WO2014112556A1 - カラーフィルタの製造方法 - Google Patents

カラーフィルタの製造方法 Download PDF

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WO2014112556A1
WO2014112556A1 PCT/JP2014/050676 JP2014050676W WO2014112556A1 WO 2014112556 A1 WO2014112556 A1 WO 2014112556A1 JP 2014050676 W JP2014050676 W JP 2014050676W WO 2014112556 A1 WO2014112556 A1 WO 2014112556A1
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group
cured film
compound
etching
groups
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PCT/JP2014/050676
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English (en)
French (fr)
Japanese (ja)
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高桑　英希
光司 吉林
嶋田　和人
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富士フイルム株式会社
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Priority to KR1020157018152A priority Critical patent/KR101678473B1/ko
Publication of WO2014112556A1 publication Critical patent/WO2014112556A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
    • A44B19/00—Slide fasteners
    • A44B19/24—Details
    • A44B19/36—Means for permanently uniting the stringers at the end; Means for stopping movement of slider at the end
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
    • A44B19/00—Slide fasteners
    • A44B19/42—Making by processes not fully provided for in one other class, e.g. B21D53/50, B21F45/18, B22D17/16, B29D5/00
    • A44B19/60—Applying end stops upon stringer tapes

Definitions

  • the present invention relates to a method for manufacturing a color filter, and more particularly to a method for manufacturing a color filter using a dry etching method.
  • a dry etching method is known as a method that is effective for forming a fine pattern with a thinner film than a manufacturing method of a color filter using a photolithography method.
  • the dry etching method has been conventionally employed as a method of forming a pattern on a dye-deposited thin film, and various methods have been proposed.
  • Patent Document 1 it is proposed to use a stopper layer made of metal in order to prevent even a part of the support in the region from which the colored layer has been removed from being cut and a step is generated. Yes.
  • an object of the present invention is to provide a method for manufacturing a color filter in which peeling of the color filter in the resist pattern removing step is suppressed.
  • the present inventors have found that the above problems can be solved by providing a cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm on a support. Completed the invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • 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-like manner; Using the resist pattern as an etching mask, an etching process for 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.
  • the cured film forming step is a step of forming a cured film using a composition for forming a cured film including at least a metal oxide particle and a compound having two or more epoxy groups or oxetanyl groups in the molecule.
  • (1)-(5) The manufacturing method of the color filter in any one of (5).
  • FIG. 3 is a cross-sectional view of a solid-state imaging device in which a color filter according to the present invention is used. Sectional drawing which showed the manufacturing method of the color filter of this invention.
  • FIG. 1 is a cross-sectional view of a solid-state imaging device.
  • 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 in which a p-type well layer is formed on an n-type substrate.
  • a transfer electrode 5 is formed above the transfer channel 4 via 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 imaging device 3.
  • a reflowed BPSG film 6 is formed on the transfer electrode 5 covered with the light shielding film by an atmospheric pressure CVD method.
  • the BPSG film 6 has a shape of a downward convex lens.
  • an inner lens 7 is formed by plasma CVD of SiN having a high refractive index and high transparency.
  • a planarizing layer 10 formed of an organic resin film, a BPSG film, a silicon oxide insulating film, or the like is formed above the in-layer lens 7, a planarizing layer 10 formed of an organic resin film, a BPSG film, a silicon oxide insulating film, or the like is formed.
  • a color filter 8 composed of the three primary colors red (R), green (G), and blue (B) is formed.
  • a microlens 9 is formed of a photoresist material.
  • the solid-state imaging device 1 has such a configuration, and light of each color is extracted when light incident from the microlens 9 passes through the color filter 8, and the light of each color collected by the in-layer lens 7 is solid-state imaging device. 3 is converted into an electric signal.
  • FIG. 2 is a cross-sectional view showing a color filter manufacturing method.
  • the method for producing 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, and a photoresist layer on the colored layer.
  • a resist pattern removing (peeling) step of removing the pattern will be described in detail.
  • 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 the support. More specifically, as shown in FIGS. 2A and 2B, the primary particle diameter is 1 nm to 100 nm on the planarizing layer 10 of the substrate 1a as the support formed up to the planarizing layer 10. A cured film 20 containing metal oxide particles is formed. In FIG. 2B, the cured film 20 is formed on the planarizing layer 10, but the planarized layer 10 itself may be the cured film.
  • the support and the material contained in the cured film will be described in detail, and the procedure of the subsequent process will be described in detail.
  • the substrate 1a serving as a support is not particularly limited as long as a color filter is used, and examples thereof include a photoelectric conversion element substrate used for a solid-state imaging element, such as a silicon substrate, an oxide film, and silicon nitride. . Further, other layers such as an intermediate layer may be provided between the support and the colored layer as long as the effects of the present invention are not impaired.
  • the primary particle diameter of the metal oxide particles contained in the cured film is 1 to 100 nm. Among these, from the viewpoint of transparency of the cured film and stability over time of the curable composition, 5 to 80 nm is preferable, and 10 to 70 nm is more preferable.
  • the primary particle diameter is less than 1 nm, the temporal stability of the curable composition is deteriorated, and the color filter is peeled off from the support when the resist pattern is removed.
  • the thickness exceeds 100 nm the transparency of the cured film decreases due to light scattering, and the color filter peels off from the support when the resist pattern is removed.
  • the primary particle diameter of the metal oxide particles is an average value.
  • the measurement method is to observe the cross section of the cured film with an electron microscope and measure the primary particle diameter (diameter) of at least 20 metal oxide particles. Find them by arithmetic averaging. In addition, when a metal oxide particle is not spherical, the major axis is handled as a diameter. As will be described later, when a composition for forming a cured film containing metal oxide particles is used, the primary particle diameter of the metal oxide particles in the composition is determined by a known device (for example, Nikkiso Microtrac UPA-EX150 (dynamic It can be measured and determined by the automatic light scattering method)).
  • the type of metal atom contained in the metal oxide particle is not particularly limited, and may include, for example, a metal atom selected from the group consisting of the fourth period, the fifth period, and the sixth period of the periodic table (IUPAC 1991). preferable. Further, it is preferable to contain one or more metals selected from the group consisting of Groups 2 to 14, and Group 2, Group 8, Group 9, Group 10, Group 11, Group 12 are preferably contained. More preferably, it contains a metal atom selected from the group consisting of Group, Group 13, and Group 14.
  • 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 chemical formula TiO 2 , preferably have a purity of 70% or more, more preferably have a purity of 80% or more, and further have a purity of 85% or more. preferable.
  • the low-order titanium oxide, titanium oxynitride, etc. represented by the general formula Ti n O 2n-1 (n represents a number of 2 to 4) is 30% by mass or less based on the total mass of the particles. Is preferable, it is more preferable that it is 20 mass% or less, and it is still more preferable that it is 15 mass% or less.
  • crystallization is preferable.
  • 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 with an Abbe refractometer (manufactured by Atago Co., Ltd.) (measurement temperature 25 ° C., wavelength 633 nm).
  • the specific surface area of the metal oxide particles is preferably 10 m 2 / g to 400 m 2 / g, more preferably 20 m 2 / g to 200 m 2 / g, and 30 m 2 / g to 150 m 2 / g. Most preferably.
  • limiting in particular in the shape of a metal oxide particle for example, it can be a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.
  • the metal oxide particles may have been surface-treated with an organic compound.
  • organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, stearic acid is preferred.
  • the surface treatment may be carried out by using a single surface treatment agent or a combination of two or more 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. Thereby, a weather resistance improves.
  • titanium dioxide particles As a metal oxide particle, what is marketed can be used preferably.
  • examples of commercially available titanium dioxide particles include TTO series (TTO-51 (A), TTO-51 (C), TTO-55 (C), etc.), TTO-S, V series (made by Ishihara Sangyo Co., Ltd.). And TTO-S-1, TTO-S-2, TTO-V-3, etc.) and MT series (MT-01, MT-05, etc.) manufactured by Teika Corporation.
  • zirconium dioxide particles examples include UEP (Daiichi Rare Element Chemical Co., Ltd.), PCS (Nippon Denko Co., Ltd.), JS-01, JS-03, JS-04 (Nippon Denko ( And UEP-100 (Daiichi Rare Element Chemical Industries, Ltd.).
  • Examples of commercially available silicon dioxide particles include OG502-31 manufactured by Clariant Co. The metal oxide particles may be used alone or in combination of two or more.
  • the content of the metal oxide particles in the cured film is not particularly limited, and is preferably 5 to 85% by mass with respect to the total mass of the cured film in terms of further suppressing peeling of the color filter. Is more preferable. In particular, 50 to 77% by mass is more preferable, and 60 to 75% by mass is particularly preferable in that peeling of the color filter is further suppressed.
  • the thickness of the cured film is not particularly limited, and is preferably from 5 to 500 nm, more preferably from 20 to 450 nm, and even more preferably from 50 to 400 nm, from the viewpoint of further suppressing 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, from the viewpoint 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 suitably achieved by containing a polymer dispersant (B) described later, but it can be achieved by any means. Good. For example, it can be achieved more reliably by adjusting the type and content of the polymerizable compound (C) described later and the binder polymer that can be further added, and adjusting the type and content of the metal oxide particles. .
  • the manufacturing method in particular of a cured film is not restrict
  • a method of applying the cured film-forming composition containing the metal oxide particles described above onto a support and performing a curing treatment (for example, a heat treatment and / or an exposure treatment) as necessary can be employed.
  • 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.
  • components other than metal oxide particles may be contained in the composition for forming a cured film as described later.
  • a polymer dispersant, a polymerizable compound, a solvent and the like which will be described later are included.
  • the cured film forming composition is preferably a transparent composition. More specifically, when a cured film having a thickness of 1.0 ⁇ m is formed from the composition, light transmission in the thickness direction of the cured film is achieved. It is preferable that the composition has a rate of 90% or more over the entire wavelength region of 400 to 700 nm. That is, the cured film (transparent film) is preferably a film having a light transmittance of 90% or more over the entire wavelength region of 400 to 700 nm when the film thickness is 1.0 ⁇ m. Such physical properties of light transmittance may be achieved by any means.
  • the light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100% over the entire wavelength region of 400 to 700 nm. It is preferable that the composition for forming a cured film does not substantially contain a colorant. More specifically, the content of the colorant is preferably 0% by mass with respect to the total solid content of the composition.
  • Components other than the metal oxide particles described above may be contained in the cured film or the composition for forming a cured film.
  • the cured film preferably contains the (B) polymer dispersant, (I) binder polymer, (J) surfactant, and the like.
  • the cured film may contain a polymer dispersant.
  • a method of making a cured film contain a polymer dispersing agent there exists the method of containing a polymeric dispersant in the composition for cured film formation mentioned above.
  • the type of the polymer dispersant is not particularly limited.
  • a general polymer dispersant (hereinafter also referred to as a dispersion resin as appropriate) [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight Saturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, etc. be able to.
  • These dispersion resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • the dispersion resin is adsorbed on the surface of the metal oxide particles and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the surface of the metal oxide particles can be cited as preferred structures. On the other hand, the dispersion resin has an effect of promoting adsorption of the dispersion resin by modifying the surface of the metal oxide particles.
  • dispersion resin examples include “DISPERBYK101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110, 180 (copolymer containing an acid group), 130 (polyamide), 161, 162, manufactured by BYK Chemie.
  • the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom, but the resin (B1) preferably contains a structure having a nitrogen atom of pKb14 or less, and a structure having a nitrogen atom of pKb10 or less.
  • the base strength pKb refers to pKb at a water temperature of 25 ° C., and is one of the indexes for quantitatively representing the strength of the base, and is synonymous with the basicity constant.
  • the resin (B1) is a resin having a repeating unit containing a nitrogen atom to which a group X having a functional group of pKa14 or less is bonded, and an oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain ( B2) is preferred.
  • Resin (B1) is composed of (i) a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit.
  • At least one selected repeating unit containing a nitrogen atom the repeating unit having a group X bonded to the nitrogen atom and having a functional group of pKa14 or less, and (ii) 40 atoms in the side chain
  • a resin having ⁇ 10,000 oligomer chains or polymer chains Y (hereinafter appropriately referred to as “specific resin”) is particularly preferable.
  • specific resin preferably includes a structure having a repeating unit represented by the general formula (I-1) and a repeating unit represented by the general formula (I-2).
  • R 101 and R 102 each independently represents a hydrogen atom, a halogen atom or an alkyl group.
  • a independently represents an integer of 1 to 5; * Represents a connecting part between repeating units.
  • X represents a group having a functional group of pKa14 or less.
  • Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.
  • the specific resin of the present invention comprises a repeating unit represented by the general formula (I-3) in addition to the repeating unit represented by the general formula (I-1) or (I-2). It is preferable to have as. By using such a repeating unit in combination, the dispersion performance is further improved when this resin is used as a dispersant for the metal oxide particles (A).
  • Y ′ represents an oligomer chain or polymer chain having an anion group and having 40 to 10,000 atoms.
  • the repeating unit represented by the general formula (I-3) is obtained by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain portion. It can be formed by reacting.
  • the anionic group CO 2 - or SO 3 - is preferable, and CO 2 - is most preferable.
  • the anionic group is preferably at the terminal position of the oligomer chain or polymer chain of Y ′.
  • R 101 and R 102 are particularly preferably hydrogen atoms.
  • a is preferably 2 from the viewpoint of obtaining raw materials.
  • the content of the repeating unit represented by formula (I-1) is preferably 1 to 80 mol% in all repeating units contained in the specific resin from the viewpoint of storage stability and developability, and 3 to 50 mol. % Is most preferred.
  • the content of the repeating unit represented by formula (I-2) is preferably 10 to 90 mol%, and most preferably 30 to 70 mol%, based on all repeating units of the specific resin.
  • the repeating unit (I-1) :( I-2) is in the range of 10: 1 to 1: 100 in molar ratio. Preferably, the range is from 1: 1 to 1:10.
  • the repeating unit represented by the general formula (I-3) used in combination optionally has a partial structure containing an oligomer chain or a polymer chain having 40 to 10,000 atoms ionically bonded to the nitrogen atom of the main chain.
  • the content is preferably 0.5 to 20 mol%, and most preferably 1 to 10 mol% in all repeating units of the specific resin.
  • the group X has a functional group having a pKa of 14 or less at a water temperature of 25 ° C.
  • pKa has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
  • the “functional group of pKa14 or less” is not particularly limited as long as the physical properties satisfy this condition, and examples thereof include those having a pKa satisfying the above range with known functional groups.
  • the following functional groups are preferred, and those having a pKa of 11 or less are most preferred.
  • carboxylic acid about pKa 3 to 5
  • sulfonic acid about pKa -3 to -2
  • phosphonic acid about pKa -1 to 4
  • -COCH 2 CO- about
  • —COCH 2 CN about pKa 8 to 11
  • CONHCO— phenolic hydroxyl group
  • RFCH 2 OH or — (RF) 2 CHOH RF represents a perfluoroalkyl group
  • RF represents a perfluoroalkyl group
  • pKa 9 to 11 Sulfonamide groups
  • pKa of about 9 to 11 and the like
  • carboxylic acid pKa of about 3 to 5
  • sulfonic acid pKa of about 3 to -2
  • —COCH 2 CO— pKa of about 8 to 10
  • the group X having a functional group of pKa14 or less is preferably directly bonded to the nitrogen atom in the repeating unit containing a nitrogen atom. However, if the nitrogen atom and X in the repeating unit containing a nitrogen atom are only covalent bonds, Instead, they may be linked in such a manner that a salt is formed by ionic bonding.
  • group X containing a functional group of pKa14 or less in the present invention those having a structure represented by general formula (V-1), general formula (V-2) or general formula (V-3) are particularly preferable. .
  • U represents a single bond or a divalent linking group.
  • d and e each independently represents 0 or 1;
  • 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 (n-C 10 H 21 )-, etc.), an alkylene group containing oxygen (more specifically, for example, -CH 2 OCH 2- , -CH 2 CH 2 OCH 2 CH 2- Etc.), arylene groups (for example, phenylene group, tolylene group, biphenylene group, naphthylene group, furylene group, pyrrolylene group, etc.), alkyleneoxy groups (for example, ethyleneoxy group, propyleneoxy group, phenyleneoxy group, etc.)
  • an alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 20 carbon atoms is particularly preferable, and an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon
  • Q represents an acyl group or an alkoxycarbonyl group.
  • the acyl group in Q is preferably an acyl group having 1 to 30 carbon atoms (for example, a formyl group, an acetyl group, an n-propanoyl group, a benzoyl group), and particularly preferably acetyl.
  • the alkoxycarbonyl group in Q is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, etc.).
  • Q is particularly preferably an acyl group, and an acetyl group is preferred 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 include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylate that can be connected to the main chain portion of the specific resin.
  • the binding site of the oligomer chain or polymer chain Y with the specific resin is preferably the terminal of the oligomer chain or polymer chain Y.
  • the oligomer chain or polymer chain Y is selected from poly (lower alkylene imine) -based repeating units, polyallylamine-based repeating units, polydiallylamine-based repeating units, metaxylenediamine-epichlorohydrin polycondensate-based repeating units, and polyvinylamine-based repeating units. It is preferably bonded to a nitrogen atom of a repeating unit containing at least one nitrogen atom.
  • At least one nitrogen atom selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit
  • the bonding mode between the main chain portion such as a repeating unit containing benzene and the oligomer chain or the polymer chain Y is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond.
  • the oligomer chain or polymer chain Y is preferably ionically bonded as a amide bond or carboxylate with a nitrogen atom of a repeating unit containing a nitrogen atom.
  • the number of atoms of the oligomer chain or polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoint of dispersibility, dispersion stability, and developability. Further, the number average molecular weight of the oligomer chain or polymer chain Y can be measured by a polystyrene conversion value by GPC method. The number average molecular weight of the oligomer chain or polymer chain Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoint of dispersibility, dispersion stability, and developability.
  • the oligomer chain or polymer chain Y preferably has a structure represented by the general formula (III-1).
  • Y ′ is preferably the general formula (III-2).
  • Z has the same meaning as Z in general formula (III-1).
  • Specific examples of the specific resin include resins exemplified in paragraphs [0075] to [0084] of JP2012-255148A.
  • polymer dispersant includes a polymer compound represented by the following general formula (1) having a weight average molecular weight of 10,000 or less.
  • R 1 represents a (m + n) -valent linking group.
  • R 2 represents a single bond or a divalent linking group.
  • a 1 is a hydrocarbon group, an acidic group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group (a group having a heterocyclic structure), an alkyloxycarbonyl group
  • a monovalent substituent having at least one group selected from the group consisting of alkylaminocarbonyl group, imide group, carboxylate group, sulfonamido group, alkoxysilyl group, epoxy group, isocyanate group and hydroxyl group (hereinafter simply Represents the substituent A 1 ).
  • n A 1 and R 2 may be the same or different.
  • m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10.
  • P 1 represents a polymer chain.
  • the m P 1 may be the same or different.
  • the polymer compound Since the substituent A 1 possessed by the polymer compound can interact with the metal oxide particles, the polymer compound has n (1 to 9) substituents A 1 to form the metal oxide particles. Can interact strongly.
  • m polymer chains P 1 of the polymer compound can function as a steric repulsion group, and by having the m number, the polymer compound can exhibit a favorable steric repulsion force and uniformly disperse the metal oxide particles. .
  • the high molecular compound does not cause adverse effects such as aggregation of particles due to cross-linking between particles, which can be generated by a conventional dispersant having a graft random structure.
  • the weight average molecular weight of the polymer compound represented by the general formula (1) is 10,000 or less, and preferably 8000 or less. If the weight average molecular weight is too large, the particle size of the metal oxide particle (A) -polymer dispersant (B) complex in the dispersion composition (cured film forming composition) becomes large, and the particles in the resulting film It is considered that it is difficult to increase the refractive index because they are not dense. On the other hand, by setting the weight average molecular weight within the above range, the particle size of the metal oxide particle (A) -polymer dispersant (B) complex can be kept small, and the particles in the resulting film become dense, It is considered that the refractive index can be increased.
  • the lower limit of the weight average molecular weight is not particularly limited, but it is preferably 1000 or more from the viewpoint of exhibiting the function as a dispersant and more reliably achieving the effects of the present invention. More preferably.
  • a 1 is a hydrocarbon group, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, an imide group, a carboxylate group , Sulfonamide group, alkoxysilyl group, epoxy group, isocyanate group, functional group having adsorption ability for metal oxide particles (A) such as hydroxyl group, adsorption ability for metal oxide particles (A) such as heterocyclic structure Represents a monovalent substituent having at least one structure which may have
  • the site having the ability to adsorb to the metal oxide particles (A) (the functional group and the structure) will be collectively referred to as “adsorption site” as appropriate.
  • a chain saturated hydrocarbon group (which may be linear or branched and has 1 to 10 carbon atoms) 2) or more, via a cyclic saturated hydrocarbon group (preferably having 3 to 10 carbon atoms), an aromatic group (preferably having 5 to 10 carbon atoms, such as a phenylene group) or the like.
  • a 1 An embodiment in which the adsorption site is bonded to form a monovalent substituent A 1 is exemplified, and an embodiment in which two or more adsorption sites are bonded through a chain saturated hydrocarbon group to form a monovalent substituent A 1 Is preferred.
  • the adsorption site itself constitutes a monovalent substituent the adsorption site itself may be a monovalent substituent represented by A 1 .
  • the adsorption site constituting A 1 will be described below.
  • hydrocarbon group includes an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Of these, a group having 1 to 20 carbon atoms is preferable, and a group having 1 to 10 carbon atoms is more preferable.
  • the “acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group.
  • Sulfuric acid ester groups, phosphoric acid groups, monophosphoric acid ester groups, phosphonic acid groups, and phosphinic acid groups are more preferred, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, and phosphinic acid groups are more preferred, and carboxylic acid groups. Is particularly preferred.
  • Examples of the “urea group” include —NR 15 CONR 16 R 17 (where R 15 , R 16 , and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number of 6 The above aryl group or an aralkyl group having 7 or more carbon atoms may be mentioned as a preferred example, and —NR 15 CONHR 17 (wherein R 15 and R 17 are each independently a hydrogen atom, 1 carbon atom) More preferably 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), and —NHCONHR 17 (wherein R 17 represents a hydrogen atom, An alkyl group of up to 10, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms is particularly preferred.
  • Examples of the “urethane group” include —NHCOOR 18 , —NR 19 COOR 20 , —OCONHR 21 , —OCONR 22 R 23 (where R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are And 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.) And the like, and —NHCOOR 18 , —OCONHR 21 ( Here, R 18 and R 21 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.
  • NHCOOR 18, -OCONHR 21 (wherein, R 18 and R 21 are each independently an alkyl group having from 1 to 10 carbon atoms, having 6 or more aryl group carbon atoms or the number of 7 or more a carbon It represents an alkyl group.) And the like are particularly preferred.
  • Examples of the “group having a coordinating oxygen atom” include acetylacetonato group, crown ether and the like.
  • Examples of the “group having a basic nitrogen atom” include an amino group (—NH 2 ), a substituted imino group (—NHR 8 , —NR 9 R 10 , wherein R 8 , R 9 , and R 10 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), a guanidyl group represented by the following formula (a1), Preferred examples include an amidinyl group represented by the following formula (a2).
  • R 11 and R 12 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.
  • R 13 and R 14 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.
  • a guanidyl group represented by the formula (a1) [in the formula (a1), R 11 and R 12 each independently represent from 1 to 10 carbon atoms. Represents an alkyl group, a phenyl group, or a benzyl group.
  • 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 having 1 to 5 carbon atoms.
  • R 8 , R 9 , and R 10 are each independently an alkyl having 1 to 5 carbon atoms.
  • Group, a phenyl group or a benzyl group a guanidyl group represented by the formula (a1) [in the formula (a1), R 11 and R 12 are each independently an alkyl having 1 to 5 carbon atoms. Represents a group, a phenyl group, or a benzyl group.
  • R 13 and R 14 each independently represent an alkyl group having from 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.
  • the alkyl group 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 group 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 group” include groups composed of ammonium salts of carboxylic acids.
  • a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group) or an acyl group (such as an acetyl group or a trifluoroacetyl group).
  • heterocyclic structure examples include, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine , Imide groups such as dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, Preferred examples include acridone and anthraquinone, and pyrroline, pyrrolidine, diox
  • the “heterocyclic structure” may further have a substituent.
  • substituents include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
  • C1-C6 acyloxy groups such as aryl groups having 6 to 16 carbon atoms, such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, and acetoxy groups, methoxy groups, and ethoxy groups
  • An alkoxy group having 1 to 20 carbon atoms such as a halogen atom such as chlorine or bromine, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a cyclohexyloxycarbonyl group, a cyano group, t- Examples thereof include carbonate ester groups such as butyl carbonate.
  • these substituents may be bonded to the heterocyclic ring through the following structural unit or a linking group constituted by combining the structural units.
  • alkoxysilyl group may be any of monoalkoxysilyl group, dialkoxysilyl group and trialkoxysilyl group, but is preferably trialkoxysilyl group, for example, trimethoxysilyl group, triethoxysilyl group Etc.
  • epoxy group include a substituted or unsubstituted oxirane group (ethylene oxide group).
  • As an epoxy group it can represent with the following general formula (a3), for example.
  • 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. * Represents a connecting hand.
  • the linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. And a linking group consisting of 0 to 20 sulfur atoms is preferred, and this 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 formed by combining the structural units.
  • examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group.
  • C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc.
  • C1-C6 acyloxy group methoxy group, ethoxy group, etc.
  • halogen atoms such as chlorine and bromine
  • alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group
  • carbonate groups such as cyano group and t-butyl carbonate, etc. It is done.
  • a 1 a monovalent substitution having at least one group selected from the group consisting of an acid group, a urea group, a urethane group, a sulfonamide group, an imide group and a group having a coordinating oxygen atom It is preferably a group.
  • a 1 is a monovalent having at least one functional group of pKa5 or higher.
  • a monovalent substituent having at least one functional group of pKa5 to 14 is more preferable.
  • pKa has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
  • the functional group of pKa5 or higher include a urea group, a urethane group, a sulfonamide group, an imide group, or a group having a coordinating oxygen atom.
  • a urea group about pKa 12 to 14
  • a urethane group about pKa 11 to 13
  • —COCH 2 CO— about pKa 8 to 10
  • Examples thereof include a sulfonamide group (about pKa 9 to 11).
  • a 1 is preferably represented as a monovalent substituent represented by the following general formula (4).
  • B 1 represents an adsorption site
  • R 24 represents a single bond or a (a + 1) -valent linking group.
  • a represents an integer of 1 to 10, and B 1 existing in the general formula (4) may be the same or different.
  • Examples of the adsorption site represented by B 1 include the same adsorption sites as those constituting A 1 in the general formula (1), and preferred examples are also the same. Among them, an acidic group, a urea group, a urethane group, a sulfonamide group, an imide group or a group having a coordinating oxygen atom is preferable, and a urea group, a functional group having a pKa of 5 to 14 is more preferable. It is more preferably a urethane group, a sulfonamide group, an imide group or a group having a coordinating oxygen atom.
  • R 24 represents a single bond or a (a + 1) -valent linking group, and a represents 1 to 10.
  • a is 1 to 7, more preferably a is 1 to 5, and particularly preferably a is 1 to 3.
  • (A + 1) valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Groups consisting of 0 to 20 sulfur atoms are included and may be unsubstituted or further substituted.
  • (a + 1) -valent linking group examples include the following structural units or groups formed by combining the structural units (which may form a ring structure).
  • R 24 may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and (A + 1) valent linking groups consisting of 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent linking groups consisting of up to oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 carbons (A + 1) valent linkage consisting of atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The group is particularly preferred.
  • examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
  • C1-C6 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., carbon atoms such as methoxy groups, ethoxy groups, etc.
  • R 2 represents a single bond or a divalent linking group.
  • the n R 2 s may be the same or different.
  • Divalent linking groups include 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 are included, which may be unsubstituted or further substituted.
  • divalent linking group examples include the following structural units or groups formed by combining the structural units.
  • R 2 may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and Divalent linking groups consisting of 0 to 10 sulfur atoms are preferred, single bonds, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are divalent linking groups consisting of oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, 0 Particularly preferred are divalent linking groups consisting of from 1 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.
  • examples of the substituent include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc. having 6 to 16 carbon atoms, methoxy group, ethoxy group, etc.
  • alkoxy groups such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, carbonic acid such as t-butyl carbonate, etc.
  • An ester group etc. are mentioned.
  • R 1 represents a (m + n) -valent linking group.
  • m + n satisfies 3 to 10.
  • Examples of the (m + n) -valent linking group represented by R 1 include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Groups consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.
  • (m + n) -valent linking group examples include the following structural units or groups formed by combining the structural units (which may form a ring structure).
  • (M + n) -valent linking groups include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and Groups consisting of 0 to 10 sulfur atoms are preferred, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 And more preferably a group consisting of 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, Particular preference is given to groups consisting of 1 to 80 hydrogen atoms and 0 to 5 sulfur atoms.
  • examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
  • C1-C6 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., carbon atoms such as methoxy groups, ethoxy groups, etc.
  • the most preferable (m + n) -valent linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.
  • n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.
  • P 1 represents a polymer chain and can be selected from known polymers according to the purpose.
  • the m P 1 may be the same or different.
  • the polymers a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, and modifications thereof are used to form a polymer chain.
  • copolymer for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer polymer, etc. (any of random copolymer, block copolymer, graft copolymer, etc. May also be included).
  • At least one selected from the group consisting of vinyl monomers selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.
  • the polymer chain P 1 preferably contains at least one repeating unit.
  • the number k of repeating units of at least one repeating unit in the polymer chain P 1 is preferably 3 or more from the viewpoint of achieving steric repulsion and improving dispersibility, achieving a high refractive index and a low viscosity. More preferably, it is 5 or more. From the viewpoint of suppressing the bulk of the polymer dispersant (B) and achieving a low viscosity, and further allowing the metal oxide particles (A) to be present in the cured film (transparent film) densely to achieve a high refractive index.
  • the number k of repeating units of at least one repeating unit is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less.
  • the polymer constituting the polymer chain is preferably soluble in an organic solvent.
  • the affinity with the organic solvent is low, the affinity with the dispersion medium is weakened, and it may be impossible to secure an adsorption layer sufficient for stabilizing the dispersion.
  • vinyl monomer For example, (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, (meth) acrylonitrile, etc.
  • (meth) acrylic acid esters are preferred, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, acid groups More preferred are vinyl monomers having a (meth) acrylic acid ester and crotonic acid ester.
  • vinyl monomers include the vinyl monomers described in paragraphs 0089 to 0094, 0096, and 0097 of JP-A-2007-277514 (corresponding US publication: US2010 / 233595 A1). Is incorporated herein.
  • vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used.
  • a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group.
  • an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.
  • 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, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
  • an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone Mono (meth) acrylates can also be used.
  • a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone Mono (meth) acrylates
  • anhydride containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.
  • (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.
  • Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.
  • vinyl monomer having an acidic group a vinyl monomer containing a phenolic hydroxyl group, a vinyl monomer containing a sulfonamide group, or the like can be used.
  • the polymer compound represented by the following general formula (2) is preferable.
  • a 2 represents a hydrocarbon group, an acidic group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, an alkyloxycarbonyl group, or an alkylaminocarbonyl group.
  • a 2 may be the same or different.
  • a 2 has the same meaning as above A 1 in the general formula (1), a preferable embodiment thereof is also the same.
  • R 4 and R 5 each independently represents a single bond or a divalent linking group.
  • the n R 4 s may be the same or different.
  • the m R 5 s may be the same or different.
  • the divalent linking group represented by R 4 or R 5 the same divalent linking groups as those represented by R 2 in the general formula (1) can be used, and a preferred embodiment is also used. It is the same.
  • R 3 represents an (m + n) -valent linking group.
  • m + n satisfies 3 to 10.
  • Examples of the (m + n) -valent linking group represented by R 3 include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100 atoms. Groups consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.
  • the (m + n) -valent linking group represented by R 3 those similar to those exemplified as the (m + n) -valent linking group represented by R 1 in the general formula (1) are used. The preferred embodiments are also the same.
  • n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.
  • P 2 of the general formula (2) represents a polymer chain, can be selected according to the purpose or the like from such known polymers.
  • the m P 2 may be the same or different.
  • the preferred embodiment of the polymer is the same as P 1 in the general formula (1).
  • R 3 Specific example (1), (2), (10), (11), (16), or (17) above
  • R 4 A single bond or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 carbon atoms”
  • a divalent linking group comprising an oxygen atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, Alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group, aryl groups having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide Groups, acyloxy groups having 1 to 6 carbon atoms such as
  • R 5 single bond, ethylene group, propylene group, the following group (a), or the following group (b)
  • R 12 represents a hydrogen atom or a methyl group
  • l represents 1 or 2.
  • P 2 Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer and modified products thereof m: 1 to 3 n: 3-6
  • 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, and 250 mgKOH. / G or less is particularly preferable.
  • the acid value is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and 250 mgKOH. / G or less is particularly preferable.
  • limiting in particular as a lower limit of an acid value From a viewpoint of the dispersion stability of a metal oxide particle, it is preferable that it is 5 mgKOH / g or more, and it is more preferable that it is 10 mgKOH / g or more.
  • the acid value of the polymer dispersant is the solid content acid value of the polymer compound.
  • the acid value of the polymer dispersant can be calculated, for example, from the average content of acidic groups in the polymer dispersant.
  • the acid value of the polymer dispersant can be adjusted by appropriately adjusting the amount of acid groups in the polymer dispersant and the amount of functional groups of pKa5 to 14 described later.
  • an acidity A polymer dispersant having a desired acid value can be synthesized by appropriately adjusting the amount of the vinyl monomer having a group.
  • the polymer compound represented by the general formula (1) or (2) is not particularly limited, but may be synthesized according to the synthesis method described in paragraphs 0114 to 0140 and 0266 to 0348 of JP-A-2007-277514. Can do. In particular, it is preferable to synthesize a polymer compound represented by the general formula (1) or (2) by radical polymerization of a vinyl monomer in the presence of a mercaptan compound having a plurality of adsorption sites.
  • the above vinyl monomers may be polymerized by only one kind, or may be copolymerized by using two or more kinds in combination.
  • Specific examples (M-1) to (M-13) of vinyl monomers are shown below, but the present invention is not limited to these.
  • R 6 , R 7 , A 3 , m, and n have the same meanings as R 3 , R 4 , A 2 , m, and n in the general formula (2), respectively. Is the same.
  • the compound represented by the general formula (3) is preferably synthesized by the following method.
  • the addition reaction is a radical addition reaction.
  • the carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group from the viewpoint of reactivity with a mercapto group.
  • Specific examples of the compound having 3 to 10 mercapto groups in one molecule include the following compounds.
  • a compound having an adsorption site and a carbon-carbon double bond (specifically, a hydrocarbon group, an acidic group, a urea group, a urethane group, a group having a coordinating oxygen atom, a basic nitrogen atom) Having at least one group selected from the group consisting of a group having an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, a heterocyclic group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group
  • the compound having a carbon-carbon double bond is not particularly limited, and examples thereof include the following.
  • 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 3 to 10 mercapto groups in one molecule” and “a compound having an adsorption site and having a carbon-carbon double bond” are dissolved in a suitable solvent, and a radical generator is prepared here. And adding at about 50 ° C. to 100 ° C. (thiol-ene reaction method).
  • Suitable solvents used in the thiol-ene reaction method include “a compound having 3 to 10 mercapto groups in one molecule”, “having an adsorption site, and a carbon-carbon double bond. It can be arbitrarily selected according to the solubility of the “compound having” and the “radical addition reaction product to be produced”.
  • solvents may be used as a mixture of two or more.
  • radical generators 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate
  • AIBN 2,2′-azobis (isobutyronitrile)
  • dimethyl 2,2′-azobisisobutyrate An azo compound such as [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.
  • the polymer compound those obtained by polymerizing these vinyl monomers and the compound represented by the general formula (3) by a known method according to a conventional method are preferable.
  • the compound represented by General formula (3) in this invention functions as a chain transfer agent, and may only be called a "chain transfer agent” hereafter.
  • a method in which these vinyl monomers and a chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. (solution polymerization method) Can be obtained using
  • suitable solvents used in the solution polymerization method can be arbitrarily selected according to the monomers used and the solubility of the resulting copolymer.
  • Examples include acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.
  • radical polymerization initiators examples include 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), and 2,2′-azobisisobutyric acid.
  • An azo compound such as dimethyl [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.
  • the content of the polymer dispersant in the cured film is not particularly limited, but is preferably in the range of 5 to 40% by mass with respect to the total mass of the cured film from the viewpoints of dispersibility, high refractive index, and coated surface shape.
  • the range of mass% is more preferable, and the range of 12 to 30 mass% is still more preferable.
  • content of the polymer dispersing agent in the composition for cured film formation is the said range with respect to the total solid of a composition.
  • the composition for forming a cured film preferably contains a polymerizable compound.
  • 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 novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy Examples thereof include resins.
  • bisphenol A type epoxy resins include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 ( (Mitsubishi Chemical Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation), and the like.
  • JER-4005, JER-4007, JER-4010 Mitsubishi Chemical Corporation
  • EPICLON 830, EPICLON 835 Made by DIC Corporation
  • LCE-21 LCE-21
  • RE-602S Nippon Kayaku Co., Ltd.
  • phenol novolac type epoxy resins include JER-152, JER-154, JER-157S70, JER-157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N -770, EPICLON N-775 (manufactured by DIC Corporation), etc.
  • cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N -680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 (above, made by Nippon Kayaku Co.,
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), JER-1031S (manufactured by Mitsubishi Chemical Corporation), and the like. These can be used alone or in combination of two or more.
  • Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX manufactured by Toagosei Co., Ltd.
  • the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.
  • an addition polymerizable compound having at least one ethylenically unsaturated double bond can also be used, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. It is preferable to use it.
  • a compound having at least one terminal ethylenically unsaturated bond preferably two or more. It is preferable to use it.
  • Such compounds are widely known in the technical field, and can be used without particular limitation in the present invention.
  • the composition for forming a cured film preferably further contains a polymerization initiator described later.
  • Such an addition polymerizable compound having at least one ethylenically unsaturated double bond is, for example, a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. It has the chemical form of Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters and amides thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
  • an addition reaction product of an unsaturated carboxylic acid ester or 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, and A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used.
  • a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving group such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is.
  • the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can be preferably used in the present invention.
  • polymerizable compound (hereinafter, also simply referred to as “polymerizable monomer”, “polymerizable monomer”) has at least one addition-polymerizable ethylene group and has a boiling point of 100 ° C. or higher under normal pressure.
  • a compound having an ethylenically unsaturated group is also preferred.
  • Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
  • compounds having a fluorene ring and having two or more functional ethylenic groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. Polymers can also be used.
  • JP-A-10-62986 compounds described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a polymerizable monomer.
  • the polymerizable monomer used in the present invention is preferably a polymerizable monomer represented by the following general formulas (MO-1) to (MO-6).
  • n is each 0 to 14, and m is 1 to 8, respectively.
  • a plurality of R, T, and Z present in one molecule may be the same or different.
  • T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.
  • At least one of R is a polymerizable group.
  • n is preferably 0 to 5, and more preferably 1 to 3.
  • m is preferably 1 to 5, and more preferably 1 to 3.
  • R is
  • dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by Co., Ltd.) (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Company), and the structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues, diglycerin EO (ethylene oxide) modified (meth) acrylate (
  • the polymerizable monomer is a polyfunctional monomer and 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 a mixture as described above, this can be used as it is.
  • the group may be introduced with an acidic group by reacting with a non-aromatic carboxylic acid anhydride.
  • non-aromatic carboxylic acid anhydride examples include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.
  • the monomer having an acidic group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polyfunctional monomer having an acidic group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
  • Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • a preferable acid value of the polyfunctional monomer having an acidic group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.
  • the acid value as the entire polyfunctional monomer is within the above range. It is.
  • the polyfunctional monomer which has a caprolactone modified structure is not particularly limited as long as it has a caprolactone-modified structure in the molecule.
  • trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane Obtained by esterifying polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone, Mention may be made of functional (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone-modified structure represented by the following formula (11) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group
  • “*” represents a bond.
  • Polyfunctional monomers having such a caprolactone-modified structure are commercially available, for example, from Nippon Kayaku Co., Ltd.
  • the polyfunctional monomer which has a caprolactone modified structure can be used individually or in mixture of 2 or more types.
  • polymerizable monomer or the like in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).
  • each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —
  • Each y independently represents an integer of 0 to 10
  • each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
  • the total number of acryloyl groups and methacryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group.
  • the total number of acryloyl groups and methacryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
  • the total 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 a terminal on the oxygen atom side. Is preferred in which X is bonded to X.
  • the compounds represented by the general formula (i) or (ii) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups is preferable.
  • the compound represented by the general formula (i) or (ii) has a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from the step of bonding and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).
  • a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available monomers such as polymerizable monomers represented by the general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • Examples of the polymerizable monomer include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, and the like. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, as polymerizable monomers, addition polymerizable monomers 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 are used.
  • a composition for forming a cured film having an excellent photosensitive speed can be obtained.
  • Commercially available products such as polymerizable monomers include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
  • a polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule is also suitable as the polymerizable monomer. Particularly preferred are those represented by the following general formula (I).
  • R 1 is an alkyl group
  • R 2 is an n-valent aliphatic group that may contain atoms other than carbon
  • R 0 is an alkyl group that is not H
  • n represents 2 to 4
  • polyfunctional thiol compound represented by the general formula (I) is specifically exemplified, 1,4-bis (3-mercaptobutyryloxy) butane [formula (II)] having the following structural formula: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H5H) -trione [formula (III)], and pentaerythritol tetrakis (3 -Mercaptobutyrate) [formula (IV)] and the like.
  • These polyfunctional thiols can be used alone or in combination.
  • esters examples include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are preferably used. Furthermore, the ester monomers described above can also be used as a mixture.
  • amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, and 1,6-hexamethylene bis.
  • examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
  • urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following formula (V) to a polyisocyanate compound having two or more isocyanate groups: Etc.
  • R 7 and R 8 each independently represent a hydrogen atom or a methyl group.
  • urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.
  • 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. Can provide a composition for forming a cured film having an excellent photosensitive speed.
  • polyester acrylates examples include polyester acrylates, epoxy resins and (meth) acrylic acid described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reaction. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, photocurable monomers and oligomers described on pages 300 to 308 (1984) can also be used.
  • the details of usage methods can be arbitrarily set according to the final performance design of the composition for cured film formation.
  • it is selected from the following viewpoints.
  • a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable.
  • those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound).
  • a method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
  • polymerizable compounds are important for compatibility and dispersibility with other components (eg, polymerization initiators, metal oxide particles, etc.) contained in the composition for forming a cured film.
  • the compatibility may be improved by using a low-purity compound or using two or more other components in combination.
  • a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.
  • the content of the polymerizable compound (C) is preferably in the range of 1% by mass to 40% by mass and preferably in the range of 3% by mass to 35% by mass with respect to the total solid content of the composition for forming a cured film. More preferably, it is more preferably in the range of 5% by mass to 30% by mass. Within this range, the curability is good and preferable without lowering the refractive index.
  • the composition for forming a cured film may contain a solvent.
  • the kind in particular of solvent used is not restrict
  • organic solvents include alcohol solvents (eg, methanol, ethanol, isopropanol), ketone solvents (eg, acetone, methyl ethyl ketone, cyclohexanone), aromatic hydrocarbon solvents (eg, toluene, xylene), amide solvents.
  • nitrile solvents eg, acetonitrile, propionitrile
  • ester solvents eg, methyl acetate, ethyl acetate
  • carbonate solvents eg, dimethyl carbonate, diethyl Carbonate
  • ether solvents halogen solvents and the like.
  • Two or more of these solvents may be mixed and used.
  • the composition for forming a cured film further contains a polymerization initiator.
  • a polymerization initiator those known as polymerization initiators described below can be used.
  • the polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a 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).
  • polymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.
  • the description after paragraph [0135] of Japanese Patent Application Laid-Open No. 2010-106268 (corresponding to [0163] of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to, and the contents thereof are described in the present specification. Embedded in the book.
  • an oxime compound can also be suitably used as the polymerization initiator.
  • Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A 2000-80068, and compounds described in JP-A 2006-342166.
  • oxime ester compounds examples include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, Journal of Applied Polymer Science (2012) pp. 725-731, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • oxime ester compounds other than those described above compounds described in JP-T-2009-519904 in which oxime is linked to carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used.
  • cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used.
  • cyclic oxime compounds in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
  • the compounds described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because high sensitivity can be achieved by regenerating the active radical from the polymerization inert radical. it can.
  • an oxime compound having a specific substituent described in JP-A-2007-267979 and an oxime compound having a thioaryl group disclosed in JP-A-2009-191061 can be used.
  • an oxime initiator Japanese Patent Application Laid-Open No. 2012-208494, paragraph 0513 (corresponding US Patent Application Publication No. 2012/235099, [0632]) and the following formulas (OX-1), (OX-2) or ( The description of the compound represented by OX-3) can be referred to, and the contents thereof are incorporated herein.
  • 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 at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
  • a known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.
  • Polymerization initiators may be used in combination of two or more as required.
  • trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl.
  • Compounds are preferred.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, ⁇ -aminoketones
  • Most preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.
  • an oxime compound as the polymerization initiator.
  • stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is required to keep the addition amount of a polymerization initiator low. Therefore, considering these points, 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 imaging device.
  • the content of the polymerization initiator contained in the cured film forming composition (the total content in the case of 2 or more types) is 0.1% by mass or more and 40% by mass or less with respect to the total solid content of the cured film forming composition. Preferably, it is 0.5 mass% or more and 20 mass% or less, more preferably 1 mass% or more and 15 mass% or less. Within this range, good curability can be obtained.
  • 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 photosensitive wavelength.
  • a sensitizer what sensitizes with the electron transfer mechanism or an energy transfer mechanism with respect to the polymerization initiator mentioned above is preferable. Examples of the sensitizer include those described in paragraphs [0228] to [0250] of JP2012-255148A.
  • the composition for forming a cured film preferably further contains a co-sensitizer.
  • the co-sensitizer has functions such as further improving the sensitivity of the polymerization initiator and sensitizer described above to actinic radiation, or suppressing polymerization inhibition of the polymerizable compound by oxygen. Examples of the co-sensitizer include those described in paragraphs [0252] to [0256] of JP2012-255148A.
  • Polymerization inhibitors include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, and cations
  • Examples include dyes, sulfide group-containing compounds, nitro group-containing compounds, transition metal compounds such as FeCl 3 and CuCl 2 .
  • the phenolic hydroxyl group-containing compound is hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), Selected from the group consisting of 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol (BHT), phenolic resins, and cresol resins It is preferable that it is a compound.
  • N-oxide compounds include 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picoline A compound selected from the group consisting of acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide is preferred.
  • Piperidine 1-oxyl free radical compounds include piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1 -Oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide A compound selected from the group consisting of -2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical Is preferred.
  • the pyrrolidine 1-oxyl free radical compound is preferably a 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).
  • N-nitrosophenylhydroxylamines are preferably compounds selected from the group consisting of N-nitrosophenylhydroxylamine cerium salts and N-nitrosophenylhydroxylamine aluminum salts.
  • the diazonium compound is selected from the group consisting of 4-diazophenyldimethylamine hydrogen sulfate, 4-diazodiphenylamine tetrafluoroborate, and 3-methoxy-4-diazodiphenylamine hexafluorophosphate Is preferred.
  • Suitable polymerization inhibitors are exemplified below, but the present invention is not limited thereto.
  • Examples of phenolic polymerization inhibitors include the following exemplified compounds (P-1) to (P-24).
  • Examples of amine polymerization inhibitors include the following exemplary compounds (N-1) to (N-7).
  • sulfur polymerization inhibitors include the following exemplary compounds (S-1) to (S-5).
  • Examples of phosphite polymerization inhibitors include the following exemplary compounds (R-1) to (R-5).
  • each compound shown below can also be used as a suitable polymerization inhibitor.
  • hydroquinone hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-) are preferable.
  • a preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.01 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polymerization initiator. And most preferably in the range of 0.05 parts by mass or more and 5 parts by mass or less.
  • the cured film preferably further contains a binder polymer from the viewpoint of improving the film properties.
  • a binder polymer there exists the method of containing a binder polymer in the composition for cured film formation mentioned above.
  • the binder polymer a linear organic polymer is preferably used.
  • a linear organic polymer a well-known thing can be used arbitrarily.
  • a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development.
  • the linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer.
  • a water-soluble organic polymer when used, water development becomes possible.
  • Examples of such a linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or in combination.
  • Polymerized resin acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half-esterified or half-amidated, epoxy resin modified with unsaturated monocarboxylic acid and acid anhydride And epoxy acrylate.
  • the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.
  • Examples of the monomer having an acid anhydride include maleic anhydride. It is done.
  • there is an acidic cellulose derivative having a carboxylic acid group in the side chain there is an acidic cellulose derivative having a carboxylic acid group in the side chain.
  • those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
  • a monomer other than the above-mentioned monomers can be used as the compound to be copolymerized.
  • examples of other monomers include the following compounds (1) to (12).
  • 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.
  • Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
  • Styrenes such as styrene, ⁇ -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
  • Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
  • Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
  • N-vinylpyrrolidone (10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
  • Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
  • a methacrylic acid monomer having a hetero atom bonded to the ⁇ -position For example, compounds described in JP-A-2002-309057, JP-A-2002-311569 and the like can be mentioned.
  • these monomers can be applied to the synthesis of a copolymer by combining them without particular limitation within the scope of the present invention.
  • this invention is not limited to this.
  • the composition ratio of the exemplary compounds shown below is mol%.
  • the binder polymer preferably contains a repeating unit obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (ED) (hereinafter also referred to as “ether dimer”).
  • ED general formula
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • 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, but for example, methyl Linear, branched alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, substituted with alicyclic groups such as t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; alkoxy such as 1-methoxyethyl, 1-e
  • ether dimers include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoe Di (stearyl)
  • dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.
  • These ether dimers may be used alone or in combination of two or more.
  • the structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.
  • ether dimer dimer dimer dimer dimer dimer examples include, for example, a monomer for introducing an acidic group, a monomer for introducing a radical polymerizable double bond, and an epoxy group. Monomers and other copolymerizable monomers other than these may be mentioned. Only 1 type may be used for such a monomer and it may use 2 or more types.
  • 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, maleic anhydride, and anhydride. And monomers having a carboxylic anhydride group such as itaconic acid.
  • (meth) acrylic acid is particularly preferable.
  • the monomer for introducing an acidic group may be a monomer that can give an acidic group after polymerization, such as a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, Examples thereof include monomers having an epoxy group such as glycidyl (meth) acrylate, and monomers having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate.
  • a monomer for introducing a radical polymerizable double bond when using a monomer capable of imparting an acidic group after polymerization, it may be required to perform a treatment for imparting an acidic group after polymerization.
  • the treatment for imparting acidic groups after polymerization varies depending on the type of monomer, and examples thereof include the following treatment.
  • a treatment of adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like can be mentioned.
  • a monomer having an epoxy group for example, a compound having an amino group and an acidic group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or, for example, (meth) acrylic
  • an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride to the hydroxyl group generated after adding an acid such as an acid
  • a monomer having an isocyanate group for example, a treatment of adding a compound having a hydroxyl group and an acidic group such as 2-hydroxybutyric acid can be mentioned.
  • the content ratio is not particularly limited, In the monomer component, the content is preferably 5 to 70% by mass, more preferably 10 to 60% by mass.
  • Examples of the monomer for introducing a radical polymerizable double bond include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; and carboxylic acid anhydride groups such as maleic anhydride and itaconic anhydride. Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. When using a monomer for introducing a radical polymerizable double bond, it is necessary to perform a treatment for imparting a radical polymerizable double bond after polymerization.
  • a monomer for introducing a radical polymerizable double bond it is necessary to perform a treatment for imparting a radical polymerizable double bond after polymerization.
  • the treatment for imparting a radical polymerizable double bond after polymerization differs depending on the type of monomer that can impart a radical polymerizable double bond to be used, and examples thereof include the following treatment.
  • a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- )
  • Treatment of adding a compound having an epoxy group such as vinylbenzyl glycidyl ether and a radically polymerizable double bond.
  • a treatment for adding a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate Is mentioned.
  • a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, (meth)
  • the process which adds the compound which has acidic groups, such as acrylic acid, and a radically polymerizable double bond is mentioned.
  • the content ratio is particularly limited. However, it is preferably 5 to 70% by mass, more preferably 10 to 60% by mass in the total monomer components.
  • Examples of the monomer for introducing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. Can be mentioned.
  • the content ratio is not particularly limited, In the monomer component, the content is preferably 5 to 70% by mass, more preferably 10 to 60% by mass.
  • copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n (meth) acrylate -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters such as hydroxyethyl; aromatic vinyl compounds such as styrene, vinyltoluene and ⁇ -methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene, isoprene and the like Butad
  • the content ratio is not particularly limited, but is 95% by mass. The following is preferable, and it is more preferable that it is 85 mass% or less.
  • the weight average molecular weight of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, but is formed by the viscosity of the composition for forming a cured film and the composition. From the viewpoint of heat resistance of the coating film, it is preferably 2000 to 200000, more preferably 5000 to 100,000, and still more preferably 5000 to 20000.
  • the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 It should be ⁇ 400 mg KOH / g.
  • a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be easily obtained by polymerizing at least the above-mentioned monomer essentially comprising 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 applied to the synthesis of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, and various conventionally known polymerization methods can be adopted. However, it is particularly preferable to use a solution polymerization method.
  • a polymer formed by polymerizing a monomer component containing a compound represented by the general formula (ED) A coalescence can be synthesized.
  • exemplary compounds of a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) are shown, but the present invention is not limited to these.
  • the composition ratio of the exemplary compounds shown below is mol%.
  • DM dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate
  • BzMA benzyl methacrylate
  • MMA methyl methacrylate
  • MAA Methacrylic acid
  • GMA glycidyl methacrylate
  • the molar ratio of DM: BzMA: MMA: MAA: GMA is preferably 5 to 15:40 to 50: 5 to 15: 5 to 15:20 to 30.
  • the weight average molecular weight of the polymer is preferably 9000 to 20000.
  • the polymer used in the present invention has a weight average molecular weight (polystyrene conversion value measured by GPC method) of preferably 1000 to 2 ⁇ 10 5 , more preferably 2000 to 1 ⁇ 10 5 , and more preferably 5000 to More preferably, it is 5 ⁇ 10 4 .
  • a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled.
  • An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.
  • Examples of the above-mentioned polymers include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co.
  • Japanese Patent Publication No. 7-12004 Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947.
  • polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
  • the weight average molecular weight (polystyrene equivalent value measured by GPC method) of the binder polymer is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably It is 1,000 or more, More preferably, it is the range of 2,000 or more and 250,000 or less.
  • the polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
  • These binder polymers may be any of random polymers, block polymers, graft polymers and the like.
  • the binder polymer can be synthesized by a conventionally known method.
  • the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy.
  • Examples include -2-propanol, 1-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 are used alone or in combination of two or more.
  • Examples of the radical polymerization initiator used when the binder polymer is synthesized include known compounds such as an azo initiator and a peroxide initiator.
  • the binder polymer can be used alone or in combination of two or more.
  • the cured film may or may not contain a binder polymer, but when it is contained, the content of the binder polymer is preferably 1% by mass or more and 40% by mass or less based on the total mass of the cured film. It is more preferably 3% by mass or more and 30% by mass or less, and further preferably 4% by mass or more and 20% by mass or less.
  • a binder polymer when a binder polymer is contained in the composition for cured film formation, it becomes preferable that it becomes the said content with respect to the total solid of the composition for cured film formation.
  • (J) Surfactant Various surfactants may be added to the composition for forming a cured film from the viewpoint of further improving applicability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the composition for forming a cured film contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved.
  • Liquidity can be further improved. That is, when forming a film using a composition for forming a cured film containing a fluorosurfactant, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. It improves and the applicability
  • the fluorine content in the fluorosurfactant 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.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a composition for forming a cured film. .
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • nonionic surfactant examples include nonionic surfactants described in paragraph 0553 of JP2012-208494A (corresponding to US Patent Application Publication No. 2012/0235099 [0679]) and the like. The contents of which are incorporated herein by reference.
  • cationic surfactant examples include the cationic surfactant described in paragraph 0554 of JP2012-208494A (corresponding to [0680] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the composition for forming a cured film may or may not contain a surfactant, but when it is contained, the addition amount of the surfactant is 0.001 with respect to the total mass of the composition for forming a cured film.
  • the content is preferably from mass% to 2.0 mass%, more preferably from 0.005 mass% to 1.0 mass%.
  • plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.
  • the colored 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.
  • the colored layer 21 can constitute at least one of the pixels of the color filter in the present invention, and is preferably formed of a curable composition containing a colorant. More specifically, in the colored layer forming step, a curable composition containing a colorant is applied directly or via another layer on the cured film, and then dried to form a coated film (coating film) Forming step) and a step of performing heat treatment (post-baking step).
  • a curable composition containing a colorant is applied directly or via another layer on the cured film, and then dried to form a coated film (coating film) Forming step) and a step of performing heat treatment (post-baking step).
  • the curable composition examples include a colored photocurable composition or a non-photosensitive colored thermosetting composition.
  • the colored layer is a non-photosensitive colored thermosetting composition. It is preferably formed using a composition.
  • the non-photosensitive colored thermosetting composition 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 colored photocurable composition contains at least a colorant and a photocurable component, and among these, the “photocurable component” is a photocurable composition usually used in a photolithographic method.
  • a composition containing at least a binder resin (alkali-soluble resin or the like), a photosensitive polymerization component (such as a photopolymerization monomer) or a photopolymerization initiator can be used.
  • the colored photocurable composition for example, the matters described in paragraph numbers 0017 to 0064 of JP-A-2005-326453 can be suitably applied.
  • the colorant contained in the colored photocurable composition or the non-photosensitive colored thermosetting composition used in the colored layer is not particularly limited, and one or two kinds of conventionally known various dyes and pigments are used. A mixture of the above can be used.
  • the pigment include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling properties, the average particle size of the pigment is 0.01 ⁇ m to 0.1 ⁇ m is preferable, and 0.01 ⁇ m to 0.05 ⁇ m is more preferable.
  • the present invention is not limited to these.
  • the colorant is a dye, it can be dissolved uniformly in the composition to obtain a non-photosensitive thermosetting colored resin composition.
  • the dye that can be used as the colorant is not particularly limited, and conventionally known dyes for color filters can be used.
  • the chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.
  • the colorant content 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 55% by mass or more and 90% by mass or less. Is more preferable.
  • the content is 50% by mass or more, an appropriate chromaticity as a color filter can be obtained.
  • photocuring can fully be advanced by setting it as less than 100 mass%, and the strength reduction as a film
  • thermosetting compound contained in the non-photosensitive colored thermosetting composition is not particularly limited as long as the film can be cured by heating.
  • a compound having a thermosetting functional group can be used.
  • the thermosetting compound for example, those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group, and an acyloxymethyl group are preferable.
  • More preferable thermosetting compounds include (a) an epoxy compound, (b) a melamine compound, a guanamine compound, and a glycoluril substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
  • thermosetting compound examples thereof include a compound or a urea compound, (c) a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group.
  • a polyfunctional epoxy compound is particularly preferable as the thermosetting compound.
  • the total content of the thermosetting compound in the colored thermosetting composition varies depending on the material, but is preferably 0.1 to 50% by mass with respect to the total solid content (mass) of the colored thermosetting composition. 0.2 to 40% by mass is more preferable, and 1 to 35% by mass is particularly preferable.
  • various additives such as a binder, a curing agent, a curing catalyst, a solvent, a filler, a polymer compound other than the above, as necessary, as long as the effects of the present invention are not impaired.
  • Surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, dispersants, and the like can be blended.
  • the binder is often added at the time of preparing the pigment dispersion, does not need alkali solubility, and may be soluble in an organic solvent, and is a linear organic high molecular polymer that is soluble in an organic solvent. preferable.
  • linear organic high molecular polymers examples include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.
  • acrylic resins include copolymers consisting of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, such as benzyl methacrylate / methacrylic.
  • acids such as benzyl methacrylate / benzyl methacrylate, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like.
  • KS resist-106 manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • cyclomer P series manufactured by Daicel Chemical Industries, Ltd.
  • an epoxy resin as a thermosetting compound
  • curing agent there are many types of curing agents for epoxy resins, and their properties, pot life with resin and curing agent mixture, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used. An appropriate curing agent must be selected according to the purpose of use, use conditions, working conditions, and the like.
  • the hardener is described in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of curing agents are as follows.
  • Those that act catalytically include tertiary amines, boron trifluoride-amine complexes, those that react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc .;
  • Examples include diethylenetriamine, polyamide resin, and medium temperature curing examples such as diethylaminopropylamine and tris (dimethylaminomethyl) phenol;
  • examples of high temperature curing include phthalic anhydride and metaphenylenediamine.
  • amines diethylenetriamine as an aliphatic polyamine; metaphenylenediamine as an aromatic polyamine; tris (dimethylaminomethyl) phenol as a tertiary amine; phthalic anhydride as an acid anhydride; polyamide resin Polysulfide resin, boron trifluoride-monoethylamine complex; Synthetic resin initial condensate includes phenol resin, dicyandiamide and the like.
  • both the binder and the curing agent are preferably as small as possible.
  • the curing agent is 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less with respect to the thermosetting compound. It is preferable that In order to realize a high colorant concentration in the present invention, curing by reaction between epoxy groups is effective in addition to curing by reaction with a curing agent. For this reason, a curing catalyst can 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 / 1,000 to mass of the epoxy resin having an epoxy equivalent of about 150 to 200. It is possible to cure with a slight amount of about 1/250.
  • the colored thermosetting composition can be used as a solution dissolved in various solvents.
  • the solvent is not particularly limited as long as the solubility of each component and the coating property of the colored thermosetting composition are satisfied.
  • a dispersing agent can be added.
  • the dispersant known ones can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorosurfactant, and a polymer dispersant. As these dispersants, many kinds of compounds are used.
  • a phthalocyanine derivative commercial product EFKA-745 (manufactured by Efka)
  • Solsperse 5000 manufactured by Nippon Lubrizol
  • organosiloxane polymer KP341 Shin-Etsu Chemical Industry Co., Ltd.
  • acrylic acid co
  • polymer polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • Nonionic surfactants such as Steal; anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, Polymer dispersing agents such as EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000,
  • a dispersing agent may be used independently and may be used in combination of 2 or more type.
  • the amount of the dispersant added to the colored thermosetting composition is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.
  • additives can be further added to the colored thermosetting composition in the present invention as necessary.
  • Specific examples of various additives include, for example, various additives described in JP-A-2005-326453.
  • the colored layer in the present invention can be formed, for example, by applying the above colored thermosetting composition on a cured film and drying it.
  • a colored thermosetting composition can be formed by coating on a cured film by a coating method such as spin coating, slit coating, cast coating, roll coating, or the like.
  • the specific thickness of the colored layer is preferably 0.005 ⁇ m to 0.9 ⁇ m, more preferably 0.05 ⁇ m to 0.8 ⁇ m, and still more preferably 0.1 ⁇ m to 0.7 ⁇ m.
  • the colored layer forming step preferably further includes a heating step (may be a post-baking step).
  • the colored layer can be formed by applying a colored thermosetting composition to a support to form a coating film, and then thermally curing the coating film by a heating step.
  • the heating step may be performed at the same time as drying after coating, or a separate thermosetting step may be provided after coating and drying.
  • the heating step uses a known heating means such as an oven or a hot plate, preferably 130 ° C. to 300 ° C., more preferably 150 ° C. to 280 ° C., particularly preferably 170 ° C. to 260 ° C., preferably 10 seconds. It can be carried out for 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 as short as possible.
  • the photoresist layer forming step is a step of forming a photoresist layer on the colored layer. More specifically, as shown in FIG. 2D, after the colored layer 21 is formed in the colored layer forming step, a photoresist layer 22 (photosensitive resin layer) is further formed on the colored layer 21. Is done.
  • the method for forming the photoresist layer is not particularly limited, but it is preferable that a positive or negative photosensitive resin composition is applied on the colored layer and dried to form the photoresist layer. Further, in the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment.
  • a pre-bake treatment it is preferable to further perform a pre-bake treatment.
  • the matters described in paragraph numbers 0112 to 0117 of JP-A No. 2007-11324 can be preferably applied to the present invention.
  • the specific thickness of the photosensitive resin layer is preferably 0.01 ⁇ m to 3 ⁇ m, more preferably 0.1 ⁇ m to 2.5 ⁇ m, and still more preferably 0.15 ⁇ m to 2 ⁇ m.
  • a positive type photosensitive resin composition suitable for positive type photoresists sensitive to radiation such as ultraviolet rays (g rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays.
  • a positive resist composition can be used.
  • the one that exposes the photosensitive resin layer is preferably g-line or i-line for the purpose of the present invention, and i-line exposure is particularly preferable.
  • a colored layer is formed into a desired shape (for example, a rectangle) by performing an etching process in an etching process described later using a resist pattern formed from a photoresist layer as a mask. Can do.
  • the pattern forming step is a step of forming a resist pattern on the colored layer by removing the photoresist layer prepared above in a pattern-like manner. More specifically, as shown in FIG. 2 (e), the photoresist layer 22 has a desired pattern, for example, a second colored layer having a color different from that of the colored layer 21 is formed on the cured film 20. A pattern corresponding to the region is exposed and developed with a developer to form a resist pattern 24 (photoresist pattern) that functions as an etching mask.
  • the pattern formation step the surface of the colored layer 21 that becomes the first colored layer in a pattern-like manner (the surface opposite to the side where the cured film 20 containing metal oxide particles and the colored layer 21 face each other) is exposed. It will be.
  • a region other than a region where the second colored layer is formed on the cured film 20 containing metal oxide particles is covered with the resist pattern 24.
  • each step such as etching is performed, the colored layer 21 is formed in a pattern, and the second colored layer is formed on the cured film 20 containing metal oxide particles again through each step.
  • another type of pixel is formed.
  • each pixel of the color filter can be formed in a fine and rectangular shape.
  • the photoresist layer 22 is exposed to a positive or negative photosensitive resin composition through a predetermined (image-like) mask pattern, such as g-line, h-line, i-line, preferably i-line. Done by applying.
  • a predetermined (image-like) mask pattern such as g-line, h-line, i-line, preferably i-line. Done by applying.
  • Any developer can be used as long as it does not affect the colored layer 21 containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist.
  • a combination of various organic solvents or an alkaline aqueous solution can be used.
  • 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, a plasma etching process, etc.) As a typical example of the dry etching method, Japanese Patent Laid-Open No. 59-126506 is disclosed. JP-A-59-46628, 58-9108, 58-2809, 57-148706, 61-41102, and the like are known.) Thus, the colored layer 21 not covered with the resist pattern 24 is removed, and a patterned colored layer is formed. In other words, the cured film exposed portion 26 is formed like the resist pattern 24 formed by the pattern forming process.
  • the type of etching gas used in the etching process is not particularly limited, but at least one fluorine-based gas is included from the viewpoint that the colored layer portion (the portion to be etched) removed by the dry etching method can be processed into a rectangle. It is preferable that A known fluorine-based gas can be used as the fluorine-based gas, but a fluorine-based compound gas represented by the following formula (I) is preferable.
  • CnHmFl Formula (I) In the formula, n represents 1 to 6, m represents 0 to 13, and l represents 1 to 14.
  • Examples of the fluorine-based gas represented by the formula (I) include 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 And at least one selected from the group consisting of CHF 3 .
  • the fluorine-based gas can be used in combination of two or more gases from the above group.
  • 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 etched portion.
  • CF 4 and / or C 2 F 6 are more preferable, and CF 4 is particularly preferable.
  • the etching gas is mixed with oxygen gas.
  • the content ratio (fluorine-based gas / oxygen gas) between the fluorine-based gas and the oxygen gas in the mixed gas is preferably 2/1 to 8/1 in terms of a flow rate ratio.
  • the content ratio of the fluorine-based gas and the oxygen gas is 2/1 to 6/1 in terms of preventing the redeposition of the etching product to the side wall of the resist pattern 24 while maintaining the rectangularity of the etched portion. It is preferable that the ratio is 3/1 to 5/1.
  • the mixed gas is further mixed with helium (He), neon (from the viewpoint of maintaining the etching plasma partial pressure control stability and the verticality of the shape to be etched.
  • He helium
  • Ne argon
  • Ar krypton
  • Xe xenon
  • other rare gases e.g., CCl 4 , CClF 3 , AlF 3 , AlCl 3, etc.
  • N 2 CO, and preferably contains at least one selected from the group consisting of CO 2
  • Ar, He, Kr at least one selected from the group consisting of N 2
  • Xe More preferably, it includes a species, and more preferably includes at least one selected from the group consisting of He, Ar, and Xe.
  • the mixed gas may consist only of a fluorine-based gas and an oxygen gas.
  • the content of other gases that may be contained in addition to the fluorine-based gas and the oxygen gas is preferably 25 or less in terms of a flow rate ratio when the oxygen gas is 1, and is 10 or more and 20 or less. More preferably, it is 14 or more and 18 or less.
  • the dry etching processing time calculation method calculates the etching rate (nm / min.) In the etching process, and calculates the processing time required for etching from the calculated etching rate.
  • the etching rate can be calculated, for example, by collecting the relationship between the etching time and the remaining film.
  • the etching time is preferably 10 minutes or less, and 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 pattern has a rectangular shape due to the internal pressure of the chamber being in the above range. And the adhesion of the sidewall protective film produced by etching 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 degree of decompression of the chamber.
  • the temperature of the substrate 1a is preferably 30 ° C. or higher and 100 ° C. or lower.
  • the temperature is preferably 30 ° C. to 80 ° C., and preferably 40 ° C. to 60 ° C. from the viewpoint of maintaining the rectangularity of the etched portion and suppressing the reattachment of the etching product to the side wall of the resist pattern 24.
  • the temperature of the substrate 1a can be set to 30 ° C. or more and 100 ° C. or less by controlling the temperature of the wafer stage to 30 ° C. or more and 100 ° C. or less.
  • the dry etching conditions in the etching process vary depending on the material, layer thickness, and the like of the colored layer 21, but 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 ° C., 1013 hPa) or less, and more preferably 500 to 1000 mL / min (0 ° C., 1013 hPa).
  • the high frequency can be selected from 400 kHz, 60 MHz, 13.56 MHz, 2.45 GHz, and the like, and can be processed with an RF power of 50 to 2000 W, preferably 100 to 1000 W.
  • RF power / antenna bias / substrate bias is preferably 600 to 1000 W / 300 to 500 W / 150 to 250 W, and more preferably 700 to 900 W, respectively. / 350 to 450 / 200W.
  • the etching process is preferably a process in which part or all of the colored layer is etched using an etching gas containing a fluorine-based gas.
  • the etching process includes two or more stages with different etching conditions.
  • the etching process may be included.
  • the colored layer is etched using an etching gas containing fluorine gas (first etching step), and the etching is stopped before the cured film containing the metal oxide particles is completely exposed.
  • the second etching may be performed using a different gas (for example, a mixed gas containing nitrogen gas and oxygen gas).
  • a mixed gas containing nitrogen gas and oxygen gas for example, a mixed gas containing nitrogen gas and oxygen gas.
  • the substrate 1a serving as a support formed by the planarizing layer 10 and the like located under the cured film 20 is exposed using only the first mixed gas.
  • the support tends to be damaged. Further, the generated support damage was particularly noticeable when an over-etching process was performed.
  • the support damage is reduced by performing the second etching step using a second mixed gas containing nitrogen gas and oxygen gas, which is different from the first mixed gas used in the first etching step. Etching with suppressed generation is possible.
  • the layer can be removed.
  • the resist pattern 24 can be easily peeled off by the stripping solution or the solvent.
  • the second mixed gas used in the second etching step includes nitrogen gas and oxygen gas, but may contain a fluorine-based gas as long as the effects of the present invention are not impaired.
  • the content ratio of the fluorine-based gas is preferably 5% or less in terms of flow rate ratio, and particularly preferably does not contain the fluorine-based gas.
  • the content ratio of nitrogen gas to oxygen gas (nitrogen gas / oxygen gas) in the second mixed gas is preferably 10/1 to 3/1 in terms of a flow rate ratio.
  • the content ratio is preferably in the range of 20/1 to 3/1 from the viewpoint of maintaining the rectangularity of the etched portion and preventing the redeposition of the etching product to the side wall of the resist pattern 24, and 15/1 to 4 / 1 is more preferable, and 10/1 to 5/1 is particularly preferable.
  • the second mixed gas is further made of helium (He), neon ( Ne), argon (Ar), krypton (Kr), and xenon (Xe) are preferably included.
  • the gas is preferably selected from the group consisting of He, Ar, and Xe. More preferably, it contains at least one kind of gas.
  • the second mixed gas can be composed of only nitrogen gas and oxygen gas.
  • the content of other gases that may be further contained is preferably 25 or less in terms of a flow rate ratio when the oxygen gas is 1. It is preferably 20 or more and particularly preferably 8 or more and 12 or less.
  • the dry etching process is performed after the processing time calculated in the same manner as in the first etching process from the start of the dry etching process for removing the colored layer 21 remaining in the first etching process. Can be terminated. Further, the dry etching processing time for removing the remaining colored layer 21 by endpoint detection may be managed. In the second etching step, it is preferable to manage the dry etching processing time for removing the colored layer 21 by endpoint detection. The etching processing time is preferably within 10 minutes, more preferably within 7 minutes.
  • the internal pressure of the chamber is preferably 1.0 to 5.0 Pa, and more preferably 2.0 to 4.0 Pa.
  • a pattern in which the occurrence of damage to the support is suppressed can be more efficiently formed without impairing the rectangularity of the pattern under conditions that satisfy the mixing ratio of the mixed gas and the internal pressure of the chamber.
  • RF power / antenna bias / substrate bias is preferably 400 to 800 W / 50 to 200 W / 100 to 300 W, more preferably 500, respectively. 700W / 100 to 150W / 200 to 300W.
  • the support temperature and other conditions during the etching process in the second etching process the matters described in the first etching process can be suitably applied.
  • the second etching step further includes an overetching treatment step.
  • the overetching treatment is preferably performed by setting an overetching time.
  • the over-etching time can be set arbitrarily, the etching process time (t1) in the first etching process and the etching process in the second etching process in terms of the etching resistance of the resist pattern 24 and the rectangularity of the pattern to be etched.
  • the total processing time (t1 + t2) with the time (t2) is preferably 30% or less, more preferably 5 to 25%, and particularly preferably 15 to 20%.
  • the resist pattern removing step is a step of removing the resist pattern remaining after the etching step. More specifically, as shown in FIG. 2G, after the etching process is completed, the resist pattern 24 of the mask is made removable with a special stripping solution or solvent and removed using cleaning water. In addition, in this invention, by applying the hardened layer containing metal oxide particles, peeling of the color filter (patterned colored layer) is sufficiently suppressed when the resist pattern 24 is peeled off, so that the resist pattern 24 is formed. Can be removed.
  • a paddle development process in which a stripping solution or a solvent is applied on at least the resist pattern 24 and is held for a predetermined time.
  • a paddle development process in which a stripping solution or a solvent is applied on at least the resist pattern 24 and is held for a predetermined time.
  • time to make stripping solution or a solvent stagnant It is preferable that it is several dozen seconds to several minutes.
  • the resist pattern 24 is removed by spraying cleaning water onto the resist pattern 24 from, for example, a spray-type or shower-type spray nozzle.
  • pure water can be preferably used.
  • the injection nozzle examples include an injection nozzle in which the entire support body is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support body.
  • the spray nozzle is movable, during the process of removing the resist pattern 24, the resist pattern 24 is more effectively moved by spraying cleaning water by moving from the center of the substrate 1a to the end of the substrate 1a at least twice. Can be removed.
  • the stripping solution generally contains an organic solvent, but may further contain an inorganic solvent.
  • the organic solvent include hydrocarbon compounds, halogenated hydrocarbon compounds, alcohol compounds, ether or acetal compounds, ketones or aldehyde compounds, ester compounds, polyhydric alcohol compounds, carboxylic acids or acids thereof. Examples thereof include an anhydride compound, a phenol compound, a nitrogen-containing compound, a sulfur-containing compound, and a fluorine-containing compound.
  • the stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.
  • the acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group.
  • they are monoethanolamine, diethanolamine, and triethanolamine, and more preferably monoethanolamine (H 2 NCH 2 CH 2 OH).
  • Cyclic nitrogen-containing compounds include isoquinoline, imidazole, N-ethylmorpholine, ⁇ -caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2-pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like are preferable, N-methyl-2-pyrrolidone and N-ethylmorpholine are preferred, and N-methyl-2-pyrrolidone (NMP) is more preferred.
  • the stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.
  • acyclic nitrogen-containing compound at least one selected from monoethanolamine, diethanolamine and triethanolamine, and cyclic
  • the nitrogen-containing compound preferably includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes monoethanolamine and N-methyl-2-pyrrolidone.
  • the content of the non-cyclic nitrogen-containing compound is 9 parts by mass to 11 parts by mass with respect to 100 parts by mass of the stripping solution, and the content of the cyclic nitrogen-containing compound is 65 parts by mass to 70 parts by mass. It is desirable.
  • stripping solution is what diluted the mixture of the non-cyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.
  • a two-color filter is manufactured by forming a colored layer different from the colored layer already formed on the cured film exposed portion 26, and the photoresist layer is again formed on the two-color filter. If a formation process is formed and the pattern formation process, the etching process, and the resist pattern removal process are similarly repeated, a multicolored color filter is formed.
  • 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 is used in the etching step.
  • an etching gas is used in the etching step.
  • the color filter produced by the production method of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS having more than 1 million pixels.
  • the color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.
  • Example 1 [Preparation of metal oxide fine particle dispersion (dispersion composition)]
  • a mixed liquid having the following composition as a circulation type dispersion apparatus (bead mill), an ultra-apex mill manufactured by Kotobuki Kogyo Co., Ltd. was used for dispersion treatment as follows to obtain a titanium dioxide dispersion as a dispersion composition. . ⁇ Composition ⁇ ⁇ Titanium dioxide (Ishihara Sangyo Co., Ltd.
  • the dispersant (B-1) was synthesized according to the synthesis method described in paragraphs [0266] to [0348] of JP-A-2007-277514. Specifically, it is as follows. 100 parts of dipentaerythritol hexakis (3-mercaptopropionate) [(33); manufactured by Sakai Chemical Industry Co., Ltd.] and the following compound having an adsorption site and having a carbon-carbon double bond ( A-3) 91.38 parts were dissolved in 446.6 parts of 1-methoxy-2-propanol and heated to 90 ° C. under a nitrogen stream.
  • V-601 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 part of V-601 was added and reacted at 90 ° C. for 2 hours under a nitrogen stream. By cooling to room temperature, a 30% by mass solution of a mercaptan compound was obtained.
  • a mixed solution of 499.57 parts of a 30% by mass solution of the mercaptan compound and 100.13 parts of methyl methacrylate (M-1) was heated to 90 ° C. in a nitrogen stream.
  • M-1 methyl methacrylate
  • 0.681 parts of dimethyl 2,2′-azobis (2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] was added 72.73 parts of propylene glycol 1-monomethyl ether 2-acetate.
  • the solution dissolved in was added dropwise over 2 hours, followed by heating at 90 ° C. for 2 hours.
  • 0.230 parts of V-601 was added and reacted at 90 ° C. for 2 hours under a nitrogen stream. Again, 0.230 parts of V-601 was added and reacted at 90 ° C.
  • the dispersing apparatus was operated under the following conditions. ⁇ Bead diameter: ⁇ 0.05mm ⁇ Bead filling rate: 75% by volume ⁇ Peripheral speed: 10m / sec ⁇ Pump supply amount: 10 kg / hour ⁇ Cooling water: Tap water ⁇ Bead mill annular passage volume: 0.15 L ⁇ Amount of liquid mixture to be dispersed: 0.44 kg
  • the average particle size was measured at 30 minute intervals (one pass time). The average particle diameter decreased with the dispersion time (pass number), but the amount of change gradually decreased. Dispersion was terminated when the change in the primary particle size when the dispersion time was extended by 30 minutes became 5 nm or less.
  • the primary particle diameter of the titanium dioxide particles in this dispersion was 40 nm.
  • the primary particle diameter of titanium dioxide is measured by diluting a mixed liquid or dispersion containing titanium dioxide 80 times with propylene glycol monomethyl ether acetate and using the dynamic light scattering method for the obtained diluted liquid. Is obtained. This measurement is the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.
  • composition for forming cured film [Preparation of composition for forming cured film] Using the metal oxide fine particle dispersion (dispersion composition) obtained above, each component was mixed so as to obtain the following composition to obtain a composition for forming a cured film.
  • the composition for forming a cured film was applied onto a silicon wafer by a spin coater (manufactured by Tokyo Electron, ACT-8). Heating was performed at 230 ° C. for 10 minutes using a hot plate to form a cured film having a thickness of 0.4 ⁇ m.
  • the cured film contains titanium dioxide having a primary particle size of 40 nm.
  • a pigment-containing thermosetting composition (colored thermosetting composition) (SG-5000L, manufactured by Fuji Film Electronics Materials) is applied onto the cured film as a spin coater (Tokyo Electron, ACT-8). The film was applied so that the film thickness was 0.8 ⁇ m.
  • the film thickness of the colored layer formed by the pigment-containing thermosetting composition was 0.6 ⁇ m.
  • a positive photoresist “FHi622BC” (manufactured by Fuji Film Electronics Materials) is applied onto the SG-5000L using a spin coater (manufactured by Tokyo Electron, ACT-8) and 100 ° C. Then, a heat treatment for 2 minutes was performed to form a photoresist layer so that the film thickness was 0.8 ⁇ m.
  • the pattern formation process the area corresponding to the filter array of RED is subjected to pattern exposure of 350 mJ / cm 2 with an i-line stepper (manufactured by Canon, FPA3000i5 +), and heat treatment is performed at 110 ° C. for 1 minute.
  • etching process As an etching process, RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, chamber internal pressure: 4.0 Pa, substrate temperature: 50 with a dry etching apparatus (U-621, manufactured by Hitachi High-Technologies Corporation) ° C, the gas type and flow rate of the mixed gas were CF 4 : 200 mL / min. , O 2 : 50 mL / min. , Ar: 800 mL / min. And an etching process for 111 seconds was performed. The etching rate of SG-5000L under the etching conditions was 326 nm / min, and the shaving amount of the colored layer was 603 nm. Therefore, all the colored layers formed of SG-5000L were removed in the etching process.
  • a dry etching apparatus U-621, manufactured by Hitachi High-Technologies Corporation
  • a resist stripping process was performed for 120 seconds using a photoresist stripping solution “MS-230C” (manufactured by Fujifilm Electronics Materials) to remove the resist pattern. According to the above procedure, a color filter pattern was formed, and a monochromatic color filter was produced.
  • Example 1 ⁇ Examples 2 to 12, Comparative Example 1> As shown in Table 1 below, the materials used and the component ratios were changed, and color filters were produced according to the same procedure as in Example 1 above, and peeled off.
  • the primary particle diameter of “titanium dioxide” shown in Table 1 was 40 nm, and the primary particle diameter of “zirconium oxide” was 20 nm.
  • the metal oxide particle is not contained in the cured film.
  • “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 Nippon Shokubai) and 100 g of the following polyester (i-1) were mixed and heated at 120 ° C. for 3 hours to obtain an intermediate. Thereafter, the mixture is allowed to cool to 65 ° C., 200 g of propylene glycol 1-monomethyl ether 2-acetate (hereinafter sometimes referred to as PGMEA) containing 2.3 g of succinic anhydride is slowly added, and the mixture is stirred for 2 hours. -2 was obtained. When the acid value of the intermediate was titrated, it was confirmed that the acid value was 6.4 mgKOH / g.
  • SP-018 number average molecular weight 1,800, manufactured by Nippon Shokubai
  • the acid value was 17.9 mgKOH / g
  • the amine value was 46.2 mgKOH / g. That is, (k) is based on the difference between the acid number of the dispersant B-2 and the acid number of the intermediate, and (l1 + l2) is based on the difference between the amine number of the dispersant B-2 and the number of nitrogen atoms in the resin before the reaction.
  • the weight average molecular weight by GPC method was 15,000.
  • Comparative Example 2 instead of a cured film containing metal oxide particles having a primary particle diameter of 1 nm to 100 nm, a color filter was produced according to the same procedure as in Example 1 except that ACCUGLASS (manufactured by Rasa Industrial Co., Ltd.) was used. Peeling evaluation was performed. Note that Comparative Example 2 corresponds to the aspect specifically disclosed in Patent Document 1 described above.
  • “dispersion amount” means the mass part of the metal oxide fine particle dispersion (dispersion composition) added to the composition for forming a cured film.
  • the “Amount” column in the “Polymerizable compound” column intends parts by mass of the polymerizable compound added to the cured film forming composition.
  • the “amount” column in the “binder polymer” column intends a part by mass of the binder polymer added to the composition for forming a cured film.
  • the “Amount” column in the “Surfactant” column intends a mass part of the surfactant added to the composition for forming a cured film.
  • the “PGMEA amount” column intends parts by mass of propylene glycol monomethyl ether acetate (PGMEA) added to the composition for forming a cured film.
  • the “metal oxide content” column intends the content (mass%: wt%) of metal oxide particles in the cured film.
  • the “number of peeling” column intends the number of peeling defects.
  • DPHA dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.).
  • OX-01 is an initiator manufactured by BASF.
  • the color filter obtained by the production method of the present invention was good with little pattern peeling after peeling of the resist pattern.
  • Examples 1 to 8 when the content of the metal oxide particles in the cured film is 50% by mass or more and 77% by mass or less with respect to the total mass of the cured film (Examples 1 to 3). In the case), it was confirmed that pattern peeling was further reduced.
  • Comparative Example 1 in which a cured film was not provided and in Comparative Example 2 specifically disclosed in Patent Document 1, pattern peeling was large and the effect was inferior.
  • SYMBOLS 1 Solid-state imaging device, 1a ... Board

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