkali resistance capable of preventing erosion of the coating film surface by an alkali developer. The object is to provide a composition, a color filter using the composition, and a liquid crystal display device.

  As a result of intensive research to solve the above problems, the present inventors have used a color resist composition containing a fluorine-based surfactant having a polymerizable group, thereby preventing uneven coating and color unevenness due to repelling, etc. The present inventors have found that the surface of the coating film can be prevented from being eroded by an alkali developer due to the development of alkali resistance in the exposed area, and that a colored pattern can be formed with high accuracy, thereby completing the present invention.

That is, the present invention is an alkali-soluble resin (A), the polymerizable compound (B), be Luke error resist composition to contain a fluorine-based surfactant (D) having a colorant (C) and a polymerizable group The fluorine-based surfactant (D) comprises a compound (d1) having a poly (perfluoroalkylene ether) chain and a structural moiety having a radically polymerizable unsaturated group at both ends thereof, and a reactive functional group (R1). A polymer (P1) obtained by copolymerizing a radically polymerizable unsaturated monomer (d2) having an essential monomer component with a functional group (R2) reactive with the functional group (R1). ) And a compound (d3) having a radically polymerizable unsaturated group (F3), or a radically polymerizable unsaturated monomer having a reactive functional group (R1) (D1). d2) polymer (P2) A compound (d1 ′) having a poly (perfluoroalkylene ether) chain and a functional group (R2) having reactivity to the reactive functional group (R1) at both ends thereof, and the functional group (R1). A color resist composition comprising a fluorine-based surfactant (D2) obtained by reacting a functional group (R2) having reactivity with a compound (d3) having a radically polymerizable unsaturated group It provides things.

  Furthermore, the present invention provides a color filter having a cured coating film of the color resist composition, and a liquid crystal display device provided with the color filter on at least a part of a substrate.

  Since the color resist composition of the present invention does not cause coating unevenness, repellency, etc., and the fluorine-containing surfactant contained in the composition has a polymerizable group, it can be cured on the coating film surface by exposure. Since only the exposed portion can exhibit alkali resistance, water spots can be prevented. Therefore, by using the color resist composition, it is possible to provide a color filter that is excellent in color reproducibility without color unevenness and has a colored pattern formed with high accuracy. In addition, by using the color filter, a liquid crystal display device having excellent display characteristics can be provided.

FIG. 1 is an IR spectrum chart of the fluorosurfactant (1) having a polymerizable group obtained in Synthesis Example 1. FIG. 2 is a ¹³ C-NMR chart of the fluorosurfactant (1) having a polymerizable group obtained in Synthesis Example 1. FIG. 3 is a ¹⁹ F-NMR chart of the fluorochemical surfactant (1) having a polymerizable group obtained in Synthesis Example 1.

  The alkali-soluble resin (A) used in the present invention is not particularly limited as long as it is soluble in an alkali developer, but at least one acidic group selected from the group of carboxyl group, phenolic hydroxyl group and sulfonic acid group. Or the resin which has the salt is preferable.

  More specifically, the alkali-soluble resin (A) is obtained by polymerizing a monomer having an acidic group. Examples of the monomer having a carboxyl group as an acid group as a raw material for the alkali-soluble resin (A) include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, These salts are mentioned.

  As a monomer which has a phenolic hydroxyl group as an acidic group used as the raw material of alkali-soluble resin (A), o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene etc. are mentioned, for example. In addition, one or more hydrogen atoms other than the phenolic hydroxyl group and vinyl group bonded to the aromatic ring of these monomers were substituted with an alkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or an amide group. A compound etc. are also mentioned.

  Examples of the monomer having a sulfonic acid group as an acidic group as a raw material for the alkali-soluble resin (A) include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, and 2-hydroxy-3- (meth). Allyloxypropanesulfonic acid, (meth) acrylic acid-2-sulfoethyl, (meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2 -Methylpropanesulfonic acid or a salt thereof.

  Moreover, although the monomer which has said acidic group can superpose | polymerize independently and can be set as alkali-soluble resin (A), you may make it copolymerize with another monomer. Such other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides. , Aromatic vinyl compounds, chloroolefins, conjugated dienes and the like. Among these, (meth) acrylic acid esters are preferable.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, (meth) acrylic acid n-hexyl, 2-ethyl- (meth) acrylate-n-hexyl, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) a 4-hydroxybutyl toluate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, (meth) acryl Acid 3-chloro-2-hydroxypropyl, glycerin mono (meth) acrylate, 1,1-dimethyl-3-oxobutyl (meth) acrylate, (meth) acrylic acid 2-acetoacetoxyethyl, (meth) acrylic acid 2- Examples include methoxyethyl, 2-ethoxyethyl (meth) acrylate, and benzyl (meth) acrylate.

  The monomer having an acidic group that is a raw material of the alkali-soluble resin (A) and the other monomer may be used alone or in combination of two or more.

  In the present invention, “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid, and “(meth) acryloyl” refers to one or both of methacryloyl and acryloyl. ) "Acrylate" refers to one or both of methacrylate and acrylate.

  The polymerizable compound (B) used in the present invention is not particularly limited as long as it is a compound having a photopolymerizable functional group that can be polymerized or cross-linked by irradiation with active energy rays such as ultraviolet rays. Specific examples include, for example, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Glycerin tri (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate (Meth) acrylate compounds such relations are exemplified.

  Also, N, N′-ethylene dimaleimide, N, N′-hexamethylene dimaleimide, N, N′-dodecamethylene dimaleimide, N, N′-m-phenylene dimaleimide, N, N′-p-pheny Rangemaleimide, N, N ′-(oxydi-p-phenylene) dimaleimide, N, N ′-(methylenedi-p-phenylene) dimaleimide, N, N′-2,4-tolylenemaleimide, N, N′-2 , 6-Tolylenedimaleimide, N, N′-dimaleimide, N, N′-m-xylylenedimaleimide, N, N′-p-xylylenedimaleimide, N, N′-oxydipropylenemaleimide, ethylenedioxy -Bis-N-ethylmaleimide, N, N'-p, p'-diphenylsulfone bismaleimide, N, N'-p, p'-diphenyl ether bismaleimide N, N'-dicyclohexylmethane bismaleimide, N, N '-(3,3'-dichloro-p, p'-bisphenylene) bismaleimide, 1,1,1,3,3,3-hexafluoro -2,2-bis (4-maleimidophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, ethoxy (3 -Maleimidopropioxy) ethane, ethoxy (3-maleimidopropoxy) butane, diethylene glycol (3-maleimidopropyl) methyl ether, methyl (3-maleimidopropyl) ether of polyethylene glycol with Mn = 400, trimethylolpropane tri (3- Maleimidopropyl ether), polyethylene glycol bis (3- Ether compounds such as (reimidopropyl) ether, polyethylene glycol mono (3-maleimidopropyl) vinylether with Mn = 400; methylmaleimide acetate, ethylmaleimide capronate, ethylene glycol monomethylethermaleimide acetate, polyethylene glycol with Mn = 400 Monomethyl ether maleimide acetate, tetrahydrofurfuryl maleimide acetate, diethylene glycol bismaleimide acetate, diethylene glycol monomaleimide acetate acrylate, bismaleimide acetate of polyethylene glycol with Mn = 400, bismaleimide acetate of polytetramethylene glycol with Mn = 250, Mn = 400 Polyethylene glycol monomaleimide capro Nate acrylate, trimethylolpropane trimaleimide acetate, ethylene oxide modified trimethylolpropane trimaleimide acetate, ethylene oxide modified trimethylolpropane dimaleimide acetate monoacrylate, pentaerythritol tetramaleimide acetate, ethylene oxide modified pentaerythritol dimaleimide acetate, ethylene oxide modified pentaerythritol trimaleimide Maleimide ester compounds such as acetate, ethylene oxide modified pentaerythritol tetramaleimide acetate, ethylene oxide modified pentaerythritol dimaleimide acetate diacrylate; N-ethyl- (2-maleimidoethyl) carbamate; sophorone diisocyanate and (poly) alkylene Urethane compounds obtained by reacting an equivalent mixture with ol with 2-maleimidoethanol; maleimide carbonate compounds such as 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-isopropyl carbonate, tetraethylene glycol bis (3-maleimidopropyl carbonate), etc. And maleimide derivatives of These polymerizable compounds (B) can be used alone or in combination of two or more.

  The mass ratio of the alkali-soluble resin (A) and the polymerizable compound (B) is preferably in the range of (A) :( B) = 40: 60 to 90:10, and in the range of 50:50 to 80:20. More preferably, the range of 55:45 to 70:30 is even more preferable.

  The colorant (C) used in the present invention can be used without particular limitation as long as it can be colored. However, a pigment is preferable from the viewpoint of high heat resistance and light resistance, and any of organic pigments and inorganic pigments can be used. Can be used.

  As said organic pigment, it uses according to the color of each pixel of red (R), green (G), and blue (B). For red (R) pixels, for example, C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Gment Red 240, C.I. I. Cement red 254, C.I. I. Red pigments such as CI Pigment Red 48: 1 can be used.

  For green (G) pixels, for example, C.I. I. Pigment green 7, C.I. I. Green pigments such as CI Pigment Green 36 can be used. For blue (B) pixels, for example, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Blue pigments such as CI Pigment Blue 64 can be used.

  In addition, for the purpose of improving the color reproducibility of each of the red (R), green (G), and blue (B) pixels, organic pigments of other colors may be used for hue adjustment. Examples of such organic pigments for hue adjustment include C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 30, C.I. I. Pigment violet 37, C.I. I. Pigment violet 40, C.I. I. Violet pigments such as CI Pigment Violet 50; I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. And yellow pigments such as CI Pigment Yellow 185.

  On the other hand, the colorant (C) used for forming the black matrix (BM) is not particularly limited as long as it is black, but is composed of carbon black, metal oxide, or two or more metal oxides. Pigments such as composite metal compounds are preferred. Further, a combination in which two or more organic pigments selected from pigments having hues of red, blue, green, purple, yellow, cyan, and magenta are mixed and made black by mixing colors may be used.

Examples of the carbon black include lamp black, acetylene black, thermal black, channel black, and furnace black. Examples of the metal oxide include titanium black obtained by oxidation of titanium or reduction of titanium dioxide. Usually, titanium black is represented by Ti _m O _2m-1 (m is a number of 1 or more). Moreover, metal oxides, such as copper, iron, chromium, manganese, cobalt, are mentioned as a metal oxide. Furthermore, as the composite metal compound composed of two or more kinds of metal oxides, for example, copper-chromium oxide, copper-chromium-manganese oxide, copper-iron-manganese oxide, or cobalt-iron-manganese An oxide etc. are mentioned.

  On the other hand, examples of organic pigments include quinacridone pigments, perylene pigments, pyrrolo-pyrrole pigments, anthraquinone pigments and the like as pigments having a red hue, and phthalocyanines as pigments having a blue hue. Pigments, indanthrene pigments, etc., pigments having a green hue include halogenated phthalocyanine pigments, and pigments having a purple hue include dioxazine violet, fast violet B, methyl Examples of pigments having a hue having a yellow hue include tetrachloroisoindolinone pigments, hansa yellow pigments, benzidine yellow pigments, and azo pigments. As a pigment having a cyan hue, metal-free phthalose Nin, merocyanine, and examples of the pigment having a magenta hue, dimethyl quinacridone, thioindigo, and the like.

  The colorant (C) used to form each pixel of red (R), green (G), and blue (B) and the black matrix (BM) can be used alone or in combination according to the required hue. It can also be used in combination.

  The blending amount of the colorant (C) is preferably in the range of 10 to 80 parts by mass on the basis of 100 parts by mass in total of the alkali-soluble resin (A) and the polymerizable compound (B). A range of 15 to 65 parts by mass is more preferable.

  In the color resist composition of the present invention, when the colorant (C) is a pigment, it is preferable to prepare and use a pigment dispersion prepared by dispersing it in an organic solvent using a dispersant. Examples of the dispersant include surfactants; intermediates or derivatives of pigments; intermediates or derivatives of dyes; resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. It is done. Among these pigment dispersants, a resin dispersant containing an acrylic polymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain is particularly preferable. Examples of such commercially available resin-type dispersants include “BYK-160”, “BYK-161”, “BYK-2001” manufactured by BYK Chemie, “Efka 46” manufactured by Fuka Chemicals, and Ajinomoto Fine. Examples include “Ajisper PB-814” manufactured by Techno Corporation. These dispersants can be used alone or in combination of two or more.

  Examples of the organic solvent used in the preparation of the pigment dispersion include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; toluene Aromatic solvents such as xylene, methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic carbonization such as hexane Hydrogen-based solvents; nitrogen compound solvents such as N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone; γ-butyrolacto Lactone solvents such as carbene; carbamates and the like. These solvents can be used alone or in combination of two or more.

  Examples of the method for preparing the pigment dispersion include a method in which the colorant (C) is kneaded and dispersed, a method in which the dispersion is performed, and a method in which only the fine dispersion is performed. In the kneading and dispersing step, the colorant (C), a part of the alkali-soluble resin (A), and, if necessary, the dispersing agent are mixed and kneaded. Examples of the machine used for kneading include two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, and single-screw or twin-screw extruders. The colorant can be dispersed by dispersing while applying force. The colorant (C) is preferably refined in particle size by a salt milling method or the like before the kneading.

  On the other hand, in the fine dispersion step, a composition obtained by adding the solvent to the composition containing the colorant (C) obtained in the kneading and dispersion step, or the colorant (C), the alkali-soluble resin (A), the solvent and necessary According to the above, the dispersion agent is mixed and dispersed together with a dispersion medium for fine particles of glass, zirconia or ceramic using a disperser, so that the colorant (C) particles are in a minute state close to primary particles. Can be dispersed.

  Further, from the viewpoint of improving the transmittance and contrast of the color filter, the average particle diameter of the primary particles of the colorant (C) is preferably 10 to 100 nm, and more preferably 10 to 60 nm. The average particle size of the colorant (C) was measured with a dynamic light scattering particle size distribution meter. For example, Nanotrac particle size distribution measuring device “UPA-EX150 manufactured by Nikkiso Co., Ltd.” ”,“ UPA-EX250 ”or the like.

  The fluorosurfactant (D) having a polymerizable group used in the present invention can be used without particular limitation as long as it has a fluorine atom and has a polymerizable group. Those having an (alkylene ether) chain are preferred.

  The fluorine-containing surfactant (D) having a poly (perfluoroalkylene ether) chain is a compound (d1) having a poly (perfluoroalkylene ether) chain and a structural moiety having a radically polymerizable unsaturated group at both ends thereof. ) And a radically polymerizable unsaturated monomer (d2) having a reactive functional group (R1) as an essential monomer component, the polymer (P1) is copolymerized with the functional group (R1). ) And a functional group (R2) having reactivity and a compound (d3) having a radically polymerizable unsaturated group, and a fluorosurfactant (D1) obtained. Further, the polymer (P2) of the radically polymerizable unsaturated monomer (d2) having a reactive functional group (R1) is added to the poly (perfluoroalkylene ether) chain and the reactive functional group (R1 at both ends). ) Having a functional group (R1) having a reactive functional group (R2), a functional group (R2) having a reactivity with respect to the functional group (R1), and a radically polymerizable unsaturated group. Also included is a fluorine-based surfactant (D2) obtained by reacting the compound (d3).

  Here, examples of the radical polymerizable unsaturated monomer (d2) include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, maleimide monomers, and the like. Examples of the reactive functional group (R1) possessed by the radical polymerizable unsaturated monomer (d2) include a hydroxyl group, an isocyanate group, an epoxy group, and a carboxyl group.

  Specific examples of the radical polymerizable unsaturated monomer (d2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone Hydroxyl group-containing unsaturated monomers such as reactive (meth) acrylates; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyl) Isocyanate group-containing unsaturated monomers such as oxymethyl) ethyl isocyanate; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyl Examples thereof include carboxyl group-containing unsaturated monomers such as loxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and itaconic acid.

  The radical polymerizable unsaturated monomer (d2) may be copolymerized with other radical polymerizable unsaturated monomers. Examples of other radical polymerizable unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylic acid esters such as nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; styrene, α-methylstyrene , P-methylstyrene, p-methoxystyrene and other aromatic vinyls; maleimide, methylmaleimide, ethyl Reimido, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, and the like maleimides such as cyclohexyl maleimide.

  Next, the poly (perfluoroalkylene ether) chain of the compound (d1) or the compound (d1 ′) is specifically composed of alternately divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms. The thing which has the structure which connected is mentioned. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds, and specifically, those represented by the following structural formula 1 can be mentioned. .

（上記構造式１中、Ｘは下記構造式ａ〜ｄであり、構造式１中の全てのＸが同一構造のものであってもよいし、また、複数の構造がランダムに又はブロック状に存在していてもよい。また、ｎは繰り返し単位を表す１以上の数である。）

(In the above structural formula 1, X is the following structural formulas a to d, and all X in the structural formula 1 may have the same structure, or a plurality of structures are randomly or block-shaped. And n is a number of 1 or more representing a repeating unit.

  Among these, a perfluoromethylene structure represented by the structural formula a and a perfluoroethylene structure represented by the structure b are provided in that a coating film having particularly excellent smoothness can be obtained and color unevenness can be prevented. Those that coexist are particularly preferred. Here, the abundance ratio between the perfluoromethylene structure represented by the structural formula a and the perfluoroethylene structure represented by the structure b is such that the molar ratio (structure a / structure b) is 1/4 to 4 /. A ratio of 1 is preferable from the viewpoint that a coating film excellent in smoothness can be obtained and color unevenness can be prevented, and the value of n in the structural formula 1 is in the range of 3 to 40. 6-30 are preferable.

  In addition, the poly (perfluoroalkylene ether) chain has a total of fluorine atoms contained in one poly (perfluoroalkylene ether) chain from the viewpoint of easily improving the compatibility with other components in the color resist composition. The range is preferably 18 to 200, and particularly preferably 25 to 80.

  The radically polymerizable unsaturated group possessed by the fluorosurfactant (D) used in the present invention is an ethylenic double bond that exhibits curability when irradiated with active energy rays, and specifically includes the following structural formula U- The thing shown by 1-U-3 is mentioned.

  In order to introduce the radical polymerizable unsaturated group described above into the fluorosurfactant (D) used in the present invention, after obtaining the polymer (P1) or the polymer (P2), the side chain of the polymer And the reactive functional group (R1) present in the compound is reacted with a compound (d3) having a functional group (R2) reactive with the reactive functional group (R1) and a radically polymerizable unsaturated group. It is done.

  Therefore, the fluorosurfactant (D) is specifically reactive with the compound (d1) having a poly (perfluoroalkylene ether) chain and a structural moiety having a radically polymerizable unsaturated group at both ends thereof. The polymer (P1) obtained by copolymerizing the radically polymerizable unsaturated monomer (d2) having the functional group (R1) as an essential monomer component has a reactivity with the functional group (R1). What is obtained by reacting the compound (d3) having a functional group (R2) and a radically polymerizable unsaturated group (hereinafter referred to as “fluorinated surfactant (D1)”) or reactive. A polymer (P2) of a radically polymerizable unsaturated monomer (B) having a functional group (R1), a poly (perfluoroalkylene ether) chain and its reactive functional group (R1) at both ends thereof Reactive functional groups ( Obtained by reacting the compound (d1 ′) having 2) with the compound (d3) having a functional group (R2) having reactivity with the functional group (R1) and a radically polymerizable unsaturated group. It is preferable that it is a product (hereinafter referred to as “fluorine-based surfactant (D2)”) because its industrial production is easy.

  Here, the compound (d1) having a structural part having a poly (perfluoroalkylene ether) chain and radically polymerizable unsaturated groups at both ends thereof, used when producing the fluorosurfactant (D1), Examples thereof include those having radically polymerizable unsaturated groups represented by the following structural formulas U′-1 to U′-4 at both ends of the poly (perfluoroalkylene ether) chain.

  Among these radically polymerizable unsaturated groups, the structural formula U′- is particularly preferable because the compound (d1) itself is easily obtained and manufactured, or has excellent reactivity with the radically polymerizable unsaturated monomer. The acryloyloxy group represented by 1 or the methacryloyloxy group represented by the structural formula U′-2 is preferable.

  Examples of the compound (d1) having the acryloyloxy group or methacryloyloxy group described above include those represented by the following structural formulas d1-1 to d1-10. In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain.

  Among these, the structural formulas d1-1, d1-2, d1 are particularly easy because the industrial production of the compound (d1) itself is easy and the polymerization reaction when producing the polymer (P1) is also easy. Those represented by −5 and d1-6 are preferred.

  In order to produce the compound (d1), for example, a method obtained by dehydrochlorinating (meth) acrylic acid chloride to a perfluoropolyether having one hydroxyl group at both ends, (meth) acrylic acid A method obtained by dehydration reaction, a method obtained by urethanation of 2- (meth) acryloyloxyethyl isocyanate, a method obtained by esterification of itaconic anhydride, perfluoro having one carboxyl group at both ends For a polyether, a method obtained by esterifying 4-hydroxybutyl acrylate glycidyl ether, a method obtained by esterifying glycidyl methacrylate, and a perfluoropolyether having one isocyanate group at both ends. , 2-hydroxyethylacrylamide reaction method And the like. Among these, a method obtained by dehydrochlorinating (meth) acrylic acid chloride to perfluoropolyether having one hydroxyl group at both ends, and urethanization of 2- (meth) acryloyloxyethyl isocyanate The method obtained by reacting is particularly preferable in that it can be easily obtained synthetically.

  Here, the method for producing the polymer (P1) includes the compound (d1), the radical polymerizable unsaturated monomer (d2) having a reactive functional group (R1), and, if necessary, other radical polymerization. And a method of polymerizing the unsaturated unsaturated monomer in an organic solvent using a radical polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  The obtained polymer (P1) preferably has a number average molecular weight in the range of 800 to 3,000, and more preferably in the range of 1,000 to 2,000. The polymer (P1) preferably has a weight average molecular weight in the range of 1,500 to 20,000, and more preferably in the range of 2,000 to 8,000. If the average molecular weight of the polymer (P1) is within these ranges, it is possible to prevent the occurrence of crosslinking insolubilization during the polymerization. In addition, the number of polymerizable unsaturated groups in one molecule of the finally obtained fluorosurfactant (D1) can be increased.

  By reacting the polymer (P1) thus obtained with a compound (d3) containing a functional group (R2) reactive with the functional group (R1) and a radically polymerizable unsaturated group, The intended fluorosurfactant (D1) is obtained.

  Here, as for the functional group (R2) which the said compound (d3) has, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group etc. are mentioned, for example. For example, when the reactive functional group (R1) is a hydroxyl group, the functional group (R2) includes an isocyanate group. When the reactive functional group (R1) is an isocyanate group, the functional group (R2) When the reactive functional group (R1) is an epoxy group, a carboxyl group is exemplified as the functional group (R2), and when the reactive functional group (R1) is a carboxyl group, the functional group is functional. An epoxy group is mentioned as group (R2).

  As such a compound (d3), the thing similar to what was illustrated as said radically polymerizable unsaturated monomer (d2) can be used. In addition, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate can also be used.

  Of these, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate are particularly preferred because of their polymerization curability upon irradiation with active energy rays such as ultraviolet rays. 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether and acrylic acid are preferred.

  A method of reacting the polymer (P1) with a compound (d3) containing a functional group (R2) having reactivity with the functional group (R1) and a radically polymerizable unsaturated group is obtained by reacting the compound (d3) For example, it is preferable to carry out the reaction while adjusting the temperature condition in the range of 30 to 120 ° C. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the functional group (R1) is a hydroxyl group and the functional group (R2) is an isocyanate group, or when the functional group (R1) is an isocyanate group and the functional group (R2) is a hydroxyl group, P-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, etc. are used as polymerization inhibitors, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, octylic acid as urethanization reaction catalysts A method of reacting at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. using zinc or the like is preferable. When the functional group (R1) is an epoxy group and the functional group (R2) is a carboxyl group, or the functional group (R1) is a carboxyl group and the functional group (R2) is an epoxy group. In this case, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and tertiary amines such as triethylamine are used as an esterification reaction catalyst, tetramethyl chloride. Using quaternary ammoniums such as ammonium, tertiary phosphines such as triphenylphosphine, and quaternary phosphoniums such as tetrabutylphosphonium chloride, the reaction is carried out at a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. It is preferable to make it.

  The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, hydrocarbons, specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  Next, in order to produce the fluorosurfactant (D2), first, a radical polymerizable unsaturated monomer (d2) having a reactive functional group (R1) is polymerized to produce a polymer (P2). To do. At this time, as described above, other radical polymerizable unsaturated monomers may be used in combination with the radical polymerizable unsaturated monomer (d2) for copolymerization. As in the case of producing the polymer (P1), the polymerization method is a radical polymerizable unsaturated monomer (d2) having a reactive functional group (R1), and if necessary, other radical polymerizable unsaturated monomers. Can be polymerized using a radical polymerization initiator. At this time, it is preferably carried out in the presence of an organic solvent, and a chain transfer agent may be used if necessary. The organic solvent, radical polymerization initiator, and chain transfer agent that can be used can be the same as those used for producing the polymer (P1).

  The polymer (P2) thus obtained preferably has a number average molecular weight in the range of 800 to 3,000 as measured by GPC, and preferably in the range of 1,000 to 2,000. The polymer (P2) preferably has a weight average molecular weight in the range of 1,200 to 6,000, and preferably in the range of 1,500 to 5,000. When the average molecular weight of the polymer (P2) is within these ranges, it is possible to prevent the occurrence of crosslinking insolubilization during the polymerization.

  Next, a compound (d1) having a poly (perfluoroalkylene ether) chain and a functional group (R2) having reactivity to the reactive functional group (R1) at both ends of the polymer (P2) is obtained. ′) And a compound (d3) containing a functional group (R2) having reactivity with the functional group (R1) and a radically polymerizable unsaturated group to react with the target fluorine-based interface. An activator (D2) is obtained.

  At this time, the compound (d1 ′) may be reacted with the polymer (P2) first, and then the compound (d3) may be reacted, or vice versa. Furthermore, the compound (d1 ′) and the compound (d3) may be reacted with the polymer (P2) at the same time.

  In addition, the amount of the reactive functional group (R1) in the polymer (P2) and the reaction ratio of the compound (d1 ′) and the compound (d3) to the reactive functional group (R1) can be adjusted appropriately. It is desirable from the point that the effect of the present invention is remarkable. Specifically, the amount of the reactive functional group (R1) in the polymer (P2) is 100 to 200 g / eq. Is preferably from the point that the functional group concentration is high and the alkali resistance is better, and the functional group (R2) in the compound (d1 ′) with respect to 1 mol of the reactive functional group (R1). The functional group (R2) having reactivity in the compound obtained (d3) is 0.80 with respect to 1 mole of the reactive functional group (R1). The reaction is preferably carried out at a ratio of ˜0.95 mol.

  Here, the functional group (R2) in the compound (d1 ′) having a poly (perfluoroalkylene ether) chain and a functional group (R2) having reactivity to the reactive functional group (R1) at both ends thereof is , Hydroxyl group, isocyanate group, epoxy group, carboxyl group and the like. For example, when the reactive functional group (R1) is a hydroxyl group, the functional group (R2) includes an isocyanate group. When the reactive functional group (R1) is an isocyanate group, the functional group (R2) When the reactive functional group (R1) is an epoxy group, a carboxyl group is exemplified as the functional group (R2), and when the reactive functional group (R1) is a carboxyl group, the functional group is functional. An epoxy group is mentioned as group (R2).

  Examples of such a compound (d1 ′) include compounds represented by the following structural formulas d1′-1 to d1′-6, and polyfunctional isocyanates such as hexamethylene diisocyanate and tolylene diisocyanate. Examples thereof include compounds and compounds modified with bifunctional epoxy resins such as bisphenol type epoxy resins. In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain. Among these, unmodified compounds represented by the following structural formulas d1′-1 to d1′-6 are preferable. In particular, when the functional group (R1) is an isocyanate group, the following structural formula d1′-1 The compound (d1 ′) represented by the formula is preferable from the viewpoint of excellent reactivity with respect to the functional group (R1).

  Moreover, the compound (d3) used here can use the same thing as the compound (d3) used in the case of manufacture of above-mentioned fluorine-type surfactant (D1).

  As described above, the reaction between the polymer (P2), the compound (d1 ′) and the compound (d3) is performed by reacting the polymer (P2) with the compound (d1 ′) and then reacting the compound (d3). Alternatively, after the polymer (P2) and the compound (d3) are reacted, the compound (d1 ′) may be reacted, or the compound (d1 ′) and the compound (d3) are simultaneously combined. You may make it react with unification | combination (P2). The reaction conditions can be appropriately selected depending on the type of functional group involved in the reaction, regardless of which method is used.

  For example, when one of the functional group (R1) in the polymer (P2) and the functional group (R2) in the compound (d1 ′) is a hydroxyl group and the other is an isocyanate group, or the polymer (P2) When one of the functional group (R1) in the compound and the functional group (R2) in the compound (d3) is a hydroxyl group and the other is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6- Di-t-butyl-4-methylphenol or the like is used, dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like is used as the urethanization reaction catalyst, and the reaction temperature is 40 to 120 ° C., particularly 60 to A method of reacting at 90 ° C. is preferred.

  In addition, when one of the functional group (R1) in the polymer (P2) and the functional group (R2) in the compound (d1 ′) is a carboxyl group and the other is an epoxy group, or the polymer (P2 ) And the functional group (R2) in the compound (d3) are carboxyl groups and the other is an epoxy group, p-methoxyphenol, hydroquinone, 2, 6-di-t-butyl-4-methylphenol or the like, tertiary amines such as triethylamine as the esterification reaction catalyst, quaternary ammoniums such as tetramethylammonium chloride, tertiary such as triphenylphosphine Use phosphines, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc., and react at a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. Preferred.

  In these reactions, an organic solvent can be appropriately used. Examples of the organic solvent that can be used include ketones, esters, amides, sulfoxides, ethers, and hydrocarbons. Specifically, , Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene Etc. These may be appropriately selected in consideration of the boiling point and compatibility.

  The fluorine-based surfactant (D) represented by the above-described fluorine-based surfactant (D1) or fluorine-based surfactant (D2) has a number average molecular weight (Mn) of 1,000 to 10,000. Preferably, the weight average molecular weight (Mw) is in the range of 2,000 to 100,000, the number average molecular weight (Mn) is in the range of 1,500 to 5,000, and the weight. The average molecular weight (Mw) is more preferably in the range of 4,000 to 50,000. These average molecular weights are preferable because a coating film having higher crosslinkability and excellent developability can be obtained without causing gelation during the production of the fluorosurfactant (D).

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on GPC measurement. The measurement conditions for GPC are as follows.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C., developing solvent tetrahydrofuran, flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight is measured according to the measurement manual “GPC-8020 Model II version 4.10”. Using.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl).

  The fluorine-based surfactant (D) preferably contains 2 to 35% by mass of fluorine atoms in the surfactant and contains 5 to 25% by mass of fluorine atoms. More preferred is When the fluorine atom in the fluorosurfactant (D) is within this range, color unevenness prevention, high alkali resistance, and water stain prevention can be obtained.

  Furthermore, the content of the radical polymerizable unsaturated group in the fluorosurfactant (D) is such that the radical polymerizable unsaturated group equivalent is 200 to 900 g / eq. The ratio is preferably from the viewpoint of excellent alkali resistance and smoothness of the cured coating film, particularly 200 to 450 g / eq. It is particularly preferable that the range is

  The compounding quantity of the said fluorosurfactant (D) is 0.01- on a mass basis with respect to a total of 100 mass parts of the said alkali-soluble resin (A), a polymeric compound (B), and a coloring agent (C). The range is preferably 10 parts by mass, and more preferably 0.05 to 5 parts by mass. If the blending amount of the fluorosurfactant (D) is within this range, coating unevenness and repellency can be prevented, and the alkali resistance is also good.

  When irradiating active energy rays, such as an ultraviolet-ray, and hardening the color resist composition of this invention, a polymerization initiator (E) is mix | blended with the color resist composition of this invention. Examples of the polymerization initiator (E) include benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzyl methyl ketal, azobisisobutyronitrile, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- Methyl-1-phenyl-1-one, 1- (4′-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4′-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4 ″ -diethylisophthalophene, 2,2-dimethoxy-1,2-diphenylethane -1-one, benzoin isopropyl ether, thioxanthone, 2 Chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6, -trimethylbenzoyl)- Examples thereof include phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and these may be used alone or in combination of two or more. Among these, 2-benzyl-2-dimethylamino-1- (4-morpholine is not affected by the colorant (C) contained in the color resist composition of the present invention, but exhibits high curability. Linophenyl) -butanone-1 is preferred.

  Moreover, if necessary, a photosensitizer such as an amine compound or a phosphorus compound can be added to promote photopolymerization.

  The compounding amount of the polymerization initiator (E) is 0 with respect to a total of 100 parts by mass of the alkali-soluble resin (A), the polymerizable compound (B), the colorant (C) and the fluorosurfactant (D). The range is preferably from 0.01 to 15 parts by mass, and more preferably from 0.3 to 7 parts by mass.

  Furthermore, the color resist composition of the present invention is an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, light resistance, within a range that does not impair the effects of the present invention, depending on purposes such as use and characteristics. Additives such as a stabilizer stabilizer, a heat-resistant stabilizer, and an antioxidant can be blended.

  In addition, in order to impart coating suitability to the color resist composition of the present invention, an organic solvent may be added to adjust the viscosity. Examples of the organic solvent that can be used here include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatics such as toluene, xylene, and methoxybenzene. Group solvents; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N- Nitrogen compound solvents such as dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone; Lactone solvents such as γ-butyrolactone; Examples thereof include bamic acid esters. These solvents can be used alone or in combination of two or more.

  Here, the amount of the organic solvent used varies depending on the application and the intended film thickness and viscosity, but with respect to the total of the alkali-soluble resin (A), the polymerizable compound (B), and the fluorosurfactant (D). The amount is preferably in the range of 0.5 to 4 times the mass.

  Examples of active energy rays for curing the color resist composition of the present invention include active energy rays such as light, electron beam, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam using a scanning type or curtain type electron beam accelerator. In addition, when making it harden | cure with an electron beam, the mixing | blending of the said polymerization initiator (E) to the color resist composition of this invention is unnecessary.

  Among these active energy rays, ultraviolet rays are particularly preferable. Further, it is preferable to irradiate in an inert gas atmosphere such as nitrogen gas since the surface curability of the coating film is improved. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with active energy rays.

  The coating method of the color resist composition of the present invention varies depending on the application. For example, gravure coater, roll coater, comma coater, knife coater, curtain coater, shower coater, spin coater, slit coater, dipping, screen printing, spray, applicator And a coating method using a bar coater or the like.

The color resist composition of the present invention is useful for color filters (RGB pixel portions and black matrix portions) used in liquid crystal display devices. In addition, the color filter of this invention can be produced by forming a colored pattern through the following processes.
(1) The color resist composition of the present invention is applied on a substrate.
(2) The applied color resist composition is dried (prebaked).
(3) Exposure to a desired pattern using a photomask.
(4) Development processing is performed using an alkali developer.
(5) Wash (rinse) with distilled water and dry.

  Said drying (prebaking) can be performed by heating at a temperature range of 50-140 degreeC with a hotplate, oven, etc. for 10 to 300 seconds. Especially, it is preferable to heat for 30 to 180 second in the temperature range of 70-130 degreeC, and it is more preferable to heat for 30-90 second in the temperature range of 80-120 degreeC. Moreover, in order to dry more completely, you may vacuum-dry before drying (prebaking).

  In the above development processing, unexposed uncured portions are eluted in an alkaline developer, leaving only the photocured cured portions. Any alkali developer can be used without particular limitation as long as it dissolves uncured portions and does not dissolve cured portions that become the RGB pixel portions and black matrix portions. Specific alkali developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy And aqueous solutions of alkaline compounds such as chodo, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. The alkali concentration of the alkali developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The development temperature is usually 20 ° C. to 30 ° C., and the development time is preferably in the range of 20 to 90 seconds.

  After the development processing, post-baking processing can be performed as necessary. Post-baking is a heat treatment after development to complete the curing, and is usually heated in a temperature range of 200 to 250 ° C. The post-baking treatment can be performed continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the layer after development is in the above-described condition.

  A substrate in which a transparent electrode such as ITO is formed on the pixel of the color filter produced as described above is used as a substrate for sandwiching a liquid crystal layer together with another substrate, and a liquid crystal display device combining a backlight, a polarizing plate, and a liquid crystal layer can do.

  The liquid crystal display device using the color filter of the present invention includes, for example, a liquid crystal television, a personal computer, a liquid crystal projector, a portable game machine, a mobile phone, a personal digital assistant (PDA), a digital audio player, a digital camera, and a digital video camera. It can be used in a wide range as an image display unit for car navigation and the like.

  In the color resist composition of the present invention, the surfactant compounded therein is a fluorine-based surfactant containing fluorine atoms. The surfactant segregates on the coating surface. Then, although a coating film hardens | cures by exposure, since the fluorochemical surfactant used by this invention has a polymeric group, it is fix | immobilized firmly on the coating-film surface. The presence of a fluorosurfactant on the surface of the coating film imparts water and oil repellency to the surface of the coating film, preventing corrosion of the exposed coating film surface of the exposed area with an alkaline developer and after development with the developer. It is considered that the unexposed resin and contaminants washed away by washing (rinsing) can prevent so-called “water spots” from adhering to the surface of the cured coating of the colored pattern of the exposed part. At this time, since the polymerizable group is not cured in the unexposed area, a pattern can be formed without deteriorating developability.

  Hereinafter, the present invention will be described in more detail with reference to specific examples.

[IR spectrum]
Apparatus: “Nicolet 380” manufactured by Thermo Electron
The resin solution obtained in each example was measured by the ATR method.

[ ^13C -NMR measurement conditions]
Apparatus: “AL-400” manufactured by JEOL Ltd.
Solvent: acetone-d ₆
[ ¹⁹ F-NMR measurement conditions]
Apparatus: “AL-400” manufactured by JEOL Ltd.
Solvent: acetone-d ₆
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C., developing solvent tetrahydrofuran, flow rate 1.0 ml / min Standard sample: The following monodisperse polystyrene having a known molecular weight according to the measurement manual of “GPC-8020 model II version 4.10”. Was used.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl).

(Synthesis Example 1)
In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (X-1), and diisopropyl ether 20 as a solvent A mass part, 0.02 part by mass of p-methoxyphenol as a polymerization inhibitor, and 3.1 parts by mass of triethylamine as a neutralizing agent, stirring was started under an air stream, and acrylic acid was maintained while maintaining the inside of the flask at 10 ° C. 2.7 parts by mass of chloride was added dropwise over 1 hour. After completion of dropping, the mixture is stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and acrylic acid is measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 40 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed and stirred, and then left to stand to separate and remove the aqueous layer, and washing was repeated 3 times. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. .

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。また、ＧＰＣによる数平均分子量は１，５００である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46. The number average molecular weight by GPC is 1,500.)

  Subsequently, the solvent was distilled off under reduced pressure to obtain a monomer represented by the following structural formula (d1-1-1).

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46.)

  In another glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 63 parts by mass of methyl isobutyl ketone was charged as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Subsequently, 21.5 parts by mass of the monomer (d1-1-1) obtained above, 41.3 parts by mass of 2-hydroxyethyl methacrylate, t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator 9.4 parts by weight and 135.4 parts by weight of an initiator solution obtained by mixing 126 parts by weight of methyl isobutyl ketone as a solvent were set in separate dropping devices, and the flask was kept at 105 ° C at the same time. It was dripped over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-1).

Next, 74.7 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, 0.06 part by mass of dibutyltin dilaurate as a urethanization catalyst, and stirring under an air stream were started. While maintaining the temperature, 44.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, 37.4 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (1) having a polymerizable group. The molecular weight of the fluorosurfactant (1) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,400, the weight average molecular weight was 7,100, and the maximum molecular weight was 200,000. FIG. 1 shows a chart of the IR spectrum of the obtained fluorosurfactant (1), FIG. 2 shows a chart of ¹³ C-NMR, and FIG. 3 shows a chart of ¹⁹ F-NMR.

(Synthesis Example 2)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 57.1 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 10.8 parts by mass of the monomer (d1-1-1) obtained in Example 1, 46.3 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexa as a radical polymerization initiator Three types of dripping liquids of 122.8 parts by mass of an initiator solution in which 8.6 parts by mass of noate and 114.2 parts by mass of methyl isobutyl ketone as a solvent were mixed were set in separate dropping apparatuses, and the inside of the flask was 105 ° C. The solution was added dropwise over 2 hours at the same time. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-2).

  Next, 74.5 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining the temperature, 50.4 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, 37.3 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (2) having a polymerizable group. As a result of measuring the molecular weight of the fluorine-based surfactant (2) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,100, the weight average molecular weight was 5,700, and the maximum molecular weight was 90,000.

(Synthesis Example 3)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 68.3 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Subsequently, 32.3 parts by mass of the monomer (d1-1-1) obtained in Example 1, 36.0 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexa as a radical polymerization initiator Three types of dropping solutions of initiator solution 146.7 parts by mass, in which 10.2 parts by mass of noate and 136.5 parts by mass of methyl isobutyl ketone as a solvent were mixed, were set in separate dropping devices, and the inside of the flask was 105 ° C. The solution was added dropwise over 2 hours at the same time. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-3).

  Next, 75.1 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining the temperature, 39.2 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, 37.5 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (3) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (3) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 1,700, the weight average molecular weight was 5,700, and the maximum molecular weight was 100,000.

(Synthesis Example 4)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 31.4 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 21.5 parts by mass of the monomer (d1-1-1) obtained in Example 1, 41.2 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexa as a radical polymerization initiator Three types of dripping liquids of 72.1 parts by mass of an initiator solution obtained by mixing 9.4 parts by mass of noate and 62.7 parts by mass of methyl isobutyl ketone as a solvent were set in separate dropping devices, respectively, and the inside of the flask was 105 ° C. The solution was added dropwise over 2 hours at the same time. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-4).

  Next, 74.8 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, 0.06 part by mass of tin octylate as a urethanization catalyst, and stirring under an air stream were started. While maintaining the temperature, 44.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, 37.4 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (4) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (4) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,500, the weight average molecular weight was 16,900, and the maximum molecular weight was 1,000,000.

(Synthesis Example 5)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 63 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 21.5 parts by mass of the monomer (d1-1-1) obtained in Example 1, 41.3 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexa as a radical polymerization initiator Three types of dripping liquid of 135.4 parts by mass of an initiator solution obtained by mixing 6.3 parts by mass of noate and 126 parts by mass of methyl isobutyl ketone as a solvent were set in separate dropping devices, and the inside of the flask was kept at 105 ° C. At the same time, it was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-5).

  Next, 74 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of dibutyltin dilaurate as a urethanization catalyst were added, and stirring was started in an air stream. While maintaining, 44.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, 37 parts by mass of methyl ethyl ketone was added as a solvent, and the insoluble matter in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (5) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (5) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 3,100, the weight average molecular weight was 25,500, and the maximum molecular weight was 2 million.

(Synthesis Example 6)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 62.9 parts by mass of polyethylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) as a solvent and stirred under a nitrogen stream. The temperature was raised to 105 ° C. Subsequently, 21.5 parts by mass of the monomer (d1-1-1) obtained in Example 1, 40.1 parts by mass of 2-hydroxyethyl methacrylate, 1.3 parts by mass of 2-hydroxybutyl methacrylate, radical polymerization initiation Three types of dripping liquids, 9.1 parts by mass of t-butylperoxy-2-ethylhexanoate as an agent and 135.1 parts by mass of an initiator solution obtained by mixing 125.7 parts by mass of PGMEA as a solvent, are respectively added to separate dropping devices. The flask was added dropwise at the same time over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P1-6).

  Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 parts by mass of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxyethyl was maintained at 60 ° C. 44.6 parts by mass of isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, 68.5 parts by mass of PGMEA was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a PGMEA solution containing 30% by mass of a fluorosurfactant (6) having a polymerizable group. The molecular weight of the fluorosurfactant (6) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,400, the weight average molecular weight was 7,900, and the maximum molecular weight was 200,000.

(Synthesis Example 7)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 60.3 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 21.5 parts by mass of the monomer (d1-1-1) obtained in Example 1, 38.8 parts by mass of 2-hydroxyethyl acrylate, and t-butylperoxy-2-ethylhexa as a radical polymerization initiator Three types of dripping liquid of 9.2 parts by mass of noate and 125.2 parts by mass of an initiator solution obtained by mixing 120.6 parts by mass of methyl isobutyl ketone as a solvent were set in separate dropping devices, and the inside of the flask was kept at 105 ° C. The solution was added dropwise over 2 hours at the same time. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-7).

  Next, 74.7 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining the temperature, 47.2 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, 37.4 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% of a fluorosurfactant (7) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (7) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,100, the weight average molecular weight was 5,700, and the maximum molecular weight was 200,000.

(Synthesis Example 8)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 60.8 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 parts by mass of the monomer (d1-1-1) obtained in Example 1, 39.3 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexa as a radical polymerization initiator Three types of dripping liquids of 130.7 parts by mass of an initiator solution obtained by mixing 9.1 parts by mass of noate and 121.6 parts by mass of methyl isobutyl ketone as a solvent were set in separate dropping devices, and the inside of the flask was 105 ° C. The solution was added dropwise over 2 hours at the same time. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-8).

  Next, 74.8 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, 0.06 part by mass of tin octylate as a urethanization catalyst, and stirring under an air stream were started. While maintaining the temperature, 46.8 parts by mass of 2-methacryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, 37.4 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (8) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (8) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,100, the weight average molecular weight was 6,300, and the maximum molecular weight was 100,000.

(Synthesis Example 9)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 70.8 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 21.5 parts by mass of the monomer (d1-1-1) obtained in Example 1, 49.3 parts by mass of 2-methacryloyloxyethyl isocyanate, and t-butylperoxy-2-ethyl as a radical polymerization initiator Three types of dropping solutions of initiator solution 76.1 parts by mass of hexanoate 10.6 parts by mass of hexaisoate and 70.8 parts by mass of methyl isobutyl ketone as a solvent were set in separate dropping devices. It was dripped simultaneously over 2 hours, keeping at ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-9).

  Next, 74.5 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining the temperature, 35.7 parts by mass of 2-hydroxyethyl acrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, 37.3 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (9) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (9) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,200, the weight average molecular weight was 9,500, and the maximum molecular weight was 300,000.

(Synthesis Example 10)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 81.9 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Next, 30.3 parts by mass of the monomer (d1-1-1) obtained in Example 1, and a polyoxyalkylene group-containing methacrylate represented by the following formula (d2-1) (wherein n is an average of 5) ) 51.6 parts by mass, 82.1 parts by mass of an initiator solution obtained by mixing 12.2 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator and 69.9 parts by mass of methyl isobutyl ketone as a solvent These three types of dripping liquids were set in separate dripping apparatuses, respectively, and were dripped simultaneously over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-10).

  Next, 70.7 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of tin octylate as a urethanization catalyst were added, and stirring was started under an air stream. While maintaining the temperature, 18.1 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, 35.4 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% of a fluorosurfactant (10) having a polymerizable group. The molecular weight of the fluorosurfactant (10) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 1,800, the weight average molecular weight was 5,400, and the maximum molecular weight was 90,000.

(Synthesis Example 11)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 56.2 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 38.7 parts by mass of the monomer (d1-1-1) obtained in Example 1, 16.6 parts by mass of 2-hydroxyethyl methacrylate, and an unsaturated fatty acid represented by the following formula (d2-2) Hydroxyalkyl ester-modified ε-caprolactone (wherein n is an average of 1) 21.9 parts by mass, 11.6 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator and methyl isobutyl ketone 112 as a solvent Three types of dropping solutions of 123.9 parts by mass of initiator solution mixed with 3 parts by mass were set in separate dropping devices, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P1-11).

  Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 parts by mass of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxyethyl was maintained at 60 ° C. 30.3 parts by mass of isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, 90.1 parts by mass of methyl isobutyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 30% of a fluorosurfactant (11) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (11) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,100, the weight average molecular weight was 15,100, and the maximum molecular weight was 600,000.

(Synthesis Example 12)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 60 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Subsequently, 60 parts by mass of 2-methacryloyloxyethyl isocyanate and 120 parts by mass of a monomer solution obtained by mixing 60 parts by mass of methyl isobutyl ketone as a solvent, and 9 parts by mass of 2,2′-azobis (2-methylbutyronitrile) as a radical polymerization initiator. Two kinds of dropping solutions of 69 parts by mass of an initiator solution mixed with 60 parts by mass of methyl isobutyl ketone as a solvent and a solvent were set in separate dropping devices, and dropped simultaneously over 2 hours while keeping the inside of the flask at 105 ° C. . After completion of dropping, the mixture is stirred at 105 ° C. for 3 hours. Next, an initiator solution in which 0.9 parts by mass of 2,2′-azobis (2-methylbutyronitrile) as a radical polymerization initiator and 9 parts by mass of methyl isobutyl ketone as a solvent were mixed while maintaining the inside of the flask at 105 ° C. 9.9 mass parts is dripped over 10 minutes, and after completion | finish of dripping, it stirs at 105 degreeC for 3 hours. Then, after dropping again in the same manner, the mixture was stirred at 105 ° C. for 8 hours to obtain a methyl isobutyl ketone solution containing the polymer (P2-1).

  Next, the temperature in the flask was lowered to 80 ° C., 0.06 part by mass of dibutyltin dilaurate was charged as a urethanization catalyst, and 23.2 parts by mass of the same perfluoropolyether compound (X-1) used in Example 1 was used. Was added and stirred at 80 ° C. for 6 hours to obtain a methyl isobutyl ketone solution containing the reaction product (P3-1).

  Subsequently, it switched from nitrogen stream to air stream, and added 0.12 mass part of p-methoxyphenol as a polymerization inhibitor. Subsequently, 41.4 mass parts of 2-hydroxyethyl acrylate was added, and it reacted by stirring at 80 degreeC for 10 hours. Next, the reaction was carried out by raising the temperature to 120 ° C. and stirring for 2 hours, and a part of the solvent was distilled off. Thereafter, a substance insoluble in the solution was separated by filtration to obtain a methyl isobutyl ketone solution containing 50% of a fluorosurfactant (12) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (12) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,100, the weight average molecular weight was 4,400, and the maximum molecular weight was 60,000.

(Synthesis Example 13)
In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 100 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the above formula (X-1), and methyl isobutyl ketone as a solvent 180 parts by mass, 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 parts by mass of tin octylate as a urethanization catalyst were added, stirring was started under an air stream, and the flask was kept at 100 ° C. However, 20.0 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 100 ° C. for 5 hours, and disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, the solvent was removed by distillation under reduced pressure to obtain the following structural formula (d1-5-1).

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。また、ＧＰＣによる数平均分子量は１，６００である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46. The number average molecular weight by GPC is 1,600.)

  In another glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 64.1 parts by mass of methyl isobutyl ketone as a solvent was charged, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Subsequently, 23.9 parts by mass of the monomer (d1-5-1) obtained above, 40.2 parts by mass of 2-hydroxyethyl methacrylate, t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator 9.6 parts by mass and 137.7 parts by mass of an initiator solution obtained by mixing 128.1 parts by mass of methyl isobutyl ketone as a solvent were set in separate dropping apparatuses, and the flask was kept at 105 ° C. At the same time, it was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-13).

  Next, 74.9 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of octyl tin as a urethanization catalyst were added, and stirring was started in an air stream at 60 ° C. While maintaining the above, 43.4 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, 37.4 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (13) having a polymerizable group. As a result of measuring the molecular weight of the fluorosurfactant (13) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,100, the weight average molecular weight was 6,800, and the maximum molecular weight was 100,000.

(Synthesis Example 14)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 79.1 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 21.5 parts by mass of the monomer (d1-1-1) obtained in Example 1, 57.7 parts by mass of glycidyl methacrylate, and t-butylperoxy-2-ethylhexanoate 11 as a radical polymerization initiator .9 parts by mass and 170.3 parts by mass of an initiator solution obtained by mixing 158.4 parts by mass of methyl isobutyl ketone as a solvent were set in separate dropping apparatuses, and the flask was kept at 105 ° C. It was dripped simultaneously over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-14).

  Next, 37.7 parts by mass of methyl isobutyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.57 parts by mass of triphenylphosphine as a catalyst were added, and stirring was started under a nitrogen stream. After adding 28.1 parts by mass of acrylic acid at ° C, the temperature was raised to 120 ° C over 1 hour. After reaching 120 ° C., the reaction is carried out until the acid value per solid content becomes 1 or less, 75.5 parts by mass of methyl isobutyl ketone is added as a solvent, and the insoluble matter in the solution is filtered off to remove the polymerizable group. A methyl isobutyl ketone solution containing 50% by mass of the fluorosurfactant (14) was obtained. As a result of measuring the molecular weight of the fluorosurfactant (14) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 1,900, the weight average molecular weight was 8,300, and the maximum molecular weight was 200,000.

(Synthesis Example 15)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 18 parts by mass of a fluorinated alkyl group-containing acrylate monomer represented by the following formula (Y), and a silicone represented by the following formula (Z) 12 parts by mass of a chain-containing ethylenically unsaturated monomer, 58 parts by mass of a monoacrylate compound having a side chain of a copolymer of ethylene oxide and propylene oxide having a molecular weight of 400, and compound 4 in which both ends of tetraethylene glycol are methacrylated 1 part by weight of azobisisobutyronitrile as an initiator and 1 part by weight of lauryl mercaptan as a chain transfer agent were added under nitrogen flow. Thereafter, the reaction was carried out by stirring at 70 ° C. for 8 hours and then at 75 ° C. for 12 hours. Subsequently, the solvent was removed by distillation under reduced pressure to obtain a fluorine-based surfactant (15) having no polymerizable group. The molecular weight of the fluorosurfactant (15) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 6,600, the weight average molecular weight was 35,700, and the maximum molecular weight was 400,000.

Preparation Example 1 Preparation of Pigment Dispersion Solution A high-speed disperser charged with 200 parts by mass of zirconia beads having a diameter of 0.5 mm was used as a coloring agent. I. 8 parts by mass of Pigment Red 254, 2.5 parts by mass of a polyester-based dispersant (“Ajisper PB-814” manufactured by Ajinomoto Fine Techno Co., Ltd.), and methacrylic acid / benzyl methacrylate = 13/87 (mass ratio) as an alkali-soluble resin 25 parts by mass of a copolymer (acid value 84, number average molecular weight 9,500) propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) solution (non-volatile content 39.7% by mass), and PGMEA 64.5 as a solvent A mass part was charged and dispersed at a rotational speed of 2000 rpm for 8 hours to obtain a red pigment dispersion.

(Examples 1-14)
2 parts by mass of dipentaerythritol hexaacrylate as a polymerizable compound and a photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd. “Irgacure 369”; 2 with respect to 100 parts by mass of the red pigment dispersion obtained in Preparation Example 1 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) 0.3 part by mass was added and mixed. After adding and mixing 0.083 parts by mass (in terms of non-volatile content) of the fluorosurfactants (1) to (14) having a polymerizable group obtained in Synthesis Examples 1 to 14 to the mixed solution, the pore size was 1 A color resist composition was prepared by filtration through a 0.0 μm filter.

(Comparative Example 1)
A color resist composition was prepared in the same manner as in Example 1 except that no fluorine-based surfactant was added.

(Comparative Example 2)
It replaced with the fluorine-type surfactant (1) which has a polymeric group, and was similar to Example 1 except having used the fluorine-type surfactant (15) which does not have a polymeric group obtained by the synthesis example 15. And a color resist composition was prepared.

  The following items were tested and evaluated for the coatability and developability of the color resist composition obtained above. The evaluation results are shown in Table 1.

[Applicability test method and evaluation criteria]
1 ml of the color resist composition prepared above is dropped onto the center of a 12 cm square glass plate, spin-coated at a rotation speed of 600 rpm and a rotation time of 30 seconds, and then heated and dried at 90 ° C. for 3 minutes to be applied. The condition was observed.
○: No coating unevenness is observed.
(Triangle | delta): Occurrence of coating unevenness is partially recognized.
X: The generation | occurrence | production of the coating nonuniformity is recognized as a whole.

[Developability test method and evaluation criteria]
The color resist composition prepared above was applied onto a glass plate using a spin coater at a rotation speed of 1000 rpm and a rotation time of 9 seconds, and then pre-dried at 60 ° C. for 5 minutes to form a coating film having a thickness of 1.5 μm. Formed. This coating film was exposed to 1000 J / m ² with a high-pressure mercury lamp using a pattern mask having a line width of 50 μm, spray-developed with a sodium carbonate aqueous solution maintained at 30 ° C. as a developing solution for 30 seconds, and then washed with distilled water. . Then, it dried at 70 degreeC for 30 minutes. The pattern shape having a line width of 50 μm and the development residue obtained by these operations were observed. From the observation results, the pattern shape and the development residue (water stain) were evaluated as evaluation of developability according to the following criteria. The “water stain” means that after exposure (curing) and development of the color resist composition, the unexposed resin and developer components washed away by washing (rinsing) are cured coatings of the colored pattern of the exposed part. A phenomenon that adheres to the surface of a film.

(1) Criteria for evaluating pattern shape A: A pattern is satisfactorily formed.
○: Slightly inferior to good pattern formation.
Δ: A part of the pattern missing.
X: A pattern having many missing portions.

(2) Evaluation criteria for development residue (water stain) ○: Water stain is not observed on the pattern.
Δ: Water spots are partially observed on the pattern.
X: The occurrence of water spots on the pattern is clearly recognized.

  The results evaluated above are shown in Table 1.

  The color resist compositions of the present invention of Examples 1 to 14 shown in Table 1 were found to have good coating properties and little coating unevenness (color unevenness). Moreover, about developability, it turned out that high alkali resistance is exhibited, the erosion of the cured coating film surface of the exposure part by an alkali developing solution can be prevented, and a favorable pattern shape can be formed. It was also found that no water spots were generated.

  On the other hand, in the color resist composition of Comparative Example 1 that did not use a fluorosurfactant, coating unevenness occurred and developability was not sufficient.

  Comparative Example 2 is an example using a fluorosurfactant having no polymerizable group, but it was found that water spots were generated although there was no coating unevenness.

Claims (9)

Alkali-soluble resin (A), the polymerizable compound (B), a Luke color resist composition to contain a fluorine-based surfactant (D) having a colorant (C) and a polymerizable group, the fluorine-based surfactant The agent (D) comprises a compound (d1) having a poly (perfluoroalkylene ether) chain and a structural site having a radically polymerizable unsaturated group at both ends thereof, and a radically polymerizable group having a reactive functional group (R1). A polymer (P1) obtained by copolymerizing a saturated monomer (d2) as an essential monomer component is combined with a functional group (R2) having reactivity with the functional group (R1) and a radical polymerizable non-polymerizable component. Fluorine surfactant (D1) obtained by reacting a compound (d3) having a saturated group or a polymer of a radical polymerizable unsaturated monomer (d2) having a reactive functional group (R1) ( P2) and poly (perfluo) A compound (d1 ′) having a functional group (R2) having reactivity to the reactive functional group (R1) at both ends of the (alkylene ether) chain, and reactivity to the functional group (R1). A color resist composition, which is a fluorine-based surfactant (D2) obtained by reacting a functional group (R2) having a compound (d3) having a radically polymerizable unsaturated group . The reactive functional group (R1) of the radical polymerizable unsaturated monomer (d2) used for obtaining the fluorosurfactant (D1) is a hydroxyl group and the functional group of the compound (d3) (R2) color resist composition according to claim 1, wherein an isocyanate group. The reactive functional group (R1) of the polymer (P2) used when obtaining the fluorosurfactant (D2) is an isocyanate group, and the compound (d1 ′) and the compound (d3) have The color resist composition according to claim 3, wherein the functional group (R2) is a hydroxyl group. The number average molecular weight (Mn) of the fluorosurfactant (D 1 ) or fluorosurfactant (D2 ) is in the range of 1,000 to 10,000, and the weight average molecular weight (Mw) is 2,000. in the range of 100,000 claims 1, 2 or serial mounting color resist composition 3. The fluorine-based surfactant (D 1) or a fluorine-based surfactant (D2) is, the color according to claim 4, wherein in which a proportion of the 2-25 wt% of fluorine atoms in the surfactant Resist composition. The poly (perfluoroalkylene ether) chain contained in the structure of the fluorosurfactant (D 1 ) or fluorosurfactant (D2) contains 25 to 80 fluorine atoms per chain. The color resist composition according to any one of claims 1 to 5 . The radical polymerizable unsaturated group content in the fluorosurfactant (D 1 ) or the fluorosurfactant (D2) is a radical polymerizable unsaturated group equivalent of 200 to 900 g / eq. As a ratio to form a color resist composition of any one of claims 1-6. Color filter characterized by having a cured coating film of the color resist composition of any one of claims 1-7. 9. A liquid crystal display device comprising: a backlight, a polarizing plate, at least two substrates, a liquid crystal layer sandwiched between the substrates, and a color filter according to claim 8 provided on at least a part of the substrate.

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