KR20150094687A - Method for producing color filter - Google Patents

Abstract

An object of the present invention is to provide a method of manufacturing a color filter in which peeling of a color filter in a resist pattern removing step is suppressed. A method of manufacturing a color filter of the present invention includes a cured film forming step of forming a cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm on a support, A step of forming a photoresist layer on the colored layer, a step of forming a photoresist layer on the colored layer, a step of forming a resist pattern on the colored layer by removing the photoresist layer in a pattern shape, An etching step of etching the colored layer by a dry etching method using an etching gas, and a resist pattern removing step of removing a resist pattern remaining after the etching step.

Description

METHOD FOR PRODUCING COLOR FILTER "

The present invention relates to a method of manufacturing a color filter, and more particularly, to a method of manufacturing a color filter using a dry etching method.

In a color filter used for a liquid crystal display element or a solid-state image pickup element, a still higher definition is expected. Particularly, miniaturization of the solid-state image pickup device is remarkable, and a high-resolution technology of less than 2.0 mu m size is required, and the resolution of the conventional photolithography method is limited.

A dry etching method is known as a method which is thinner and effective for forming a fine pattern as compared with a manufacturing method of a color filter using a photolithography method. A dry etching method has conventionally been employed as a method of forming a pattern on a thin film of a dye to be deposited, and various methods have been proposed.

For example, in Patent Document 1, it has been proposed to use a stopper layer made of a metal in order to prevent a step from being generated by cutting even a part of a support in a region where a colored layer is removed.

Japanese Patent Application Laid-Open No. 2008-241744

However, as a result of evaluating the inventors using a stopper film (ACCUGLASS made by LASAKO CO., LTD.) Specifically disclosed in Patent Document 1, when the resist pattern in the subsequent step is removed, the formed color filter is peeled from the support We know that there is case to throw away.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of manufacturing a color filter in which peeling of a color filter in a resist pattern removing step is suppressed.

Means for Solving the Problems As a result of intensive research to achieve the above object, the present inventors have found that the above problems can be solved by forming a cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm on a support, Completed.

That is, the inventors of the present invention have found that the above problems can be solved by the following constitution.

(1) a cured film forming step of forming a cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm on a support,

A colored layer forming step of forming a colored layer on the cured film,

A photoresist layer forming step of forming a photoresist layer on the colored layer,

A pattern forming step of forming a resist pattern on the colored layer by removing the photoresist layer in a pattern shape,

An etching step of etching the colored layer by a dry etching method using an etching gas using the resist pattern as an etching mask,

And a resist pattern removing step of removing the resist pattern remaining after the etching process.

(2) The method for producing a color filter according to (1), wherein the content of the metal oxide particles in the cured film is from 50 mass% to 77 mass% with respect to the total mass of the cured film.

(3) The method for producing a color filter according to (1) or (2), wherein the metal oxide particles are at least one selected from the group consisting of titanium dioxide and zirconium oxide.

(4) The method for producing a color filter according to any one of (1) to (3), wherein the thickness of the cured film is from 5 nm to 500 nm.

(5) The process for producing a color filter according to any one of (1) to (4), wherein the cured film contains a polymer compound (A) represented by the following general formula (1) having a weight average molecular weight of 10,000 or less.

(6) The process for producing a cured film according to any one of (1) to (5), wherein the cured film forming step comprises the step of forming a cured film using a composition for forming a cured film containing at least a metal oxide particle and a compound having two or more epoxy groups or oxetanyl groups in the molecule, Wherein the color filter is formed on the substrate.

(Effects of the Invention)

According to the present invention, it is possible to provide a method of manufacturing a color filter in which peeling of a color filter in a resist pattern removing step is suppressed.

1 is a sectional view of a solid-state image pickup device in which a color filter according to the present invention is used.
2 is a cross-sectional view illustrating a method of manufacturing a color filter of the present invention.

Hereinafter, preferred embodiments of the method of manufacturing a color filter according to the present invention will be described in detail with reference to the accompanying drawings.

First, an example of a solid-state image pickup device or the like using a color filter formed by the method of manufacturing a color filter according to the present invention is shown. 1 is a cross-sectional view of a solid-state image pickup device.

In the solid-state imaging device 1, an n-type solid-state imaging device 3 and an n-type transfer channel 4 are formed on the surface of a semiconductor substrate 2 on which a p-type well layer is formed on an n-type substrate. A transfer electrode 5 is formed above the transfer channel 4 through an insulating film made of silicon oxide or the like.

The transfer electrode 5 is formed of W (tungsten) or the like, and is covered with a light-shielding film having an opening above the solid-state image pickup device 3. A BPSG film 6 formed by an atmospheric pressure CVD method and reflowed is formed on the transfer electrode 5 covered with the light-shielding film.

The BPSG film 6 is formed with a convex lens shape, and the in-layer lens 7 is formed by plasma CVD of a SiN film having a high refractive index and a high transmittance.

A planarization layer 10 formed of an organic resin film, a BPSG film, a silicon oxide-based insulating film or the like is formed above the in-layer lens 7.

On the planarization layer 10, a color filter 8 composed of three primary colors of red (R), green (G) and blue (B) is formed. A microlens 9 is formed on the color filter 8 by a photoresist material.

The solid-state imaging device 1 has such a configuration that the light incident on the microlenses 9 passes through the color filter 8 to extract light of each color and the light of each color collected by the in- The light is converted into an electric signal by the solid-state image pickup device 3.

Next, a method of manufacturing a color filter according to the present invention will be described. 2 is a cross-sectional view showing a method of manufacturing a color filter.

A method of manufacturing a color filter of the present invention includes a cured film forming step of forming a cured film on a support, a colored layer forming step of forming a colored layer on the cured film, a photoresist layer A pattern forming step of forming a resist pattern on the colored layer by removing the photoresist layer in a pattern shape, an etching step of etching the colored layer using the resist pattern as an etching mask, And a pattern removing (peeling) process.

Hereinafter, the materials and procedures used in each step will be described in detail.

≪ Cured film forming step &

The cured film forming step is a step of forming a cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm on a support.

More specifically, as shown in Figs. 2A and 2B, on the planarization layer 10 of the substrate 1a as a support formed up to the planarization layer 10, primary particle diameters of 1 nm to 100 The cured film 20 containing the metal oxide particles is formed.

2 (b), the cured film 20 is formed on the planarization layer 10, but the planarization layer 10 itself may be the cured film.

First, the materials contained in the support and the cured film will be described in detail, and the order of the steps thereafter will be described in detail.

(Support)

The substrate 1a to be a support is not particularly limited as long as a color filter can be used. However, a photoelectric conversion element substrate used for a solid-state image pickup element or the like, for example, a silicon substrate, an oxide film or silicon nitride can be used. Further, other layers such as an intermediate layer may be formed between the support and the colored layer so long as the effect of the present invention is not impaired.

[(A) Metal oxide particles]

The primary particle diameter of the metal oxide particles contained in the cured film is 1 to 100 nm. Among them, from the viewpoints of the transparency of the cured film and the stability with time of the curable composition, it is preferably from 5 to 80 nm, more preferably from 10 to 70 nm.

When the primary particle diameter is less than 1 nm, the stability of the curable composition over time is deteriorated, and the color filter is peeled from the support at the time of removing the resist pattern. In addition, in the case of more than 100 nm, transparency of the cured film is lowered due to light scattering, and peeling of the color filter from the support occurs at the time of removing the resist pattern.

The primary particle diameter of the metal oxide particles is an average value. As a measuring method, the cross section of the cured film is observed with an electron microscope to measure the primary particle diameters (diameters) of at least 20 or more metal oxide particles, . When the metal oxide particles are not in a spherical shape, their long diameters are treated as diameters.

When a composition for forming a cured film containing metal oxide particles is used as described later, the primary particle diameter of the metal oxide particles in the composition is measured by a known apparatus [for example, Nikkiso Microtrack UPA- EX150 (dynamic light scattering method)].

The kind of the metal atom contained in the metal oxide particle is not particularly limited and preferably contains a metal atom selected from the group consisting of the fourth period, the fifth period, and the sixth period of the periodic table (IUPAC1991). It is preferable to contain one or more metals selected from the group consisting of Groups 2 to 14, and it is preferable that Group 2, Group 8, Group 9, Group 10, Group 11, Group 12 , Group 13, and Group 14 is more preferable.

More specifically, for example, a metal such as copper, silver, gold, platinum, zinc, palladium, nickel, tin, indium, rhodium, iridium, iron, silicon, aluminum, ruthenium, osmium, manganese, molybdenum, tungsten, And at least one metal atom selected from the group consisting of titanium, bismuth, antimony, zirconium and lead. Among them, titanium, zirconium, zinc and aluminum are more preferable, and titanium is more preferable. As a reason why these metal atoms are preferable, it is presumed that a high electron density affects them.

Specific examples of the metal oxide particles include titanium oxide, zirconium oxide, zinc oxide, and aluminum oxide.

The colorless or transparent titanium dioxide particles can be represented by the formula Tio ₂ , and the purity is preferably 70% or more, more preferably 80% or more, and more preferably 85% or more. Titanium oxides and titanium oxynitrides represented by the general formula Ti _n O _{2n- 1} (n is a number of 2 to 4) are preferably contained in an amount of 30 mass% or less, preferably 20 mass% or less, based on the total mass of the particles And more preferably 15 mass% or less. The titanium dioxide particles are preferably rutile crystals.

The refractive index of the metal oxide particles is not particularly limited, but is preferably 1.75 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index. This refractive index can be measured by Abbe's refractometer (manufactured by Atago Co., Ltd.) (measurement temperature: 25 DEG C, wavelength: 633 nm).

The specific surface area of the metal oxide particles is preferably 10 m2 / g to 400 m2 / g, more preferably 20 m2 / g to 200 m2 / g, and most preferably 30 m2 / g to 150 m2 / g desirable.

The shape of the metal oxide particles is not particularly limited. For example, be in the form of an atomic, spherical, cubic, spindle-shaped or amorphous phase.

The metal oxide particles may be surface-treated with an organic compound. Examples of the organic compound used in the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Among them, stearic acid is preferable.

The surface treatment may be a single kind of surface treatment agent or a combination of two or more kinds of surface treatment agents.

It is also preferable that the surface of the metal oxide particles is treated with an oxide such as aluminum, silicon or zirconia. As a result, the weather resistance is improved.

Commercially available metal oxide particles can be preferably used.

(TTO-51 (A), TTO-51 (C), and TTO-55 (C) manufactured by Ishihara Sangyo Co., Ltd., TTO- TTO-S-1, TTO-S-2 and TTO-V-3) and MT series (MT-01 and MT-05 manufactured by Teika).

Examples of commercial products of zirconium dioxide particles include UEP (manufactured by Daiseki Kensakagakukogyo Co., Ltd.), PCS (manufactured by Nihon Denko Corporation), JS-01, JS-03, JS-04 , UEP-100 (manufactured by Daiseki Kensakagakukogyo Co., Ltd.), and the like.

Commercially available products of the silicon dioxide particles include, for example, OG502-31 made by Clariant Co., and the like.

The metal oxide particles may be used singly or in combination of two or more kinds.

The content of the metal oxide particles in the cured film is not particularly limited and is preferably 5 to 85% by mass, more preferably 5 to 80% by mass based on the total mass of the cured film in view of further suppressing the peeling of the color filter . In particular, 50 to 77 mass% is more preferable, and 60 to 75 mass% is particularly preferable in view of further suppressing peeling of the color filter.

The thickness of the cured film is not particularly limited and is preferably from 5 nm to 500 nm, more preferably from 20 nm to 450 nm, and further preferably from 50 nm to 400 nm from the viewpoint of further suppressing the peeling of the color filter.

The cured film preferably has a refractive index of 1.85 to 2.60, more preferably 1.90 to 2.60 in view of adhesion of the color filter.

The physical property that the refractive index of the cured film is 1.85 to 2.60 can be preferably achieved by containing a polymer dispersant (B) described later, but may be achieved by any other means. For example, it can be achieved more surely by adjusting the type and content of the polymerizable compound (C) to be described later and the binder polymer which can be further added, or by adjusting the kind and content of the metal oxide particles.

(Production method of cured film)

The method of producing the cured film is not particularly limited, and a known method can be employed. For example, a method may be employed in which a composition for forming a cured film containing the metal oxide particles described above is applied on a support and curing treatment (for example, heat treatment and / or exposure treatment) have.

The coating method is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method (spin coating method), and a bar coating method.

The composition for forming a cured film may contain components other than the metal oxide particles as described later. For example, a polymer dispersant, a polymerizable compound, a solvent, and the like described later can be mentioned.

The composition for forming a cured film is preferably a transparent composition. More specifically, when a cured film having a film thickness of 1.0 占 퐉 is formed by the composition, the light transmittance of the cured film in the thickness direction is in the range of 400 to 700 nm Of the total amount of the composition is 90% or more.

That is, the cured film (transparent film) is preferably a film having a light transmittance of 90% or more over the entire wavelength range of 400 to 700 nm in the film thickness direction of 1.0 占 퐉.

The physical properties of the light transmittance may be achieved by any means. For example, the kind and content of the polymerizable compound (C) to be described later and the binder polymer (I) to be added may be adjusted . Also, the physical properties of the light transmittance can be preferably achieved by adjusting the particle diameter of the metal oxide particles (A), the type and the amount of the polymer dispersant (B) to be described later.

In addition, the light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100% over the entire wavelength range of 400 to 700 nm.

It is preferable that the composition for forming a cured film substantially does not contain a coloring agent. More specifically, the content of the colorant is preferably 0% by mass relative to the total solid content of the composition.

(Other optional components)

The composition for forming a cured film or a cured film may contain components other than the above-mentioned metal oxide particles. (D) a solvent, (E) a polymerization initiator, (F) a sensitizer, (G) a notarization accelerator, (H) a polymerization inhibitor, (I) a polymeric dispersant, A binder polymer, and (J) a surfactant. In particular, it is preferable that the cured film contains (B) the polymer dispersant, (I) the binder polymer, and (J) the surfactant.

Hereinafter, each component will be described in detail.

[(B) Polymer Dispersant]

The cured film may contain a polymer dispersant. As a method for containing a polymer dispersant in the cured film, there is a method in which a polymer dispersant is contained in the composition for forming a cured film.

The kind of the polymeric dispersant is not particularly limited, and examples thereof include a general polymeric dispersant (hereinafter also appropriately referred to as a dispersion resin) (for example, a polyamideamine and its salt, a polycarboxylic acid and its salt, a high molecular weight unsaturated acid ester , Modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine and the like.

These dispersed resins can also be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on the structure.

The dispersion resin functions to adsorb on the surface of the metal oxide particles to prevent re-aggregation. Therefore, an end-modified polymer having an anchor portion to the surface of the metal oxide particle, a graft-type polymer, and a block-type polymer can be mentioned as preferable structures.

On the other hand, the dispersion resin has an effect of promoting the adsorption of the dispersion resin by modifying the surface of the metal oxide particles.

Specific examples of the dispersion resin include DISPERBYK 101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110, 180 (copolymer containing an acidic group), 130 (polyamide), 161, 162, 163 BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "EFKA 4047, 4050, 4010, 4165 (polyurethane)", EFKA 4330 (High molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (high molecular weight polycarboxylate), 4340 (block copolymer), 4400, 4402 (modified polyacrylate) AzoPhase PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., 50E, No. (Aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, DA (dibutyl terephthalate), and DA -705, DA-725 "available from Kao Corporation," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L- (Polyoxyethylene nonylphenyl ether), acetamine 86 (stearylamine acetate), Lubrizol sold under the trademark "Solpus 5000" (phthalocyanine derivative), " 24,000, 28,000, 32000, 38500 (graft type polymer) ", NIKKO T106 (trade name, manufactured by Nikko Chemical Co., Ltd.) Polyoxyethylene sorbitan monooleate), and MYS-IEX (polyoxyethylene monostearate).

These resins may be used alone or in combination of two or more.

One preferred form of the dispersing resin is a resin having a repeating unit having a group X having a pKa of 14 or less and an oligomer chain or a polymer chain Y of 40 to 10,000 atoms in the side chain and containing a basic nitrogen atom ).

Details of the oligomer chain or polymer chain Y having a functional group having a pKa of 14 or less and a group X having an atomic number of 40 to 10,000 will be described later.

Although the basic nitrogen source is not particularly limited as long as it is a nitrogen atom showing basicity, it is preferable that the resin (B1) contains a structure having a nitrogen atom of pKb 14 or less, more preferably a structure having a nitrogen atom of pKb 10 or less Do.

Base strength pKb refers to pKb at a water temperature of 25 ° C. It is one of the indicators for quantitatively indicating the strength of a base, and it is synonymous with a basic degree. The base strength pKb and the acid strength pKa described later are in the relationship of pKb = 14-pKa.

The resin (B1) is preferably a resin (B2) having a repeating unit containing a nitrogen atom to which a group X having a functional group having a pKa of 14 or less is bonded and an oligomer chain or a polymer chain Y of 40 to 10,000 atoms in the side chain Do.

The resin (B1) is preferably a copolymer comprising (i) a repeating unit based on a poly (lower alkyleneimine), a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin- A repeating unit containing at least one nitrogen atom selected from vinylamine-based repeating units and having a group X bonded to a nitrogen atom and having a functional group having a pKa of 14 or less and (ii) And a resin having an oligomer chain or a polymer chain Y of 40 to 10,000 (hereinafter appropriately referred to as " specific resin "). The lower level in the poly (lower alkyleneimine) means that the number of carbon atoms is 1 to 5, and the lower alkyleneimine means an alkyleneimine having 1 to 5 carbon atoms.

The specific resin of the present invention preferably contains a structure having a repeating unit represented by formula (I-1) and a repeating unit represented by formula (I-2).

In the general formulas (I-1) and (I-2), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom, a halogen atom or an alkyl group. a independently represents an integer of 1 to 5; * Represents a connection between repeating units.

X represents a group having a functional group having a pKa of 14 or less.

And Y represents an oligomer chain or polymer chain having 40 to 10,000 atoms.

The specific resin of the present invention preferably has a repeating unit represented by the general formula (I-3) as a copolymer component in addition to the repeating unit represented by the general formula (I-1) or the general formula (I-2) Do. When such a repeating unit is used in combination, dispersion performance is further improved when the resin is used as a dispersant for the metal oxide particles (A).

In the general formula (I-3), *, R ¹⁰¹ , R ¹⁰² and a are synonymous with the general formula (I-1).

Y 'represents an oligomer chain or polymer chain having 40 to 10,000 atoms having an anionic group.

The repeating unit represented by the above general formula (I-3) can be formed by reacting a resin having a primary or secondary amino group in its main chain portion with an oligomer or polymer having a group capable of forming a salt by reacting with an amine Do. Here, as the anion group, CO ₂ ^- or SO ₃ ^- is preferable, and CO ₂ ^- is most preferable. The anionic group is preferably located at the terminal position of the oligomer chain or the polymer chain of Y '.

In the general formulas (I-1), (I-2) and (I-3), R ¹⁰¹ and R ¹⁰² are preferably hydrogen atoms. a is preferably 2 from the viewpoint of raw material availability.

The content of the repeating unit represented by formula (I-1) is preferably 1 to 80 mol%, and most preferably 3 to 50 mol%, of the total repeating units contained in the specific resin from the viewpoints of storage stability and developability.

The content of the repeating unit represented by formula (I-2) is preferably 10 to 90 mol%, and most preferably 30 to 70 mol%, of the total repeating units of the specific resin from the viewpoint of storage stability.

(I-1) :( I-2) is preferably in the range of 10: 1 to 1: 100 in terms of the mole ratio of the repeating unit (I-1) to the repeating unit : 1 to 1: 10.

The repeating unit represented by the general formula (I-3) which is used in combination with the desired one is one having a partial structure including an oligomer chain or a polymer chain having 40 to 10,000 atoms ionically bonded to the nitrogen atom of the main chain From the viewpoint of the effect of all the repeating units of the specific resin, 0.5 to 20 mol%, and most preferably 1 to 10 mol%.

The fact that the polymer chain Y is ionically bound can be confirmed by infrared spectroscopy or base titration.

(group X having a functional group having a pKa of 14 or less)

The group X has a functional group having a pKa of 14 or less at a water temperature of 25 캜. The term " pKa " referred to herein is a definition described in the Chemical Manual (II) (revised fourth edition, 1993, Nihon Kagaku Kaishi, Maruzen Co., Ltd.).

The "functional group having a pKa of 14 or less" is not particularly limited as long as the physical properties satisfy this condition, and the pKa satisfies the above range by a known functional group. Particularly, a functional group having a pKa of 12 or less And most preferably a functional group having a pKa of 11 or less. Specific examples thereof include carboxylic acid (about 3 to 5 pKa), sulfonic acid (about pKa -3 to -2), phosphonic acid (about pKa -1 to 4), -COCH ₂ CO- (pKa 8 to 10 -COCH ₂ CN (pKa about 8 to about 11), -CONHCO-, phenolic hydroxyl group, -RFCH ₂ OH or - (RF) ₂ CHOH (RF stands for perfluoroalkyl group, pKa is about 9 to about 11) (About pKa 3 to about 5), sulfonic acid (about pKa -3 to about -2), -COCH ₂ CO- (pKa 8 to 10), and sulfonamide group (about 9 to 11 pKa) Is preferable.

When the pKa of the functional group of the group X is 14 or less, stronger interaction of the metal oxide particles can be achieved.

The group X having a functional group having a pKa of 14 or less is preferably bonded directly to the nitrogen atom in the repeating unit containing a nitrogen atom, but the nitrogen atom and X of the repeating unit containing the nitrogen atom are not only covalent bonds but also ionic bonds Or may be connected in the form of a salt.

The group X containing a functional group having a pKa of 14 or less in the present invention preferably has a structure represented by the general formula (V-1), the general formula (V-2) or the general formula (V-3).

In the general formulas (V-1) and (V-2), U represents a single bond or a divalent linking group. d and e independently represent 0 or 1; In the general formula (V-3), Q represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include an alkylene group (more specifically, for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CHMe-, - (CH ₂ ) ₅ -, - _{CH 2 CH (nC 10 H 21} ) - , etc.], an alkylene group containing an oxygen (more specifically, for example, _{-CH 2 OCH 2 -, -CH 2} CH 2 OCH 2 CH 2 - , etc.), an arylene group (Such as a phenylene group, a tolylene group, a biphenylene group, a naphthylene group, a furanylene group and a pyrrolylene group), an alkyleneoxy group (such as an ethyleneoxy group, a propyleneoxy group, Particularly preferably an alkylene group of 1 to 30 carbon atoms or an arylene group of 6 to 20 carbon atoms, and most preferably an alkylene group of 1 to 20 carbon atoms or an arylene group of 6 to 15 carbon atoms.

From the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents an acyl group or an alkoxycarbonyl group. As the acyl group in Q, an acyl group having 1 to 30 carbon atoms (for example, formyl group, acetyl group, n-propanoyl group, benzoyl group and the like) is preferable, and acetyl is particularly preferable. As the alkoxycarbonyl group in Q, an alkoxycarbonyl group having 2 to 30 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group and the like) is preferable. Q is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoint of ease of production and availability of raw materials.

(Oligomer chain or polymer chain Y having 40 to 10,000 atoms)

Examples of the oligomer chain or polymer chain Y include known polymer chains such as polyesters, polyamides, polyimides, and poly (meth) acrylates, which can be connected to the main chain portion of a specific resin. The bonding site of the oligomer chain or the polymer chain Y with the specific resin is preferably the oligomer chain or the terminal of the polymer chain Y. [

The oligomer chain or the polymer chain Y is a repeating unit of a poly (lower alkyleneimine) type, a polyallylamine type repeating unit, a polydiallylamine type repeating unit, a repeating unit of a metaxylenediamine-epichlorohydrin polycondensate, Is preferably bonded to the nitrogen atom of the repeating unit containing at least one nitrogen atom selected from amine-based repeating units. A repeating unit selected from the group consisting of a poly (lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a metaxylenediamine-epichlorohydrin polycondensation repeating unit, and a polyvinylamine repeating unit The bonding mode of the oligomer chain or the polymer chain Y in the main chain portion such as a repeating unit containing at least one kind of nitrogen atom is a covalent bond, an ionic bond, or a combination of a covalent bond and an ionic bond. The ratio of the bonding mode of the oligomer chain or the polymer chain Y to the main chain portion is preferably from 95: 5 to 5:95, most preferably from 90: 10 to 10:90, Do. Outside this range, the dispersibility and dispersion stability are deteriorated, and the solvent solubility is lowered.

It is preferable that the oligomer chain or the polymer chain Y is ionically bonded to the nitrogen atom of the repeating unit containing a nitrogen atom as an amide bond or a carboxylate.

The number of atoms of the oligomer chain or the polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000 from the viewpoints of dispersibility, dispersion stability, and developability. The number average molecular weight of the oligomer chain or the polymer chain Y can be measured by polystyrene conversion value by the GPC method. The number average molecular weight of the oligomer chain or the polymer chain Y is preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability.

In particular, the oligomer chain or the polymer chain Y preferably has a structure represented by the general formula (III-1). When the specific resin contains a repeating unit represented by the general formula (I-3) or (II-3), it is preferable that Y 'is a general formula (III-2). In the general formula (III-2), Z is synonymous with Z of the general formula (III-1).

Specific examples of the specific resin include resins exemplified by paragraphs [0075] to [0084] of Japanese Patent Application Laid-Open Publication No. 2012-255148.

Another preferred embodiment of the polymer dispersant is a polymer compound represented by the following general formula (1) having a weight average molecular weight of 10,000 or less.

R ¹ represents an (m + n) linking group. R ² represents a single bond or a divalent linking group. A ¹ represents a hydrocarbon group, an acid group, a urea group, a urethane group, a group having a saturated oxygen atom, a group having a basic nitrogen atom, a heterocyclic group (a group having a heterocyclic structure), an alkyloxycarbonyl group, Represents a monovalent substituent having at least one group selected from the group consisting of a carboxyl group, a sulfonic acid group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group (hereinafter, also simply referred to as substituent A ¹ ). n A ¹ and R ² may be the same or different.

m represents a positive number of not more than 8, n represents 1 to 9, and m + n satisfies 3 to 10.

P ¹ represents a polymer chain. The m < ¹ > P < ¹ > may be the same or different.

Since the substituent A ¹ of the polymer compound can interact with the metal oxide particle, the polymer compound can strongly interact with the metal oxide particle by having n (1 to 9) substituents A ¹ . In addition, the polymer chain P ¹ having m polymer compounds can function as a three-dimensional rebounder, and when the number is m, the metal oxide particles can be uniformly dispersed by exhibiting a good steric repulsion. In addition, it is presumed that the macromolecule compound does not cause adverse effects such as agglomeration of particles due to intergranular crosslinking, which could be caused by a conventional graft random structure dispersant in molecular structure.

The weight average molecular weight of the polymer compound represented by the general formula (1) is preferably 10,000 or less, and more preferably 8,000 or less.

If the weight average molecular weight is too large, the particle size of the metal oxide particle (A) -module dispersant (B) complex in the dispersion composition (composition for forming a cured film) becomes large and particles in the resulting film are not closely adhered to each other, I think. On the other hand, by setting the weight average molecular weight within the above range, the particle size of the metal oxide particle (A) -modular dispersant (B) composite can be suppressed to be small, and the particles in the resulting film become dense and the refractive index can be increased. Although the reason is not clear, it is considered that the dispersibility can be improved and the viscosity can be reduced by setting the above range.

The lower limit of the weight average molecular weight is not particularly limited, but is preferably 1,000 or more, and more preferably 3,000 or more, from the viewpoint of exhibiting the function as a dispersant and further attaining the effect of the present invention more reliably.

Hereinafter, each group in the general formula (1) will be described in detail.

A ¹ represents a group having a hydrocarbon group, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a saturated oxygen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, an imide group, a carboxylate group, (1) having at least one structure capable of adsorbing to metal oxide particles (A) such as functional groups and heterocyclic structures having adsorptivity to metal oxide particles (A) such as alkoxysilyl groups, epoxy groups, isocyanate groups and hydroxyl groups ≪ / RTI >

Hereinafter, the site (the above-mentioned functional group and structure) having adsorption ability to the metal oxide particle (A) will be collectively referred to as "adsorption site" appropriately.

The adsorption site may contain at least one A ¹ or two or more adsorption sites.

Examples of the form in which two or more adsorption sites are contained in one A ¹ include a chain saturated hydrocarbon group (linear or branched, preferably having 1 to 10 carbon atoms), cyclic saturated hydrocarbon group (having 3 to 10 carbon atoms , A form in which two or more adsorption sites are bonded through an aromatic group (preferably having 5 to 10 carbon atoms, for example, a phenylene group) to form a monovalent substituent A ¹ , and the like, A form in which two or more adsorption sites bind to each other through a chain saturated hydrocarbon group to form a monovalent substituent A ¹ is preferable. In addition, when the adsorption site itself constitutes a monovalent substituent, a monovalent substitutional group represented by A ¹ in the adsorption site itself may be used.

First, the adsorption sites constituting A ¹ will be described below.

Examples of the "hydrocarbon group" include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among them, a group of 1 to 20 carbon atoms is preferable, and a group of 1 to 10 carbon atoms is more preferable.

Preferable examples of the "acidic group" include a carboxylic acid group, a sulfonic acid group, a mono sulfuric acid ester group, a phosphoric acid group, a mono phosphate ester group and a boric acid group, More preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group or a phosphinic acid group, and particularly preferably a carboxylic acid group.

For example, -NR ¹⁵ CONR ¹⁶ R ¹⁷ wherein R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, Or an aralkyl group having 7 or more carbon atoms), and -NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms -NHCONHR ¹⁷ wherein R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms) ) Is particularly preferable.

Examples of the "urethane group" include -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , -OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ Are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like are exemplified, and -NHCOOR ¹⁸ , -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), more preferably -NHCOOR ¹⁸ , -OCONHR ²¹ (wherein R ¹⁸ and R ²¹ Each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms).

Examples of the "group having a radial oxygen atom" include acetylacetonato group, crown ether, and the like.

Further, as the "group having a basic nitrogen atom", for example, an amino group (-NH _2), substituted imino group ^{(-NHR 8, -NR 9 R 10} , where, R ^8, R ^9, and R ¹⁰ is Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), guanidyl group represented by the following formula (a1), amido group represented by the following formula And the like can be mentioned as preferable examples.

In formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

In formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among them, an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 10 carbon atoms, And a guanidyl group represented by the formula (a1) wherein each of R ¹¹ and R ¹² independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group; (Wherein R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group), and the like are more preferable.

In particular, an amino group (-NH ₂ ), a substituted imino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms, And a guanidyl group represented by formula (a1), wherein in formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group; (Wherein R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group), and the like are preferably used.

The alkyl moiety in the "alkyloxycarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group and an ethyl group.

The alkyl moiety in the "alkylaminocarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.

Examples of the " carboxylic acid base " include a group formed by an ammonium salt of a carboxylic acid.

As the "sulfonamide group", the hydrogen atom bonded to the nitrogen atom may be substituted with an alkyl group (methyl group, etc.), an acyl group (acetyl group, trifluoroacetyl group, etc.)

Examples of the "heterocyclic structure" include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, But are not limited to, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolinone, Preferable examples are imidazoles such as imidazolone, benzothiazole, succinimide, phthalimide and naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone and anthraquinone. And can be selected from the group consisting of pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline , Isoindolinone, benzimidazolone, benzothiazole, hydantoin, carbazole, acridine, acridone, ant Quinone is more preferable.

Examples of the "imide group" include succinimide, phthalimide, naphthalimide, and the like.

The "heterocyclic structure" may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, An alkoxy group having 1 to 20 carbon atoms such as an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group, an acyloxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as an methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like. Here, these substituents may be bonded to a heterocycle through a linking group composed of the following structural unit or a combination of the structural units.

The "alkoxysilyl group" may be any one of a monoalkoxysilyl group, a dialkoxysilyl group and a trialkoxysilyl group, but it is preferably a trialkoxysilyl group, and examples thereof include a trimethoxysilyl group, a triethoxysilyl group and the like. .

Examples of the "epoxy group" include a substituted or unsubstituted oxirane group (ethylene oxide group). The epoxy group can be represented, for example, by the following general formula (a3).

In the general formula (a3), R ^EP1 to R ^EP3 each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. * Indicates a connected hand.

The linking group to be bonded to the adsorption site may be a single bond, or a single bond, or a single bond, or an alkylene group having 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms Is preferable, and the organic linking group may be unsubstituted or may further have a substituent.

Specific examples of this linking group include the following structural units or groups in which the structural units are combined.

When the linking group has another substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, An alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as chlorine and bromine, a methoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

Among them, A ¹ is preferably a monovalent substituent having at least one group selected from the group consisting of an acidic group, urea group, urethane group, sulfonamide group, imide group and group having a saturated oxygen atom.

In particular, from the viewpoint of improving the interaction with the metal oxide particles (A), improving the refractive index, and reducing the viscosity of the composition, A ¹ is preferably a monovalent substituent having at least one functional group having a pKa of 5 or more, more preferably a monovalent substituent having at least one functional group of pKa 5 to 14.

The term " pKa " referred to herein is a definition described in the Chemical Manual (II) (revised fourth edition, 1993, Nihon Kagaku Kaishi, Maruzen Co., Ltd.).

Examples of the functional group having a pKa of 5 or more include a urea group, a urethane group, a sulfonamide group, an imide group, or a group having a saturated oxygen atom.

Specific examples thereof include urea (pKa 12-14), urethane (pKa 11-13), -COCH ₂ CO- (pKa 8-10), sulfonamide (PKa about 9 to 11), and the like.

A ¹ is preferably represented by a monovalent substituent represented by the following general formula (4).

In the general formula (4), B ¹ represents an adsorption site, and R ²⁴ represents a single bond or a linking group of (a + 1). a represents an integer of 1 to 10, and B ¹ in a general formula (4) in which a is present may be the same or different.

The adsorption site represented by B ¹ is the same as the adsorption site constituting A ¹ in the above-mentioned general formula (1), and preferable examples are also the same.

Among them, those having an acidic group, an urea group, a urethane group, a sulfonamide group, an imide group or a group having a saturated oxygen atom are preferred, and from the viewpoint of more preferably a functional group having a pKa of 5 to 14, urea group, urethane group, , A group having an imido group or a double-oxygen atom.

R ²⁴ represents a single bond or a linking group of (a + 1), and a represents 1 to 10. Preferably, a is 1 to 7, more preferably a is 1 to 5, and particularly preferably a is 1 to 3.

(a + 1) linking group is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms Group, which may be unsubstituted or may further have a substituent.

The linking group of (a + 1) may include, for example, the following structural unit or a group in which the structural unit is combined (may form a ring structure) as a specific example.

R ^{24 is a} single bond or a single bond consisting of 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms ( a + 1) linking group is preferable, and a single bond or a linking group of 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, (A + 1) -valent linking group composed of seven sulfur atoms, more preferably a single bond, or a single bond, or an alkylene group having 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 (A + 1) < / RTI > bridged group consisting of 1 to 5 hydrogen atoms and 0 to 5 sulfur atoms is particularly preferred.

Examples of the substituent of the above (a + 1) -valent connecting group include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, An alkoxy group having 1 to 6 carbon atoms such as an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group, an acyloxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as an methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

In the general formula (1), R ² represents a single bond or a divalent linking group. n R ² may be the same or different.

The divalent linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, Which may be unsubstituted or may further have a substituent.

Specific examples of the bivalent linking group include groups represented by the following structural units or groups formed by combining the structural units.

R ^{2 is a} single bond or a single bond consisting of 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms Is preferably a single bond or a single bond or a single bond, or a single bond, or a single bond, or a single bond, or one to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms More preferably a divalent linking group constituted by a single bond, or a single bond or a divalent linking group consisting of 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, A divalent linking group consisting of five sulfur atoms is particularly preferred.

When the divalent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as methyl and ethyl, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, An acyloxy group having 1 to 6 carbon atoms such as an amide group, an N-sulfonylamide group and an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as chlorine or bromine, a methoxycarbonyl group , Alkoxycarbonyl groups having 2 to 7 carbon atoms such as an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, carbonic ester groups such as cyano group and t-butylcarbonate, and the like.

In the general formula (1), R ¹ represents an (m + n) linking group. m + n satisfies 3 to 10.

The (m + n) linking group represented by R ¹ is preferably a linking group having 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 A sulfur atom, and may be unsubstituted or may further have a substituent.

(m + n) may include, for example, the following structural units or groups in which the structural units are combined (may form a cyclic structure).

(m + n) bond group is composed of 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 sulfur atoms Group is preferable and a group composed of 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur atoms is more preferable , A group consisting of 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms is particularly preferable.

When the (m + n) th connecting group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, An alkoxy group having 1 to 6 carbon atoms such as an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group, an acyloxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, An alkoxycarbonyl group having 2 to 7 carbon atoms such as an methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a carbonic ester group such as a cyano group and t-butylcarbonate, and the like.

Specific examples (specific examples (1) to (17)) of the (m + n) linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

Among these specific examples, the most preferable (m + n) linking group from the viewpoints of availability of raw materials, easiness of synthesis, and solubility in various solvents are the following groups.

In the general formula (1), m represents a positive number of 8 or less. m is preferably from 0.5 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3.

In the general formula (1), n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In the general formula (1), P ¹ represents a polymer chain, and can be selected according to the purpose or the like in a known polymer or the like. The m < ¹ > P < ¹ > may be the same or different.

In order to form a polymer chain among the polymers, a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer and their modified products or copolymers (Including random copolymers, block copolymers and graft copolymers) of a polyether / polyurethane copolymer, a polymer of a polyether / vinyl monomer, and the like At least one is preferable, and it is more preferable to use at least one member selected from the group consisting of polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer, and modified product or copolymer thereof, Or copolymers are particularly preferred.

It is preferable that the polymer chain P ¹ contains at least one kind of repeating unit.

The number of repeating units (k) of at least one repeating unit in the polymer chain P ¹ is preferably 3 or more, more preferably 5 or more from the viewpoint of exhibiting a steric repulsion to improve dispersibility and achieving a high refractive index and a low viscosity More preferable.

From the viewpoint of achieving a low viscosity by suppressing the volume of the polymeric dispersing agent (B) to be large and also by densely presenting the metal oxide particles (A) in the cured film (transparent film) to achieve a high refractive index, The number of repeating units (k) in the unit is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less.

The polymer constituting the polymer chain is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, the affinity with the dispersion medium becomes weak, so that it may become impossible to secure a sufficient adsorption layer for dispersion stabilization.

Examples of the vinyl monomer include, but not limited to, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, vinyl monomers having an acid group, maleic acid diesters, fumaric acid diesters, itaconic acid diesters (Meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides and (meth) acrylonitrile are preferable, and (meth) acrylic acid esters, crotonic acid esters, vinyl esters More preferably a vinyl monomer having an acid or an acid group, and more preferably a (meth) acrylic acid ester or a crotonic acid ester.

Preferred examples of these vinyl monomers include the vinyl monomers described in paragraphs 0089 to 0094, 0096, and 0097 of Japanese Patent Application Laid-Open No. 2007-277514 (corresponding US publication No. US2010 / 233595 A1) .

In addition to the above compounds, vinyl monomers having functional groups such as urethane groups, urea groups, sulfonamide groups, phenol groups and imide groups can also be used. As such a monomer having a urethane group or a urea group, for example, it can be suitably synthesized by using an addition reaction of an isocyanato group and a hydroxyl group or an amino group. Specifically, an addition reaction of an isocyanato group-containing monomer with a compound containing one hydroxyl group or a compound containing one primary or secondary amino group or an addition reaction between a hydroxyl group-containing monomer or a monomer containing a primary or secondary amino group and a mono Can be appropriately synthesized by addition reaction of isocyanate and the like.

Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic anhydride such as maleic anhydride or phthalic anhydride or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone mono Methacrylate) can also be used. In addition, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as a precursor of a carboxyl group. Among these, (meth) acrylic acid is particularly preferable from the viewpoint of copolymerization, cost, solubility and the like.

As vinyl monomers having sulfonic acid group, 2-acrylamide-2-methylpropane sulfonic acid and the like can be given. As vinyl monomers having a phosphoric acid group, mono (2-acryloyloxyethyl ester) phosphate, mono (1- 2-acryloyloxyethyl ester) and the like.

As the vinyl monomer having an acidic group, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group may also be used.

Among the polymer compounds represented by the general formula (1), the polymer compounds represented by the following general formula (2) are preferable.

In formula (2), A ² represents a hydrocarbon group, an acid group, a urea group, a urethane group, a group having a radial oxygen atom, a group having a basic nitrogen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, Represents a monovalent substituent group having at least one group selected from the group consisting of a hydroxyl group, a carboxylate group, a carboxylate group, a carboxylate group, a carboxylate group, a carboxylate group, a carboxylate group, a carboxylate group, n A ² may be the same or different.

A ² is synonymous with A ¹ in the general formula (1), and the preferable form thereof is also the same.

In the general formula (2), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. n R ⁴ may be the same or different. In addition, m is different or different R ⁵ may be the same.

The divalent linking groups represented by R ⁴ and R ⁵ are the same as those exemplified as the divalent linking group represented by R ² in the general formula (1), and the preferred embodiments are also the same.

In the general formula (2), R ³ represents a linking group of (m + n). m + n satisfies 3 to 10.

The (m + n) linking group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 A sulfur atom, and may be unsubstituted or may further have a substituent.

The (m + n) linking group represented by R ³ is specifically exemplified as the linking group exemplified as the (m + n) linking group represented by R ¹ in the general formula (1).

In the general formula (2), m represents a positive number of 8 or less. m is preferably from 0.5 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3.

In the general formula (2), n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In addition, P ² in the general formula (2) represents a polymer chain, which can be selected according to the object or the like in a known polymer or the like. The m < ² > P < ² > may be the same or different. The preferred form of the polymer is the same as P ¹ in the general formula (1).

It is most preferable that all the R ³ , R ⁴ , R ⁵ , P ² , m and n shown below be satisfied among the polymer compounds represented by the general formula (2).

R ³ : In the above Examples (1), (2), (10), (11), (16)

R ^{4 represents a} single bond or a "single bond consisting of 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 carbon atoms, (Having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group and the like) having 6 or more carbon atoms An alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy and the like, such as a methoxy group, an ethoxy group and the like, an aryloxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, Halogen atoms such as chlorine, bromine and the like, carbonic ester groups such as an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a cyano group and t-butylcarbonate. )

R ^{5 represents a} single bond, an ethylene group, a propylene group, the following group (a), or the following group (b)

In the following groups, R ¹² represents a hydrogen atom or a methyl group, and 1 represents 1 or 2.

P ² : polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer and modified products thereof

m: 1-3

n: 3 to 6

The acid value of the polymer dispersant (B) is not particularly limited, but from the viewpoint of viscosity or dispersibility, the acid value is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, desirable.

The lower limit of the acid value is not particularly limited, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more from the viewpoint of dispersion stability of the metal oxide particles.

Here, the acid value of the polymer dispersant is the solid content of the polymer compound.

In the present invention, the acid value of the polymer dispersant can be calculated from, for example, the average content of the acid groups in the polymer dispersant. The acid value of the polymer dispersant can be adjusted by appropriately adjusting the amount of the acid group in the polymer dispersant and the amount of the functional group of pKa 5 to 14 described later. For example, the amount of the compound having an acidic group and a carbon-carbon double bond to be a raw material in the synthesis of the polymeric dispersant, the amount of the compound having a pKa of 5 to 14 and the compound having a carbon-carbon double bond, The polymer dispersant having a desired acid value can be synthesized.

[Method for synthesizing a polymer represented by the general formula (1) or (2)] [

The polymer compound represented by the general formula (1) or (2) is not particularly limited, but can be synthesized according to the synthesis method described in paragraphs 0114 to 0140 and 0266 to 0348 of Japanese Patent Application Laid-Open No. 2007-277514.

In particular, it is preferable to synthesize a polymer compound represented by the general formula (1) or (2) by a method of radical polymerization of a vinyl monomer in the presence of a mercaptan compound having a plurality of adsorption sites.

The vinyl monomers may be polymerized singly or in combination of two or more.

Specific examples (M-1) to (M-13) of vinyl monomers are shown below, but the present invention is not limited thereto.

As a method of synthesizing a polymer compound represented by the general formula (1) or (2), more specifically, a method of radically polymerizing a vinyl monomer in the presence of a compound represented by the following general formula (3) is preferred.

In the general formula (3), R ⁶ , R ⁷ , A ³ , m and n are the same as R ³ , R ⁴ , A ² , m and n in the general formula (2) The same goes for forms.

The compound represented by the general formula (3) is preferably synthesized by the following method.

A compound having 3 to 10 mercapto groups in one molecule and a compound having an adsorption site and having a carbon-carbon double bond capable of reacting with a mercapto group.

It is particularly preferable that the addition reaction is a radical addition reaction. The carbon-carbon double bond is more preferably a monovalent or divalent vinyl group in view of reactivity with a mercapto group.

Specific examples (specific examples (18) to (34)) of the compound having 3 to 10 mercapto groups in one molecule include the following compounds.

Of these, particularly preferred compounds from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents are the following compounds.

(33) is available as a commercial product (for example, (33) is dipentaerythritol hexakis (3-mercaptopropionate) manufactured by Sakai Kagaku Kogyo Co., Ltd.).

(Specifically, a compound having a hydrocarbon group, an acid group, a urea group, a urethane group, a group having a saturated oxygen atom, a group having a basic nitrogen atom, an alkyloxycarbonyl group, an alkylamino group A compound having at least one group selected from the group consisting of a carbonyl group, a carboxylate group, a sulfonamide group, a heterocyclic group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group, and having a carbon-carbon double bond) However, the following may be mentioned.

The radical addition reaction product of "a compound having 3 to 10 mercapto groups in one molecule" and a "compound having an adsorption site and having a carbon-carbon double bond" is, for example, A compound having 10 mercapto groups "and" a compound having an adsorption site and having a carbon-carbon double bond "in an appropriate solvent, adding a radical generating agent thereto, and adding the compound at about 50 ° C to 100 ° C (Thiol-ene reaction method).

Examples of a suitable solvent to be used in the thiol-ene reaction method include a compound having three to ten mercapto groups in one molecule, a compound having an adsorption site and having a carbon-carbon double bond, Can be arbitrarily selected depending on the solubility of the resulting radical addition reaction product.

Methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxy (methoxy) propyl acetate, isopropanol, isopropanol, Propyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used in a mixture of two or more kinds.

Examples of the radical generator include 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis- (2,4'-dimethylvaleronitrile), 2,2'-azobis An azo compound such as dimethyl isobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

The polymer compound is preferably obtained by polymerizing these vinyl monomers and a compound represented by the general formula (3) according to a conventional method by a known method. The compound represented by the general formula (3) in the present invention functions as a chain transfer agent. Hereinafter, the compound represented by the general formula (3) may be simply referred to as a " chain transfer agent ".

For example, a method of dissolving these vinyl monomers and chain transfer agent in a proper solvent, adding a radical polymerization initiator thereto, and polymerizing the solution in a solution at about 50 ° C to 220 ° C (solution polymerization method).

Examples of a suitable solvent to be used in the solution polymerization method may be arbitrarily selected depending on the monomers to be used and the solubility of the resulting copolymer. Propanol, isopropanol, 1-methoxy-2-propanol, 2-ethylhexanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl Acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used in a mixture of two or more kinds.

Examples of the radical polymerization initiator include 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis- (2,4'-dimethylvaleronitrile), 2,2'-azobis An azo compound such as dimethyl isobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

The content of the polymer dispersant in the cured film is not particularly limited, but is preferably in the range of 5 to 40 mass% with respect to the total mass of the cured film from the viewpoint of the dispersibility, the high refractive index and the shape of the coated surface, and is preferably in the range of 10 to 35 mass% , And more preferably in the range of 12 to 30 mass%.

The content of the polymer dispersant in the composition for forming a cured film is preferably in the above range with respect to the total solid content of the composition.

[(C) Polymerizable compound]

From the viewpoint of the solvent resistance of the cured film, it is preferable that the composition for forming a cured film contains a polymerizable compound. Among them, it is preferable to use a compound having two or more epoxy groups or oxetanyl groups in the molecule as the polymerizable compound.

Specific examples of the compound having two or more epoxy groups in the molecule as the polymerizable compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin and the like have.

These are available as commercial products. Examples of the bisphenol A epoxy resin include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER- JER-806, JER-4004, JER-4005 (manufactured by Mitsubishi Kagaku Co., Ltd.), EPICLON 860, EPICLON1050, EPICLON1051, EPICLON1055 , JER-4007, JER-4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON 830, EPICLON 835 [manufactured by DIC Corporation], LCE-21 and RE- EPICLON N-740, EPICLON N-740, EPICLON N-740, and EPICLON N-740 as the phenol novolak type epoxy resin, and JER-152, JER-154, JER-157S70 and JER-157S65 (manufactured by Mitsubishi Kagaku K.K.) EPICLON N-670, EPICLON N-670, EPICLON N-670, EPICLON N-670, EPICLON N-670 and EPICLON N-670. EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation) and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) EP-4088S, EP-4088S (manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE-3150, EPOLEAD PB 3600 , PB 4700 (manufactured by Daicel Chemical Industries Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L and EX- ), And so on. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- 501, EPPN-502 [manufactured by ADEKA Corporation] and JER-1031S [manufactured by Mitsubishi Kagaku Co., Ltd.].

These may be used singly or in combination of two or more.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aromoxetane OXT-121, OXT-221, OX-SQ and PNOX [manufactured by Toagosei Co., Ltd.] can be used.

The oxetanyl group-containing compound is preferably used alone or in combination with a compound containing an epoxy group.

Further, as the polymerizable compound, an addition polymerizable compound having at least one ethylenic unsaturated double bond may be used, or a compound having at least one, preferably two or more, terminal ethylenic unsaturated bonds is preferably used. Such compounds are well known in the art, and they can be used without any particular limitation in the present invention.

When such a compound is used as a polymerizable compound, it is preferable that the composition for forming a cured film further contains a polymerization initiator described later.

Such an addition polymerizable compound having at least one ethylenically unsaturated double bond has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of the monomer and the copolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof and amides An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used. Further, an addition reaction product of an unsaturated carboxylic acid ester or an unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, A dehydration condensation reaction product of a polyfunctional carboxylic acid and the like are also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or an unsaturated carboxylic acid amide having an electrophilic substituent such as an isocyanate group or an epoxy group and monofunctional or polyfunctional alcohols, amines and thiols; Unsaturated carboxylic acid esters or unsaturated carboxylic acid amides having a clearing substituent such as a halogen group or a tosyloxy group and substitution reaction products of alcohols, amines and thiols with monofunctional or polyfunctional are also preferable. As another example, it is also possible to use a compound group substituted by an unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. As specific compounds of these, compounds described in paragraphs 0095 to 0108 of Japanese Patent Laid-Open Publication No. 2009-288705 can be preferably used in the present invention.

As the polymerizable compound (hereinafter simply referred to as "polymerizable monomer etc.", "polymerizable monomer"), a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of 100 ° C. or higher at normal pressure desirable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylates such as polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tripentaerythritol hexa (meth) acrylate, (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Urethane (meth) acrylates as disclosed in JP-A-51-37193, JP-A-48-64183, JP-A- 49-43191, JP-A-52-30490, polyfunctional acrylates such as polyester acrylates and epoxy acrylates, reaction products of epoxy polymer and (meth) acrylic acid, methacrylic And mixtures thereof.

(Meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenic unsaturated group.

Other preferable polymerizable monomers include fluorinated rings described in Japanese Patent Application Laid-Open Nos. 2010-160418, 2010-129825, and 4364216, and compounds having two or more ethylenic polymerizable groups and cardo polymers are also used It is possible to do.

Also, as the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 캜 or more at normal pressure, the compounds described in paragraphs [0254] to [0257] of JP-A No. 2008-292970 are also preferable.

Further, in Japanese Patent Application Laid-Open No. 10-62986, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol represented by general formulas (1) and (2) May also be used as polymerizable monomers.

The polymerizable monomer used in the present invention is also preferably a polymerizable monomer represented by the following general formula (MO-1) to (MO-6).

(Wherein n is 0 to 14, and m is 1 to 8. When R is an oxyalkylene group, R, T and Z, which are plural in one molecule, may be the same or different, Is bonded to R. At least one of R is a polymerizable group.

n is preferably 0 to 5, more preferably 1 to 3.

m is preferably from 1 to 5, more preferably from 1 to 3.

R is

Is preferably a group represented by the following formula

Is more preferably a group represented by

Specific examples of the radically polymerizable monomers represented by the above-mentioned general formulas (MO-1) to (MO-6) include compounds represented by the compounds described in paragraphs [0248] to [0251] of JP-A No. 2007-269779 And can be preferably used in the invention.

Among them, dipentaerythritol triacrylate (trade name: KAYARAD D-330, manufactured by Nippon Kayaku K.K.) and dipentaerythritol tetraacrylate (KAYARAD D-320, available from Nippon Kayaku Kabu Co., (KAYARAD D-310 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; available from Nippon Kayaku Co., Ltd.), dipentaerythritol penta (Ethylene oxide) modified (meth) acrylate (trade name: M-460; available from Showa Denko K.K.), and a structure in which these (meth) acryloyl groups are interposed between ethylene glycol and propylene glycol moieties and diglycerin EO (ethylene oxide) Manufactured by Toagosei Co., Ltd.). These oligomer types can also be used.

For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like.

As the polymerizable monomer or the like, the polyfunctional monomer may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, it can be used as it is. However, if necessary, the non-aromatic carboxylic acid anhydride is reacted with the hydroxyl group of the above- An acidic group may be introduced. In this case, specific examples of the nonaromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the non-aromatic carboxylic acid anhydride is reacted with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acidic group A polyfunctional monomer is preferable, and particularly, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, M-305, M-510 and M-520 of Aronix series as polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd.

The preferred acid value of the polyfunctional monomer having an acidic group is 0.1 to 40 mg-KOH / g, particularly preferably 5 to 30 mg-KOH / g. When two or more kinds of polyfunctional monomers having different acid groups are used in combination or when a polyfunctional monomer having no acidic group is used in combination, it is necessary to prepare such that the acid value as the total polyfunctional monomer falls within the above range.

Further, it is preferable to contain a polyfunctional monomer having a caprolactone-modified structure as a polymerizable monomer or the like.

The polyfunctional monomer having a caprolactone-modified structure is not particularly limited as long as it has a caprolactone-modified structure in its molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, Caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying a polyhydric alcohol such as dipentaerythritol, tripentaerythritol, glycerin, diglycerol and trimethylolmelamine with (meth) acrylic acid and? -Caprolactone, . Among them, a polyfunctional monomer having a caprolactone-modified structure represented by the following formula (11) is preferable.

Wherein all six Rs are groups represented by the following formula (12), or one to five of the six Rs are groups represented by the following formula (12), and the remainder is a group represented by the following formula (13) It is a flag that is represented.]

(Wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.)

The multifunctional monomer having such a caprolactone-modified structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 [m = 1 in the above formulas (11) the number of groups represented by formula (12) = 2, R ¹ are both the compound], DPCA-30 [the same formula, m = 1, the number of groups represented by the formula (2) = 3, R ¹ is hydrogen atom DPCA-120 [in the formula, m = 1, the number of groups represented by formula (12) = 6 and R ¹ are all hydrogen atoms] 2, the number of groups represented by formula (12) = 6, and R ¹ are all hydrogen atoms].

In the present invention, the polyfunctional monomers having a caprolactone-modified structure may be used singly or in combination of two or more.

The polymerizable monomer or the like in the present invention is preferably at least one member selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), E independently represents - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) Each independently represent an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (i), the sum of the acryloyl group and the methacryloyl group is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40. Provided that when the sum of each m is 0, any one of X is a carboxyl group.

In the general formula (ii), the sum of the acryloyl group and the methacryloyl group is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60. Provided that when the sum of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the general formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

- ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the general formula (i) or the general formula (ii) Is preferable.

The compounds represented by the general formula (i) or (ii) may be used singly or in combination of two or more. Particularly, in the general formula (ii), all of the six X's are preferably acryloyl groups.

The compound represented by the general formula (i) or (ii) can be obtained by a process comprising the steps of binding a ring opening skeleton to pentaerythritol or dipentaerythritol, which is a conventionally known process, by ring-opening addition reaction of ethylene oxide or propylene oxide, For example, (meth) acryloyl chloride to introduce a (meth) acryloyl group. Each process is a well-known process, and a person skilled in the art can easily synthesize the compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (i) or (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

Specific examples include the compounds represented by the following formulas (a) to (f) [hereinafter also referred to as "exemplified compounds (a) to (f)") , (e) and (f) are preferable.

Examples of commercially available products such as the polymerizable monomers represented by the general formulas (i) and (ii) include SR-494 which is a tetrafunctional acrylate having four ethylene oxy chains in the form of a silicate, Nippon Kayaku Co., Ltd., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the radical polymerizable monomers include urethane acrylates such as those described in Japanese Patent Publication Nos. 48-41708, 51-37193, 2-32293, and 2-16765 , Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication Nos. 58-49860, 56-17654, 62-39417 and 62-39418 are also preferable . As polymerizable monomers, addition polymerizable monomers having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A- A composition for forming a cured film having a very high photosensitive speed can be obtained.

Examples of commercially available products such as urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Chemical Industries, Ltd.), UA-7200 (Shin Nakamura Kagaku Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., UA-306T, UA-306I, AH-600, T-600 and AI-600 (manufactured by Kyowa Kasei).

As the polymerizable monomer or the like, a polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule is also preferable. In particular, those represented by the following general formula (I) are preferable.

(Wherein R ¹ is an alkyl group, R ² is an n-valent aliphatic group which may contain an atom other than carbon, R ⁰ is an alkyl group other than H, and n is 2 to 4).

Specific examples of the polyfunctional thiol compound represented by the above general formula (I) include 1,4-bis (3-mercaptobutyryloxy) butane having the following structural formula (formula (II) -Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H5H) -trione [formula (III)], and pentaerythritol tetrakis (Formula (IV)), and the like. These polyfunctional thiols may be used singly or in combination.

Examples of other esters include aliphatic alcohol esters disclosed in Japanese Patent Application Laid-Open Nos. 51-47334 and 57-196231, Japanese Laid-Open Patent Application No. 59-5240, Japanese Patent Laid- 59-5241, an aromatic skeleton disclosed in JP-A-2-226149, and an amino group described in JP-A-1-165613 are preferably used. The above-mentioned ester monomer can also be used as a mixture.

Specific examples of the amide-based monomer of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebisacrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis -Methacrylamide, diethylenetriamintrisacrylamide, xylylenebisacrylamide, xylylene bismethacrylamide, and the like.

Examples of other preferable amide-based monomers include those having a cyclohexylene structure disclosed in Japanese Patent Publication No. 54-21726.

Further, a urethane-based addition polymerizable compound produced by the addition reaction of isocyanate and hydroxyl group is also preferable. Examples of such urethane-based addition polymerizable compounds include two or more isocyanates in one molecule described in Japanese Patent Publication No. 48-41708 And vinyl urethane compounds containing two or more polymerizable vinyl groups in a molecule to which a vinyl monomer having a hydroxyl group represented by the following formula (V) is added to the polyisocyanate compound having a group represented by the following formula (V).

In the formula (V), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.

Further, urethane acrylates as described in JP-A-51-37193, JP-A-2-32293, JP-A-2-16765, JP-A-58-49860 The urethane compounds having an ethylene oxide skeleton described in JP-A-56-17654, JP-A-62-39417 and JP-A-62-39418 are also preferable. In addition, polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 A composition for forming a cured film having a very high photosensitive speed can be obtained.

Other examples include polyester acrylates such as those described in JP-B-48-64183, JP-A-49-43191, JP-B-52-30490, epoxy resins, epoxy resins and (meth) acrylic acid Acrylate or methacrylate such as epoxy acrylates obtained by reacting a polyfunctional acrylate or methacrylate. The specific unsaturated compounds described in JP-A-46-43946, JP-A-1-40337, JP-A-1-40336, and the vinyl compounds disclosed in JP-A-2-25493 Phosphonic acid-based compounds and the like. In addition, in either case, a structure containing a perfluoroalkyl group as disclosed in JP-A-61-22048 is preferably used. Photocurable monomers and oligomers described in Japan Adhesion Society vol.20, No. 7, pages 300 to 308 (1984) can also be used.

The details of the structure, the use of the polymerizable compound, whether it is used singly or in combination, and the like can be arbitrarily set in accordance with the final performance design of the composition for forming a cured film. For example, it is selected from the following viewpoints.

In view of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferable, and in many cases, bifunctionality or more is preferable. Further, in order to increase the strength of the cured film, trifunctional or higher functional groups are preferable, and when combined with other functional groups and other polymerizable groups (for example, acrylate ester, methacrylate ester, styrene group compound and vinyl ether group compound) It is also effective to adjust both strength and strength.

Also, the compatibility and dispersibility with other components (for example, polymerization initiator, metal oxide particles, etc.) contained in the composition for forming a cured film is an important factor for selecting and using polymerizable compounds. For example, The compatibility may be improved by the use of a compound or by the combination of two or more different components. In addition, a specific structure may be selected for the purpose of improving adhesion with a hard surface such as a substrate.

The content of the polymerizable compound (C) in the total solid content of the composition for forming a cured film is preferably in the range of 1% by mass to 40% by mass, more preferably in the range of 3% by mass to 35% by mass, And more preferably in the range of from 30% by mass to 30% by mass.

Within this range, it is preferable that the curing property is good without lowering the refractive index.

[(D) solvent]

The composition for forming a cured film may contain a solvent.

The type of the solvent to be used is not particularly limited, and a known solvent (water or an organic solvent) may be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, aromatic hydrocarbon solvents such as toluene, , Xylene), an amide solvent (for example, formamide, dimethylacetamide, N-methylpyrrolidone), a nitrile solvent (for example, acetonitrile or propionitrile) , Methyl acetate, ethyl acetate), a carbonate solvent (e.g., dimethyl carbonate, diethyl carbonate), an ether solvent, a halogen solvent, and the like. Two or more of these solvents may be mixed and used. Particularly, it is preferable that propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, and ethyl ethoxypropionate, which have good spreading phase on spin coating, are contained as a main component of the solvent.

[(E) Polymerization initiator]

It is preferable that the composition for forming a cured film further contains a polymerization initiator from the viewpoint of better curability. As the polymerization initiator, those known as polymerization initiators described below can be used.

The polymerization initiator is not particularly limited as far as it has an ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known polymerization initiators.

The polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 500 nm (more preferably 330 nm to 400 nm).

Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbimidazole, oxime An organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketooxime ether, an aminoacetophenone compound, and a hydroxyacetophenone.

As specific examples of these, it is possible to consider the following description of the publication paragraph [0135] (Corresponding United States Patent Application Publication No. 2011/0124824 specification [0163]) of Japanese Patent Application Laid-Open No. 2010-106268, Are incorporated herein by reference.

As the polymerization initiator, an oxime-based compound can also be preferably used. As specific examples of the oxime-based initiator, the compounds described in JP 2001-233842 A, the compound disclosed in JP 2000-80068 A, and the compound disclosed in JP 2006-342166 A can be used.

Examples of the oxime compounds such as oxime derivatives which are preferably used as a polymerization initiator include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3- 1-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

Examples of the oxime ester compounds include JCSPerkin II (1979) pp.1653-1660, JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Journal of Applied Polymer Science (2012) pp.725-731, Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open Nos. 2000-80068, 2004-534797, and 2006-342166 And the compounds described in the respective publications.

As a commercial product, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are preferably used.

Further, as oxime ester compounds other than the above-mentioned compounds, compounds described in Japanese Patent Publication No. 2009-519904 in which oxime is linked to carbazole N position, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in JP-A-2010-15025 and US-2009-292039 wherein nitro groups are introduced, ketoxime compounds described in WO 2009-131189, triazine skeletons and oxime skeletons in the same molecule Compounds described in U.S. Patent No. 7556910, compounds described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, or the like may be used.

Also, the annular oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can be preferably used. Among the cyclic oxime compounds, cyclic oxime compounds which are coordinated to carbazole dyes described in JP-A-2010-32985 and JP-A-2010-185072 are preferred from the viewpoint of high sensitivity due to their high light absorption.

The compound described in JP-A-2009-242469 having an unsaturated bond in a specific part of the oxime compound can also be used preferably because it can achieve high sensitivity by regenerating an active radical from a polymerization-inactive radical.

Other oxime compounds having a specific substituent group as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A No. 2009-191061 can be mentioned.

(OX-1), (OX-2) or (OX-3) following the Japanese Patent Application Laid-Open Publication No. 2012-208494 (corresponding to US Patent Application Publication No. 2012/235099 [0632] ), And the contents of these are incorporated herein by reference.

The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000 from the viewpoint of sensitivity.

The molar extinction coefficient of the compound can be determined by a known method. Specifically, the molar extinction coefficient of the compound is measured by using an ultraviolet visible spectrophotometer (Varian Carry-5 spectrophotometer) at a concentration of 0.01 g / L using an ethyl acetate solvent desirable.

The polymerization initiator may be used in combination of two or more as necessary.

As the polymerization initiator, from the viewpoint of curing properties, trihalomethyltriazine compounds, benzyldimethylketal compounds,? -Hydroxyketone compounds,? -Amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds , Triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substitution And a coumarin compound.

More preferred are trihalomethyltriazine compounds,? -Amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds and acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is most preferable.

It is particularly preferable to use an oxime compound as the polymerization initiator. Particularly, in the case of forming a fine pattern in a solid-state image pickup device, stepper exposure is used for exposure for curing, but this exposure device is sometimes damaged by halogen and it is required to suppress the addition amount of the polymerization initiator to a low level. It is most preferable to use an oxime compound as a polymerization initiator in order to form a fine pattern such as a solid-state image pickup device.

The content (the total content in the case of two or more kinds) of the polymerization initiator contained in the cured film forming composition is preferably not less than 0.1% by mass and not more than 40% by mass relative to the total solid content of the cured film forming composition, more preferably not less than 0.5% 20 mass% or less, and more preferably 1 mass% or more and 15 mass% or less. Good curability is obtained in this range.

[(F) sensitizer]

The composition for forming a cured film may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength. As the sensitizer, it is preferable to increase or decrease the above-mentioned polymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

Examples of sensitizers include those described in paragraphs [0228] to [0250] of Japanese Patent Application Laid-Open Publication No. 2012-255148.

[(G) Notarized Attorney]

It is also preferable that the composition for forming a cured film further contains a notarization agent. The notarization sensitizer has an action of further improving the sensitivity to the active radiation of the above-mentioned polymerization initiator or sensitizer, or inhibiting polymerization inhibition of the polymerizable compound by oxygen.

Examples of the notarization agent include those described in paragraphs [0252] to [0256] of Japanese Patent Application Laid-Open Publication No. 2012-255148.

[(H) polymerization inhibitor]

It is preferable to add a polymerization inhibitor in order to prevent unnecessary polymerization of the polymerizable ethylenically unsaturated double bond-containing compound during or during the preparation of the composition for forming a cured film.

Examples of the polymerization inhibitor include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, And cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, and transition metal compounds such as FeCl ₃ and CuCl ₂ .

A more preferable mode is as follows.

Wherein the phenolic hydroxyl group-containing compound is at least one selected from the group consisting of hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,6- And a tributary.

Wherein the N-oxide compound is selected from the group consisting of 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, , Picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

Wherein the piperidine 1 -oxylpyridyl compounds are selected from the group consisting of piperidine 1 -oxylpyridyl, 2,2,6,6-tetramethylpiperidine 1-oxylpyridyl, 4-oxo-2,2,6,6 -Tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamide-2,2,6,6-tetra Methylpiperidine 1-oxylfuryl radical, 4-maleimide-2,2,6,6-tetramethylpiperidine 1-oxylfuryl radical, and 4-phosphonooxy-2,2,6,6-tetra Methylpiperidine 1-oxyl free radical.

It is preferred that the pyrrolidine 1-oxyl free radical compound is a 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

It is preferable that the N-nitrosophenylhydroxylamines are compounds selected from the group consisting of compounds consisting of a first cerium salt of N-nitrosophenylhydroxylamine and an N-nitrosophenylhydroxylamine aluminum salt.

The diazonium compounds are selected from the group consisting of hydrogenphosphate salts of 4-diazophenyldimethylamine, tetrafluoroborate salts of 4-diazodiphenylamine, and hexafluorophosphates of 3-methoxy-4-diazodiphenylamine It is preferable that the compound is selected.

Preferred polymerization inhibitors are exemplified below, but the present invention is not limited thereto. Examples of the phenolic polymerization inhibitor include the following exemplified compounds (P-1) to (P-24).

Examples of the amine-based polymerization inhibitor include the following exemplary compounds (N-1) to (N-7).

Examples of the sulfur-based polymerization inhibitor include the following exemplary compounds (S-1) to (S-5).

Examples of the phosphite-based polymerization inhibitor include the following exemplary compounds (R-1) to (R-5).

In addition, each of the compounds shown below may also be used as a preferable polymerization inhibitor.

Among the above exemplified compounds, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4- butylphenol), phenolic hydroxyl group-containing compounds of 2,2'-methylenebis (4-methyl-6-t-butylphenol), piperidine 1-oxyl free radical compounds or 2,2,6,6,6 -Tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethyl Piperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide-2,2,6,6-tetramethyl piperidine Piperidine 1-oxyl free radical of a 4-phosphonooxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, or an N-nitrosophenyl radical Lt; RTI ID = 0.0 > N-nitrosophenylhydroxylamine < / RTI > aluminum salt N-nitrosophenylhydroxylamine compound, more preferably 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxylfuryl radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1 -Oxyl radical, 4-maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonooxy-2,2,6,6-tetramethylpiperidine 1 Oxydiphenylhydroxylamine compound of the N-nitrosophenylhydroxylamine and N-nitrosophenylhydroxylamine compound of the N-nitrosophenylhydroxylamine aluminum salt, and the piperidine 1- More preferred are N-nitrosophenylhydroxylamine first-cerium salts and N-nitrosophenylhydroxylamine aluminum salts of N-nitrosophenylhydroxylamine compounds.

The amount of the polymerization inhibitor to be added is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 8 parts by mass or less, and more preferably 0.05 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the polymerization initiator .

[(I) Binder polymer]

It is preferable that the cured film further contains a binder polymer from the viewpoint of improving the film property and the like. Further, as a method of containing the binder polymer in the cured film, there is a method of including the binder polymer in the above-mentioned composition for forming a cured film.

As the binder polymer, it is preferable to use a linear organic polymer. As such a linear organic polymer, any known one can be used. Preferably linear organic polymers that are soluble or swellable in water or weak alkaline water are selected to enable water development or weak alkaline water development. The linear organic polymer is used not only as a film-forming agent, but also as a water, weakly alkaline water or organic solvent developer. For example, water-soluble organic polymers enable water development. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, for example, Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Those described in JP-A-54-25957, JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048, that is, monomers having a carboxyl group A resin in which an acid anhydride unit is hydrolyzed or half-esterified or half-amidated, a resin obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride, And the like. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Monomers having an acid anhydride include maleic anhydride.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in its side chain. In addition, it is useful that a cyclic acid anhydride is added to a polymer having a hydroxyl group.

When a copolymer is used as the binder polymer, monomers other than the monomers exemplified above may be used as the copolymerizing compound. Examples of other monomers include the following compounds (1) to (12).

(1) a polyfunctional monomer selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, Acrylate esters having an aliphatic hydroxyl group such as acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate, and methacrylic acid esters.

(2) acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, Acrylate such as vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate and the like such as 3,4-epoxycyclohexylmethyl acrylate, Late.

(3) a polyfunctional monomer selected from the group consisting of methylmethacrylate, ethylmethacrylate, propylmethacrylate, butylmethacrylate, isobutylmethacrylate, amylmethacrylate, hexylmethacrylate, 2-ethylhexylmethacrylate, methacrylic acid Cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1 - alkyl methacrylates such as propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate and the like.

(4) A method for producing a polymer comprising the steps of: (1) polymerizing an acrylamide, a methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexylmethacrylamide, N-cyclohexyl acrylamide, N- , N-nitrophenylacrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, Acrylamide or methacrylamide such as allyl methacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(7) styrenes such as styrene,? -Methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like.

(11) Unsaturated imides such as maleimide, N-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide and N- (p-chlorobenzoyl) methacrylamide.

(12) A methacrylic acid-based monomer having a hetero atom bonded to the? -Position. For example, the compounds disclosed in the respective publications such as Japanese Patent Application Laid-Open No. 2002-309057 and Japanese Patent Application Laid-Open No. 2002-311569.

In the present invention, these monomers can be applied to the synthesis of a copolymer by combining them without particular limitation within the scope of the present invention. For example, an example of a copolymer obtained by polymerizing a monomer component containing these monomers is shown below, but the present invention is not limited thereto. The composition ratio of the exemplified compounds shown below is in mol%.

It is also preferable that the binder polymer contains a repeating unit obtained by polymerizing a monomer component comprising a compound represented by the following formula (ED) (hereinafter sometimes referred to as "ether dimer") as essential.

In the formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 25 carbon atoms which may have a substituent.

As a result, the composition for forming a cured film can form a cured coating film having excellent heat resistance as well as transparency. In the general formula (ED) representing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ is not particularly limited and includes, for example, methyl, ethyl, , straight or branched alkyl groups such as n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like or a substituent of a primary or secondary carbon which is difficult to desorb by heat is preferable in view of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Bis (2-propyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Propane, di (n-butyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2' (T-butyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2' - [ Di (stearyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2' Di (2-ethylhexyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (1-methoxy Ethyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Bis (2-hydroxyethyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, dibenzyl- Bis (2-methoxyphenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- Bis (cyclohexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (Isobornyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) ] Bis-2-propenoate, diadamanthyl-2,2 '- [oxybis (methylene)] bis- - [oxybis (methylene)] bis-2-propenoate. Among these, especially preferred are dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl- Bis [2-propenyl] hexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be used alone or in combination of two or more. Further, the structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

Examples of other monomers copolymerizable with the ether dimer include monomers for introducing an acidic group, monomers for introducing radically polymerizable double bonds, monomers for introducing an epoxy group, and copolymerizable monomers other than these . These monomers may be used alone, or two or more monomers may be used.

Examples of the monomer for introducing an acidic group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, monomers having maleic anhydride and itaconic anhydride And monomers having a carboxylic acid anhydride group. Among these, (meth) acrylic acid is particularly preferable.

The monomer for introducing the acidic group may be a monomer capable of giving an acidic group after polymerization, and examples thereof include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate , Monomers having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate, and the like. When a monomer for introducing a radically polymerizable double bond is used, when a monomer capable of giving an acidic group after polymerization is used, it may be required to carry out a treatment to give an acidic group after polymerization. The treatment for imparting an acidic group after polymerization varies depending on the kind of the monomer, and for example, the following treatment can be mentioned. When a monomer having a hydroxyl group is used, for example, a treatment for adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride may be mentioned. When a monomer having an epoxy group is used, for example, a compound having an amino group and an acidic group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or an acid such as (meth) acrylic acid is added For example, an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, or maleic anhydride is added to the hydroxyl group generated later. When a monomer having an isocyanate group is used, for example, there can be mentioned a treatment for adding a compound having a hydroxyl group and an acidic group such as 2-hydroxybutyric acid.

When the polymer obtained by polymerizing a monomer component containing a compound represented by formula (ED) contains a monomer for introducing an acidic group, the content thereof is not particularly limited, but it is preferably 5 to 70 mass% , And more preferably from 10 to 60 mass%.

Examples of the monomer for introducing the radical polymerizable double bond include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; Monomers having a carboxylic anhydride group such as maleic anhydride and itaconic anhydride; Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and o- (or m- or p-) vinylbenzyl glycidyl ether; And the like. When a monomer for introducing a radically polymerizable double bond is used, it is necessary to perform a treatment for imparting a radically polymerizable double bond after polymerization. The treatment for imparting a radically polymerizable double bond after polymerization varies depending on the kind of monomers capable of imparting a radical polymerizable double bond to be used, for example, the following treatment. (Meth) acrylate, o- (or m-, or p- (meth) acrylate, or o- (or methacrylate) is used in the case of using a monomer having a carboxyl group such as -) vinylbenzyl glycidyl ether, and a compound having a radically polymerizable double bond. In the case of using a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride, a process of adding a compound having a hydroxyl group and a radically polymerizable double bond such as 2-hydroxyethyl (meth) acrylate have. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate or o- (or m- or p-) vinylbenzyl glycidyl ether is used And a process of adding a compound having an acidic group such as (meth) acrylic acid and a radically polymerizable double bond.

When the polymer obtained by polymerizing the monomer component containing a compound represented by formula (ED) contains a monomer for introducing a radically polymerizable double bond, the content thereof is not particularly limited, Is preferably 70 mass%, more preferably 10 mass% to 60 mass%.

Examples of the monomer for introducing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m- or p-) vinylbenzylglycidyl Ether, and the like.

When the polymer obtained by polymerizing a monomer component containing a compound represented by formula (ED) contains a monomer for introducing an epoxy group, the content thereof is not particularly limited, but it is preferably 5 to 70 mass% , And more preferably from 10 to 60 mass%.

Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylates such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate; Aromatic vinyl compounds such as styrene, vinyltoluene, and? -Methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Butadiene or substituted butadiene compounds such as butadiene and isoprene; Ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; Vinyl esters such as vinyl acetate; And the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate and styrene are preferable because they are excellent in transparency and hardly deteriorate heat resistance.

When the polymer obtained by polymerizing the monomer component containing a compound represented by formula (ED) contains other copolymerizable monomers, the content thereof is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less Is more preferable.

The weight average molecular weight of a polymer obtained by polymerizing a monomer component containing a compound represented by formula (ED) is not particularly limited, but from the viewpoint of the viscosity of the composition for forming a cured film and the heat resistance of the coating film formed by the composition Preferably from 2,000 to 200,000, more preferably from 5,000 to 100,000, and still more preferably from 5,000 to 20,000.

When the polymer obtained by polymerizing the monomer component containing a compound represented by formula (ED) has an acidic group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g.

A polymer obtained by polymerizing a monomer component containing a compound represented by the formula (ED) can be easily obtained by polymerizing at least the above-mentioned monomer containing an ether dimer. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.

The polymerization method to be applied to the synthesis of the polymer obtained by polymerizing the monomer component containing the compound represented by the formula (ED) is not particularly limited and various polymerization methods of the prior art can be employed. In particular, . Specifically, a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be synthesized, for example, in accordance with the synthesis method of the polymer (a) described in JP 2004-300204 A have.

Hereinafter, an exemplary compound of a polymer obtained by polymerizing a monomer component containing a compound represented by formula (ED) is shown, but the present invention is not limited thereto. The composition ratio of the exemplified compounds shown below is in mol%.

(Hereinafter referred to as "DM"), benzyl methacrylate (hereinafter referred to as "BzMA"), methacrylic acid (hereinafter referred to as " A polymer obtained by copolymerizing methyl (hereinafter referred to as "MMA"), methacrylic acid (hereinafter referred to as "MAA") and glycidyl methacrylate (hereinafter referred to as "GMA") is preferable. In particular, the molar ratio of DM: BzMA: MMA: MAA: GMA is preferably 5:15:40 to 50: 5 to 15: 5 to 15:20 to 30. It is preferable that 95% by mass or more of the components constituting the copolymer used in the present invention are these components. The weight average molecular weight of the polymer is preferably 9000 to 20,000.

The polymer used in the present invention preferably has a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 x 10 ⁵ , more preferably 2000 to 1 x 10 ⁵ , ⁴ is more preferable.

Among them, a (meth) acrylic resin having an allyl group, a vinyl ester group and a carboxyl group in the side chain, and an alkali-soluble resin having a double bond in the side chain described in JP-A-2000-187322 and JP- , And an alkali-soluble resin having an amide group in the side chain described in JP-A-2001-242612 are excellent in balance between film strength, sensitivity and developability. Examples of the above-mentioned polymers include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co. Ltd.), Viscot R-264 and KS resist 106 (Manufactured by Kyowa Chemical Industry Co., Ltd.) and Cychromer P ACA230AA; and Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.). have.

In addition, Japanese Patent Application Laid-Open Nos. 7-12004, 7-120041, 7-120042, 8-12424, 63-287944 A urethane binder polymer containing an acid group described in Japanese Patent Application Laid-Open Nos. 63-287947 and 1-271741 and an acidic group-containing binder polymer disclosed in Japanese Patent Application Laid-Open No. 2002-107918 The urethane binder polymer is excellent in strength and is therefore advantageous in terms of film strength.

Also, the acetal-modified polyvinyl alcohol-based binder polymer having an acidic group described in European Patent No. 993966, European Patent No. 1204000, Japanese Patent Laid-Open No. 2001-318463 and the like is preferable because it has excellent film strength.

In addition, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin and the like are also useful for increasing the strength of the cured coating.

The weight average molecular weight (polystyrene conversion value measured by GPC method) of the binder polymer is preferably 5,000 or more, more preferably from 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more , More preferably from 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 or more and 10 or less.

These binder polymers may be random polymers, block polymers, graft polymers, or the like.

The binder polymer can be synthesized by a conventionally known method. Examples of the solvent used for the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate , Ethyl lactate, dimethyl sulfoxide, water and the like. These solvents may be used alone or in combination of two or more.

Examples of the radical polymerization initiator used in synthesizing the binder polymer include known compounds such as azo-based initiators and peroxide initiators.

The binder polymer may be used alone or in combination of two or more.

The content of the binder polymer in the cured film is preferably 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less based on the total mass of the cured film. And more preferably from 4% by mass to 20% by mass.

When the binder polymer is contained in the composition for forming a cured film, it is preferable that the content of the binder polymer is the above content with respect to the total solid content of the composition for forming a cured film.

[(J) Surfactant]

Various surfactants may be added to the composition for forming a cured film from the viewpoint of further improving the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

Particularly, since the composition for forming a cured film contains a fluorine-based surfactant, the liquid property (particularly, fluidity) when it is prepared as a coating liquid is further improved, and uniformity of coating thickness and liquid saving can be further improved.

That is, when a film is formed using a composition for forming a cured film containing a fluorine-containing surfactant, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, do. Therefore, even when a thin film of about several micrometers is formed at a small liquid amount, it is effective in that it is possible to more preferably form a film having a uniform thickness with a small thickness unevenness.

The fluorine content in the fluorine surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoints of uniformity of the coating film thickness and liquid-saving property, and also has good solubility in the composition for forming a cured film.

Examples of the fluorochemical surfactant include Megapac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482 (Manufactured by Sumitomo 3M Ltd.), Surflon S-382, and SC-101 (manufactured by Sumitomo 3M Ltd.), F554, F780, and F781 [manufactured by DIC Corporation], Fluorad FC430, , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Glass Co., PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.

Specific examples of nonionic surfactants include nonionic surfactants described in Japanese Patent Application Laid-Open Publication No. 2012-208494, paragraph 0553 (corresponding to United States Patent Application Publication No. 2012/0235099 [0679]), These contents are incorporated herein by reference.

Specific examples of the cationic surfactants include cationic surfactants described in paragraph 0554 of Japanese Patent Application Laid-Open No. 20-204949 (corresponding to [0680] of U.S. Patent Application Publication No. 2012/0235099) Are incorporated herein by reference.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusoh Co., Ltd.) and the like.

Examples of silicon based surfactants include "TORAY Silicone DC3PA", "TORAY Silicone SH7PA", "TORAY Silicone DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "TORAY Silicone SH29PA" TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "and" TSF-4440 "manufactured by Momentive Performance Materials Corporation," TORAY Silicone SH30PA " KF341 "," KF6001 ", and" KF6002 "manufactured by Shin-Etsu Silicones Co., Ltd.," BYK307 "," BYK323 ", and" BYK330 "

Only one surfactant may be used, or two or more surfactants may be combined.

The composition for forming a cured film may or may not contain a surfactant. When it is contained, the amount of the surfactant added is preferably from 0.001 mass% to 2.0 mass% with respect to the total mass of the composition for forming a cured film, 0.005 mass% to 1.0 mass%.

[(K) Other additives]

For the composition for forming a cured film, known additives such as a plasticizer and a sensitizer may be added in order to improve physical properties of the cured film.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like. , It may be added in an amount of 10 mass% or less based on the total mass of the polymerizable compound and the binder polymer.

≪ Coloring layer forming step &

The coloring layer forming step is a step of forming a colored layer on the cured film.

More specifically, the colored layer 21 is formed on the cured film 20 as shown in Fig. 2 (c). The coloring layer 21 can constitute at least one color filter pixel in the present invention, and is preferably formed of a curing composition containing a coloring agent. More specifically, in the coloring layer forming step, a step of coating a curable composition containing a colorant directly or through another layer on the cured film and then drying to form a coating film (coating film forming step) and a heating treatment (A post-baking step).

Hereinafter, the form using the curable composition will be described in detail.

(Curable composition)

As the curable composition, there may be mentioned a colored photocurable composition or a non-photosensitive colored thermosetting composition, and in view of spectral characteristics, the colored layer is preferably formed using a non-photosensitive colored thermosetting composition.

The non-photosensitive colored thermosetting composition preferably contains a colorant and a thermosetting compound, and the colorant concentration in the total solid content is preferably 50% by mass or more and less than 100% by mass.

The photo-curable composition includes at least a colorant and a photo-curing component. Among these, the photo-curable component is a photo-curable composition usually used in photolithography, and includes a binder resin (alkali-soluble resin, etc.) (Photopolymerizable monomer or the like), a photopolymerization initiator, and the like.

For the colored photo-curing composition, for example, the items described in paragraphs 0017 to 0064 of Japanese Patent Application Laid-Open No. 2005-326453 can be suitably applied.

(coloring agent)

The coloring agent contained in the colored photocurable composition used for the coloring layer or the coloring agent contained in the non-photosensitive colored thermosetting composition is not particularly limited, and various conventionally known dyes and pigments may be used singly or in combination.

As the pigment, various conventionally known inorganic pigments or organic pigments can be mentioned. Considering that it is preferable that the inorganic pigment and the organic pigment have a high transmittance, it is preferable to use a pigment having an average particle diameter as small as possible, and considering the handling property, the average particle diameter of the pigment is preferably from 0.01 mu m to 0.1 mu m, More preferably 0.01 占 퐉 to 0.05 占 퐉.

Preferable examples of the pigment include the following pigments. However, the present invention is not limited to these.

C.I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;

C.I. Pigment Orange 36, 71;

C.I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;

C.I. Pigment Violet 19, 23, 32;

C.I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Black 1

Further, when the coloring agent is a dye, it is uniformly dissolved in the composition, and a non-photosensitive thermosetting colored resin composition can be obtained.

The dye that can be used as the colorant is not particularly limited, and known dyes for color filters can be used.

Examples of the chemical structure include a pyrazole group, anilino group, triphenylmethane group, anthraquinone group, anthrapyridone group, benzilidene group, oxolin group, pyrazolotriazole group, pyridazo group, cyanine group, phenothiazine group, Dyes such as pyrazolomethane, xanthane, phthalocyanine, benzopyran, indigo and the like can be used.

The content of the colorant in the total solid content of the colored thermosetting composition in the present invention is not particularly limited, but is preferably 50% by mass or more and less than 100% by mass and more preferably 55% by mass or more and 90% by mass or less. When it is 50 mass% or more, suitable chromaticity can be obtained as a color filter. On the other hand, when it is less than 100% by mass, the photocuring can be sufficiently promoted, and the decrease in strength as a film can be suppressed.

(Thermosetting compound)

The thermosetting compound contained in the non-photosensitive colored thermosetting composition is not particularly limited as long as it can perform film curing by heating. For example, a compound having a thermosetting functional group can be used. The thermosetting compound preferably has at least one group selected from, for example, an epoxy group, a methylol group, an alkoxymethyl group and an acyloxymethyl group.

(B) a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group, (c) an epoxy compound, ) Phenol compounds substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group, a naphthol compound or a hydroxyanthracene compound. Among them, a polyfunctional epoxy compound is particularly preferable as the thermosetting compound.

The total content of the thermosetting compound in the colored thermosetting composition is preferably from 0.1 to 50 mass%, more preferably from 0.2 to 40 mass%, and most preferably from 1 to 35 mass%, based on the total solid content (mass) % By mass is particularly preferable.

The colored thermosetting composition may contain various additives such as a binder, a curing agent, a curing catalyst, a solvent, a filler, a polymer compound other than the above, a surfactant, a contact promoter, an antioxidant, An ultraviolet absorber, an anti-aggregation agent, a dispersant, and the like.

The binder is often added at the time of preparation of the pigment dispersion, and it is preferable that the binder is soluble in an organic solvent without alkali solubility, and is preferably soluble in an organic solvent in the linear organic polymer. Examples of such linear organic polymer polymers include polymers having carboxylic acids in the side chains, such as those disclosed in Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, and acrylic acid copolymers as disclosed in the respective publications of JP-A-54-25957, JP-A 59-53836 and JP-A 59-71048, Maleic acid copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

Of these various binders, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable from the viewpoint of heat resistance, and from the viewpoint of development control, an acrylic resin, an acrylamide Resin and acrylic / acrylamide copolymer resin are preferable.

Particularly, as the acrylic resin, a copolymer comprising a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide and the like, for example, benzyl methacrylate / , Benzyl methacrylate / benzylmethacrylamide, KS Resist-106 [manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.] and Cyclomer P series [manufactured by Dai-ichi Kagakuko Kogyo Co., Ltd.] .

By dispersing the colorant in these binders at a high concentration, adhesion with the lower layer can be imparted, and these contribute to the shape of the coated surface during spin coating and slit coating.

When an epoxy resin is used as the thermosetting compound in the present invention, it is preferable to add a curing agent. The curing agent of the epoxy resin is very different and varies greatly depending on the nature of the curing agent used, the pot life, the viscosity, the curing temperature, the curing time, and the heat of the mixture of the resin and the curing agent. Therefore, It is necessary to select a suitable hardening agent depending on the working conditions. The hardener is explained in detail in Chapter 5 of "Epoxy resin (Shokodo)" Hiroshi Kakii. Examples of the curing agent are as follows.

Examples of catalytically acting compounds that react stoichiometrically with tertiary amines, boron trifluoride-amine complexes, and functional groups of epoxy resins include polyamines, acid anhydrides and the like; Examples of the compounds which are cured at room temperature include diethylenetriamine, polyamide resins, medium temperature curing diethylaminopropylamine, tris (dimethylaminomethyl) phenol; Examples of high temperature curing include phthalic anhydride, metaphenylene diamine, and the like. As to the chemical structures, in the case of amines, aliphatic polyamines include diethylenetriamine; As the aromatic polyamines, there may be mentioned metaphenylenediamine; Examples of tertiary amines include tris (dimethylaminomethyl) phenol; Examples of the acid anhydride include phthalic anhydride, polyamide resin, polysulfide resin, boron trifluoride-monoethylamine complex; As early condensation products of synthetic resins, phenol resins and other dicyandiamides can be mentioned.

These curing agents react with an epoxy group by heating, and when they are polymerized, the cross-linking density is increased and cured. For thinning, it is preferable that the binder and the curing agent are as small as possible, and in particular, the curing agent is preferably 35 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less with respect to the thermosetting compound.

In order to achieve a high colorant concentration in the present invention, curing by reaction between epoxy groups is effective, besides curing by reaction with a curing agent. Therefore, a curing catalyst may be used without using a curing agent. The addition amount of the curing catalyst is about 1/10 to 1/1000, preferably about 1/20 to 1/500, more preferably about 1/30 to 1/500, in terms of mass, based on the epoxy resin having an epoxy equivalent of about 150 to 200 / 250. ≪ / RTI >

The colored thermosetting composition can be used as a solution dissolved in various solvents. The solvent is not particularly limited so long as it satisfies solubility of each component and applicability of the colored thermosetting composition.

Further, a dispersant may be added to improve the dispersibility of the pigment. As the dispersing agent, known ones can be suitably selected and used, and examples thereof include cationic surfactants, fluorine-based surfactants, and polymer dispersing agents.

As these dispersants, many kinds of compounds are used. For example, phthalocyanine derivatives [commercial product EFKA-745 (manufactured by FPC)], Solspers 5000 (manufactured by Nippon Lubricos Co., Ltd.); The organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), the (meth) acrylic acid-based (co) 75, No. 90, No. 95 cationic surfactant such as [Kyoeisha Kagaku Co., Ltd.], W001 [Yusho Co., Ltd.]; Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol distearate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, and W017 (manufactured by Yuso Co., Ltd.); (EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 15, and Disperse Aid 9100 (manufactured by Sanno Foucault Corporation); Various Sol Spurs dispersants (Nippon Rubbers) such as Sol Spurs 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000 and 28000; (Manufactured by Asahi Denka Kogyo K.K.), and the like were added to the reaction mixture, and the reaction was carried out in the same manner as in Example 1, And Isonet S-20 (manufactured by Sanyo Chemical Industries, Ltd.).

The dispersant may be used alone or in combination of two or more.

The amount of the dispersant to be added in the colored thermosetting composition is usually about 0.1 to 50 parts by mass based on 100 parts by mass of the pigment.

Various additives may be further added to the colored thermosetting composition of the present invention as required. Specific examples of various additives include the various additives described in Japanese Patent Laid-Open Publication No. 2005-326453.

The colored layer in the present invention can be formed, for example, by applying the colored thermosetting composition on a cured film and drying it. Specifically, for example, the colored thermosetting composition can be formed on the cured film by applying by spin coating, slit coating, flexible coating, roll coating or the like.

The specific thickness of the colored layer is preferably 0.005 mu m to 0.9 mu m, more preferably 0.05 mu m to 0.8 mu m, and more preferably 0.1 mu m to 0.7 mu m.

The coloring layer forming step preferably further includes a heating step (which may be a post-baking step). Specifically, the colored layer can be formed by applying a colored thermosetting composition to a support to form a coated film, and then thermally curing the coated film by a heating process.

The heating step may be performed simultaneously with the drying after the application, or the step of thermal curing may be formed after the application and drying. The heating process is preferably carried out under the conditions of 130 占 폚 to 300 占 폚, more preferably 150 占 폚 to 280 占 폚, particularly preferably 170 占 폚 to 260 占 폚, using a known heating means such as an oven and a hot plate Can be performed in the range of 10 seconds to 3 hours, more preferably 30 seconds to 2 hours, particularly preferably 60 seconds to 60 minutes. However, considering the production, the time required for curing is preferably shorter.

≪ Photoresist layer forming step &

The photoresist layer forming step is a step of forming a photoresist layer on the colored layer.

More specifically, as shown in Fig. 2 (d), after the colored layer 21 is formed by the colored layer forming step, a photoresist layer 22 (photosensitive resin layer) is further formed on the colored layer 21 .

The method of forming the photoresist layer is not particularly limited, but it is preferable that a positive or negative photosensitive resin composition is coated on the colored layer and dried to form a photoresist layer. Further, in forming the photoresist layer, it is preferable to further perform the prebaking treatment.

Hereinafter, the preferred method for forming the photoresist layer will be described in detail.

As the positive or negative photosensitive resin composition, for example, those described in paragraphs 0112 to 0117 of Japanese Patent Application Laid-Open No. 2007-11324 can be preferably applied to the present invention.

As the application method of the photosensitive resin composition, the above-mentioned application method can be preferably used. The specific thickness of the photosensitive resin layer is preferably from 0.01 mu m to 3 mu m, more preferably from 0.1 mu m to 2.5 mu m, and further preferably from 0.15 mu m to 2 mu m.

As the positive type photosensitive resin composition, a positive resist composition preferable for a positive type photoresist sensitive to radiation such as deep ultraviolet ray, electron beam, ion beam and X-ray including ultraviolet ray (g line, i line) . Among the radiation, for exposing the photosensitive resin layer, g line and i line are preferable for the purpose of the present invention, and among them, i line exposure is preferable.

In the method of manufacturing a color filter of the present invention, the colored layer can be formed in a desired shape (for example, a rectangle) by etching using a resist pattern formed from a photoresist layer as a mask by an etching process to be described later .

<Pattern Forming Step>

The pattern forming step is a step of forming the resist pattern on the sacrificial layer by removing the photoresist layer formed as described above in a pattern shape.

More specifically, as shown in Fig. 2 (e), the photoresist layer 22 is patterned into a desired pattern, for example, a second colored layer made of a color different from that of the colored layer 21, And then developed with a developing solution to form a resist pattern 24 (photoresist pattern) which functions as an etching mask.

The surface of the colored layer 21 (the side opposite to the side where the cured film 20 containing the metal oxide particles and the colored layer 21 face) which becomes the first colored layer in a pattern shape Exposed. On the other hand, in the colored layer 21, the region other than the region where the second colored layer is formed on the cured film 20 containing the metal oxide particles is covered with the resist pattern 24.

After the pattern forming process, etching and other steps are performed to form the coloring layer 21 in a pattern, and the second coloring layer is formed on the cured film 20 containing the metal oxide particles through the respective steps , And another color pixel is formed in addition to the pixel made up of the coloring layer 21 that is etched and formed in a pattern shape.

Since the resist pattern 24 to be a mask material can be made finer and has a rectangular shape, each pixel of the color filter can be formed into a fine and rectangular shape.

Exposure of the photoresist layer 22 is performed by exposing the positive or negative photosensitive resin composition to a g-line, h-line or i-line, preferably i-line, through a predetermined (image-shaped) mask pattern .

Any developer may be used as long as it does not affect the coloring layer 21 containing the colorant and dissolves the exposed portions of the positive resist and the uncured portions of the negative resist. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

<Etching Process>

The etching step is a step of etching the colored layer by a dry etching method using an etching gas using the resist pattern as an etching mask.

More specifically, as shown in Fig. 2 (f), a dry etching method using an etching gas (for example, plasma etching, etc. As a representative example of the dry etching method, Japanese Patent Application Laid-open No. 59-126506, 59-46628, 58-9108, 58-2809, 57-148706, and 61-41102 disclose a method of forming a resist pattern 24 The colored layer 21 not covered is removed to form a colored layer having a pattern shape. In other words, the cured film exposed portion 26 is formed in the shape of the resist pattern 24 formed by the pattern forming process.

The kind of the etching gas to be used in the etching process is not particularly limited, but preferably includes at least one of the fluorine-based gases from the viewpoint that the colored layer portion (etched portion) removed by the dry etching method can be processed into a rectangle Do.

As the fluorine-based gas, a known fluorine-based gas can be used, but it is preferable that the gas is a fluorine-based compound gas represented by the following formula (I).

CnHmFl Formula (I)

In the formulas, n represents 1 to 6, m represents 0 to 13, and 1 represents 1 to 14.

As the fluorinated gas represented by the formula (I), for example, _{CF 4, C 2 F 6,} C 3 F 8, C 2 F 4, C 4 F 8, C 4 F 6, C 5 F 8, and CHF ₃ And at least one selected from the group consisting of The fluorine-based gas may be used in combination of two or more gases out of the above-mentioned groups.

The fluorine-based gas is preferably at least one selected from the group consisting of CF ₄ , C ₂ F ₆ , C ₄ F ₈ and CHF ₃ from the viewpoint of maintaining the rectangularity of the etching portion, and CF ₄ and / or C ₂ F ₆ is more preferable, and CF ₄ is particularly preferable.

More preferably, the etching gas is mixed with oxygen gas. The content ratio of the fluorine-based gas and the oxygen gas (fluorine-based gas / oxygen gas) in the mixed gas is preferably 2/1 to 8/1 in terms of the flow rate ratio. Within this range, the etching products can be prevented from adhering to the sidewalls of the resist pattern 24 during the etching process, and the resist pattern 24 can be easily peeled off in the resist pattern removing step to be described later. Particularly, it is preferable that the content ratio of the fluorine-based gas and the oxygen gas is 2/1 to 6/1 from the viewpoint of preventing the etching product from reattaching to the side wall of the resist pattern 24 while maintaining the rectangularity of the etched portion , And particularly preferably 3/1 to 5/1.

In addition to the fluorine-based gas and the oxygen gas, helium (He), neon (Ne), argon (Ar) and the like are used as the mixed gas in order to maintain the stability of the partial pressure control of the etching plasma and the perpendicularity of the etched shape. (For example, CCl ₄ , CClF ₃ , AlF ₃ , AlCl _3, etc.) containing a rare gas such as krypton (Kr) or xenon (Xe), halogen atoms such as chlorine atom, fluorine atom and bromine atom, N ₂ , CO, and CO ₂ , and preferably contains at least one species selected from the group consisting of Ar, He, Kr, N ₂ , and Xe And more preferably at least one selected from the group consisting of He, Ar, and Xe.

However, when it is possible to maintain the stability of the partial pressure control of the etched plasma and the perpendicularity of the etched shape, the mixed gas may be composed of only the fluorine-based gas and the oxygen gas.

In the mixed gas, the content of other gases which may be contained in addition to the fluorine-based gas and the oxygen gas is preferably 25 or less, more preferably 10 or more and 20 or less, and more preferably 14 or more Or less.

In order to suppress damage to the cured film 20 as much as possible, it is preferable to terminate the dry etching treatment after the elapse of the following predetermined treatment time from the start of the dry etching treatment.

The dry etching process time is calculated by calculating the etching rate (nm / min.) In the etching process and calculating the process time required for etching from the calculated etching rate. The etching rate can be calculated, for example, by taking the relationship between the etching time and the residual film.

The etching treatment time is preferably 10 minutes or less, more preferably 7 minutes or less.

The internal pressure of the chamber in the etching process is preferably 2.0 to 6.0 Pa, more preferably 4.0 to 5.0 Pa, and the rectangularity of the pattern is improved by the internal pressure of the chamber being in the above range, The adhesion of the side wall protective film to the photoresist can be suppressed. The internal pressure of the chamber can be adjusted, for example, by appropriately controlling the flow rate of the etching gas and the pressure reduction degree of the chamber.

In the etching step, the temperature of the substrate 1a is preferably 30 DEG C or more and 100 DEG C or less. This makes it possible to further suppress the adherence of the etching products to the sidewalls of the resist pattern 24 during the etching process and further to facilitate the stripping of the resist pattern 24 in the resist pattern removing step to be described later . More preferably 30 占 폚 to 80 占 폚, and particularly preferably 40 占 폚 to 60 占 폚, from the viewpoints of maintaining the rectangularity of the etched portion and restraining the etching product from adhering to the side wall of the resist pattern 24.

In the etching step, for example, the temperature of the wafer stage may be controlled to 30 占 폚 or more and 100 占 폚 or less, whereby the temperature of the substrate 1a can be 30 占 폚 or more and 100 占 폚 or less.

The conditions of the dry etching in the etching process depend on the material and the layer thickness of the colored layer 21, and preferable conditions other than the above conditions will be described below.

The gas flow rate of the mixed gas is preferably 1500 mL / min (0 DEG C, 1013 hPa) or less, more preferably 500 to 1000 mL / min (0 DEG C, 1013 hPa).

The RF power can be selected from 400 kHz, 60 MHz, 13.56 MHz, 2.45 GHz, and the like. The RF power can be 50 to 2000 W, preferably 100 to 1000 W.

The relationship between the source power RF and the bias is preferably 600 to 1000 W / 300 to 500 W / 150 to 250 W, more preferably 700 to 900 W / 350 to 500 W, 450 / 200W.

As described above, as the etching step, a step of etching a part or the whole of the colored layer by using an etching gas containing a fluorine-based gas is preferable, but the etching step may have two or more etching steps with different etching conditions . For example, it may have an etching process using another etching gas. More specifically, etching of the colored layer (first etching step) is performed using an etching gas containing fluorine gas, etching is stopped before the cured film containing the metal oxide particles is completely exposed, and another gas For example, a mixed gas containing a nitrogen gas and an oxygen gas) may be performed.

Hereinafter, the case where the gas used in the second etching is a mixed gas containing a nitrogen gas and an oxygen gas will be described in detail.

In the etching process for removing the conventional colored layer 21 in a pattern shape, the substrate 1a serving as a support formed by the planarization layer 10 or the like positioned under the cured film 20 using only the first mixed gas If the etching treatment is performed until exposed, there is a tendency that the support is damaged. In addition, the occurrence of the support damage was remarkable especially when the over-etching treatment was carried out. On the other hand, by performing the second etching process using a second mixed gas containing nitrogen gas and oxygen gas, which is different from the first mixed gas used in the first etching process, the etching process Lt; / RTI &gt;

Further, by performing the second etching process using the second mixed gas containing nitrogen gas and oxygen gas, it is possible to remove the altered layer due to the plasma formed on the surface layer of the resist pattern 24 in the first etching process have. As a result, the resist pattern 24 can be more easily peeled off by the peeling liquid or the solvent in the subsequent step of removing the resist pattern.

The cured film 20 formed on the planarization layer 10 of the substrate 1a is only slightly etched because the etching rate is low with respect to the second mixed gas and the damage to the support under the cured film 20 is suppressed do.

The second mixed gas used in the second etching step contains a nitrogen gas and an oxygen gas, but may contain a fluorine gas within a range not to impair the effect of the present invention. It is preferable that the content ratio of the fluorine-based gas (fluorine-based gas / oxygen gas) is 5% or less in terms of the flow rate, and it is particularly preferable that the fluorine-based gas is not contained. When the content of the fluorine-based gas is within the above range, damage to the support can be more effectively suppressed.

The content ratio of the nitrogen gas and the oxygen gas in the second mixed gas (nitrogen gas / oxygen gas) is preferably 10/1 to 3/1 as the flow ratio. Within this range, it is possible to more effectively suppress the adherence of the etching products to the sidewalls of the resist pattern 24 during the etching process, and to more easily remove the resist pattern 24 in the resist pattern removing process can do. The content ratio is preferably in the range of 20/1 to 3/1, more preferably in the range of 15/1 to 4/1, in terms of maintaining the rectangularity of the etched portion and preventing the etching product from reattaching to the side wall of the resist pattern 24 , More preferably from 10/1 to 5/1.

The second mixed gas may be a mixture of helium (He), neon (Ne), argon (Ar), and argon (Ar) as other gases in addition to the nitrogen gas and the oxygen gas from the standpoint of maintaining the stability of the partial pressure control of the etched plasma, Krypton (Kr), and xenon (Xe), and further contains at least one kind of gas selected from the group consisting of He, Ar, and Xe Is more preferable.

However, when it is possible to maintain the stability of the partial pressure control of the etched plasma and the perpendicularity of the etched shape, the second mixed gas may be composed of only nitrogen gas and oxygen gas.

In the second mixed gas, the content of the other gas which may be contained in addition to the nitrogen gas and the oxygen gas is preferably 25 or less, more preferably 5 or more and 20 or less, more preferably 8 or more And particularly preferably 12 or less.

In the second etching process, for example, after the start of the dry etching process for removing the colored layer 21 remaining in the first etching process, the dry etching process is terminated after the elapse of the process time calculated in the same manner as the first etching process . Further, the dry etching process time for removing the remaining colored layer 21 by end point detection may be managed. In the second etching step, it is preferable to manage dry etching processing time for removing the colored layer 21 by end point detection.

The etching treatment time is preferably 10 minutes or less, more preferably 7 minutes or less.

The second etching step preferably has an internal pressure of the chamber of 1.0 to 5.0 Pa, more preferably 2.0 to 4.0 Pa.

It is possible to more efficiently form the pattern in which the occurrence of the support damage is suppressed without impairing the rectangularity of the pattern in the condition of satisfying the mixture ratio of the mixed gas and the internal pressure of the chamber.

As a relation between the source power RF and the bias in the second etching step, the RF power / antenna bias / substrate bias is preferably 400 to 800 W / 50 to 200 W / 100 to 300 W, more preferably 500 to 700 W / 100 to 150W / 200 to 300W.

Regarding the support temperature and other conditions during the etching treatment in the second etching treatment step, the matters described in the first etching treatment step can be preferably applied.

The second etching process preferably further includes an over-etching treatment process. After the colored layer 21 is removed by dry etching using the second mixed gas and the cured film exposed portion 26 is formed and then overetching treatment is performed using the second mixed gas to leave the etching residue remaining as a rectangular It is possible to efficiently remove the support member while maintaining the property, and further, the occurrence of the support member damage can be suppressed more effectively.

The overetching process is preferably performed by setting the overetching time. The overetching time can be arbitrarily set, but the etching treatment time t1 in the first etching step and the etching in the second etching step in terms of the etching resistance of the resist pattern 24 and the maintaining of the rectangularity of the etching pattern, Is preferably 30% or less, more preferably 5-25%, and particularly preferably 15-20% of the total treatment time (t1 + t2) of the treatment time t2.

&Lt; Resist pattern removal step &

The resist pattern removing step is a step of removing the resist pattern remaining after the etching step.

More specifically, as shown in Fig. 2 (g), the resist pattern 24 of the mask is removed by a dedicated exfoliation liquid or solvent after the completion of the etching process, and is removed by using washing water.

Further, in the present invention, since the cured layer containing metal oxide particles is applied, the resist pattern 24 can be sufficiently removed by suppressing the peeling of the color filter (patterned colored layer) sufficiently at the time of peeling off the resist pattern 24 .

In order to allow the resist pattern 24 to be removed with a removing liquid or a solvent, there is a paddle developing process in which, for example, a stripping liquid or a solvent is provided on at least the resist pattern 24 and stagnated for a predetermined time . The time for stucking the peeling liquid or the solvent is not particularly limited, but it is preferably several tens seconds to several minutes.

In order to remove the resist pattern 24 by using the cleansing water, cleansing water is sprayed onto the resist pattern 24 from a spraying or spraying nozzle, for example, to remove the resist pattern 24. As the washing water, pure water can be preferably used.

As the injection nozzle, there can be mentioned a spray nozzle including the entire support within its spray range, and a spray nozzle having a movable range of its movable range including the entire support. The resist pattern 24 can be removed more effectively by moving the substrate 1a from the central portion of the substrate 1a to the end portion of the substrate 1a more than once during the process of removing the resist pattern 24, .

The release liquid generally contains an organic solvent, but may further contain an inorganic solvent. Examples of the organic solvent include a hydrocarbon compound, a halogenated hydrocarbon compound, an alcohol compound, an ether or acetal compound, a ketone or an aldehyde compound, an ester compound, a polyhydric alcohol compound, a carboxylic acid or an acid anhydride compound , A phenol compound, a nitrogen compound, a sulfur compound, or a fluorine compound.

The release liquid preferably contains a nitrogen-containing compound, and more preferably contains a non-cyclic nitrogen compound and a cyclic nitrogen compound.

The non-cyclic nitrogen compound is preferably a non-cyclic nitrogen compound having a hydroxyl group. Specific examples of the solvent include mono isopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine , Preferably monoethanolamine, diethanolamine or triethanolamine, and more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH).

Examples of the cyclic nitrogen compound include isoquinoline, imidazole, N-ethylmorpholine, epsilon -caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone,? -Picoline,? -Picoline, Pyrrolidine, N-methylpyrrolidone, N-phenylmorpholine, 2, 3-piperidine, 2-piperidine, 4-lutidine, 2,6-lutidine and the like, preferably N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl- (NMP).

It is preferable that the exfoliating liquid contains a non-cyclic nitrogen compound and a cyclic nitrogen compound. Among them, as the non-cyclic nitrogen compound, at least one selected from monoethanolamine, diethanolamine and triethanolamine, and cyclic nitrogen compound More preferably at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably containing monoethanolamine and N-methyl-2-pyrrolidone .

The content of the noncyclic nitrogen compound is preferably 9 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the exfoliant, and the content of the cyclic nitrogen compound is preferably 65 parts by mass or more and 70 parts by mass or less.

It is also preferable that the exfoliation liquid is a mixture of a non-cyclic nitrogen compound and a cyclic nitrogen compound diluted with pure water.

After the resist pattern 24 is peeled off, a coloring layer different from the coloring layer already formed in the cured film exposed portion 26 is formed. Thus, a color filter of two colors is formed, and then a photoresist layer forming process And repeating the pattern forming step, the etching step and the resist pattern removing step likewise form a multicolor color filter.

As described above, according to the method of manufacturing a color filter according to the present invention, a cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm is formed on a support, and an etching gas It is possible to suppress the pattern separation of the colored layer at the time of peeling off the resist pattern by forming the colored layer by patterning the colored layer by performing the dry etching treatment.

The color filter manufactured by the manufacturing method of the present invention can be used for a solid-state image pickup device such as a liquid crystal display device or a CCD, and is particularly preferable for a high-resolution CCD device or CMOS exceeding one million pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

In the following processes, when a treatment using a commercially available treatment liquid was carried out, each treatment was carried out according to a manufacturer's designation unless otherwise specified.

In the following embodiments, &quot; part &quot; is intended to mean &quot; part by mass &quot;.

&Lt; Example 1 >

[Preparation of metal oxide fine particle dispersion (dispersion composition)] [

A dispersion liquid of a titanium dioxide dispersion was obtained as a dispersion composition by using Ultra Apex Mill manufactured by Kotobuki Kogyo K.K. as a circulation type dispersion apparatus (bead mill) as follows.

~ Composition ~

Titanium dioxide [TTO-51 (C), manufactured by Ishihara Sangyo Co., Ltd.)

Crystal form: rutile, TiO ₂ %: 79 to 85%, surface treatment with Al ₂ O ₃ and stearic acid, specific surface area 50 to 60 m 2 / g, primary particle diameter 10 to 30 nm, oil absorption amount 24 to 30 g / part

Dispersant [Polymer Dispersant (B)] B-1 (30 mass% solution): 133.3 parts

Propylene glycol monomethyl ether acetate (PGMEA): 284.9 parts

The dispersant (B-1) was synthesized in accordance with the synthesis method described in paragraphs [0266] to [0348] of Japanese Patent Application Laid-Open No. 2007-277514. Specifically, it is as follows.

Dipentaerythritol hexakis (3-mercaptopropionate) [(33); , And 91.38 parts of a compound (A-3) having a carbon-carbon double bond and having the following adsorption sites were dissolved in 446.6 parts of 1-methoxy-2-propanol, Lt; 0 &gt; C. 0.81 parts of dimethyl 2,2'-azobis (2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated for 2 hours. Further, 0.81 parts of V-601 was added and reacted at 90 占 폚 for 2 hours in a nitrogen stream. Followed by cooling to room temperature to obtain a 30 mass% solution of the mercaptan compound.

A mixed solution of 499.57 parts of a 30 mass% solution of the mercaptan compound and 100.13 parts of methyl methacrylate (M-1) was heated to 90 占 폚 under a nitrogen stream. To the solution, 0.681 part of dimethyl 2,2'-azobis (2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 72.73 parts of propylene glycol 1-monomethyl ether 2-acetate Was added dropwise over 2 hours, followed by heating at 90 占 폚 for 2 hours. Further, 0.230 part of V-601 was added, and the mixture was reacted at 90 DEG C for 2 hours under a nitrogen stream. Then, 0.230 part of V-601 was added and reacted at 90 DEG C for 2 hours under a nitrogen stream. Then, 160.9 parts of propylene glycol 1-monomethyl ether 2-acetate was added and the mixture was cooled to room temperature to obtain a dispersant (polymer dispersant (B)) B-1 (B-1: weight average molecular weight of 3300 in terms of polystyrene, 241 mg KOH / g).

The dispersing apparatus was operated under the following conditions.

· Bead diameter: φ0.05㎜

· Bead filling rate: 75 vol%

· Speed: 10m / sec

· Pump feed rate: 10㎏ / hour

· Cooling water: Tap water

· Bead mill annular passage inner volume: 0.15ℓ

· Mixed liquid amount to be dispersed: 0.44 kg

After the initiation of dispersion, the average particle diameter was measured at intervals of 30 minutes (time of one pass).

The average particle diameter decreased with the dispersion time (the number of passes), but the amount of change gradually decreased. The dispersion was terminated when the change of the primary particle size when the dispersion time was prolonged for 30 minutes became 5 nm or less. The primary particle size of the titanium dioxide particles in this dispersion was 40 nm.

The primary particle diameter of titanium dioxide is obtained by diluting a mixed solution or dispersion containing titanium dioxide with propylene glycol monomethyl ether acetate to 80 times and measuring the obtained diluted solution using dynamic light scattering method. This measurement is made on the basis of the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

[Preparation of composition for forming a cured film]

Using the metal oxide fine particle dispersion (dispersion composition) obtained above, the respective components were mixed so as to have the following composition to obtain a composition for forming a cured film.

Composition of composition for forming a cured film -

· Titanium Dioxide Dispersion (dispersion composition) prepared above ... 82.00 part

Polymerizable compound: JER-157S65 [manufactured by Mitsubishi Chemical Corporation] [polymerizable compound (C)] 3.70 parts

· Binder Polymer M-1 [Binder Polymer (I)] ... 0.44 part

[The following M-1; Weight average molecular weight (Mw) and copolymerization ratio (weight ratio) are as follows]

· Surfactant Megapack F-781 [Surfactant (J)] ... 0.03 part

· P-methoxyphenol [polymerization inhibitor (H)] ... 0.01 part

· Propylene glycol monomethyl ether acetate ... 13.82 part

As the cured film forming step, the composition for forming a cured film was coated on a silicon wafer with a spin coater (ACT-8 made by Tokyo Electron). Using a hot plate, the film was heated at 230 DEG C for 10 minutes to form a cured film having a film thickness of 0.4 mu m. In addition, the cured film contains titanium dioxide having a primary particle size of 40 nm.

As a coloring layer forming step, a pigment-containing thermosetting composition (colored thermosetting composition) (SG-5000L, manufactured by FUJIFILM ELECTRONIC MATERIALS) was coated on a cured film with a spin coater (ACT-8 made by Tokyo Electron Co., Ltd.) So as to be a coating film. Using a hot plate, the coating film was cured by heating at 220 DEG C for 5 minutes to form a colored layer 21. [ The thickness of the colored layer formed by the pigment-containing thermosetting composition (colored thermosetting composition) was 0.6 탆.

As a photoresist layer forming step, a positive type photoresist &quot; FHi622BC &quot; (made by FUJIFILM ELECTRONIC MATERIALS CO., LTD.) Was coated on the SG-5000L with a spin coater (ACT-8 made by Tokyo Electron) Minute to form a photoresist layer having a thickness of 0.8 mu m.

As a pattern forming process, a pattern exposure of 350 mJ / cm 2 was performed with an i-line stepper (FPA3000i5 +, manufactured by Canon Inc.) corresponding to the filter array of RED, and heat treatment was performed at 110 캜 for 1 minute. (Manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.) For 1 minute, post-baking treatment was performed at 110 DEG C for 2 minutes to remove the photoresist in the region where the RED filter array was to be formed, Thereby forming an island pattern (resist pattern) having a size of 1.4 mu m.

As the etching process, an RF power of 800 W, an antenna bias of 400 W, a wafer bias of 200 W, an inner pressure of the chamber of 4.0 Pa, a substrate temperature of 50 占 폚, and a mixed gas of a dry etching apparatus (U-621 manufactured by Hitachi High Technologies) The etching was performed for 111 seconds with the gas type and the flow rate of CF ₄ : 200 ml / min., O ₂ : 50 ml / min. And Ar: 800 ml / min.

The etching rate of SG-5000L under the etching condition was 326 nm / min, and the amount of wear of the colored layer was 603 nm. Therefore, all of the colored layers formed by SG-5000L in the etching process were removed.

As a resist pattern removing step, a 120 second peeling treatment was performed using a photoresist peeling solution "MS-230C" (manufactured by Fuji Film Electrolytic Matrix Co., Ltd.) to remove the resist pattern.

A color filter pattern was formed in accordance with the above procedure, and a monochromatic color filter was produced.

(Peeling evaluation)

With respect to the color filter fabricated above, the number of pattern peeling occurred was inspected by a defect inspection device ComPLUS3 manufactured by Applied Materials technology to detect defective portions, and the number of defects due to peeling was extracted from these defective portions. More specifically, the number of color filters in which peeling is occurring among the color filters (patterned coloring layers) having a pixel shape of 1.4 billion mu x 1.4 mu m prepared above using the above apparatus ) Were measured and evaluated according to the following evaluation criteria. In practice, A or B is required.

~ Evaluation Criteria ~

A: Number of peeling defects is 0 to 10

B: Number of peeling defects 11 to 20 (practically acceptable)

C: 21 or more delamination defects

&Lt; Examples 2 to 12, Comparative Example 1 >

As shown in the following Table 1, a color filter was produced in the same manner as in Example 1 except that the material and the composition ratio to be used were changed, and the peeling evaluation was performed.

The primary particle diameter of &quot; titanium dioxide &quot; shown in Table 1 was 40 nm, and the primary particle diameter of &quot; zirconium oxide &quot; was 20 nm.

In Comparative Example 1, the metal oxide particles were not contained in the cured film.

Further, "B-2" shown in Table 1 is the following compound.

Dispersant B-2 was synthesized according to the following procedure.

10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nihon Shokubai) and 100 g of the following polyester (i-1) were mixed and heated at 120 캜 for 3 hours to obtain an intermediate. 200 g of propylene glycol 1-monomethyl ether 2-acetate (hereinafter sometimes referred to as PGMEA) containing 2.3 g of succinic anhydride was slowly added and stirred for 2 hours to disperse the dispersant B-2 .

As a result of acid value titration of the intermediate, it was confirmed that the acid value was 6.4 mgKOH / g. The amine value of dispersant B-2 was titrated and acid titration was carried out. As a result, the acid value was 17.9 mgKOH / g and the amine value was 46.2 mgKOH / g. That is, (k) is calculated from the difference between the acid value of the dispersant B-2 and the acid value of the intermediate, (l1 + l2) from the difference between the amine value of the dispersant B-2 and the nitrogen number of the resin before the reaction, (m1 + m2) / n = 10/50/5/35.

The weight-average molecular weight by the GPC method was 15,000.

&Lt; Comparative Example 2 &

A color filter was produced in the same manner as in Example 1 except that ACCUGLASS (manufactured by LASAKO CO., LTD.) Was used instead of the cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm, And evaluated.

In addition, Comparative Example 2 corresponds to a form specifically disclosed in the above-described Patent Document 1.

In Table 1, &quot; amount of dispersed liquid &quot; is intended to be a part by mass of the dispersion of metal oxide fine particles (dispersion composition) added to the composition for forming a cured film.

The term &quot; amount &quot; in the &quot; polymerizable compound &quot; column is intended to mean a part by mass of the polymerizable compound added to the composition for forming a cured film.

The term &quot; amount &quot; in the &quot; binder polymer &quot; column is intended to mean a part by mass of the binder polymer added to the composition for forming a cured film.

The term &quot; amount &quot; in the &quot; surfactant &quot; column is intended to mean a part by mass of the surfactant to be added in the composition for forming a cured film.

The &quot; amount of PGMEA &quot; is intended to mean the part by mass of propylene glycol monomethyl ether acetate (PGMEA) added to the composition for forming a cured film.

The term &quot; metal oxide content &quot; is intended to mean the content (mass%: wt%) of the metal oxide particles in the cured film.

The &quot; peeling number &quot; field is intended to indicate the number of peeling defects.

In Table 1, DPHA means dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.).

In Table 1, OXE-01 is an initiator made by BASF.

As shown in Table 1, in the color filter obtained by the production method of the present invention, the pattern peeling after the resist pattern was peeled off was small and good.

Among them, in comparison between Examples 1 and 10, it was confirmed that when titanium oxide was used as the metal oxide particles, the pattern peeling became smaller.

In addition, by comparing Examples 1 to 8, it was found that when the content of the metal oxide particles in the cured film was 50 mass% or more and 77 mass% or less with respect to the total mass of the cured film (in the case of Examples 1 to 3) It was confirmed that the peeling was reduced.

Further, by comparison between Examples 1 and 9, it was confirmed that pattern separation was less when the polymer compound represented by the general formula (1) was used.

Further, by comparison between Examples 1 and 11, it was confirmed that when a compound having two or more epoxy groups or oxetanyl groups in a molecule was used as the polymerizable compound, the pattern peeling became smaller.

On the other hand, in Comparative Example 1 in which a cured film was not formed, and Comparative Example 2, which was specifically disclosed in Patent Document 1, the effect of pattern detachment was large and the effect was inferior.

1: Solid state imaging device 1a: substrate (support)
2: Semiconductor substrate 3: Solid-state image sensor
4: Transmission channel 5: Transmission electrode
6: BPSG film 7: In-layer lens
8: Color filter 9: Micro lens
10: planarization layer 20: cured film
21: colored layer 22: photoresist layer
24: Resist pattern 26: Cured film exposure unit

Claims (6)

A cured film forming step of forming a cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm on a support,
A colored layer forming step of forming a colored layer on the cured film,
A photoresist layer forming step of forming a photoresist layer on the colored layer,
A pattern forming step of forming a resist pattern on the colored layer by removing the photoresist layer in a pattern shape;
An etching step of etching the colored layer by a dry etching method using an etching gas using the resist pattern as an etching mask,
And a resist pattern removing step of removing the resist pattern remaining after the etching process. The method according to claim 1,
Wherein the content of the metal oxide particles in the cured film is from 50 mass% to 77 mass% with respect to the total mass of the cured film. 3. The method according to claim 1 or 2,
Wherein the metal oxide particles are at least one selected from the group consisting of titanium dioxide and zirconium oxide. 4. The method according to any one of claims 1 to 3,
Wherein the thickness of the cured film is 5 nm to 500 nm. 5. The method according to any one of claims 1 to 4,
Wherein the cured film contains a polymeric compound (A) represented by the following general formula (1) having a weight average molecular weight of 10,000 or less.

[In the general formula (1), R ¹ represents a linking group of (m + n). R ² represents a single bond or a divalent linking group. A ¹ represents a hydrocarbon group, an acid group, a urea group, a urethane group, a group having a radial oxygen atom, a group having a basic nitrogen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, An imido group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group. n A ¹ and R ² may be the same or different.
m is a positive number of not more than 8, n is 1 to 9, and m + n satisfies 3 to 10.
P ¹ represents a polymer chain. m P ¹ may be the same or different.] 6. The method according to any one of claims 1 to 5,
Wherein the cured film forming step is a step of forming a cured film by using the composition for forming a cured film containing at least the metal oxide particles and a compound having two or more epoxy groups or oxetanyl groups in the molecule Way.

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