TWI627498B - Color resist composition, color filter, liquid crystal display device, and organic electro luminescence display device - Google Patents

Abstract

An object of the present invention is to provide a color photoresist composition obtained by using a fluorine-based surfactant that does not generate a compound having a high cumulative effect on the environment and the human body, and has excellent coatability in coating methods such as a spin coating method, In addition, the coating film has good smoothness, it is difficult to have liquid reflow during coating, and the manufacturing efficiency is high. In addition, a color filter, a liquid crystal display device, and an organic EL display device using the same are also provided. The present invention provides a color photoresist composition, which is a color photoresist composition containing an alkali-soluble resin (A), a polymerizable compound (B), a colorant (C), and a fluorine-based surfactant (D). The fluorine-based surfactant (D) -based polymer has a polymer structure of a polymerizable monomer and a poly (perfluoroalkylene ether) chain, and a plurality of the polymer structures are passed through the poly (perfluoroalkylene) (Ether) chain, and has an oxyalkylene group in a side chain of the aforementioned polymer structure.

Description

Color photoresist composition, color filter, liquid crystal display device and organic EL display device

The present invention relates to a color photoresist composition, which is obtained by using a fluorine-based surfactant that does not generate a compound having a high cumulative effect on the environment and the human body. It has excellent coatability in coating methods such as a spin coating method and a coating film. It has good smoothness, and it is difficult to have liquid reflow during coating. In addition, it also relates to a color filter, a liquid crystal display device, and an organic EL display device using the same.

The color filters used in color liquid crystal display devices generally have red (R), green (G), and blue (B) pixels, and a black matrix (BM) formed between them for the purpose of improving display contrast. basic structure. In the production of a color filter, a color photoresist composition is generally coated on a glass substrate by a coating method such as a spin coating method or a slit coating method, dried, and then exposed using a photomask, and then developed to form a colored pattern.

In the manufacture of color filters, when a color photoresist composition is coated on a glass substrate, the smoothness of the coating surface (coating film surface) may be poor and the thickness of the coating film may be uneven. Pixel shrinkage and other conditions can cause pixel color unevenness. When such a color filter having color unevenness is used to make a liquid crystal display device or an organic EL display device, an image obtained by the display device may cause color unevenness. Therefore, the surface of each of the R, G, and B pixels and the BM of the color filter is required to have high smoothness. Therefore, when applying the color photoresist composition, it is necessary to make the film thickness uniform without causing uneven coating and shrinkage. Holes are applied in a way that does not have uneven color.

In order to prevent uneven color due to uneven coating, shrinkage, etc., There is a method of including a fluorine-based surfactant in a color photoresist composition, and in order to improve the effect, a structural component of a copolymer of the surfactant is improved (for example, refer to Patent Document 1). Specifically, Patent Document 1 discloses a fluorine-based interface composed of a copolymer of an ethylenically unsaturated monomer containing a perfluoroalkyl group having 8 or more carbon atoms and a ethylenically unsaturated monomer having a siloxane chain. Active agent. The color photoresist composition using these fluorine-based surfactants can reduce the surface tension, improve the leveling property of the color photoresist composition, and improve the smoothness of the coating film.

However, in the case where the fluorine-based surfactant disclosed in Patent Document 1 is used as one of the components of the color photoresist composition, the substrate of a color filter has been enlarged in recent years, a spin coating method, a slit coating method, and the like. Under the current state of progress in diversification of coating methods, the effect of preventing uneven coating of the composition is no longer required for practical use, and improvement is required.

In addition, the color photoresist composition is required to have the above-mentioned characteristics that it is not easy to cause uneven coating, and also to have less reflow (liquid reflow) of the composition in the peripheral portion of the glass substrate when applied by a spin coating method or the like. characteristic. However, even if the fluorine-based surfactant disclosed in the aforementioned Patent Document 1 is used, it is difficult to reduce the reflux of the liquid to a required level.

In recent years, it has become clear that ethylenically unsaturated monomers having a perfluoroalkyl group having 8 carbon atoms, which are used in Patent Documents 1 and the like, undergo decomposition to generate perfluorooctane which is highly cumulative to the environment and organisms. Sulfonic acid (hereinafter referred to as "PFOS") or perfluorooctanoic acid (hereinafter referred to as "PFOA"). Therefore, it is required to use a surfactant without a compound having a perfluoroalkyl group having 8 carbon atoms.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-230154

The problem to be solved by the present invention is to provide a color photoresist composition obtained by using a fluorine-based surfactant that does not generate a compound having a high cumulative effect on the environment and the human body. Excellent, and the coating film is smooth, and it is not easy to have liquid reflow. In addition, it provides color filters, liquid crystal display devices, and organic EL display devices.

In order to solve the above problems, the team of the present invention has continuously researched and found a polymer having a polymer structure of a polymerizable monomer and a poly (perfluoroalkylene ether) chain. A plurality of the aforementioned polymer structures are transmitted through the aforementioned Poly (perfluoroalkylene ether) chain is connected, and the side chain of the aforementioned polymer structure has an oxyalkylene group. When the polymer is used as a fluorosurfactant, it does not generate high accumulation to the environment and the human body. By using this compound, a color photoresist composition having excellent coating properties, good smoothness of the coating film, and less likely to have liquid reflow can be obtained by using the fluorine-based surfactant, and the present invention has finally been completed.

That is, the present invention provides a color photoresist composition which is a color photoresist composition containing an alkali-soluble resin (A), a polymerizable compound (B), a colorant (C), and a fluorine-based surfactant (D). , Characterized in that the aforementioned fluorine-based surfactant (D) -based polymer has a polymer structure of a polymerizable monomer and a poly (perfluoroalkylene ether) chain, and a plurality of the aforementioned polymer structures It is connected through the poly (perfluoroalkylene ether) chain, and has an oxyalkylene group in a side chain of the polymer structure.

In addition, the present invention provides a color filter having a hardened coating film of the aforementioned color photoresist composition.

Furthermore, the present invention provides a liquid crystal display device, comprising: a backlight plate, a polarizing plate, at least two substrates, a liquid crystal layer sandwiched between the substrates, and the color filter mounted on at least a part of the substrates. sheet.

The invention further provides an organic EL display device, which is characterized by having the color filter of the invention.

The color photoresist composition of the present invention is obtained by using a fluorine-based surfactant that does not generate a compound having a high cumulative effect on the environment and the human body. It has excellent coating properties, good smoothness of the coating film, and no liquid reflow. Therefore, by using the color photoresist composition, a color filter without color unevenness, excellent color reproducibility, and a colored pattern formed with high accuracy can be manufactured at a high yield. In addition, by using this color filter, a liquid crystal display device and an organic EL display device having excellent display characteristics can be provided.

[Form of Implementing Invention]

The alkali-soluble resin (A) used in the present invention is not particularly limited as long as it is soluble in an alkaline developer, and preferably has at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. Resin of acid group or its salt.

To explain the alkali-soluble resin (A) more specifically, for example, the following Of resin, etc.

‧Base-soluble resin (A1) obtained by polymerizing a (meth) acrylic polymerizable monomer having an acidic group as an essential component.

‧The polymer without (acid group) obtained by polymerizing a (meth) acrylic polymerizable monomer having a functional group as an essential component, and a compound having a reactive group and an acid group reactive with the functional group The alkali-soluble resin (A2) obtained by the reaction.

‧For a copolymer of (meth) acrylate containing epoxy groups and other polymerizable monomers, an unsaturated monocarboxylic acid is added to at least a part of the epoxy groups of the copolymer, and further passed An alkali-soluble resin (A3) obtained by adding at least a part of the hydroxyl groups generated by the addition reaction of an unsaturated monocarboxylic acid to an acid anhydride of a polycarboxylic acid.

‧Epoxy (meth) acrylate resin (A4) with a carboxyl group.

Hereinafter, the above (A1) to (A4) will be described in detail.

Examples of the alkali-soluble resin (A1) include an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component and a (meth) acrylic acid having a sulfonic acid group. The polymerizable monomer is an alkali-soluble resin or the like obtained by polymerizing an essential component. Among these, an alkali-soluble resin obtained by polymerizing a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component is preferred.

Examples of the (meth) acrylic polymerizable monomer having a carboxyl group include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, and succinic acid. 2- (meth) acryloxyethyl ester, 2- (meth) acryloxyethyl adipate, 2- (meth) acryloxyethyl maleate, hexahydroortho 2- (meth) acryloxyethyl phthalate , 2- (meth) acryloxyethyl phthalate, 2- (meth) acryloxypropyl succinate, 2- (meth) acryloxypropyl adipate, 2- (meth) acryloxypropyl maleate, 2- (meth) acryloxypropyl hexahydrophthalate, 2- (meth) acryloxy phthalate Propyl propyl ester, 2- (meth) acryloxybutyl succinate, 2- (meth) acryloxybutyl adipate, 2- (meth) acryloxy maleate Polymerizable monomers such as butyl butyl, 2- (meth) acryloxybutyl hexahydrophthalate, and 2- (meth) acryloxybutyl phthalate; Polymerizable monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid; let succinic acid, maleic acid, Phthalic acid or a polymerizable monomer obtained by adding an anhydride thereof to a hydroxyalkyl (meth) acrylate. These (meth) acrylic polymerizable monomers having a carboxyl group may be used alone or in combination of two or more. Among the (meth) acrylic polymerizable monomers having a carboxyl group, (meth) acrylic acid and 2- (meth) acrylic acid ethoxyethyl succinate are preferred.

Examples of the (meth) acrylic polymerizable monomer having a sulfonic acid group include 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, and 2-hydroxy-3 -(Meth) acrylic acid oxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, or a salt thereof, and the like.

When preparing the alkali-soluble resin (A1), other polymerizable monomers may be used in combination as long as the effect of the present invention is not impaired. Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, ( Isobutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, Phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol mono (methyl) ) (Meth) acrylates such as acrylate, tetrahydrofurfuryl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate, and glycerol mono (meth) acrylate (Meth) acrylic acid esters with hydroxyl groups; Aromatic vinyl compounds such as styrene and its derivatives; Vinyl compounds such as N-vinylpyrrolidone; N-cyclohexylcis-butenedifluoreneimide, N-phenylcis-butenedifluorine -N-substituted maleimide, such as benzylcis butene diimide; Poly (meth) acrylate polymer monomer, polystyrene polymer monomer, poly (meth) acrylate 2-hydroxyethyl polymer monomer, polyethylene glycol polymer monomer, polypropylene glycol polymer Monomers, polymer monomers such as polycaprolactone polymer monomers, and the like. The other polymerizable monomers may be used alone or in combination of two or more.

Among the other polymerizable monomers, styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) are preferred in terms of good transparency without impairing heat resistance. Benzyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate Ester, N-cyclohexylcis-butenedifluoreneimide, N-benzylcisbutenedifluoreneimine, N-phenylcisbutenedifluoreneimine.

The use amount of these other polymerizable monomers is preferably 95% by mass or less, more preferably 85% by mass or less, of the total polymerizable monomer components.

Specific examples of the alkali-soluble resin (A1) include, for example, (meth) acrylic acid and methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Hydroxyl-free polymerizable monomers such as butyl ester, cyclohexyl (meth) acrylate, cyclohexyl succinimide, and 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate Copolymers of polymerizable monomers containing hydroxyl groups such as 4-hydroxybutyl (meth) acrylate; (Meth) acrylic acid and methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. Based) acrylate copolymer; Copolymer of (meth) acrylic acid and styrene; copolymer of (meth) acrylic acid, styrene and α-methylstyrene; copolymer of (meth) acrylic acid and cyclohexyl maleimide . Among the alkali-soluble resins (A1), an alkali-soluble resin using benzyl (meth) acrylate is preferable in terms of obtaining a color photoresist composition having excellent pigment dispersibility.

The acid value of the alkali-soluble resin (A1) is preferably in the range of 30 to 500, more preferably in the range of 40 to 350, and even more preferably in the range of 50 to 300. The weight-average molecular weight (Mw) of the aforementioned alkali-soluble resin (A1) measured by GPC in terms of polystyrene is preferably in the range of 2,000 to 80,000, more preferably in the range of 3,000 to 50,000, and even more preferably in the range of 4,000 to 4,000. 30,000 range.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values obtained in terms of polystyrene based on GPC measurement. The measurement conditions of GPC are as follows.

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Column: Tosoh Co., Ltd. Protective Column "HHR-H" (6.0mmI.D. x 4cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR" (7.8mmI.D. x 30cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR" (7.8mmI.D. × 30cm) made by the company + "TSK-GEL GMHHR" (7.8mmI.D. × 30cm) made by Tosoh Corporation + "TSK-GEL GMHHR" made by Tosoh Corporation (7.8mmI.D. × 30cm)

Detector: ELSD ("ELSD2000" manufactured by ORTEC)

Data processing: "GPC-8020 Model II version.4.10" made by Tosoh Corporation

Measurement conditions: column temperature 40 ° C, developing solvent tetrahydrofuran, flow rate 1.0ml / min

Standard: According to the measurement manual of "GPC-8020 Model II version. 4.10", the following monodisperse polystyrene with a known molecular weight is used.

(Using polystyrene)

Tosoh Corporation `` A-500 ''

Tosoh Corporation `` A-1000 ''

`` A-2500 '' by Tosoh Corporation

Tosoh Corporation `` A-5000 ''

Tosoh Corporation `` F-1 ''

Tosoh Corporation `` F-2 ''

Tosoh Corporation `` F-4 ''

Tosoh Corporation `` F-10 ''

Tosoh Corporation `` F-20 ''

Tosoh Corporation `` F-40 ''

Tosoh Corporation `` F-80 ''

Tosoh Corporation `` F-128 ''

Sample: A tetrahydrofuran solution having a resin solid content of 1.0% by mass was filtered with a microporous filter (100 μl).

In the present invention, a carboxyl group of an alkali-soluble resin containing a carboxyl group obtained by adding an unsaturated compound containing an epoxy group to a (meth) acrylic polymerizable monomer having a carboxyl group as an essential component may be used. , The resulting alkali-soluble resin (A1-1).

Examples of the unsaturated compound containing an epoxy group include, for example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, and crotonyl glycidyl propyl Ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4-hydroxybutyl (meth) acrylate glycidol Ether. From the viewpoint of improving heat resistance and improving dispersibility when a pigment is used as a coloring agent (C) described later, an unsaturated compound containing an alicyclic epoxy group is preferred.

Examples of the alicyclic epoxy group contained in the alicyclic epoxy-containing unsaturated compound include, for example, 2,3-epoxycyclopentyl, 3,4-epoxycyclohexyl, and 7,8- Epoxy [tricyclo [5.2.1.0] dec-2-yl] yl and the like. As the ethylenically unsaturated group, a (meth) acrylfluorenyl group is preferred. The unsaturated compound containing an alicyclic epoxy group may be used alone or in combination of two or more.

In order to add the said unsaturated compound containing an epoxy group to the carboxyl part of the said alkali-soluble resin containing a carboxyl group, a well-known method can be used. For example, an alkali-soluble resin containing a carboxyl group and an unsaturated compound containing an epoxy group can be used in tertiary amines such as triethylamine and benzylmethylamine; dodecyltrimethylammonium chloride and tetramethyl chloride Ammonium, tetraethylammonium chloride, tetrabutyl chloride Quaternary ammonium salts such as ammonium chloride and benzyltriethylammonium chloride; in the presence of catalysts such as pyridine and triphenylphosphine, in an organic solvent at a reaction temperature of 50 to 150 ° C for several hours to dozens The reaction lasts for an hour to add an unsaturated compound containing an epoxy group to the carboxyl group of the resin.

The acid value of the alkali-soluble resin (A1-1) is preferably in the range of 10 to 200, more preferably in the range of 20 to 150, and even more preferably in the range of 30 to 150. The weight-average molecular weight of the alkali-soluble resin (A1-1) measured by GPC in terms of polystyrene is preferably in the range of 2,000 to 100,000, more preferably in the range of 4,000 to 50,000, and even more preferably in the range of 5,000 to 30,000. range.

Among the above-mentioned alkali-soluble resins (A1), more preferred are alkali-soluble resins (A1- obtained by using an ether dimer or a (meth) acrylate having an alicyclic structure such as adamantyl group as a polymerizable monomer. 2).

Examples of the ether dimer include dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate and diethyl-2,2'-[oxy Bis (methylene)] bis-2-acrylate, di-n-propyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diisopropyl-2,2' -[Oxybis (methylene)] bis-2-acrylate, di-n-butyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diisobutyl- 2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (tertiary butyl) -2,2'-[oxybis (methylene)] bis-2-acrylic acid Ester, bis (tertiary pentyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (octadecyl) -2,2'-[oxybis (ethylene (Meth)] bis-2-acrylate, di (lauryl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (2-ethylhexyl) -2, 2 '-[oxybis (methylene)] bis-2-acrylate, bis (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2- Acrylate, bis (1-ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-acrylate, di Phenyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2-acrylate Bis (tri-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (dicyclopentadienyl) -2,2'-[oxy Bis (methylene)] bis-2-acrylate, bis (tricyclodecyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, diisofluorenyl- 2,2 '-[oxybis (methylene)] bis-2-acrylate, diadamantyl-2,2'-[oxybis (methylene)] bis-2-acrylate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diethyl-2,2'-[oxybis (methylene )] Bis-2-acrylate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, dibenzyl-2,2'-[oxybis (methylene (Meth)] bis-2-acrylate. These ether dimers may be used alone or in combination of two or more.

When an ether dimer is used as a raw material of the alkali-soluble resin (A1-2), from the viewpoint of suppressing gelation and obtaining a low-molecular-weight alkali-soluble resin, and being a color photoresist composition having excellent transparency and heat resistance, The proportion of the ether dimer in the polymerizable monomer is preferably in the range of 2 to 60% by mass based on the mass of the total polymerizable monomer, more preferably in the range of 5 to 55% by mass, and even more preferably 5 to 50% by weight. Range.

On the other hand, when a (meth) acrylic acid ester having an alicyclic structure such as adamantyl is used as a raw material for the alkali-soluble resin (A1-2), the pigment dispersion when using a pigment as the colorant (C) can be improved. From the viewpoint of obtaining a color photoresist composition with good scum properties, the use ratio of the (meth) acrylate is preferably 0.5 to 60% of the mass of all polymerizable monomers. The range of mass% is more preferably in the range of 1 to 55 mass%, and even more preferably in the range of 5 to 50% by weight.

The method for producing the alkali-soluble resin (A1) used in the present invention is not particularly limited, and various conventionally known methods can be adopted, and a solution polymerization method is particularly preferred. Among them, the polymerization temperature or the polymerization concentration (polymerization concentration = [total weight of polymerizable monomer / (total weight of polymerizable monomer + solvent weight)] × 100) is based on the type and ratio of the polymerizable monomer used, The molecular weight of the target alkali-soluble resin varies. The polymerization temperature is preferably in the range of 40 to 150 ° C, and the polymerization temperature is more preferably in the range of 60 to 130 ° C. The polymerization concentration is preferably in the range of 5 to 50%, and more preferably in the range of 10 to 40%.

The solvent used in the solution polymerization method can be used by a user generally used for radical polymerization. Specific examples include: tetrahydrofuran, Ethers such as alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate Esters, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and other esters; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether ; Toluene, xylene, ethylbenzene and other aromatic hydrocarbons; chloroform; dimethyl sulfene and so on. These solvents may be used alone or in combination of two or more.

When polymerizing the polymerizable monomer, a polymerization initiator may be used as necessary. Examples of the polymerization initiator include cumene hydroperoxide, dicumyl hydroperoxide, di (tertiary butyl) peroxide, lauryl peroxide, benzamyl peroxide, and isopropyl peroxide. Propyl tert-butyl carbonate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, etc. Organic peroxides; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylformaldehyde) Valeronitrile), azo compounds such as 2,2'-azobis (2-methylpropanoic acid) dimethyl, and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of these polymerization initiators to be used may be appropriately set depending on the combination of monomers used, reaction conditions, the molecular weight of the target alkali-soluble resin (A1), and the like, and is not particularly limited. From the viewpoint of obtaining an alkali-soluble resin having a weight-average molecular weight of several thousands to tens of thousands, it is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 0.5 to 10% by mass, relative to the total polymerizable monomer component.

Further, in order to adjust the molecular weight, a chain transfer agent may be added. Examples of the chain transfer agent include thiol-based chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, and methyl mercaptoacetate; and examples include α-methylstyrene dimer, and chain transfer is preferred. The effect is high, and the polymerizable monomers remaining in the reaction system can be reduced, and n-dodecyl mercaptan and thioglycolic acid can be easily obtained. In the case of using a chain transfer agent, the amount to be used may be appropriately set depending on the combination of monomers used, reaction conditions, the molecular weight of the target monomer, and the like, and is not particularly limited. From the viewpoint of the alkali-soluble resin having a weight-average molecular weight of thousands to tens of thousands, it is preferably in the range of 0.1 to 15% by mass, and more preferably in the range of 0.5 to 10% by mass, relative to all monomers.

The alkali-soluble resin (A2) used in the present invention is a polymer having no acidic group obtained by polymerizing a (meth) acrylic polymerizable monomer having a functional group as an essential component, and a polymer having the functional group. It is obtained by reacting a reactive group of an acid group with a compound of an acid group. Examples of the alkali-soluble resin (A2) include the following alkali-soluble resin.

‧ Polymerization with hydroxyl groups such as 2-hydroxyethyl (meth) acrylate Alkali-soluble resins obtained by adding an essential monomer to a polymer of an essential component, and adding acid anhydrides such as succinic anhydride, tetrahydrophthalic anhydride, and maleic anhydride.

‧After obtaining a polymer containing an epoxy-based polymerizable monomer such as glycidyl (meth) acrylate as an essential component, addition of N-methylaminobenzoic acid, N-methylaminophenol, etc. Alkali-soluble resins obtained from amine and acid compounds.

‧Obtaining a polymer containing a polymerizable monomer having an isocyanate group such as 2-isocyanate ethyl (meth) acrylate as an essential component, and adding a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid Alkali-soluble resin.

The weight-average molecular weight of the alkali-soluble resin (A2) is preferably in the range of 1,000 to 200,000 in terms of polystyrene-equivalent weight-average molecular weight measured by GPC from the viewpoint that a coating film having good coating film formation and excellent heat resistance can be obtained. , More preferably in the range of 2,000 to 50,000, and even more preferably in the range of 2,000 to 30,000. Further, if necessary, a polymerizable monomer prepared for use in the alkali-soluble resin (A1) may be used in combination to obtain an alkali-soluble resin (A2).

In the present invention, "(meth) acrylic acid" refers to one or both of methacrylic acid and acrylic acid, and "(meth) acrylfluorenyl" refers to one of methacrylfluorenyl and acrylfluorenyl. Either or both, "(meth) acrylate" means one or both of methacrylate and acrylate.

The alkali-soluble resin (A3) used in the present invention is a copolymer of (meth) acrylate containing epoxy groups and other polymerizable monomers, and an unsaturated monocarboxylic acid is added to the copolymer. At least a part of the epoxy group, and then the hydroxyl group generated by the addition reaction of the unsaturated monocarboxylic acid At least a part of the polycarboxylic acid anhydride is obtained by an addition reaction.

Examples of the epoxy-containing (meth) acrylate include, for example, glycidyl (meth) acrylate, 3,4-butylene oxide (meth) acrylate, and (3,4) (meth) acrylate -Epoxycyclohexyl) methyl ester, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Among them, propylene oxide (meth) acrylate is preferred. These (meth) acrylates containing an epoxy group may be used alone, or two or more of them may be used in combination.

In addition, as for the polymerizable monomers other than the epoxy-containing (meth) acrylate containing the raw material of the alkali-soluble resin (A3), an alicyclic structure such as norbornene skeleton and dicyclopentadiene skeleton is used. The monomer is preferred because it can improve the heat resistance and mechanical strength of the cured product of the color photoresist composition of the present invention.

In addition, a polymerizable monomer having no alicyclic structure may be used as a polymerizable monomer other than the epoxy group-containing (meth) acrylate. Examples of such polymerizable monomers include vinyl aromatics such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amido, and ester derivatives of styrene. ; Butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate Ester, isopropyl (meth) acrylate, n-butyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, amyl (meth) acrylate, (formyl) Base) neopentyl acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid Dodecyl ester, cyclopentyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isoamyl (meth) acrylate, adamantane (meth) acrylate Alkyl ester, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracene (meth) acrylate, anthrone (meth) acrylate, (meth) acrylic acid Sunflower ester, salicyl (meth) acrylate, furan (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuran (meth) acrylate, piperanyl (meth) acrylate, benzyl (meth) acrylate Base, phenethyl (meth) acrylate, cresol (meth) acrylate, -1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, (methyl) Perfluoron-propyl acrylate, perfluoroisopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumene (meth) acrylate, 3- (N) acrylic acid (meth) acrylate (N-dimethylamine) propyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylates; (meth) acrylamide , (Meth) acrylic acid N, N-dimethylamine, (meth) acrylic acid N, N-diethylamine (Meth) acrylic acid N, N-dipropylamine, (meth) acrylic acid N-N, N-diisopropylamine, (meth) acrylic acid anthracenylamine, etc. ; (Meth) acrylic acid aniline, (meth) acrylic acid nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate Vinyl compounds such as esters; unsaturated dicarboxylic acid diesters such as methyl maleate, diethyl maleate, diethyl fumarate, diethyl iconate, etc. Class; N-phenyl-cis-butene-diimide, N-cyclohexyl-cis-butene-diimide, N-dodecyl-cis-butene-diimide, N- (4-hydroxyphenyl) -cis-butene Mono-cis-butene diimides such as enediimides; N- (meth) acrylfluorenyl phthalates 醯 imine and so on.

Among the other polymerizable monomers mentioned above, from the viewpoint of improving the heat resistance and mechanical strength of the cured product of the color photoresist composition of the present invention, it is preferable to use styrene, benzyl (meth) acrylate, and monocis. At least one of enediimides. The proportion of styrene, benzyl (meth) acrylate, and mono-cis-butene diimide, based on the total amount of other polymerizable monomers, is preferably 1 to 70 mole%, and more preferably 3 ~ 50 Mol%.

Among them, the copolymerization reaction of the epoxy group-containing (meth) acrylate and the other polymerizable monomers can be performed by a known polymerization method such as a solution polymerization method using a radical polymerization initiator. The solvent to be used is not particularly limited as long as it is inactive to radical polymerization, and an organic solvent generally used may be used.

As the copolymer of the epoxy group-containing (meth) acrylate and the other polymerizable monomer, it is preferred that the copolymer derived from the epoxy group-containing (meth) acrylate is repeated in an amount of 5 to 90 mole%. Units composed of 10 to 95 mol% of repeating units derived from other radically polymerizable monomers, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter It is further more preferable that the former is composed of 30 to 70 mol% and the latter is composed of 70 to 30 mol%.

The alkali-soluble resin (A3) can be obtained by allowing an epoxy group of a copolymer of the epoxy-containing (meth) acrylate and another polymerizable monomer to react with an unsaturated monocarboxylic acid (polymerizable component), An acid anhydride (an alkali-soluble component) of a polycarboxylic acid is obtained by reaction.

Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, ortho-, meta-, p-vinylbenzoic acid, an a-haloalkyl group at the α-position, Monocarboxylic acids such as (meth) acrylic acid substituted with alkoxy, halogen atom, nitro, or cyano. Among these, (meth) acrylic acid is preferred. These unsaturated monocarboxylic acids may be used alone or in combination of two or more. By using this unsaturated monocarboxylic acid, polymerizability can be imparted to the alkali-soluble resin (A3).

The unsaturated monocarboxylic acid is usually preferably added to 10 to 100 mol% of the epoxy group of the copolymer, more preferably to 30 to 100 mol%, and even more preferably to the addition. To 50 ~ 100 mol%.

Examples of the anhydride of the polycarboxylic acid include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorobridged anhydride. And other dicarboxylic acid anhydrides; trimellitic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride and other carboxylic acid anhydrides having more than three carboxyl groups. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polycarboxylic acid anhydrides may be used alone or in combination of two or more. By using the acid anhydride of this polycarboxylic acid, the said alkali-soluble resin (A3) can be made alkali-soluble.

The anhydride of the aforementioned polycarboxylic acid is usually preferably an addition of an unsaturated monocarboxylic acid to 10 to 100 mole% of the hydroxyl group generated from the epoxy group of the copolymer, and more preferably 20 ~ 90 Molar% bonus, even better is 30 ~ 80 Molar% bonus.

The weight-average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A3) is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. The dispersion degree (Mw / Mn) of the alkali-soluble resin (A3) is preferably in the range of 2.0 to 5.0.

The epoxypropyl (meth) acrylate resin (A4) used in the present invention is, for example, by allowing an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid having a carboxyl group in the ester portion. The ester is added to the epoxy resin and further reacted with a polybasic acid anhydride to obtain it.

The epoxy resin can be, for example, bisphenol A epoxy resin (commercially available are "EPIKOTE 828", "EPIKOTE 1001", "EPIKOTE 1002", "EPIKOTE 1004", etc., manufactured by Japan Epoxy Resin Co., Ltd.), An epoxy resin obtained by reacting an alcoholic hydroxyl group of bisphenol A epoxy resin with epichlorohydrin (commercially available is "NER-1302" (epoxy equivalent 323, softening point 76, manufactured by Nippon Kayaku Co., Ltd.) ° C)), bisphenol F-type resin (commercially available are "EPIKOTE 807", "EP-4001", "EP-4002", "EP-4004", etc., manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol F Epoxy resin obtained by reacting an alcoholic hydroxyl group of an epoxy resin with epichlorohydrin (commercially available product is "NER-7406" (epoxy equivalent 350, softening point 66 ° C) manufactured by Nippon Kayaku Co., Ltd.) Bisphenol S-type epoxy resin, biphenylepoxypropyl ether (commercially available as "YX-4000" manufactured by Japan Epoxy Resin Co., Ltd.), phenolic epoxy resin (commercially available as Nippon Kayaku Co., Ltd. Co., Ltd.'s "EPPN-201", Japan Epoxy Resin Co., Ltd. "EP-152", "EP-154", Dow Chemical Japan `` DEN-438 '' by Co., Ltd.), cresol novolac epoxy resin (commercially available are EOCN-102S, EOCN-1020, and EOCN-104S by Nippon Kayaku Co., Ltd.) , Triglycidyl isocyanate (commercially available "TEPIC" manufactured by Nissan Chemical Industry Co., Ltd.), ginsenophenol methane type epoxy resin (commercially available is "Nippon Chemical Co., Ltd." EPPN-501 "," EPN-502 "," EPPN-503 "), 茀 epoxy resin (commercially available Cardo epoxy resin" ESF-300 "manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (Daicel Chemical Industry Co., Ltd. "CELLOXIDE 2021P" and "CELLOXIDE EHPE" manufactured by the company), and dicyclopentadiene-type epoxy resins (e.g., Nippon Chemical Co., Ltd.) obtained by epoxy-propylating a phenol resin produced by the reaction of dicyclopentadiene and phenol. "XD-1000" by Pharma Co., Ltd., "EXA-7200" by DIC Co., Ltd., "NC-3000" and "NC-7300" by Nippon Kayaku Co., Ltd.), Ring with osmium skeleton Oxygen resin (see Japanese Patent Application Laid-Open No. 4-355450) and the like. These epoxy resins may be used alone or in combination of two or more.

Other examples of the epoxy resin include a copolymer type epoxy resin. Examples of the copolymerizable epoxy resin include epoxy-based (meth) acrylic acid, (meth) acryl-methyl methyl epoxycyclohexane, and vinyl epoxycyclohexane. Monomers with methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerol mono (meth) acrylate, A copolymer obtained by copolymerizing a polymerizable monomer having no epoxy group such as a meth) acrylate.

Examples of the (meth) acrylate having a polyoxyalkylene chain include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono ( Polyethylene glycol mono (meth) acrylate such as meth) acrylate; methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, methoxy Alkoxy polyethylene glycol (meth) acrylate and the like such as tetrakiethylene glycol mono (meth) acrylate and the like.

The molecular weight of the copolymerized epoxy resin is preferably in the range of 1,000 to 200,000. In addition, the amount of the epoxy-containing monomer used as a raw material of the copolymerized epoxy resin is preferably in the range of 10 to 70% by mass, and more preferably in the range of 20 to 70% by weight relative to the monomer having no epoxy group. A range of 50% by mass.

Examples of the commercially available products of the copolymerized epoxy resin include "CP-15", "CP-30", "CP-50", "CP-20SA", "CP- 510SA "," CP-50S "," CP-50M "," CP-20MA ", etc.

The molecular weight of the epoxy resin is good in terms of polystyrene conversion as measured by GPC from the viewpoint of allowing the coating film to form well and preventing gelation during the addition reaction of α, β-unsaturated monocarboxylic acids. The average molecular weight is preferably in the range of 200 to 200,000, and more preferably in the range of 300 to 100,000.

Examples of the α, β-unsaturated monocarboxylic acid include iconic acid, crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid. Acrylic acid and methacrylic acid are preferable, and the reactivity is more preferable. For acrylic. Examples of α, β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester portion include 2-succinyloxyethyl acrylate, 2-maleyloxyethyl acrylate, and 2-phthaloyl acrylate Ethyl ester, 2-hexahydrophthaloyloxyethyl acrylate, 2-succinyloxyethyl methacrylate, 2-maleoxyethyl methacrylate, 2-methyl acrylate Phthalomethylethoxyethyl, 2-hexahydrophthaloyloxyethyl methacrylate, crotonic acid-2-succinomethyloxyethyl, etc., preferably 2-maleyloxyethyl acrylate and Acrylic-2-phthaloethoxyethyl is more preferred, and 2-maleimoxyethyl acrylate is preferred. These α, β-unsaturated monocarboxylic acids and α, β-unsaturated monocarboxylic acid esters may be used alone or in combination of two or more.

A known method can be used for the addition reaction of the α, β-unsaturated monocarboxylic acid or an ester thereof with an epoxy resin, and examples thereof include a method of reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. Esterification catalysts can be used: triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine and other tertiary amines; tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrichloride Quaternary ammonium salts such as methyl ammonium and the like.

The amount of α, β-unsaturated monocarboxylic acid or its ester is preferably in the range of 0.5 to 1.2 equivalents, and more preferably in the range of 0.7 to 1.1 equivalents relative to 1 equivalent of epoxy groups in the epoxy resin as the raw material. range.

Examples of the polybasic acid anhydride to be added to the epoxy resin added with an α, β-unsaturated carboxylic acid or an ester thereof include maleic anhydride, succinic anhydride, itaconic anhydride, and phthalic acid. Acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, diphenylketone tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, internal Methylenetetrahydrophthalic anhydride, chlorobridged anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc. Among these, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and Trimellitic anhydride and biphenyltetracarboxylic dianhydride, more preferably tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These polybasic acid anhydrides may be used alone or in combination of two or more.

The addition reaction of the polybasic acid anhydride can also use a known method, and the reaction can be continuously performed under the same conditions as the addition reaction of an α, β-unsaturated carboxylic acid or an ester thereof. The amount of the polybasic acid anhydride is from the viewpoint of improving the alkali developability and coating film formation. The amount of the acid value of the epoxy (meth) acrylate resin to be produced is preferably in the range of 10 to 150, more preferably 20 Amount in the range of ~ 140.

An epoxy (meth) acrylate resin having a carboxyl group can be exemplified by a resin containing naphthalene described in Japanese Unexamined Patent Publication No. 6-49174; Japanese Unexamined Patent Publication No. 2003-89716 and Japanese Unexamined Patent Application No. 2003-165830 Japanese Patent Laid-Open No. 2005-325331, Japanese Patent Laid-Open No. 2001-354735, a resin containing thallium; described in Japanese Patent Laid-Open No. 2005-126674, Japanese Patent Laid-Open No. 2005-55814, and Japanese Patent Laid-Open 2004-295084 and other resins. In addition, as a commercially available product, "ACA-200M" manufactured by Daicel Chemical Industry Co., Ltd. can also be exemplified.

The alkali-soluble resin (A) used in the present invention may be used alone or in combination of two or more of the above-mentioned alkali-soluble resins (A1) to (A4). In addition, the alkali-soluble resin (A) is preferably used in combination with a pigment dispersant to be described later, because it can be formed in a non-pixel portion on a substrate without leaving undissolved matter and has a high concentration of color pixels with excellent adhesion to the substrate. . Specifically, it is preferable to use a part of the alkali-soluble resin (A) together with a pigment dispersant described later in the dispersion treatment step. In this case, the alkali-soluble resin (A) is preferably used in a range of 5 to 200% by mass, and more preferably in a range of 10 to 100% by mass, relative to the pigment.

In addition, the alkali-soluble resin (A) used in the present invention may be an alkali-soluble resin other than the above-mentioned alkali-soluble resins (A1) to (A4). Examples of such a resin include an alkali-soluble resin obtained using a polymerizable monomer having a phenolic hydroxyl group as an acidic group as an essential component, and a resin obtained using a polymerizable monomer having a sulfonic acid group as an acidic group as an essential component. Alkali-soluble resins. Here, the polymerizable monomer having a phenolic hydroxyl group includes, for example, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition In addition, one or more hydrogen atoms other than the phenolic hydroxyl group and the vinyl group of the aromatic ring bonded to these monomers may be substituted with an alkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, and amidine. Based compounds. Examples of the polymerizable monomer having a sulfonic acid group as an acidic group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, and 2-hydroxy-3- (meth) allyl. Oxypropanesulfonic acid, 2-sulfoethyl (meth) acrylate, or salts thereof.

In the color photoresist composition of the present invention, the content ratio of the alkali-soluble resin (A) is preferably 0.1 to 80 in the total solid content in terms of improving the appearance of the coating film and adhesion to the substrate. The mass% range is more preferably in the range of 1 to 60 mass%.

The polymerizable compound (B) used in the present invention can be used without particular limitation as long as it is a compound having a photopolymerizable functional group capable of undergoing polymerization or crosslinking reaction by irradiation with active energy rays such as ultraviolet rays. Examples of such polymerizable compounds (B) include unsaturated carboxylic acids such as (meth) acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatics. An ester of a polyhydroxy compound and an unsaturated carboxylic acid, an ester obtained from an esterification reaction of an unsaturated carboxylic acid with a polycarboxylic acid and the aforementioned polyhydric hydroxy compound such as an aliphatic polyhydroxy compound, an aromatic polyhydroxy compound, etc., and a polyisocyanate compound and A polymerizable compound having a urethane skeleton and the like formed by reacting a (meth) acrylfluorenyl-containing hydroxy compound.

Examples of the ester of the aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and trimethylolpropane tri (methyl) ) Acrylate, Trimethylolethane Tris (meth) acrylate, neopentaerythritol di (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (Meth) acrylates, such as (di) pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate and the like. In addition, the (meth) acrylic acid part of these acrylates may be replaced by the itonic acid ester of itaconic acid, the crotonic acid ester of crotonic acid, or the maleic acid of maleic acid. Esterates and the like.

Examples of the ester of the aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcinol di (meth) acrylate, and pyrogallol tri (meth) acrylate. Wait. The ester obtained from the esterification reaction of unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound may be a pure substance or a mixture. Examples of such esters include: esters obtained from (meth) acrylic acid, phthalic acid, and ethylene glycol; esters obtained from (meth) acrylic acid, maleic acid, and diethylene glycol; Esters of (meth) acrylic acid, terephthalic acid and neopentyl tetraol, which are obtained from esters of (meth) acrylic acid, adipic acid, butanediol, and glycerol.

Examples of the polymerizable compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acrylfluorene-containing hydroxy compound include hexamethylene diisocyanate and trimethylhexamethylene Aliphatic diisocyanates such as diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, and (meth) acrylic acid 2 Reaction of hydroxy compounds having (meth) acrylfluorenyl groups such as 3-hydroxyethyl ester, 3-hydroxy [1,1,1-tris (meth) acryloxymethyl] propane Thing.

Examples of the polymerizable compound (B) used in the present invention other than the above include (meth) acrylamide such as ethylene bis (meth) acrylamide, and allyl esters such as diallyl phthalate. ; Vinyl compounds, such as divinyl phthalate.

In addition, as the polymerizable compound (B), a polymerizable compound having an acid group may be used. The polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably an acid formed by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Polyfunctional monomer. In addition, it is particularly preferable to use neopentyl tetraol and dipentaerythritol as the aliphatic polyhydroxy compound. These monomers may be used alone or in combination of two or more. In addition, a monomer having an acid group and a monomer having no acid group may be used in combination.

Examples of preferable specific examples of the polyfunctional polymerizable compound having an acid group include, for example, dipentaerythritol hexaacrylate commercially available from East Asia Synthesis Co., Ltd. as "ARONIX TO-1382", dixin A mixture of succinate esters of pentaerythritol pentaacrylate and dinepentaerythritol pentaacrylate as main components. This polyfunctional polymerizable compound may be used in combination with other polyfunctional polymerizable compounds.

The acid value of the polyfunctional polymerizable compound having an acid group is preferably in the range of 0.1 to 40, and more preferably in the range of 5 to 30 in terms of improving developability and hardenability. In the case where two or more kinds of polyfunctional polymerizable compounds having different acid values are used in combination, or in the case where a polyfunctional polymerizable compound having no acid group is used in combination, the acid of the mixture obtained by mixing all the polyfunctional polymerizable compounds is preferred. The price is within the above range.

In the color photoresist composition of the present invention, the content ratio of the polymerizable compound (B) in the total solid content is preferably in a range of 5 to 80% by mass, more preferably in a range of 10 to 70% by mass, and further more It is preferably in a range of 20 to 50% by mass. The ratio of the polymerizable compound (B) to the colorant (C) described later is preferably 5 to 200% by mass, more preferably 10 to 100% by mass, and still more preferably 20 to 80% by mass. range.

As the coloring agent (C) used in the present invention, any pigment or dye can be used without particular limitation as long as it can be colored. As the pigment, any of an organic pigment and an inorganic pigment can be used. As the organic pigment, pigments of various colors such as a red pigment, a green pigment, a blue pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. Examples of the chemical structure of the organic pigment include: azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, and Department, Yin Dan Shilin Department, Sacrifice Department, etc. The "CI" below refers to a color index.

Examples of the red pigment include: CIPigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53 : 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144 , 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200 , 202, 206 , 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251 , 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among these, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferable, and C.I. Pigment Red 177, 209, 224, or 254 is more preferable.

Examples of the green pigment include: CIPigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 , 58 and so on. Among these, C.I. Pigment Green 7, 36, or 58 is preferred.

Examples of the blue pigment include: CIPigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and so on. Among these, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6 is preferable, and C.I.Pigment Blue 15: 6 is more preferable.

Examples of the yellow pigment include: CIPigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35 , 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81 , 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120 , 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162 , 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1 , 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185 is preferable, and C.I. Pigment Yellow 83, 138, 139, 150, or 180 is more preferable.

Examples of the purple pigment include: CIPigment Violet 1, 1, 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25 , 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, C.I.Pigment Violet 19 or 23 is preferable, and C.I.Pigment Violet 23 is more preferable.

Examples of the orange pigment include: CIPigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and so on. Among these, C.I. Pigment Orange 38 or 71 is preferable.

Since each pixel of the three primary colors of the color filter used in the liquid crystal display device and the organic EL display device is red (R), green (G), and blue (B), the aforementioned red pigment, green pigment, and blue pigment are used. As the main component, and for the purpose of improving color reproducibility, yellow, purple, orange and other organic pigments can also be used for hue adjustment.

Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, chrome yellow, ferric oxide, and chromium oxide.

The average particle diameter of the organic pigment is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less in order to improve the brightness of the color liquid crystal display device and the organic EL display device. It is preferred to disperse the organic pigment to such an average particle diameter before use. The average primary particle diameter of the organic pigment is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 40 nm or less, and particularly preferably in a range of 10 to 30 nm. Here, the average particle diameter of the organic pigment is measured with a dynamic light scattering particle size distribution meter, and can be measured with, for example, NanoTrac particle size distribution measuring devices "UPA-EX150" and "UPA-EX250" manufactured by Nikkiso Co., Ltd.

On the other hand, the coloring agent (C) used when the color photoresist composition of the present invention is used to form a black matrix (BM) is not particularly limited as long as it is black, and examples include carbon black and lamp black. , Acetylene black, bone black, thermal cracking carbon black, channel black, furnace black, graphite, iron black, and titanium black. It does not matter if you mix two or more organic pigments and mix them to make them black. Among these, carbon black and titanium black are preferred from the viewpoints of light shielding rate and image characteristics.

Examples of the commercially available carbon black include MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, and the like manufactured by Mitsubishi Chemical Corporation. # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990 , # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250 , # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc. Evonik Degussa Japan Co., Ltd. can include Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1 Color Black FW2 Color Black FW2V Color Black FW18 Color Black FW18 Color Black FW200 Color Black S160 Color Black S170 MonarcH900, MonarcH1000, MonarcH1100, MonarcH1300, MonarcH1400, MonarcH4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130V, PEARLS130V TEX-8, etc., manufactured by Columbia Carbon include RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080 , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000 , RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc.

Among the above-mentioned carbon blacks, as the high optical density and high surface resistivity required for a black matrix having a color filter, it is preferable to use a resin-coated carbon black. The carbon black coated with a resin can be described in, for example, Japanese Patent Laid-Open No. 9-26571, Japanese Patent Laid-Open No. 9-71733, Japanese Patent Laid-Open No. 9-95625, Japanese Patent Laid-Open No. 9-238863 The method disclosed in Japanese Patent Laid-Open No. 11-60989 is obtained by treating known carbon black.

The method for producing the aforementioned titanium black includes the method described in Japanese Patent Application Laid-Open No. 49-5432, which is a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing environment; Japanese Patent Application Laid-Open No. 57-205322 It describes the method of reducing ultrafine titanium dioxide obtained by high temperature hydrolysis of titanium tetrachloride in a reducing environment containing hydrogen; it is described in Japanese Patent Application Laid-Open No. 60-65069 and Japanese Patent Application Laid-Open No. 61-201610. A method for high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia; a method described in Japanese Patent Application Laid-Open No. 61-201610, a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide, and high-temperature reduction is performed in the presence of ammonia. Examples of commercially available titanium blacks include titanium blacks 10S, 12S, 13R, 13M, 13M-C, and the like manufactured by Mitsubishi Material Co., Ltd.

A combination in which two or more organic pigments are mixed and the mixture becomes black by mixing colors includes a black pigment made by mixing red, green, and blue pigments. Examples of color materials that can be mixed for the preparation of black pigments include: Victoria Pure Blue (C.I.42595), Auramine O (C.I.41000), Cathilon Brilliant Flavin (Basic 13), Rhodamine 6GCP (CI45160), Rhodamine B (CI45170), Safranine OK70: 100 (CI50240), Erioglaucine X (CI42080), No. 120 / Lionel Yellow (CI21090), Lionel Yellow GRO (CI21090), Symuler Fast Yellow 8GF (CI21105), Benzidine Yellow 4T-564D (CI21095), Symuler Fast Red 4015 (CI12355), Lionel Red 7B4401 (CI15850), Fastogen Blue TGR-L (CI74160), Lionel Blue SM (CI26150) , Lionel Blue ES (CIPigment Blue 15: 6), Lionogen Red GD (CIPigment Red 168), Lionel Green 2YS (CIPigment Green 36), etc.

Other color materials that can be mixed for use in the preparation of black pigments include, for example: CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, CI purple pigment 19, 23, 29, 30, 37, 40, 50, CI blue pigment 15, 15: 1, 15: 4, 22, 60, 64, CI green pigment 7, CI Brown pigments 23, 25, 26 and so on.

On the other hand, when carbon black is used as the black pigment, the average primary particle diameter is preferably in the range of 0.01 to 0.08 μm, and more preferably in the range of 0.02 to 0.05 μm from the viewpoint of good developability. The carbon black dibutyl phthalate (hereinafter referred to as "DBP") absorption is preferably in the range of 40 ~ 100cm ³ / 100g, and from the viewpoint of good dispersibility / developing property, it is more preferable. The range is 50 ~ 80cm ³ / 100g. In addition, the specific surface area of the carbon black used measured by the BET method is preferably in the range of 50 to 120 m ² / g, and from the viewpoint of good dispersion stability, more preferably in the range of 60 to 95 m ² / g.

In addition, the particle shape of carbon black is different from organic pigments and the like, and it may be in a state called a structure formed by primary particle fusion, and fine pores may be formed on the particle surface after the treatment. Therefore, in order to express the particle shape of carbon black, it is generally better to measure the ratio of the DBP absorption (JIS K6221) to the BET method, except for the average particle diameter of the primary particles obtained by the same method as the organic pigment. The surface area (JIS K6217) is used as an index of the structure and the amount of pores.

In addition, a dye may be used as a coloring agent used in the present invention. Examples of such dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of the azo dye include: CIacid Yellow 11, CIacid Orange 7, CIacid Red 37, CIacid Red 180, CIacid Blue 29, CIDirect Red 28, CIDirect Red 83, CIDirect Yellow 12, CIDirect Orange 26, CIDirect Green 28, CIDirect Green 59, CIReactive Yellow 2, CIReactive Red 17, CIReactive Red 120, CIReactive Black 5, CIDisperse Orange 5, CIDisperse Red 58, CIDisperse Blue 165, CIBasic Blue41, CIBasic Red 18, CIMordant Red 7, CIMordant Yellow 5, CIMordant Black 7, etc.

Examples of the anthraquinone dye include C.I.Vat Blue 4, C.I.Acid Blue 40, C.I.Acid Green 25, and C.I.Reactive Blue. 19. C.I.Reactive Blue 49, C.I.Disperse Red 60, C.I.Disperse Blue 56, C.I.Disperse Blue 60, etc.

Examples of the phthalocyanine dyes include CIVat Blue5, and examples of the quinimine dyes include CIBasic Blue 3, CIBasic Blue 9, and the like. Examples of the quinoline dyes include CISolvent Yellow 33, CI. Acid Yellow 3, CIDisperse Yellow 64, and the like. Examples of the nitro dye include CIacid Yellow 1, CIacid Orange 3, and CIDisperse Yellow 42.

Among the colorants (C) listed above, in terms of the light resistance, weather resistance, and fastness of the coating film finally obtained, it is preferable to use a pigment, and in order to adjust the hue, It is necessary to use dyes in combination with pigments.

The content ratio of the colorant (C) in the color photoresist composition of the present invention is preferably 1% by mass or more, more preferably 5 to 80% by mass, and still more preferably 5 to 80% by mass in the total solid content. A range of 70% by mass.

In the case where the red (R), green (G), and blue (B) pixels of the color filter are formed using the color photoresist composition of the present invention, the aforementioned colorant in the color photoresist composition of the present invention The content ratio of (C) is preferably in a range of 5 to 60% by mass, and more preferably in a range of 10 to 50% by mass in the total solid content.

In addition, in the case where the black matrix of a color filter is formed using the color photoresist composition of the present invention, the content ratio of the colorant (C) in the color photoresist composition of the present invention is relatively small in the total solid content. It is preferably in a range of 20 to 80% by mass, and more preferably in a range of 30 to 70% by mass.

In the color photoresist composition of the present invention, the colorant (C) is a pigment. In the case of raw materials, it is preferred to use a pigment dispersion liquid prepared in advance 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; polyamide resins, polyurethane resins, polyester resins, and acrylic resins And other resin-based dispersants. Among these, a graft copolymer having a nitrogen atom, an acrylic block copolymer having a nitrogen atom, a urethane resin dispersant, and the like are preferred. These dispersants have nitrogen atoms, and the nitrogen atoms have an affinity for the pigment surface, and the dispersion stability is improved by increasing the affinity of the parts other than the nitrogen atoms to the medium. Moreover, these dispersing agents may be used individually by 1 type, and may use 2 or more types together.

Examples of commercially available dispersants include: "EFKA" series ("EFKA 46", etc.) manufactured by Efka Chemicals; "Disperbyk" series, "BYK" series ("BYK-160"), manufactured by BYK Japan Co., Ltd. , "BYK-161", "BYK-2001", etc.); "SolSPerSe" series by Lubrizol Japan Co., Ltd .; "KP" series by Shin-Etsu Chemical Industry Co., Ltd., and "KP" by Kyoeisha Chemical Co., Ltd. "Polyflow" series; "DISPARLON" series manufactured by Kusumoto Chemical Co., Ltd .; "AJISPER" series ("AJISPER PB-814", etc.) manufactured by Ajinomoto Fine-Techno Co., Ltd.

Examples of the organic solvent used in preparing the pigment dispersion liquid include acetate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; and acrylic solvents such as ethoxypropionate. Ester-based solvents; Aromatic solvents such as toluene, xylene, and methoxybenzene; Ethers such as butylcellulose, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether Series solvents; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Solvent; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N, N-dimethylformamidine, γ-butyrolactam, N-methyl-2-pyrrolidone; γ-butane Lactone-based solvents such as esters; urethanes and the like. These solvents may be used alone or in combination of two or more.

Examples of the method for preparing the pigment dispersion include a method in which a kneading and dispersing step and a microdispersing step of the colorant (C) are performed, and a method in which only the microdispersing step is performed. In the kneading and dispersing step, the colorant (C), a part of the alkali-soluble resin (A), and the dispersant, if necessary, are mixed and kneaded. Machines used for kneading include double rolls, three rolls, ball mills, stone mills, dispersers, kneaders, co-kneaders, homogenizers, mixers, uniaxial or biaxial extruders, etc. These kneaders disperse while applying strong shearing forces to disperse the colorant. In addition, before the colorant (C) is subjected to the above-mentioned kneading, the particle size is preferably reduced by a salt milling method or the like.

On the other hand, in the micro-dispersing step, a solvent is added to the composition containing the coloring agent (C) obtained in the kneading and dispersing step, or the coloring agent (C) and alkali-soluble are mixed. The resin (A), the solvent, and the aforementioned dispersant, if necessary, can be mixed and dispersed by using a disperser and a dispersion medium such as glass, zirconia, or ceramic particles to disperse the particles of the colorant (C) close to each other. The tiny state of a primary particle.

From the viewpoint of improving the light 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 diameter of the colorant (C) is measured by a dynamic light scattering particle size distribution meter, and, for example, NanoTrac particle size distribution measuring devices "UPA-EX150" and "UPA-EX150" manufactured by Nikkiso Co., Ltd. can be used. UPA-EX250 "and other measurements.

The fluorine-based surfactant (D) used in the present invention is a polymer structure having a polymerizable monomer and a poly (perfluoroalkylene ether) chain, and a plurality of the aforementioned polymer structures are transmitted through the poly (perfluoroalkylene) An ether) chain-linked polymer having a resin structure having an oxyalkylene group in a side chain of the aforementioned polymer structure.

Examples of the polymerizable monomer constituting the polymer structure include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, maleimide monomers, and the like. The aforementioned polymers The structure is a structural part of the linear structure of their homopolymer or copolymer. The fluorine-based surfactant (D) used in the present invention is as described later, and it is preferably a polymerizable monomer (d1) having a poly (perfluoroalkylene ether) chain and polymerizable unsaturated groups at both ends thereof. A copolymer obtained by copolymerizing a polymerizable monomer (d2) having an oxyalkylene group and a polymerizable unsaturated group as an essential monomer. In this case, the polymer structure includes the polymerizable origin Structural parts of the monomer (d1) and the polymerizable monomer (d2). Hereinafter, a copolymer obtained by copolymerizing the polymerizable monomer (d1) and the polymerizable monomer (d2) as essential monomers will be described in detail.

Examples of the poly (perfluoroalkylene ether) chain possessed by the polymerizable monomer (d1) include a structure in which a divalent fluorocarbon group having 1 to 3 carbon atoms and an oxygen atom are alternately connected. The divalent fluorinated carbon group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds, and specific examples thereof include those represented by the following structural formula (a1).

(In the above structural formula (a1), X is the following structural formulas (a1-1) to (a1-5), and all X in the structural formula (a1) may be the same structure, or a plurality of structures may be random. Or in the form of a block. In addition, n is an integer of 1 or more.)

-CF ₂ -(a1-1)

-CF ₂ CF ₂ -(a1-2)

-CF ₂ CF ₂ CF ₂ -(a1-3)

Among these, from the viewpoint of improving the leveling property of the coating composition to which the fluorine-based surfactant of the present invention is added and obtaining a smooth coating film, it is particularly preferable to use the aforementioned structural formula (a1-1). The perfluoromethylene structure represented by) coexists with the perfluoroethylene structure represented by the aforementioned structural formula (a1-2). Here, the existence ratio of the perfluoromethylene structure represented by the aforementioned structural formula (a1-1) to the perfluoroethylene ethane structure represented by the aforementioned structural formula (a1-2) is in the molar ratio [ When the ratio of the structure (a1-1) / structure (a1-2)] is 1/10 to 10/1, it is preferable because a coating composition having excellent leveling property can be obtained. In the aforementioned structural formula (a1), The value of n is preferably in the range of 3 to 100, and more preferably in the range of 6 to 70.

The poly (perfluoroalkylene ether) chain can balance the leveling property of the coating composition with the solubility of non-fluorine-based materials in the coating composition. Alkyl ether) The total number is preferably in the range of 18 to 200, and more preferably in the range of 25 to 150.

Here, both ends of the poly (perfluoroalkylene ether) chain are bonded to a polymer structure of a polymerizable monomer, and a plurality of the polymer structures are allowed to pass through the poly (perfluoroalkylene ether). In a state where the chains are connected, as long as the polymerizable monomer (d2) having an oxyalkylene group and a polymerizable unsaturated group described below is radically polymerized with the poly (perfluoroalkylene ether) chain and both ends thereof The compounds (d1) at the structural site of the unsaturated group may be copolymerized together.

The said compound (d1) can introduce the polymerizable unsaturated group represented by (U-1) to (U-6) shown below into the following general formula (a2-1) by the method mentioned later, for example. (a2-7) It is obtained by exemplifying a compound having a reactive group at both ends.

The general formulae (a2-1) to (a2-7) are shown below. Here, "-PFPE-" in each structural formula represents the above-mentioned poly (perfluoroalkylene ether) chain.

HO-CH ₂ -PFPE-CH ₂ -OH (a2-1)

HO-CH ₂ CH ₂ -PFPE-CH ₂ CH ₂ -OH (a2-2)

OCN-PFPE-NCO (a2-5)

Examples of the polymerizable unsaturated groups of the polymerizable monomer (d1) at both ends of the poly (perfluoroalkylene ether) chain include those represented by the following structural formulas U-1 to U-6. Those with polymerizable unsaturated groups.

In the polymerizable unsaturated group represented by the aforementioned U-6, A is a halogen atom.

Among these polymerizable unsaturated groups, the ease of obtaining or producing the polymerizable monomer (d1) itself, or the ease of copolymerization with the polymerizable monomer (d2) described later, is particularly disadvantageous. Preferably, it is a propylene fluorenyl group represented by the structural formula U-1, or a methacryl fluorenyl group represented by the structural formula U-2. In addition, by using a propenyloxy group represented by the structural formula U-6, a halogen atom of the propenyl group is used to make the main of the fluorine-based surfactant (D) The chain does not move easily. As a result, the group having a fluorine atom is fixed, and more favorable leveling properties can be exhibited by surface segregation.

Examples of the method for producing the polymerizable monomer (d1) include, for example, dehydrochlorinated (meth) acrylic acid for a compound having one hydroxyl group at each end of a poly (perfluoroalkylene ether) chain. A method of obtaining by reaction, a method of obtaining (meth) acrylic acid by dehydration reaction, a method of obtaining by urethane reaction of 2- (meth) acrylfluorenyloxyethyl isocyanate, Iconic anhydride is obtained by an esterification reaction, a method in which chloromethyl-containing styrene is reacted in the presence of a base; each of the poly (perfluoroalkylene ether) chain has 1 at each end A carboxyl compound, a method obtained by esterifying 4-hydroxybutyl acrylate glycidyl ether, and a method obtained by subjecting glycidyl (meth) acrylate to esterification; Perfluoroalkylene ether) A compound having one isocyanate group at each end of the chain, and a method of introducing and reacting 2-hydroxyethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylic acid Method for amine reaction. Among these, a compound obtained by dehydrochlorinating a (meth) acrylic acid with a compound having one hydroxyl group at each end of a poly (perfluoroalkylene ether) chain, and isocyanate 2 -A method in which (meth) acrylfluorenyloxyethyl ester is subjected to an amine esterification reaction is particularly preferable from the viewpoint of easy synthesis.

In the present invention, "(meth) acrylfluorenyl" refers to one or both of methacrylfluorenyl and acrylfluorenyl, and "(meth) acrylate" refers to methacrylate and acrylate. "(Meth) acrylic acid" means one or both of methacrylic acid and acrylic acid.

Specific examples of the polymerizable monomer (A) include the following structural formulas. (A-1) ~ (A-13). Here, "-PFPE-" in each of the following structural formulas represents a poly (perfluoroalkylene ether) chain.

Among these, from the point that it is easy to manufacture the polymerizable monomer (A) industrially, it is preferable to use the aforementioned structural formulae (d1-1), (d1-2), (d1-5), (d1- 6) From the standpoint of improving the performance as a leveling agent, it is more preferable to have propylene at both ends of the poly (perfluoroalkylene ether) chain represented by the aforementioned structural formula (d1-1).醯 基 者.

The polymerizable monomer (d2) is a polymerizable monomer having an oxyalkylene group and a polymerizable unsaturated group. Examples of the polymerizable unsaturated group possessed by the polymerizable monomer (d2) include a (meth) acrylfluorenyl group, a vinyl group, and a maleimide group, and the polymerizable monomer (d2) is easily compatible with the polymerizable monomer. In view of (d1) copolymerization, a (meth) acrylfluorenyl group is preferred.

In addition, specific examples of the polymerizable monomer (d2) include, for example, monomers represented by the following general formula (d2-1).

(Wherein R ¹ is a hydrogen atom or a methyl group, X, Y, and Z are independent alkylene groups, p, q, and r are each an integer of 0 or more, and the total of p, q, and r is 1 In the above integer, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

X, Y, and Z in the general formula (d2-1) are alkylene groups, and the alkylene groups also include those having a substituent. Specific examples of the -O- (XO) p- (YO) q- (ZO) r- moiety include: the number of repeating units p is 1, q and r are 0, and X is ethylene glycol residue The number of repeating units p is 1 and q and r are 0, and X is a propylene glycol residue of propylene; the number of repeating units p is 1 and q and r are 0, and X is a butylene glycol residue of butylene The number of repeating units p is an integer of 2 or more and q and r are 0, and X is a polyethylene glycol residue of ethylene; the number of repeating units is an integer of 2 or more and q and r are 0, and X Is a polypropylene glycol residue of 1-methylethylene (propylene); the number of repeating units p and q are both integers of 1 or more and r is 0, and X or Y is ethylene and the other is 1 -A residue of a copolymer of ethylene oxide and propylene oxide of methyl ethylene (propylene); the number of repeating units p, q and r are all integers of 1 or more, and X and Z are ethylene And Y is a residue of a poly (alkylene glycol) such as a residue of a copolymer of ethylene oxide and propylene oxide of 1-methylethylene (propylene).

The degree of polymerization of the aforementioned polyalkylene glycol, that is, the sum of p, q, and r in the general formula (d2-1) is preferably 1 to 80, and more preferably 3 to 50. Among them, the repeating unit including X, the repeating unit including Y, and the repeating unit including Z may be arranged in a random shape or in a block shape.

R ² in the general formula (d2-1) is hydrogen or an alkyl group having 1 to 6 carbon atoms. When R ² is hydrogen, the polymerizable monomer (d2) becomes a mono (meth) acrylate of an alkylene glycol such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, and R ² is a carbon atom. When the number is from 1 to 6, the non- (meth) acrylic acid terminal of the mono (meth) acrylate of butanediol is terminated with an alkyl group having 1 to 6 carbon atoms.

More specific examples of the monomer (d2-1) include polypropylene glycol mono ( (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polybutylene glycol (meth) acrylate, poly (ethylene glycol, propylene glycol) mono (meth) acrylate, polyethylene glycol ‧Polypropylene glycol mono (meth) acrylate, poly (ethylene glycol‧butylene glycol) mono (meth) acrylate, polyethylene glycol‧polybutylene glycol mono (meth) acrylate, poly ( Propylene glycol, butylene glycol) mono (meth) acrylate, polypropylene glycol, polybutylene glycol mono (meth) acrylate, poly (propylene glycol, butanediol) mono (meth) acrylate, polypropylene glycol, etc. Polybutylene glycol mono (meth) acrylate, poly (ethylene glycol‧butanediol) mono (meth) acrylate, polyethylene glycol‧polybutylene glycol mono (meth) acrylate, poly (quad Ethylene glycol, butylene glycol) mono (meth) acrylate, polytetraethylene glycol, polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (ethylene glycol) Alcohol‧propylene glycol) mono (meth) acrylate, polyethylene glycol‧polypropylene glycol mono (meth) acrylate, poly (propylene glycol‧propylene glycol) mono (meth) acrylate, polypropylene glycol‧polypropylene glycol Mono (meth) acrylic Esters, poly (propylene glycol, butylene glycol) mono (meth) acrylate, poly (propylene glycol), poly (butylene glycol) mono (meth) acrylate, poly (butylene glycol, butylene glycol) mono (methyl) ) Acrylate, polybutylene glycol, polypropylene glycol mono (meth) acrylate, etc. Among them, "poly (ethylene glycol · propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol · polypropylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol. The other is the same. Among these monomers (d2-1), in view of good compatibility with other components in the color photoresist composition of the present invention, polypropylene glycol mono (meth) acrylate and polyethylene glycol are preferred. Alcohol mono (meth) acrylate, polyethylene glycol ‧ polypropylene glycol mono (meth) acrylate.

In addition, as a commercially available product of the monomer (d2-1), for example, new "NK Ester M-20G", "NK Ester M-40G", "NK Ester M-90G", "NK Ester M-230G", "NK Ester AM-90G", "NK" "Ester AMP-10G", "NK Ester AMP-20G", "NK Ester AMP-60G", "BLEMMER PE-90", "BLEMMER PE-200", "BLEMMER PE-350", manufactured by Japan Oil Corporation, "BLEMMER PME-100", "BLEMMER PME-200", "BLEMMER PME-400", "BLEMMER PME-4000", "BLEMMER PP-1000", "BLEMMER PP-500", "BLEMMER PP-800", " "BLEMMER 70PEP-350B", "BLEMMER 55PET-800", "BLEMMER 50POEP-800B", "BLEMMER 10PPB-500B", "BLEMMER NKH-5050", "BLEMMER AP-400", "BLEMMER AE-350", etc. These monomers (d2-1) may be used individually by 1 type, and may use 2 or more types together.

The fluorine-based surfactant (D) used in the present invention can be obtained by copolymerizing the polymerizable monomer (d1) and the polymerizable monomer (d2) as essential components, as described above. As other polymerizable monomers, alkyl (meth) acrylate (d3) can also be used in combination. Specific examples of the alkyl (meth) acrylate (d3) include those represented by the following general formula (d3-1).

(In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms.)

R ⁴ in the above general formula (d3-1) is a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, and includes an aliphatic or aromatic hydrocarbon group in the alkyl group And hydroxyl groups. More specific examples of the alkyl (meth) acrylate (d3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Ester, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, etc. Base) alkyl esters of acrylic acid having 1 to 18 carbon atoms; tricyclo [5.2.1.0 ^2,6 ] dec-8-oxyethyl (meth) acrylate, isoamyloxyethyl (meth) acrylate , Isoamyl (meth) acrylate, adamantane (meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclic (meth) acrylate [5.2.1.0 ^2,6 ] dec-8- (5.2.1.0 ^2,6 ] dec-3-ene-8-ester such as (meth) acrylic acid, bridged cyclic alkyl esters having 1 to 18 carbon atoms of (meth) acrylic acid, etc.). These polymerizable monomers (d3) may be used alone or in combination of two or more.

As the raw material of the fluorine-based surfactant (D) used in the present invention, as the polymerizable monomer other than the polymerizable monomers (d1), (d2), and (d3), styrene, α-formaldehyde can be used. Aromatic vinyl compounds such as methylstyrene, p-methylstyrene, p-methoxystyrene; maleimide, methylmaleimide, methylimide, ethylmaleimide Imine, propyl maleimide diimide, butyl maleimide diimide, hexyl maleimide diimide, octyl maleimide diimide, dodecyl maleimide diimide, ten Maleic compounds such as octayl maleimide, phenyl maleimide diimide, cyclohexyl maleimide diimide, and the like. In addition, a polymerizable monomer or the like having a fluorinated alkyl group having 1 to 6 carbon atoms can also be used.

The method for producing the fluorine-based surfactant (D) used in the present invention is not particularly limited, and examples thereof include the use of a radical polymerization initiator to allow the polymerizable monomer (d1), the polymerizable monomer (d2), and the A method of polymerizing other polymerizable monomers in an organic solvent is required. The organic solvents used herein are preferably ketones, esters, amidines, fluorenes, ethers, and hydrocarbons. Specific examples include acetone, methyl ethyl ketone, and methyl isobutyl. Ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfenyl , Diethyl ether, diisopropyl ether, tetrahydrofuran, di Alkane, toluene, xylene, etc. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzamyl peroxide and azo compounds such as azobisisobutyronitrile. Further, if necessary, chain transfer agents such as dodecyl mercaptan, 2-mercaptoethanol, thioglycerin, ethyl hydrothioacetate, and octyl hydrothioacetate can be used.

The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the fluorine-based surfactant (D) used in the present invention are good from the alkali-soluble resin (A), the polymerizable compound (B), and the colorant (C) In terms of compatibility and high leveling, the number average molecular weight (Mn) is preferably in the range of 500 to 20,000, and more preferably in the range of 1,500 to 10,000. The weight average molecular weight (Mw) is preferably in the range of 2,000 to 100,000, and more preferably in the range of 3,000 to 50,000. Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by gel permeation chromatography (hereinafter referred to simply as "GPC") and converted into polystyrene.

In addition, the polymerizable monomer (d1), the polymerizable monomer (d2), and other polymerizable monomers used as necessary as the raw material of the fluorine-based surfactant (D) used in the present invention are used. Content of fluorine atom in total From the viewpoint of allowing the color photoresist composition of the present invention to have sufficient leveling properties and good compatibility with other components in the color photoresist composition, it is preferably in the range of 2 to 40% by mass, and more preferably In the range of 5 to 30% by mass, it is more preferably in the range of 10 to 25% by mass. The above-mentioned fluorine content is a mass ratio of the fluorine atom calculated with respect to the total amount of the polymerizable monomer used as a raw material of the fluorine-based surfactant (D) used in the present invention.

From the viewpoint of obtaining leveling properties and suppressing foaming during the coating process, the amount of the fluorine-based surfactant (D) in the color photoresist composition of the present invention is relative to that in the color photoresist composition. The total solid content is 100 parts by mass, preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, and still more preferably 0.01 to 2 parts by mass.

When the color photoresist composition of the present invention is cured by irradiating active energy rays such as ultraviolet rays and visible light, the color photoresist composition of the present invention is formulated with a photopolymerization initiator (E). Examples of the photopolymerization initiator (E) include titanocene derivatives, biimidazole derivatives, and halomethylation. Diazole derivatives, halomethyl symmetrical tris Derivatives, α-Aminoalkylphenylketone derivatives, oxime ester derivatives, benzoin alkyl ether derivatives, anthraquinone derivatives, diphenylketone derivatives, acetophenone derivatives, 9-oxo sulfur Derivatives, benzoate derivatives, acridine derivatives, brown Derivatives, anthrone derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acids, N-aryl-α-amino acids, N-aryl-α-amino acids Esters, etc.

Specific examples of the titanocene derivative include titanocene dichloride, bisphenyl titanocene, and bis (2,3,4,5,6-pentafluorophenyl-1-yl) titanocene Bis (2,3,5,6-tetrafluorophenyl-1-yl) titanocene, bis (2,4,6-trifluorophenyl-1-yl) titanocene, bis (2,6-di Fluorophenyl-1-yl) titanocene, bis (2,4-difluorobenzene-1-yl) Titanocene, bis (2,3,4,5,6-pentafluorophenyl-1-yl) dimethyl titanocene, bis (2,6-difluorophenyl-1-yl) dimethyl titanocene, [2 , 6-di-fluoro-3- (pyrrole-1-yl) -phenyl-1-yl] titanocene and the like.

Specific examples of the biimidazole derivative include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5- Bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) ) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.

Halomethylation Specific examples of the diazole derivative include 2-trichloromethyl-5- (2'-benzofuranyl) -1,3,4- Diazole, 2-trichloromethyl-5- [β- (2'-benzofuranyl) vinyl] -1,3,4- Diazole, 2-trichloromethyl-5- [β- (2 '-(6 ”-benzofuranyl) vinyl)]-1,3,4- Diazole, 2-trichloromethyl-5-furanyl-1,3,4- Diazole and so on.

Halomethyl Specific examples of the derivative include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) symmetric tris , 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) symmetrical tris , 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) symmetrical tris , 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) symmetric tris Wait.

Specific examples of the α-aminoalkylphenyl ketone derivative include 2-methyl-1- [4- (methylthio) phenyl] -2-N- Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-N- Phenylphenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-N- (Phenylphenyl) butan-1-one, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-diethylaminoacetophenone, 4-dimethylamino group Propylbenzene, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-Diethylaminobenzyl) coumarin, 4- (diethylamino) chaconone, and the like.

Specific examples of the oxime ester derivative include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzophenyIxime), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl], 1- (o-acetamidooxime), and the like.

Specific examples of the benzoin alkyl ether derivative include benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, and the like.

Specific examples of the anthraquinone derivative include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone.

Specific examples of the diphenyl ketone derivative include diphenyl ketone, Michler's Ketone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, and 4-methyl Diphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl ketone and the like.

Specific examples of the acetophenone derivative include 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and 1-hydroxycyclohexylphenylketone. , Α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) -2- Phenyl-1-acetone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone and the like.

The aforementioned 9-oxysulfur Specific examples of derivatives are: 9-oxysulfur , 2-ethyl-9-oxysulfur , 2-isopropyl-9-oxysulfur , 2-chloro-9-oxysulfur 2,4-dimethyl-9-oxysulfur , 2,4-diethyl-9-oxysulfur 2,4-diisopropyl-9-oxysulfur And other types.

Specific examples of the benzoate derivative include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate. Specific examples of the acridine derivative include 9-phenylacridine and 9- (p-methoxyphenyl) acridine. Aforementioned brown Specific examples of the derivatives include 9,10-dimethylbenzophene Wait. Specific examples of the anthrone derivative include benzoanthrone and the like. These photopolymerization initiators (E) may be used alone or in combination of two or more.

If necessary, a polymerization accelerator may be used in addition to the photopolymerization initiator (E). Examples of the polymerization accelerator include: N, N-dialkylaminobenzoic acid alkyl esters such as ethyl N, N-dimethylaminobenzoate; 2-mercaptobenzothiazole, 2-mercaptobenzo Heterocyclic mercapto compounds such as azole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds and the like. These polymerization accelerators may be used alone or in combination of two or more.

The blending amount of the polymerization initiator (E) is preferably in the range of 0.01 to 30 parts by mass and more preferably in the range of 0.1 to 15 parts by mass relative to 100 parts by mass of the total solid content in the color photoresist composition. More preferably, it is in the range of 0.5 to 10 parts by mass. In the case of using a polymerization accelerator, it is also preferable that the total of the polymerization initiator (E) and the polymerization accelerator falls within this range.

In addition, in order to increase the polymerization sensitivity, a sensitizing dye may be used. This sensitizing dye is appropriately selected depending on the wavelength of light used for polymerization, and examples include: Pigments, coumarin pigments, 3-ketocoumarin pigments, pigments having a dialkylaminobenzene skeleton, and the like.

Among the sensitizing dyes, those having an amine group are preferred, and those having an amine group and a phenyl group are more preferred. Specific examples include: 4,4'-dimethylaminodiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, 4-aminodiphenyl Diphenyl ketone compounds such as methyl ketone, 4,4'-diamino diphenyl ketone, 3,3'-diamino diphenyl ketone, 3,4-diamino diphenyl ketone; 2- (P-dimethylaminophenyl) benzo Azole, 2- (p-diethylaminophenyl) benzo Azole, 2- (p-dimethylaminophenyl) benzo [4,5] benzo Azole, 2- (p-dimethylaminophenyl) benzo [6,7] benzo Azole, 2,5-bis (p-diethylaminophenyl) -1,3,4- Azole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- ( P-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-dimethylaminophenyl) Diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylamino) Phenyl) pyrimidine and other compounds containing p-dialkylaminophenyl and the like. Among them, 4,4'-dialkylamino diphenyl ketone is the most preferable. These sensitizing dyes may be used alone or in combination of two or more.

The blending amount of the photosensitizer is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 15 parts by mass, and even more preferably 0.5 in relation to 100 parts by mass of the total solid content in the color photoresist composition. Range of ~ 10 parts by mass.

In addition, the color photoresist composition of the present invention may be provided with an organic solvent, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity adjusting agent, a Additives such as stabilizers, thermal stabilizers, antioxidants.

In addition, in order to impart coating suitability to the color photoresist composition of the present invention, an organic solvent may be added to adjust viscosity. The organic solvent usable here is preferably the above-mentioned alkali-soluble resin (A), polymerizable compound (B), colorant (C), fluorine-based surfactant (D), and photopolymerization initiator (E). Such as those with good solubility. Examples of such organic solvents include: alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol; thioluth solvents such as methoxy alcohol and ethoxy alcohol; 2- (2-methoxyethoxy Carbitol solvents such as ethyl alcohol, 2- (2-ethoxyethoxy) ethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate Ester solvents such as esters; ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, ethyl celex acetate Solvents; carbitol acetate solvents such as 2- (2-methoxyethoxy) ethyl acetate and 2- (2-ethoxyethoxy) ethyl acetate; diethyl ether, ethyl Ether solvents such as glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidine Aprotic solvents such as ketones; lactone solvents such as γ-butyrolactone; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane And other organic solvents. Among these solvents, particularly suitable are: 2-methoxyethyl acetate, 2-ethoxyethyl acetate, ethyl cyrusthru acetate acetate, etc .; 2- (2-methoxyethoxyacetate) Carbitol acetate solvents such as ethyl), 2- (2-ethoxyethoxy) ethyl acetate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol diethyl Ether solvents such as methyl ether; aprotic solvents such as N, N-dimethylacetamide; and ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate. Particularly good to use: N, N-dimethylacetamide, MBA (3-methoxybutyl acetate, CH ₃ CH (OCH ₃ ) CH ₂ CH ₂ OCOCH ₃ ), PGMEA (propylene glycol monomethyl ether ethyl) Acid ester, CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), DMDG (diethylene glycol dimethyl ether, H ₃ COC ₂ H ₄ OCH ₃ ), or a mixture of these. In the color photoresist composition of the present invention, it is preferable to use these organic solvents to adjust the solid content concentration to 10 to 70% by mass.

In addition, it is preferable to select an appropriate organic solvent according to the coating method of the color photoresist composition of the present invention. For example, when a coating film is formed by a spin coater, a slit & spin coater, a slit die coater, or the like, for example, Japanese Patent Application Laid-Open No. 2003-330187, Japanese Patent Application Laid-Open No. 2004-246340, As disclosed in Japanese Patent Application Laid-Open No. 2004-346218, Japanese Patent Application Laid-Open No. 2004-354601, and the like, it is preferable to appropriately use solvents having different physical properties such as boiling points. When a pixel is formed by an inkjet method, for example, as disclosed in Japanese Patent Application Laid-Open No. 2009-7560, it is preferable to use a high boiling point solvent.

Examples of the active energy rays which harden the color photoresist composition of the present invention include active energy rays such as light, electron rays, and radiation. Specific energy sources or hardening devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high-pressure mercury lamps for replication, medium- or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, and metals. Halogen lamps, natural light, etc. are the ultraviolet rays of light sources, or electron beams generated by scanning, curtain electron beam accelerators, etc. However, when the electron beam is hardened, it is not necessary to mix the aforementioned polymerization initiator (E) with the color photoresist composition of the present invention.

Among these active energy rays, ultraviolet rays are particularly preferred. In addition, when irradiated in an inert gas environment such as nitrogen, it is preferable to improve the surface hardenability of the coating film. In addition, heat may be used in combination as an energy source as required, and after being hardened with active energy rays, heat treatment may be performed.

The color filter of the present invention is characterized by having the color light of the present invention. Resistive composition hardened coating film. The color filter can be manufactured through the following steps as described later.

(1) The color photoresist composition of the present invention is coated on a substrate.

(2) The coated color photoresist composition is dried (pre-baking).

(3) Use a photomask to expose to a desired pattern.

(4) Development processing is performed using an alkaline developer.

(5) After washing (rinsing) with distilled water, it is dried.

The substrate used in the step (1) is not particularly limited as long as it is transparent and has a suitable strength. Examples of the material include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; acrylic resins such as polymethyl methacrylate; polyfluorene Sheets made of thermoplastic resins such as resins; thermosetting resin sheets such as epoxy resins and unsaturated polyester resins; or various glasses. Among them, glass and a heat-resistant resin are preferred from the viewpoint of heat resistance. In order to improve surface properties such as adhesion to these transparent substrates, surface treatments such as corona discharge treatment and ozone treatment may be performed as needed, and film formation treatments using various resins such as silane coupling agents and urethane resins, etc. . The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, and preferably 7 mm or less. In the case where various resins are used for thin film formation, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, and preferably 5 μm or less.

By providing a black matrix on the transparent substrate, and further forming each pixel image that is usually red, green, and blue, a color filter can be produced. The black matrix uses a light-shielding metal film, or a work of the present invention The colored resin composition is formed on a transparent substrate.

As the light-shielding metal material, a chromium compound such as metallic chromium, chromium oxide, and chromium nitride, an alloy of nickel and tungsten, or the like may be used, or these may be laminated in a plurality of layers. These light-shielding metal thin films can be formed by a general sputtering method, and can also form a desired pattern on the film with a positive photoresist.

For the above-mentioned chromium-based etching solution containing ammonium cerium nitrate mixed with perchloric acid and / or nitric acid, for other materials, etching is performed by using an etching solution depending on the material, and finally, the positive-type photoresist is peeled off by using a special release agent. This can form a black matrix. In this case, first, a thin film of such a metal or metal ‧ metal oxide is formed on a transparent substrate by a vapor deposition method or a sputtering method. Next, a coating film of the color photoresist composition of the present invention is formed on the thin film. Next, using a photomask having repeated patterns such as stripes, mosaics, and triangles, the coating film is exposed and developed to form an image. Then, the coating film may be subjected to an etching treatment to form a black matrix.

In addition, a black matrix may be formed using a photopolymerizable colored resin composition containing a black pigment. For example, a colored resin composition containing black pigments such as carbon black, graphite, iron black, and titanium black alone, or pigments such as red, green, and blue, which are appropriately selected from inorganic or organic pigments, are used. The coloring resin composition of the black pigment obtained by mixing can form a black matrix in the same manner as described later to form pixel images of red, green, and blue.

The black coloring composition is formed on the transparent substrate, and is subjected to various processes such as coating, heating and drying, image exposure, development, and thermal curing to form a black pixel image, and the red, green, and blue coloring composition Is formed by a resin black matrix formed on a transparent substrate On the surface, or on a metal black matrix formation surface formed using other light-shielding metal materials such as a chromium compound, a pixel image of each color is formed through various processes such as coating, heating and drying, image exposure, development, and thermal curing.

On a transparent substrate provided with a black matrix, a coloring resin composition containing one color material of red, green, and blue is coated, and after drying, a coating is covered on the coating film, and the image is exposed through this mask , Develop, if necessary, form a pixel image by thermal curing or light curing, and make a colored layer. By performing this operation on the colored resin compositions of red, green, and blue, respectively, a color filter image can be formed.

Examples of the method for supplying the color photoresist composition of the present invention to a substrate include a gravure coater, a roll coater, a comma coater, a blade coater, a curtain coater, Coating methods such as shower coater, spin coater, slit coater, slit & spin coater, slit die coater, dip, screen printing, spray coating, applicator, bar coater, etc.

If the thickness of the coating film is too thick, it will be difficult to adjust the gap in the liquid crystal cellization step while pattern development becomes difficult. On the other hand, if it is too thin, it will be difficult to increase the pigment concentration and the desired color will not be displayed. . The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, and more preferably 5 μm. The following range.

The coating film after the colored resin composition is applied to the substrate is dried (pre-baked) in step (2). Drying (pre-baking) can be performed by heating a hot plate, an oven, or the like in a temperature range of 50 to 140 ° C for 10 to 300 seconds. Among them, heating is preferably performed at a temperature range of 70 to 130 ° C for 30 to 180 seconds, and more preferably, heating is performed at a temperature range of 80 to 120 ° C for 30 to 90 seconds. For more complete drying, vacuum drying may be performed before drying (pre-baking).

After drying (pre-baking), a photomask is used in step (3) to expose a desired pattern. Specifically, for example, a dried (pre-baked) coating film is covered with a negative matrix pattern, and the light source pattern is irradiated with ultraviolet or visible light through this mask pattern. At this time, in order to prevent the photopolymerizable layer formed of the colored resin composition from reducing sensitivity due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer before exposure.

After the exposure, a development process is performed in step (4). The unexposed unhardened portion is eluted into the alkaline developing solution in the above-mentioned development process, leaving only the hardened portion that has undergone photo-hardening. The alkaline developer can be used without particular limitation as long as it dissolves the uncured portion and does not dissolve the pixel portions of RGB and the cured portion that becomes the black matrix portion. Specific examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, and hydrogen. Tetramethylammonium oxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazinebi- [5,4,0] -7-undecene and other basic compounds Aqueous solution. The alkali concentration of this alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. In addition, 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 process, it is washed (rinsed) with distilled water in step (5), and then dried. After washing and drying, post-baking treatment can be performed as required. After baking The baking system is usually heated at a temperature in the range of 200 to 250 ° C. for post-development heat treatment for complete curing. The post-baking treatment can be performed continuously or batchwise on the developed layer using heating means such as a hot plate, a convection oven (hot-air circulation type dryer), and a high-frequency heater so that the conditions described above are achieved.

The substrate with transparent electrodes such as ITO formed on the pixels of the color filter manufactured as described above is used as a substrate by sandwiching the liquid crystal layer with other substrates, and then combining the backlight plate, polarizing plate, and liquid crystal layer to form the invention. Liquid crystal display device.

The liquid crystal display device using the color filter of the present invention can be widely used in, for example, liquid crystal televisions, personal computers, liquid crystal projectors, portable game consoles, mobile phones, personal digital assistants (PDAs), digital audio players, digital Cameras, digital cameras, car navigation and other image display units.

In addition, a substrate having electrodes such as ITO and a single-layer or multi-layer organic light-emitting layer on the pixels of the color filter prepared as described above is used as described in "Organic EL Display" (Ohm Corporation, August 20, 2004) Released at the time, and methods of Jing Shi, Adachi Chiwaya, Hideki Murata, etc., can produce organic EL displays. In addition, the color filter of the present invention can be applied to an organic EL display device of a passive driving type and an organic EL display device of an active driving type.

In addition, the color photoresist composition of the present invention can also be used for manufacturing color filters such as solid-state imaging devices such as CCD image sensors and CMOS image sensors, and organic EL display devices.

[Example]

Hereinafter, the present invention will be described in more detail with reference to specific examples. In the examples, "part" and "%" are quality standards unless otherwise specified.

Synthesis Example 1 [Synthesis of polymerizable monomer (d1)]

In a glass flask equipped with a stirring device, a thermometer, a condensing tube, and a dropping device, 20 g of the following formula (a2-1-1) was fed. As a solvent, 20 g of a perfluoropolyether compound having hydroxyl groups at both ends was used. Diisopropyl ether, 0.02 g of p-methoxyphenol as a polymerization inhibitor, and 3.1 g of triethylamine as a neutralizing agent, start stirring under an air stream, and spend 1 hour while keeping the inside of the flask at 10 ° C. 2.7 g of chlorinated acrylic acid was dropped. After completion of the dropping, the mixture was stirred at 10 ° C. for 1 hour and heated up, and after stirring at 30 ° C. for 1 hour, the temperature was raised to 50 ° C., and the reaction was performed by stirring for 10 hours. Next, after adding 40 g of diisopropyl ether as a solvent, 80 g of ion-exchanged water was mixed and stirred, and then the water layer was separated and removed by standing, and the washing was repeated 3 times. Next, 0.02 parts of p-methoxyphenol as a polymerization inhibitor was added, and 8 parts of magnesium sulfate as a dehydrating agent was added. After being left to stand for 1 day to completely dehydrate, the dehydrating agent was filtered off.

(In the formula, X is perfluoromethylene and perfluoroethylene. In each molecule, there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups. The average number of fluorine atoms is 46. In addition, the number average molecular weight measured by GPC is 1,500.)

Next, by distilling off the solvent under reduced pressure, a poly (perfluoroalkylene ether) chain having the following formula (d1-1-1) is obtained, and propylene is provided at both ends thereof. Alkenyl group polymerizable monomer.

(In the formula, X is perfluoromethylene and perfluoroethylene. In each molecule, there are 7 perfluoromethylene groups on average, 8 perfluoroethylene groups on average, and the average number of fluorine atoms is 46. Each.)

Synthesis Example 2 [Synthesis of polymerizable monomer (d2)]

In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 30 g of a block copolymer of ethylene oxide and propylene oxide represented by the following formula (d2'-1), 2.8 g of acrylic acid, 64 g of toluene as a solvent and 0.03 g of phenanthrene as a polymerization inhibitor And 0.6 g of methanesulfonic acid as a catalyst, stirring was started under an air flow, heated to 120 ° C, and dehydrated under reflux. After confirming 0.63 g of dehydration, it was cooled to 65 ° C and neutralized with triethylamine. After neutralization, the temperature was raised to 85 ° C., 2.3 g of ion-exchanged water was added, and the liquid was separated to extract the lower layer. The pH of the lower layer was measured, and the washing operation was repeatedly performed until the pH reached 7 or more. After cooling to 30 ° C, it was diluted with toluene to obtain a toluene solution containing 55 mass% of a polymerizable monomer represented by the following formula (d2-1).

Synthesis Example 3 [Synthesis of fluorine-based surfactant (D)]

For those equipped with a stirring device, thermometer, condensation tube, and dripping device A glass flask was charged with 297.5 g of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 59.5 g of the polymerizable monomer obtained in Synthesis Example 1 and 238 g of polypropylene glycol monomethacrylate ("BLEMMER PP-1000" manufactured by Nippon Oil Co., Ltd.) were used. : Average 6) A monomer solution prepared by dissolving 154.4 parts by mass of methyl isobutyl ketone, and 44.6 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator was dissolved in Three kinds of dripping solutions of a polymerization initiator solution made of 100.6 g of methyl isobutyl ketone were set in respective dropping devices, and the flask was dropped for 2 hours while keeping the inside of the flask at 105 ° C. After the dropwise addition was completed, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a fluorine-based copolymer (D1) of a fluorine-based surfactant. As a result of measuring the molecular weight of this fluorine-based copolymer (D1) by GPC (molecular weight converted into polystyrene), the number average molecular weight was 2,500, and the weight average molecular weight was 6,000. The fluorine content in the raw material monomer used was 11% by mass.

Synthesis Example 4 (ibid.)

A glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device was charged with 112.4 g of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, the number of repeats of 59.5 g of the polymerizable monomer obtained in Synthesis Example 1, 238 g of polypropylene glycol monomethacrylate ("BLEMMER PP-1000" manufactured by Nippon Oil Co., Ltd., and oxypropylene units was repeated. : Average 6) A monomer solution prepared by dissolving in 167.5 g of methyl isobutyl ketone, and 44.6 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator were dissolved in 83.7 Three kinds of drops of a polymerization initiator solution made of g of methyl isobutyl ketone were set in respective drops. The apparatus was lowered, and it was dripped in for 2 hours while keeping the inside of the flask at 105 ° C. After the dropwise addition was completed, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a fluorine-based copolymer (D2) of a fluorine-based surfactant. As a result of measuring the molecular weight of this fluorine-based copolymer (D2) by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 3,000, and the weight average molecular weight was 12,000. The fluorine content in the raw material monomer used was 11% by mass.

Synthesis example 5 (same as above)

100.3 g of methyl isobutyl ketone as a solvent was poured into a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, a monomer solution obtained by mixing 20 g of the polymerizable monomer obtained in Synthesis Example 1 with 145.5 g of the polymerizable monomer solution (80 g of monomer) obtained in Synthesis Example 2 and 15 g 3 kinds of dripping solution of polymerization initiator solution obtained by dissolving tertiary butyl peroxy-2-ethylhexanoate of free radical polymerization initiator in 20 g of methyl isobutyl ketone, respectively The dropping device was dripped for 2 hours while keeping the inside of the flask at 105 ° C. After the dropwise addition was completed, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a fluorine-based copolymer (D3) of a fluorine-based surfactant. As a result of measuring the molecular weight of this fluorine-based copolymer (D3) by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 5,500, and the weight average molecular weight was 25,000. The fluorine content in the raw material monomer used was 11% by mass.

Synthesis example 6 (same as above)

143.4 g of methyl isobutyl ketone as a solvent was poured into a glass flask equipped with a stirring device, a thermometer, a condensing tube, and a dropping device. The temperature was raised to 105 ° C while stirring. Next, 68.1 g of the polymerizable monomer obtained in Synthesis Example 1, 57.9 g of polypropylene glycol monomethacrylate ("BLEMMER PP-1000" manufactured by Nippon Oil Co., Ltd., and oxypropylene units were repeated. Number: Average 6) A monomer solution prepared by dissolving in 68.5 g of methyl isobutyl ketone, and 18.9 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator were dissolved in Three kinds of drops of a polymerization initiator solution made of 21.9 g of methyl isobutyl ketone were set in respective dropping devices, and the flask was kept dripping for 2 hours while keeping the inside of the flask at 105 ° C. After the dropwise addition was completed, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a fluorine-based copolymer (D4) of a fluorine-based surfactant. As a result of measuring the molecular weight of this fluorine-based copolymer (D4) by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 2,600, and the weight average molecular weight was 7,000. The fluorine content in the raw material monomer used was 30% by mass.

Synthesis Example 7 (ibid.)

141.3 g of methyl isobutyl ketone as a solvent was poured into a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 68.5 g of the polymerizable monomer obtained in Synthesis Example 1 and 58.4 g of a polyethylene glycol monomethacrylate ("BLEMMER PE-350" manufactured by Nippon Oil Co., Ltd.) and an oxyethyl unit were used. Repeat number: on average 8) A monomer solution prepared by dissolving in 72.4 g of methyl isobutyl ketone, and 19 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator are dissolved Three kinds of drops of a polymerization initiator solution made of 22 g of methyl isobutyl ketone were set in respective dropping devices, and the flask was dropped for 2 hours while keeping the inside of the flask at 105 ° C. After completion of the dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a fluorine-based copolymer (D5) of a fluorine-based surfactant. As a result of measuring the molecular weight of this fluorine-based copolymer (D5) by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 1,800, and the weight average molecular weight was 20,500. The fluorine content in the raw material monomer used was 30% by mass.

Synthesis Example 8 (ibid.)

148.3 g of methyl isobutyl ketone as a solvent was poured into a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 70 g of the polymerizable monomer obtained in Synthesis Example 1 and 59.6 g of polyethylene glycol monomethacrylate ("BLEMMER PE-200" manufactured by Nippon Oil Co., Ltd.) were used. Repeat number: 4.5 on average) A monomer solution prepared by dissolving in 71 g of methyl isobutyl ketone, and 19.4 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator were dissolved in Three kinds of dripping solutions of a polymerization initiator solution made of 21.3 g of methyl isobutyl ketone were set in respective dropping devices, and while keeping the inside of the flask at 105 ° C., dripping was performed for 2 hours. After completion of the dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a fluorine-based copolymer (D6) of a fluorine-based surfactant. As a result of measuring the molecular weight of this fluorine-based copolymer (D6) by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 1,800, and the weight average molecular weight was 11,500. The fluorine content in the raw material monomer used was 30% by mass.

Synthesis Example 9 (ibid.)

For those equipped with a stirring device, thermometer, condensation tube, and dripping device A glass flask was charged with 152.7 g of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 70 g of the polymerizable monomer obtained in Synthesis Example 1 and 59.6 g of polypropylene glycol monomethacrylate ("BLEMMER PP-800" manufactured by Nippon Oil Co., Ltd.) were used. : Average 13) Monomer solution prepared by dissolving in 66.5 g of methyl isobutyl ketone, and 19.4 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator was dissolved in 21.5 Three kinds of drops of a polymerization initiator solution made of g of methyl isobutyl ketone were set in respective dropping devices, and the flask was kept dripping for 2 hours while keeping the inside of the flask at 105 ° C. After the dropwise addition was completed, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a fluorine-based copolymer (D7) of a fluorine-based surfactant. As a result of measuring the molecular weight of this fluorine-based copolymer (D7) by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 2,200, and the weight average molecular weight was 4,200. The fluorine content in the raw material monomer used was 30% by mass.

Synthesis Example 10

146.6 g of methyl isobutyl ketone as a solvent was poured into a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 69.9 g of the polymerizable monomer obtained in Synthesis Example 1 and 45.9 g of methoxypolyethylene glycol methacrylate ("NK Ester M-230G" manufactured by Shin Nakamura Chemical Industry Co., Ltd. Repeat number of propylene units: 23 on average, 13.7 g of tricyclo [5.2.1.0 ^2,6 ] dec-8-yl acrylate ("Fancryl FA-513A" manufactured by Hitachi Chemical Co., Ltd.) was dissolved in 72.2 g Monomer solution made of methyl isobutyl ketone, and 19.4 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator was dissolved in 21.6 g of methyl isobutyl ketone Three kinds of dripping solution of the obtained polymerization initiator solution were set in respective dropping devices, and while keeping the inside of the flask at 105 ° C., dripping was performed for 2 hours. After the dropwise addition was completed, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a fluorine-based copolymer (D8) of a fluorine-based surfactant. As a result of measuring the molecular weight of this fluorine-based copolymer (D8) by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 3,300, and the weight average molecular weight was 8,800. The fluorine content in the raw material monomer used was 30% by mass.

Synthesis Example 11 [Synthesis of fluorine-based surfactant (D ') for comparison]

134 g of methyl isobutyl ketone as a solvent was poured into a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, and the temperature was raised to 110 ° C. while stirring under a nitrogen stream. Next, 30.2 parts of ethyl acrylate (perfluorooctyl) (hereinafter referred to as "PFOEA") and 70.4 g of polypropylene glycol monomethacrylate ("BLEMMER PP-1000" manufactured by Nippon Oil Co., Ltd.) Number of repeats of oxypropylene units: on average 6) a monomer solution dissolved in 50.3 g of methyl isobutyl ketone, and 7.5 g of peroxy-2-ethyl as a radical polymerization initiator Two drops of a polymerization initiator solution in which tertiary butyl hexanoate was dissolved in 50.3 parts of methyl isobutyl ketone were placed in separate dropping devices, and the flask was kept at 110 ° C while being maintained. , While taking 2 hours to drip. After the dropwise addition was completed, the mixture was stirred at 110 ° C for 10 hours to obtain a fluorine-based copolymer (D'1) of a fluorine-based surfactant for comparison. When the molecular weight of this fluorine-based copolymer (D'1) was measured by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 2,400, and the weight average molecular weight was 4,000. In addition, the raw materials used The fluorine content in the compound was 19% by mass.

Synthesis Example 12 (ibid.)

126.3 g of methyl isobutyl ketone as a solvent was poured into a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, and the temperature was raised to 110 ° C. while stirring under a nitrogen stream. Next, 50.5 g of PFOEA and 50.5 g of polypropylene glycol monomethacrylate ("BLEMMER PP-1000" manufactured by Nippon Oil Co., Ltd., repeat number of oxypropylene units: 6 on average) were dissolved in 12.6 g Monomer solution made of methyl isobutyl ketone, and 5.1 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator was dissolved in 12.6 g of methyl isobutyl ketone The two kinds of dripping liquids, such as the polymerization initiator solution, were set in respective dropping devices, and the mixture was dropped for 2 hours while keeping the inside of the flask at 110 ° C. After the dropwise addition was completed, the mixture was stirred at 110 ° C for 10 hours to obtain a fluorine-based copolymer (D'2) of a fluorine-based surfactant for comparison. When the molecular weight of this fluorine-based copolymer (D'2) was measured by GPC (molecular weight in terms of polystyrene), the number average molecular weight was 3,500, and the weight average molecular weight was 6,500. The fluorine content in the raw material monomer used was 31% by mass.

Preparation example 1 (preparation of pigment dispersion liquid)

For a high-speed disperser with 200 parts of zirconia beads with a diameter of 0.5 mm, 8 parts of CIPigment Red 254 as a colorant and 2.5 parts of a polyester-based dispersant (made by Ajinomoto Fine-Techno Co., Ltd. AJISPER PB-814 ''), 25 parts of propylene glycol monomethyl ether acetic acid, methacrylic acid / benzyl methacrylate = 13/87 (mass ratio) copolymer (acid value 84, number average molecular weight 9,500) as alkali-soluble resin Ester (hereinafter referred to as "PGMEA") solution (non-volatile content 39.7% by mass), and 64.5 Parts of PGMEA as a solvent were dispersed at a rotation speed of 2000 rpm for 8 hours to obtain a red pigment dispersion liquid.

Example 1

To 100 parts of the red pigment dispersion liquid obtained in Preparation Example 1, 7 parts of dipentaerythritol hexaacrylate as a polymerizable compound and 0.3 parts of a photopolymerization initiator (BASF Japan Co., Ltd. "IRGACURE 369" were added. "; 2-benzyl-2-dimethylamino-1- (4-N- Phenylphenyl) -butanone-1) and mixed to obtain a composition. The mixed solution was added with 0.5% of the fluorine-based copolymer (D1) obtained in Synthesis Example 3 to the non-volatile components contained in the composition, and then filtered through a filter having a pore diameter of 1.0 μm to prepare a color. Photoresist composition (1).

The coating properties and liquid repellency of the color photoresist composition (1) were tested by the methods shown below and evaluated. The evaluation results are shown in Table 1.

<Test method of coating property>

1ml of colored photoresist composition was dropped on the central part of a 12cm square glass plate, spin-coated at a speed of 600rpm and a rotation time of 30 seconds, and then dried by heating at 90 ° C for 3 minutes to form a color on the glass plate Test piece of coating film of photoresist composition. The occurrence of coating unevenness of the coating film on the test piece was visually observed, and evaluated according to the following criteria. In addition, this coating unevenness includes a liquid reflow region in the "Test Method for Liquid Reflow Resistance" described later.

Evaluation 1: The area where coating unevenness occurred was 10% or less of the coating area.

Evaluation 2: The area where coating unevenness occurred was 10 to 50% of the coating area.

Evaluation 3: The area where coating unevenness occurred was 50% or more of the coating area.

<Test method for liquid repellency resistance>

The width of the liquid recirculation region formed at the end of the test piece was measured, and there were 3 locations on each side, a total of 12 locations, and the average value was calculated. The smaller this value is the color photoresist composition that the liquid is less likely to flow back.

Examples 2 to 8 and Comparative Examples 1 and 2

A color photoresist composition (2) to (8) and a comparative photoresist composition (1 ') were obtained in the same manner as in Example 1 except that the fluorine-based copolymers shown in Tables 1 and 2 were used. And (2 '). The same applicability and evaluation of liquid repellency as in Example 1 were evaluated. The evaluation results are shown in Table 1.

Claims (8)

A color photoresist composition, which is a color photoresist composition containing an alkali-soluble resin (A), a polymerizable compound (B), a colorant (C), and a fluorine-based surfactant (D). A fluorine-based surfactant (D) polymer having a polymer structure of a polymerizable monomer and a poly (perfluoroalkylene ether) chain. A plurality of the polymer structures are permeated through the poly (perfluoroalkylene). (Ether) chain, and an oxyalkylene group on the side chain of the polymer structure; the content ratio of the alkali-soluble resin (A) in the total solid content is 0.1 to 80% by mass, and the amount of the polymerizable compound (B) The content ratio is 5 to 80% by mass in the total solid content, and the content ratio of the colorant (C) is 5 to 80% by mass in the total solid content. The blending amount of the fluorine-based surfactant (D) is relative to The total solid content in the color photoresist composition is 100 parts by mass, and is 0.0001 to 10 parts by mass. For example, the color photoresist composition in the scope of patent application, wherein the fluorine-based surfactant (D) is polymerized by a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both ends thereof. The copolymer of the monomer (d1) and the polymerizable monomer (d2) having an oxyalkylene group and a polymerizable unsaturated group is an essential monomer and is copolymerized. For example, the color photoresist composition of the second patent application range, wherein the polymerizable monomer (d2) is a polymerizable monomer represented by the following general formula (d2-1): (In the formula, R ¹ is a hydrogen atom or a methyl group; X, Y, and Z are independent alkylene groups; p, q, and r are each an integer of 0 or more, and the total of p, q, and r is 1 The above integer; R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). For example, the color photoresist composition of the first patent application range, wherein the number average molecular weight (Mn) of the fluorine-based surfactant (D) is in the range of 1,000 to 10,000, and the weight average molecular weight (Mw) is in the range of 2,000 to A range of 100,000. For example, the color photoresist composition according to any one of claims 1 to 4, wherein the fluorine-based surfactant (D) contains fluorine atoms in the surfactant in a proportion of 5 to 30% by mass. A color filter, which is characterized by having a hardened coating film of a color photoresist composition according to any one of claims 1 to 5. A liquid crystal display device, comprising: a backlight plate, a polarizing plate, at least two substrates, a liquid crystal layer sandwiched between the substrates, and a color filter according to item 6 of the patent application scope, which is mounted on at least a part of the substrate. Light film. An organic EL display device having a color filter as described in the sixth item of the application.