JP2015052753A - Manufacturing method of resin cured product, solid state imaging element using the same, and manufacturing method of liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a resin cured product employing exposure development conditions, which is particularly suitable for a technology to cure a radical polymerization type photosensitive resin composition by exposure, a solid state imaging element using the same, and a manufacturing method of a liquid crystal display device.SOLUTION: There is provided a manufacturing method of a resin cured product, which is a method of forming a patterned resin cured product by irradiating a radical polymerization type photosensitive resin composition with exposure energy, and subsequently developing an exposed part, in which the irradiation of the exposure energy is performed to obtain a pattern having a width of 5 μm or less under the atmosphere of an oxygen density exceeding 21 volume%.

Description

  The present invention relates to a method for producing a cured resin, a solid-state imaging device using the same, and a method for producing a liquid crystal display device.

  In general, a method for producing a color filter used in a liquid crystal display device or a solid-state imaging device is to apply a photosensitive colored resin composition on a substrate and then cure the same. In this case, the resin composition is irradiated with ultraviolet rays through a predetermined mask pattern, and then developed with an alkaline solution. Thereby, a desired pattern image can be obtained. Specifically, taking a solid-state imaging device as an example, organic pixels of a plurality of colors such as red pixels, green pixels, and blue pixels are formed on a support such as a semiconductor substrate. The resin composition of each color is arranged so that these are two-dimensionally arranged, and this is sequentially cured to form a color filter.

  For example, Patent Document 1 describes a method for forming a color filter pattern in which an exposure method is devised from the viewpoint of suppressing residues and forming small openings in a color filter. Patent Document 2 describes a scanning exposure type pattern drawing apparatus that draws a regular pattern on the surface of a substrate such as a color filter substrate.

JP 2006-119177 A JP 2008-129248 A JP 2007-094066 A

  On the other hand, the relationship between the resin for exposure and development and the exposure conditions has not been sufficiently studied. In particular, when a radical polymerization type photosensitive resin composition is used and a fine pattern having a width of 5 μm or less is formed by exposure, what conditions should be set to obtain an appropriate resin cured product. There was nothing to give enough. Patent Document 3 discloses a technique for adjusting the oxygen concentration in the exposure atmosphere by adopting a proximity exposure method (usually used for patterning with a width exceeding 5 μm) for forming a black matrix, not a color filter. . It has not been understood what kind of influence is exerted in the formation of the fine pattern as described above.

  Therefore, the present invention relates to a method for producing a cured resin using a light-exposure developing condition particularly suitable for a technique for curing a radical polymerization type photosensitive resin composition by exposure, and a solid-state imaging device and a liquid crystal using the same. An object is to provide a method for manufacturing a display device. In particular, in the formation of a fine pattern with a width of 5 μm or less, a method for producing a cured resin that exhibits a remarkable effect in improving resolution (pattern separation), and a solid-state imaging device and a liquid crystal display device using the same The purpose is to provide a manufacturing method.

  In view of the above problems, the present inventor has conducted experimental confirmation on curing and patterning of the radical polymerizable resin composition from various viewpoints such as exposure conditions and development conditions as well as resin blending. As a result of analyzing the large number of data, when the radical polymerization type photosensitive resin composition is exposed to form a pattern having a width of 5 μm or less, a significant effect is exhibited in the pattern resolution by increasing the oxygen concentration. I found out. The present invention has been completed based on such findings, and has the following means.

[1] A method of forming a patterned resin cured product by irradiating a radical polymerization type photosensitive resin composition with exposure energy and then developing an exposed portion, wherein the exposure energy is irradiated with an oxygen concentration A method for producing a cured resin, which is carried out in a pattern having a width of 5 μm or less in an atmosphere exceeding 21% by volume.
[2] The method for producing a cured resin product according to [1], wherein the oxygen concentration is 55% by volume or less.
[3] Resin curing according to [1] or [2], wherein the exposure energy is irradiated with an active energy ray selected from g-line, h-line, i-line, KrF excimer laser line, and ArF excimer laser line. Manufacturing method.
[4] The method for producing a cured resin according to any one of [1] to [3], wherein the illuminance of the exposure energy is 5000 W / m ^{2 to} 18000 W / m ² .
[5] The method for producing a cured resin according to any one of [1] to [4], wherein the exposure energy is irradiated by reduced projection exposure.
[6] The resin curing according to any one of [1] to [5], wherein the radical polymerization type photosensitive resin composition is a colored photosensitive composition comprising an organic pigment and / or an inorganic pigment. Manufacturing method.
[7] The exposure energy is irradiated by a projection optical system having a coherence factor (σ) of 0.5 or less and a lens aperture ratio (NA) of 0.5 or more. The manufacturing method of the resin cured material of description.
[8] The method for producing a cured resin according to any one of [1] to [7], wherein the radical polymerization type photosensitive resin composition is a photocurable composition.
[9] In any one of [1] to [8], the radical polymerization type photosensitive resin composition contains a specific polymer, a monomer having an ethylenically unsaturated double bond, a polymerization initiator, and a colorant. The manufacturing method of the resin cured material of description.
[10] The method for producing a cured resin according to [9], wherein the monomer is a monomer represented by any of the following formulas (MO-1) to (MO-7).
(In the formula, R is a group having a hydroxy group or a vinyl group at the terminal. However, it has at least one vinyl group in the molecule. T, Z ² and Z are linking groups. N is an integer. )
[11] The method for producing a cured resin according to any one of [1] to [10], wherein the cured resin is a pixel portion of a color filter.
[12] The method for producing a cured resin according to [11], wherein a plurality of pixel portions of different colors are adjacent to each other for the pixel portion of the color filter.
[13] A method for manufacturing a solid-state imaging device, wherein a solid-state imaging device having a color filter is produced through the manufacturing method according to [11] or [12].
[14] A method for producing a liquid crystal display device, wherein a liquid crystal display device having a color filter is produced through the production method according to [11] or [12].

  According to the production method of the present invention, exposure / development particularly suitable for a technique for curing a radical polymerization type photosensitive resin composition by projection exposure becomes possible. In particular, in the formation of a fine pattern having a width of 5 μm or less, a remarkable effect is exhibited in improving the resolution (pattern separation property).

1 is a partial cross-sectional view of a solid-state imaging device according to a preferred embodiment of the present invention. It is explanatory drawing which shows typically the projection exposure apparatus which concerns on preferable embodiment of this invention, and light irradiation conditions. FIG. 4 is a plan view (a) and a cross-sectional view (b) schematically showing a situation in which a strain occurs in a pixel portion of a color filter. It is an enlarged photograph (drawing substitute photograph) which showed the distinction of the evaluation regarding the resolution of the resin cured material (pixel part) produced in the Example.

  In the method for producing a cured resin of the present invention, the radical polymerization type photosensitive resin composition is exposed in a specific oxygen concentration atmosphere. Before describing in detail the exposure and development, a solid-state imaging device to which a color filter, which is a preferred application example of a cured resin obtained by the production method of the present invention, will be described with reference to FIG.

[Solid-state imaging device]
In the figure, the solid-state imaging device 10 is illustrated only on the upper side (light incident side) of the lower planarizing film 12. The lower side includes a circuit, a light receiving element, and the like, but the illustration is omitted. In the solid-state imaging device 10 of the present embodiment, a light receiving element (photodiode) (not shown) provided on a silicon substrate (not shown), a color filter 20, an upper planarizing film 11, a microlens 15 and the like. Consists of The upper and lower planarizing films 12 and 11 are not necessarily provided. In FIG. 1, in order to clarify each part, the ratios of the thicknesses and widths are disregarded and some of them are exaggerated.

  The color filter 20 includes red (R), green (G), and blue (B) color filter pixel portions 20R, 20G, and 20B. In the present specification, as described above, the structural unit of each color of the color filter is referred to as a “pixel portion”, but an area (g in the drawing) partitioned by the pixel portion is referred to as a pixel and is distinguished. There is.

  As described above, the color filter 20 includes a plurality of green pixel portions 20G, 20R, and 20B that are two-dimensionally arranged. In the present embodiment, there is no black matrix between them. Each of the colored pixel portions 20R, 20G, and 20B is formed above the light receiving element. The green pixel portion 20G is formed in a Bayer pattern (checkered pattern), and the blue pixel portion 20B and the red pixel portion 20R are formed between the green pixel portions 20G. In FIG. 1, the colored pixel portions 20R, 20G, and 20B are displayed in a line in order to explain that the color filter 20 includes three color pixel portions.

  The planarizing film 11 is formed so as to cover the upper surface of the color filter 20 and planarizes the color filter surface. The microlens 15 is a condensing lens disposed with the convex surface facing upward, and is provided above the planarizing film 11 and above the light receiving element. That is, the microlens, the color filter pixel unit, and the light receiving element are arranged in series along the light incident direction, and the light from the outside is efficiently guided to each light receiving element. In addition, although detailed description about a light receiving element and a microlens is abbreviate | omitted, what is normally applied to this kind of product can be utilized suitably.

  In the manufacturing method of the present invention, the width g of the pixel portion is not particularly limited, but since the effect appears remarkably, it is 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, It is more preferable that it is 1 micrometer or less, and it is especially preferable that it is 0.8 micrometer or less. Although there is no lower limit in particular, it is practical that it is 100 nm or more. Speaking of the rectangular pixels of the Bayer pattern, in plan view, it is preferably 5 μm □ or less, more preferably 3 μm □ or less, further preferably 2 μm □ or less, and further preferably 1 μm □ or less. It is particularly preferably 0.8 μm □ or less. Although there is no particular lower limit, it is practical that it is 100 nm □ or more. Moreover, it is preferable that the pixel portions are adjacent to each other because the effects of the present invention are more conspicuous. In addition, (sq) means that it is the length of one side of a square. The line width of the pixel portion is based on the conditions measured in the examples described later unless otherwise specified.

[Hardened resin (color filter)]
Each pixel portion of the color filter according to a preferred embodiment of the present invention is preferably formed by curing the following photosensitive resin composition. The photosensitive resin composition includes a specific polymer (a polymer having no polymerizable group, a dispersant, an acrylic polymer having a polymerizable group, etc.), an ethylenically unsaturated double bond (preferably two or more, more preferably Contains a monomer having 3 or more), a polymerization initiator, and a colorant. Especially, it is preferable that the photosensitive resin composition has photocurability, and it is preferable to use it as a negative resin.

・ Specific polymers Polymers that do not have a polymerizable group Polymers that do not have a polymerizable group include, in particular, alkali-soluble resins, dispersants, and dispersion resins other than alkali-soluble resins used as dispersion resins and additional resins. Illustrated. The polymer preferably includes an acrylic polymer having no polymerizable group, and a preferable example thereof is an alkali-soluble resin.

Alkali-soluble resin The alkali-soluble resin is a linear organic high-molecular polymer having at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, but are soluble in a solvent and can be developed with a weak alkaline aqueous solution. Of these, (meth) acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, a treatment for imparting an acid group after polymerization is required by a conventional method.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl methacrylate is suitable. . Other monomers in this case include 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl described in JP-A-7-140654. Acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / A methacrylic acid copolymer etc. are mentioned.

The alkali-soluble resin is also preferably the following.
As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (iso) pentyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) ) Acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and other vinyl compounds include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile , Vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like, as N-substituted maleimide monomers described in JP-A-10-300922, jN-phenylmaleimide, N-cyclohexyl A maleimide etc. can be mentioned.
The other monomer copolymerizable with (meth) acrylic acid is preferably a repeating unit represented by the following formula (A1).

In the above formula (A1), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 2 or 3 carbon atoms. R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10), or an aralkyl group having 7 to 22 carbon atoms (preferably 7 to 10). n represents an integer of 1 to 15. m represents an integer of 1 to 5, preferably 1 to 3, and more preferably 1. R ³ is preferably substituted at least in the para position. The repeating unit represented by the above formula (A1) has good adsorption and / or orientation on the pigment surface due to the effect of π electrons of the benzene ring present in the side chain. In particular, when this side chain portion has an ethylene oxide or propylene oxide structure of paracumylphenol, its steric effect is added, and a better adsorption and / or orientation plane can be formed on the pigment. Therefore, it is more effective and preferable.
In particular, R ³ is preferably an alkyl group or an aralkyl group having the above carbon number. This is because when R ³ is an alkyl group or an aralkyl group, this group becomes an obstacle to suppress the approach between the resins and promote the adsorption and / or orientation to the colorant (for example, pigment). However, if the carbon number is too large, the steric hindrance effect of the alkyl group is increased, and the adsorption and / or orientation of the benzene ring on the pigment surface may be hindered. This phenomenon becomes more prominent as the chain length of the alkyl group of R ³ becomes longer, and the adsorption and / or orientation of the benzene ring extremely decreases as the carbon number further increases. Therefore, the alkyl group or aralkyl group represented by R ³ preferably has the carbon number within the above range.

R ² in formula (A1) is preferably a C ² alkylene group (ethylene group) from the viewpoint of developability.
Furthermore, n in the formula (A1) is preferably in the range of 1 to 12 from the viewpoint of developability.

The acid value of the polymer having no polymerizable group is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g, and still more preferably 70 to 120 mgKOH / g. By setting it as such a range, the image development residue of an unexposed part can be reduced effectively.
The weight average molecular weight (Mw) of the polymer having no polymerizable group is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.
As a density | concentration of the polymer which does not have a polymeric group, 10-50 mass% is preferable with respect to the total solid of the photosensitive resin composition, More preferably, it is 15-40 mass%, Especially preferably, 20- 35% by mass.

  In the present invention, the molecular weight means a weight average molecular weight (Mw) unless otherwise specified. The measurement employs a value in terms of polystyrene by gel permeation chromatography (GPC). The carrier and column may be selected as appropriate. For example, HLC-8220 (manufactured by Tosoh Corporation) is used, TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) is used as a column, and 10 mmol / L lithium bromide NMP (N— It can be determined by using a methylpyrrolidinone) solution.

Dispersant In the present invention, it is also preferable to use a dispersant in the photosensitive resin composition.
As the dispersant, a polymer dispersant (for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type) Copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present embodiment include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group)”, 130 (manufactured by BYK Chemie). Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 ”,“ EFKA4047, manufactured by EFKA, 4050, 4010, 4165 (polyurethane), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester) , 6745 (Phthalocyanine invitation Body), 6750 (azo pigment derivative) "," Ajispur PB821, PB822 "manufactured by Ajinomoto Fan Techno Co.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co.," Polyflow No. 50E, No. 300 (acrylic type). Copolymer) ”, manufactured by Enomoto Kasei Co., Ltd.“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA -725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (polymeric polycondensate) " Carboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) Tel) "," Acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (functional part at the end part) 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd., etc. Is mentioned.

  These dispersants may be used alone or in combination of two or more. In this embodiment, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

  As a density | concentration of a dispersing agent, it is preferable that it is 1-100 mass parts with respect to 1 part of coloring agents, 3-100 mass parts is more preferable, and 5-80 mass parts is further more preferable. Moreover, it is preferable that it is 10-30 mass% with respect to the total solid of a composition.

Specific acrylic polymer having a polymerizable group Examples of the polymerizable group possessed by the specific acrylic polymer include an ethylenically unsaturated bond group, preferably a (meth) acryloyl group and a vinyl group, and further a (meth) acryloyl group. preferable. The acrylic polymer is preferably a vinyl polymer having a repeating unit derived from one or more of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylamide.

  As a ratio of the polymerizable group contained in the specific acrylic polymer, a molar copolymerization ratio is preferably 5 to 50, and more preferably 10 to 40. By setting it as such a range, coexistence of curability and developability is achieved more effectively. As another structural unit, the structural unit containing an acid group is illustrated. Examples of the acid group include a carboxyl group, a phosphate group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable. The acid value of the specific acrylic polymer is preferably 10 to 200 mgKOH / g, and more preferably 20 to 150 mgKOH / g. By setting it as such a range, it becomes possible to improve the solubility of the unexposed part at the time of pattern formation. The acid value refers to a value obtained by neutralization titration with a potassium hydroxide solution.

  Specific acrylic polymers include, for example, carboxyl group-containing resins such as glycidyl group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether, and unsaturated alcohols such as allyl alcohol, 2-hydroxy acrylate, and 2-hydroxy methacrylate. Resin reacted, carboxyl group-containing resin having hydroxyl group, free isocyanate group-containing unsaturated compound, resin reacted with unsaturated acid anhydride, addition reaction product of epoxy resin and unsaturated carboxylic acid polybasic acid anhydride , A resin obtained by reacting a hydroxyl group-containing polyfunctional monomer with an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride, and a base treatment to cause an elimination reaction to give an unsaturated group By synthesizing a resin having a functional group and subjecting the resin to base treatment, Resins were generated KazuHajime can be cited as typical resins.

  The specific acrylic polymer is preferably a resin containing at least one selected from structural units (specific structural units) represented by any of the following formulas (1) to (3).

A ¹ , A ² and A ³ each represent an oxygen atom, a sulfur atom, N (R ^N ), or a group obtained by combining these. ^RN is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, particularly preferably 1 to 3), and an aryl group (preferably having 6 to 14 carbon atoms, more preferably 6 to 6 carbon atoms). 10), or an aralkyl group (preferably having a carbon number of 7 to 20, more preferably 7 to 15, particularly preferably 7 to 11). In the present specification, an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group, or a group having these may be branched or linear, unless otherwise specified. Alternatively, it may be annular. Further, each substituent and linking group may further have an arbitrary substituent as long as the effects of the present invention are exhibited, unless otherwise specified.

X, Y, and Z each represent a single bond, an oxygen atom, a sulfur atom, a phenylene group, N (R ^N ), or a combination thereof.

G ¹ , G ² , and G ³ represent a divalent organic group, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these Groups consisting of combinations are preferred. Specifically, a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms and a combination thereof are more preferable. A group consisting of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a combination thereof is particularly preferable. These groups may further have a substituent, and the substituent is preferably a hydroxyl group. More preferable embodiments of G ¹ , G ² , and G ³ are — (CH ₂ ) _n — (cycloalkylene group that may have a substituent) — (CH ₂ ) _n —, and each n is 0. And an cycloalkylene group is a 5-membered ring or a 6-membered ring (more preferably a 6-membered ring).

R ^{1 to} R ²⁰ each independently represents a hydrogen atom or a monovalent organic group.
R ^{1 to} R ⁴ , R ^{7 to} R ¹⁰ , and R ^{13 to} R ¹⁸ each represent a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ¹ and R ² are more preferably a hydrogen atom, and R ³ is more preferably a hydrogen atom or a methyl group.
R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹⁹ , R ²⁰ are each a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryl group. Examples include an oxy group, an alkylsulfonyl group, and an arylsulfonyl group, preferably a hydrogen atom, an alkoxycarbonyl group, an alkyl group, and an aryl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

  The synthesis of the polymer compound having the specific structural unit can be performed based on the synthesis method described in paragraph Nos. 0027 to 0057 of JP-A No. 2003-262958. Of these, the synthesis method 1) in the publication is preferred. Specific examples of the polymer compound having the specific structural unit include the following compounds. The present invention is not limited to these compounds.

  The use of the specific acrylic polymer having a polymerizable group is optional, and when used, it is preferably 1% by mass or more, more preferably 5% by mass or more in the photosensitive resin composition. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 14% by mass or less. By setting it within this range, when the cured colored layer is cured, film shrinkage hardly occurs, and a colored layer having excellent pattern formability and less surface roughness can be formed. The acid value of the resin is preferably 10 to 200 mgKOH / g, and more preferably 20 to 150 mgKOH / g. By setting it as this range, it becomes possible to reduce the residue of the unexposed part after image development. The total solid content is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.

Monomers having an ethylenically unsaturated double bond Monomers having an ethylenically unsaturated double bond (hereinafter sometimes referred to as “polyfunctional monomers”) can be used without particular limitation. A polyfunctional monomer may be used individually by 1 type, and may use 2 or more types together. The polyfunctional monomer is preferably a (meth) acrylate monomer. As these specific compounds, the compounds described in JP-A 2009-288705, paragraphs 0095 to 0108 can also be suitably used in this embodiment.

The monomer having an ethylenically unsaturated double bond preferably has the following reactive group RA in the molecule.
(Reactive group RA: vinyl group, (meth) acryloyl group, or (meth) acryloyloxy group)
As the monomer having an ethylenically unsaturated double bond, a radical polymerizable monomer represented by any of the following formulas (MO-1) to (MO-7) can be preferably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.
In the photosensitive resin composition of the present invention, the number of functional groups of the polyfunctional monomer tends to improve the pattern resolution. This is considered to be related to the amount of exposure energy required for adhesion.

In the formula, R is a group having a hydroxy group or a vinyl group at the terminal. However, at least one has a vinyl group in the molecule, preferably two or more vinyl groups, more preferably three or more. R is preferably a substituent of any of R1 to R5 below. T is a linking group, preferably a linking group according to any one of the following T1 to T5, or a combination thereof. Z is a linking group and is preferably the following Z ¹ . Z ² is a linking group, and is preferably the following formula Z2. It should be noted that the directions of T ^{1 to} T ⁵ may be reversed according to the equation.

In the formula, n is an integer, preferably 0-14, more preferably 0-5, and particularly preferably 1-3. Each m is 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. A plurality of R, T and Z present in one molecule may be the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least two of R are preferably polymerizable groups, and more preferably three are polymerizable groups. Z ³ is a linking group, preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. Of these, a 2,2-propanediyl group is particularly preferable.
As specific examples of the radical polymerizable monomer, compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-26979 can be suitably used in this embodiment.

  Among them, as a polymerizable monomer, 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 K.K.) and dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Company-made), 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 (commercially available product is M-460; Etsu Chemical Co., Ltd.) is preferable. These oligomer types can also be used.

  The polyfunctional monomer is particularly preferably at least one selected from a compound represented by the following formula (i) and a compound represented by the formula (ii).

In the above formulae, E represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —, and — ((CH ₂ ) _y CH ₂ O)-is preferred.
y represents the integer of 1-10, respectively, the integer of 1-5 is preferable and 1-3 are more preferable.
X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.
In the formula (i), the total number of acryloyl groups and methacryloyl groups is preferably 3 or 4, more preferably 4.
m represents the integer of 0-10, respectively, and 1-5 are preferable. The total of each m is an integer of 1-40, and 4-20 pieces are preferable.
In formula (ii), the total number of acryloyl groups and methacryloyl groups is preferably 5 or 6, and more preferably 6.
n represents the integer of 0-10, respectively, and 1-5 are preferable. The total of n is an integer of 1-60, respectively, and 4-30 are preferable.

  The polyfunctional monomer may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, it is preferable that the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, and this can be used as it is. The hydroxyl group may be reacted with a non-aromatic carboxylic anhydride to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably 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 acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.

  About these polyfunctional monomers, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a composition. In the present embodiment, a method of adjusting both sensitivity and strength by using different functional numbers and / or different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). Is also effective. Furthermore, it is preferable to use a polyfunctional monomer having an ethylene oxide chain length of 3 or more and 8 or less in that the developability of the composition can be adjusted and an excellent pattern forming ability can be obtained. In addition, the selection and use of polyfunctional monomers is important for compatibility and dispersibility with other components (for example, polymerization initiators, colorants (pigments), resins, etc.) contained in the composition. For example, compatibility may be improved by the use of a low-purity compound or a combination of two or more. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

  The concentration (mixing ratio) of the polyfunctional monomer is preferably 1% by mass or more, and preferably 5% by mass or more, based on the total solid content in the photosensitive resin composition. Although there is no restriction | limiting in particular about an upper limit, It is preferable that it is 50 mass% or less, and it is more preferable that it is 40 mass% or less.

Polymerization initiator The polymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polyfunctional monomer, and can be appropriately selected from known polymerization initiators. Those having photosensitivity are preferred. It may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and may be an initiator that initiates cationic polymerization according to the type of monomer. The polymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the polymerization initiator 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. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include, for example, compounds having an oxadiazole skeleton, JP-A-53-133428, JP-B-57-1819, and JP-A-57-6096. And compounds described in US Pat. No. 3,615,455.

As the polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the polymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

Examples of oxime compounds such as oxime derivatives that are preferably used as a polymerization initiator in the present embodiment include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
Specifically, the oxime polymerization initiator is preferably a compound represented by the following formula (O1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

As an oxime compound used as a polymerization initiator, what is represented by a following formula (OX) is preferable, and what is represented by a formula (OX-1) is more preferable.
・ A ¹
A ¹ is preferably -AC or an alkyl group of the formula (OX-1). The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent O described later. Further, the substituent O may be substituted via a linking group L described later.

・ R
R represents a monovalent substituent, and is preferably a monovalent nonmetallic atomic group. Examples of the monovalent non-metallic atomic group include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, particularly preferably 1 to 3), and an aryl group (preferably having 6 to 14 carbon atoms, more preferably 6-10), acyl group (preferably 2-12 carbon atoms, more preferably 2-6, particularly preferably 2-3), aryloyl group (preferably 7-15 carbon atoms, more preferably 7-11). An alkoxycarbonyl group (preferably having a carbon number of 2-12, more preferably 2-6, particularly preferably 2-3), an aryloxycarbonyl group (preferably having a carbon number of 7-15, more preferably 7-11), a complex A cyclic group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkylthiocarbonyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms), Over thiocarbonyl group include (preferably having 7 to 15, more preferably 7 to 11 carbon atoms) and the like. Moreover, these groups may have one or more substituents. In addition, the above-described substituent may be further substituted with another substituent O. As the substituent O, a halogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, particularly preferably 1 to 3), an aryl group (preferably having 6 to 14 carbon atoms, more preferably 6 to 6 carbon atoms). 10) and the like. Substituent O is via an optional linking group L (an alkylene group having 1 to 6 carbon atoms, O, S, CO, NR ^N , or a combination thereof: ^RN is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). May be substituted.

・ B
B represents a monovalent substituent, and is an alkyl group (preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms, more preferably having 6 to 10 carbon atoms), or a heterocyclic group (preferably having carbon atoms). Number 2-18, more preferably carbon number 2-12). These groups may be bonded via a linking group L. In addition, these groups may have one or more substituents O. Substituent O may also be substituted via any linking group L. Specific examples of B include the following. * Indicates a bonding position, but may be bonded at different positions. Further, these groups may be further accompanied by a substituent O. Specific examples include a benzoyl group, a phenylthio group, and a phenyloxy group.

・ A
A is a single bond or a linking group. Preferred examples of the linking group include the linking group L or arylene group (preferably having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms) or a heterocyclic linking group (preferably an aromatic heterocyclic linking group) (preferably Has 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms.

・ C
C represents SAr or COAr.
・ Ar
Ar is an aryl group or heteroaryl (aromatic heterocyclic group). As an aryl group, Preferably it is C6-C14, More preferably, it is C6-C10, and a phenyl group and a naphthyl group are preferable. As a heteroaryl group, Preferably it is C2-C18, More preferably, it is C2-C12, and the carbazolyl group which may have substituents, such as an alkyl group, in N-position is preferable.

  As the oxime initiator, paragraph 0513 of JP 2012-208494 A (corresponding US Patent Application Publication No. 2012/235099, [0632]) and the following formulas (OX-1), (OX-2) or ( Description of the compound represented by OX-3) can be referred to, and the contents thereof are incorporated in the present specification.

  Specific examples (PIox-1) to (PIox-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a function as a thermal polymerization initiator that decomposes by heat to start and accelerate polymerization. The above oxime compound (PIox-1) is preferable because it has particularly high sensitivity at the I-line (365 nm). Further, the above oxime compound (particularly PIox-2) has very high reactivity, and its application is preferable. As described above, oxime compounds (particularly PIox-1 and PIox-2) have high exposure wavelength sensitivity or reactivity, and also have low oxygen inhibition, so that sufficient resolution can be obtained even in a high oxygen concentration region. It can be used particularly preferably for the present invention which requires exposure at a high oxygen concentration.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the 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, in an ultraviolet-visible spectrophotometer (Varian's Carry-5 spectrophotometer), an ethyl acetate solvent is used, and 0.01 g It is preferable to measure at a concentration of / L.
As the oxime compound, commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and the like can be suitably used.

  You may use a polymerization initiator in combination of 2 or more type as needed. The concentration of the polymerization initiator in the photosensitive resin composition (in the case of two or more types) is preferably in the range of 0.1 to 20% by mass with respect to the total solid content of the photosensitive resin composition, More preferably, it is the range of 0.5-10 mass%, Most preferably, it is the range of 1-8 mass%. Within this range, good sensitivity and pattern formability can be obtained.

  A sensitizer may be contained for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. As a sensitizer that can be used in this embodiment, a sensitizer that sensitizes a polymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer include compounds described in paragraph numbers 0101 to 0154 of JP-A-2008-32803.
When blended, the concentration of the sensitizer in the composition is preferably 0.1% by mass to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. 0.5 mass%-15 mass% are more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Colorant The colorant is not particularly limited, and various conventionally known dyes and pigments can be used singly or in combination of two or more, depending on the use of the composition of the present embodiment. It is selected appropriately. It is preferable that the composition of the present embodiment is used for producing a color filter, and chromatic colorants such as red, magenta, yellow, blue, cyan, and green that form the color pixel portion of the color filter ( Any of a chromatic colorant) and a black colorant (black colorant) generally used for forming a black matrix can be used. In the present embodiment, the colorant is preferably at least one selected from red, magenta, yellow, blue, cyan, and green.

Hereinafter, the colorant will be described in detail using a colorant suitable for a color filter application as an example.
As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. 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 finer one as much as possible, and considering the handling properties, the average primary particle diameter of the pigment is 0.01 μm. ˜0.1 μm is preferable, and 0.01 μm to 0.05 m is more preferable.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Examples thereof include metal oxides such as silver and complex oxides of the above metals. Titanium nitrides, silver tin compounds, silver compounds, and the like can also be used.

When the colorant is a dye, a colored composition in a state of being uniformly dissolved in the composition can be obtained.
The dye that can be used as the colorant contained in the photosensitive resin composition is not particularly limited, and conventionally known dyes for color filters can be used. For example, pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Dyes such as phthalocyanine, benzopyran, indigo, and pyromethene can be used. Moreover, you may use the multimer of these dyes.

Moreover, when performing water or alkali image development, an acidic dye and / or its derivative may be used suitably from a viewpoint that the binder and / or dye of a light non-irradiation part are removed completely by image development.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

Among them, as the colorant, triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo It is preferable that the colorant is selected from a series, anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone pyromethene.
Further, pigments and dyes may be used in combination. In particular, C.I. I. Pigment red 122, C.I. I. Pigment Yellow 185 is preferable.

  In the present invention, known colorants such as inorganic pigments, organic pigments and dyes may be added as appropriate. Some specific examples overlap, but specific examples are shown below.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Mention may be made of metal oxides such as zirconium, and complex pigments of the above metals, black pigments such as carbon black and titanium black.

As an organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1;
Etc.

  Known dyes include, for example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-51115 The pigment | dye currently disclosed by 6-194828 gazette etc. can be used. The chemical structure includes pyrazole azo, pyromethene, anilinoazo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, etc. Dyes can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097.

The colorant that can be used in the photosensitive resin composition is preferably a dye or a pigment. In particular, a pigment having an average particle size (r) of 20 nm ≦ r ≦ 300 nm, preferably 125 nm ≦ r ≦ 250 nm, particularly preferably 30 nm ≦ r ≦ 200 nm is desirable. By using a pigment having such an average particle diameter, a pixel having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated. The average primary particle diameter can be obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.
The particle size distribution of the secondary particles of the pigment (hereinafter, simply referred to as “particle size distribution”) is 70% by mass or more, preferably 80% by mass or more of the total secondary particles entering (average particle size ± 100) nm. It is desirable that The particle size distribution was measured using a scattering intensity distribution.

  The pigment having the average particle size and particle size distribution described above is preferably a commercially available pigment mixed with other pigments used in some cases (average particle size is usually more than 300 nm), preferably with a dispersant and a solvent. The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

The concentration of the colorant contained in the photosensitive resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more in the total solid content of the photosensitive resin composition. Further preferred. Although there is no restriction | limiting in particular about an upper limit, Preferably it is 45 mass% or less.
By setting the concentration of the colorant within the above range, an appropriate chromaticity can be obtained when a color filter is produced from the photosensitive resin composition. Further, since photocuring sufficiently proceeds and the strength as a film can be maintained, it is possible to prevent the development latitude during alkali development from becoming narrow.

  The photosensitive resin composition can also contain other components. Examples of other components include a solvent, a surfactant, a UV absorber, a polymerization inhibitor, and an adhesion improver.

-Solvent The photosensitive resin composition can generally be comprised using a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the photosensitive resin composition, but in particular, considers the solubility, applicability, and safety of the UV absorber and binder resin. Are preferably selected. Moreover, when preparing the photosensitive resin composition, it is preferable to contain at least two types of solvents.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) ), 2-Oki Propionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And examples of ethers Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Suitable examples of aromatic hydrocarbons include xylene.

  The concentration of the solvent in the photosensitive resin composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. ˜50 mass% is particularly preferred.

-Other additives Surfactant Various surfactants may be added to the composition from the viewpoint of further improving coatability. As the surfactant, 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 amount of the surfactant added is preferably 0.001% by mass to 2% by mass, more preferably 0.005% by mass to 1% by mass, based on the total mass of the composition, when blended.

Polymerization inhibitor It is desirable to add a small amount of polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polyfunctional monomer during the production or storage of the composition. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, o-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Further, the photosensitive resin composition may contain a co-sensitizer for the purpose of further improving the sensitivity of the sensitizing dye or initiator to actinic radiation or suppressing polymerization inhibition of the polyfunctional monomer by oxygen. Good. Moreover, in order to improve the physical property of a cured film, you may add well-known additives, such as a diluent, a plasticizer, a fat-sensitizing agent, as needed. In the case of using a polymerization inhibitor, the addition amount is preferably in the range of 0.001% by mass to 0.015% by mass in the total solid content in the colored photosensitive resin composition, preferably 0.03% by mass to 0.09 mass% is more preferable.

Adhesion improver The addition amount in the case of using an adhesion improver is preferably in the range of 0.1% by mass to 5% by mass, and 0.2% by mass in the total solid content in the colored photosensitive resin composition. -3 mass% is more preferable.

Ultraviolet absorber The photosensitive resin composition may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. When the ultraviolet absorber is included, the concentration of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and 0.01% by mass or more and 0.1% by mass or less with respect to the total solid mass. It is more preferable that

-Preparation of photosensitive resin composition Although it does not restrict | limit especially about the preparation aspect of the photosensitive resin composition, For example, an essential component and the various additives used together as needed can be mixed and prepared.

Cured film and method for producing the same:
A cured film obtained by curing the composition has high color purity, a high absorption coefficient in a thin layer, and good fastness (especially heat resistance and light resistance). Further, even when a white LED is used as a backlight, a colored pixel portion having a good hue can be formed. Therefore, the effect is remarkable when applied to a liquid crystal display device including a white LED. Used to form a colored pixel portion in a filter.
The manufacturing method of a cured film includes the process of applying the photosensitive resin composition on a board | substrate, and the process of exposing this photosensitive resin composition. Specifically, when forming a cured film on an arbitrary substrate or substrate, the photosensitive resin composition is applied, or the substrate or the like is immersed in the photosensitive resin composition to form a photosensitive resin composition. A physical layer may be formed and cured. Further, when forming a patterned cured film, it may be applied on a substrate by an inkjet recording method, or a known printing method such as textile printing or offset printing may be applied, but a high-definition pattern is formed. From the viewpoint of being able to be obtained, a method of forming a photosensitive resin composition layer on a substrate and exposing it in a pattern shape, which will be described later, and then developing to remove an unexposed portion of the photosensitive resin composition layer is preferable.
The thickness of the cured resin film is, for example, preferably 0.3 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.75 μm or more. The upper limit is preferably 2 μm or less, more preferably 1.5 μm or less, and particularly preferably 1 μm or less. In this specification, unless otherwise specified, the thickness of the film depends on the conditions measured in the examples described later.

Color filter and manufacturing method thereof:
The manufacturing method of a color filter includes the process of applying the photosensitive resin composition on a board | substrate, and the process of carrying out pattern exposure of this photosensitive resin composition. Specifically, a step of forming the photosensitive resin composition layer by applying the above-described photosensitive resin composition on the support (hereinafter also referred to as “photosensitive resin composition layer forming step”), A step of pattern exposure of the photosensitive resin composition layer through a mask (hereinafter also referred to as “exposure step”), and development of the exposed photosensitive resin composition layer to form a colored pattern (hereinafter referred to as “colored pixel portion”). And a step of forming (hereinafter also referred to as “developing step”).

[Exposure process]
In preferable embodiment which concerns on the manufacturing method of this invention, exposure energy is irradiated to said photosensitive resin composition, The exposed part is developed, and the pattern of resin cured | curing material is formed. In this embodiment, prior to the above exposure, a photosensitive resin composition is applied on a support or the like to form a layer of the photosensitive resin composition. As the support, for example, a solid-state imaging device substrate in which an imaging device (light receiving device) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate) is used. be able to. The coloring pattern may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface). A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate. Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As a method for applying the photosensitive resin composition on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied. The film thickness of the photosensitive resin composition layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and further preferably 0.2 μm to 3 μm. Drying (pre-baking) of the photosensitive resin composition layer coated on the support can be performed at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, an oven or the like.

In the exposure step, the layer of the photosensitive resin composition is subjected to pattern exposure through a mask having a predetermined mask pattern, for example, using an exposure apparatus such as a stepper. The exposure energy is preferably irradiated by active energy rays selected from g-line, h-line, i-line, KrF line (excimer laser line), and ArF line (excimer laser line). Preferably illuminance of the exposure energy is 5000 W / ^{m 2} or more, more preferably 7000 W / ^{m 2} or more, and particularly preferably 8000W / ^{m 2} or more. The provisions of the upper limit, is preferably 18000W / ^{m 2} or less, more preferably 15000W / ^{m 2} or less, particularly preferably 10000 W / ^{m 2} or less. By setting the irradiation energy within this range, a good pattern resolution can be obtained.

FIG. 2 is an explanatory view schematically showing a reduction projection exposure apparatus and light irradiation conditions according to a preferred embodiment of the present invention. As shown in the figure, in the projection exposure apparatus of the present embodiment, an active energy ray emitted from a specific light source (not shown) passes through a condenser lens 1 and a reticle 5 and is a projection lens (projection lens). 2 is incident. In the present projection optical system, a mask with a predetermined pattern may be installed before or after the condenser lens 1 so that the active energy ray having the predetermined pattern reaches the projection lens 2. . Here, the numerical aperture on the condenser lens side is NA _1, and the numerical aperture on the projection lens side is NA ₂ . The active energy ray that has passed through the reduced projection optical system is emitted from the opposite side and irradiated onto the exposure substrate (workpiece) 4. By irradiation with this active energy ray, the photosensitive resin composition layer on the substrate is exposed, and a negative type (exposure curable) is preferable, and the exposed portion is cured. In the present embodiment, the numerical aperture of the emission side of the projection lens with NA _3. Incidentally, just when expressed as NA means the NA _3.

In the proximity exposure, a mask is disposed immediately above or very close to the surface of the substrate (work). The exposure resolution (pattern precision) differs greatly between the proximity exposure and the projection exposure, and the accuracy and error that are problematic in the projection exposure may not be a problem in the proximity exposure.
Although excellent resolution (pattern separation) is achieved by the manufacturing method of the present invention, the difference becomes apparent because of pattern exposure that requires high accuracy by reduced projection exposure. The effect becomes remarkable especially in the pattern formation below 5 μm.

In the present invention, the numerical aperture NA ₃ is preferably 0.5 or more, more preferably 0.55 or more, and particularly preferably 0.6 or more. Although there is no upper limit, it is practical that NA is 0.65 or less in the stepper in the batch exposure method. In general, it is understood that the resolving power is in a relationship of k × λ / NA (k: optical constant, λ: wavelength). Therefore, the limit resolution improves as the NA increases. However, DOF has a relationship of DOF = k · λ / NA ² . The DOF decreases as the NA increases. k depends on the illumination conditions of the stepper and is not fixed. On the other hand, in the limit resolving power region, there is a possibility that the limit resolving power improvement = DOF can be secured. For the exposure mode according to the preferred embodiment of the present invention, it is preferable that the pattern width is close to the limit resolving power, and therefore the NA is increased.
The coherence factor σ, which is the ratio of the numerical apertures NA ₁ and NA ₂ (NA ₁ / NA ₂ ), is preferably 0.5 or less, more preferably 0.45 or less, and 0.4 or less. It is particularly preferred. Although there is no lower limit in particular, it is practical that it is 0.38 or more. When the coherent factor (σ) is small, the contrast of the image to be increased is improved. This improvement in contrast is thought to contribute to an improvement in DOF.
In the present invention, by setting the numerical aperture NA ₃ and the coherence factor σ within this range, it is possible to achieve good rectangularity (plan view) of the pattern and to obtain good DOF (depth of focus) characteristics.

In the production method of the present invention, the exposure step (exposure energy irradiation) is performed in an oxygen concentration environment exceeding 21% by volume. This oxygen concentration can be controlled by a normal method. For example, it is possible to adjust the oxygen concentration in the room by supplying a desired ratio of oxygen gas and nitrogen gas to the inside of the apparatus chamber containing the projection exposure apparatus as a sealed structure. Alternatively, a predetermined flow rate of oxygen gas and nitrogen gas may be circulated in the chamber of the projection exposure apparatus so that the exposure atmosphere has a predetermined oxygen concentration. The oxygen concentration is preferably 22% by volume or more, more preferably 25% by volume or more, and particularly preferably 30% by volume or more. The upper limit is preferably 55% by volume or less, more preferably 50% by volume or less, further preferably 45% by volume or less, and further preferably 40% by volume or less, It is particularly preferably 35% by volume or less. From the viewpoint of ensuring the safety of the apparatus, avoiding the possibility of contamination (rust) of the apparatus, and the effect of patterning, it is preferable that the oxygen concentration is comprehensively set in the above range.
Further, in a preferred embodiment of the present invention, it is preferable to make a color filter in which a plurality of color filter pixel portions having different colors are adjacent to each other, taking advantage of the advantage. For example, in the manufacture of a color filter, in a form in which pixel portions of different colors are adjacent to each other, the material of the adjacent pixel portion overlaps the already formed pixel portion, and there is a gap (gap near the surface) at the corner. May be easier to do. FIG. 3 is a schematic diagram showing the situation, and shows a situation where a cell (M) occurs at the corners of the red pixel portion (20R), the blue pixel portion (20B), and the green pixel portion (20G). This is considered to be caused by poor pattern formation of the composition to be applied, that is, poor resolution. On the other hand, according to a preferred embodiment of the present invention, since polymerization is not performed due to oxygen inhibition, it is understood that overlap is unlikely to occur at the corners of the pixel portion. Further, since the absolute resolving power is improved, the rounding of the corners of the pattern can be suppressed, so that it is understood that the generation of the above-described soot can be suppressed or prevented.

-Development process Next, by performing development such as an alkali development treatment, the photosensitive resin composition layer in the light unirradiated part in the exposure process is eluted in the alkaline aqueous solution, and only the photocured part remains. The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is, for example, 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable.
Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like can be mentioned (among these, organic alkali is preferable. ).
In the case where an alkaline aqueous solution is used as a developer, a washing treatment with water is generally performed after development.

-Post-baking Next, it is preferable to perform heat processing (post-baking) after drying. It is preferable to form a multicolored pattern, and the cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained. Post-baking is a heat treatment after development for complete curing. The heating temperature is preferably 240 ° C. or lower, more preferably 220 ° C. or lower, further preferably 200 ° C. or lower, and particularly preferably 190 ° C. or lower from the viewpoint of suppressing damage to the organic photoelectric conversion part. Although there is no particular lower limit, in view of an efficient and effective treatment, it is preferable to perform a thermosetting treatment of 50 ° C. or higher, and more preferably 100 ° C. or higher.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coating film after development is in the above condition. be able to.

  In the present invention, the pixel of the color filter may be cured by UV (ultraviolet) irradiation instead of the post-baking by heating. At this time, the UV curing agent is preferably one that can be cured at a wavelength of a single wave from 365 nm which is an exposure wavelength of an initiator added for a lithography process by normal I-line exposure. Examples of the UV curing agent include Ciba-Iru Gacure 2959 (trade name). The specific wavelength of the UV irradiation light is preferably a material that cures at 340 nm or less. Although there is no lower limit of wavelength, it is generally 220 nm or more. Moreover, the exposure amount of UV irradiation is preferably 100 to 5000 mJ, preferably 300 to 4000 mJ, and more preferably 800 to 3500 mJ. This UV curing step is preferably performed after the lithography step in order to perform low-temperature curing more effectively. The exposure light source is preferably an ozoneless mercury lamp.

  In the present invention, the post-baking of the radiation-sensitive composition is preferably performed in an atmosphere having a low oxygen concentration. The oxygen concentration is preferably 19% (volume basis), more preferably 15% (volume basis), further preferably 10% (volume basis), and 7% (volume basis). More preferably, it is 3% (volume basis). There is no particular lower limit, but 10 ppm (volume basis) or more is practical.

  The thickness of the colored pattern (colored pixel portion) in the color filter is preferably an example of the thickness of the cured product of the photosensitive resin.

Application Form The color filter according to a preferred embodiment of the present invention can be used for a liquid crystal display device, a solid-state imaging device, and an organic EL device, and is particularly suitable for solid-state imaging applications. The solid-state imaging device according to a preferred embodiment of the present invention has already been described with reference to FIG. 1, and examples thereof include the following configurations. A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on the support, and the transfer electrodes are formed on the photodiodes and the transfer electrodes. Having a light-shielding film made of tungsten or the like that is opened only in the light-receiving part of the photodiode, and having a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, In this configuration, a color filter for a solid-state image sensor is provided on the device protective film. Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.
The color filter according to a preferred embodiment of the present invention has a colored pixel that is excellent in hue and excellent in light resistance, and thus is particularly suitable as a color filter for liquid crystal display devices (particularly for color TFT liquid crystal display devices). It is. A liquid crystal display device provided with such a color filter can display a high-quality image having a good display image color and excellent display characteristics.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

(Example 1 and Comparative Example 1)
<Preparation of photosensitive green composition>
By mixing the following components, a photosensitive (green) resin composition having a colorant concentration of 41.0% by mass in the composition solid content was prepared.
・ Pigment dispersion ... 59.9g
Green pigment Dispersant Dispersion resin Dispersant / dispersion resin ratio (mass ratio) = 4/21
Solid content: 19.6% by mass
Mass of pigment content: 12.0% by mass
・ Radically polymerizable monomer ・ ・ ・ 1.42g
・ Photo radical polymerization initiator ・ ・ ・ 0.49g
・ Binder-containing solution: 3.42 g
・ Surfactant ... 0.18g
・ Solvent: PGMEA / EEP: 12.1 g / 16.5 g

Green pigment: PG36 / PG7 / PY139 = 80/20/30 (mass ratio)
Dispersant: BYK-2001 manufactured by BYK
Dispersing resin: benzyl methacrylate / methacrylic acid copolymer
(70/30 molar ratio, Mw: 30000)
Radical polymerizable monomer: KAYARAD DPHA manufactured by Nippon Kayaku
The following exemplary compound A-1
Photoradical polymerization initiator: Irgacure OXE02 manufactured by BASF
The following exemplary compound B-1
Binder-containing solution: Daicel Chemical's Cyclomer P
Surfactant: Nonionic surfactant Pionein D-6315 (Takemoto Yushi Co., Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate EEP: Ethyl 3-ethoxypropionate [Preparation of color filter]
An 8-inch substrate in which a transparent organic film layer (CT-4000L: manufactured by FUJIFILM Electronics Materials) was formed so as to have a film thickness of 0.1 μm after post-baking was prepared.
[Conditions for CT-4000L]
・ Spin coating ・ No pre-bake ・ Post-bake (on hot plate) 220 ° C. × 300 seconds A film obtained by drying the green (G) photosensitive resin composition prepared above on the 8-inch (200 mm) silicon substrate. The film was applied using a spin coater so that the thickness became 1.0 μm after pre-baking, and heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. Next, pattern exposure was performed using an i-line (wavelength 365 nm) stepper exposure apparatus FPA-5510iZ (manufactured by Canon Inc.). Using the above stepper, a Bayer pattern having a color filter pixel portion width of 0.625 μm was created. Each apparatus condition is as follows.
Lighting condition NA ₃ /σ=0.57/0.40
Exposure illuminance (W / m ² ) See Table 1 below Exposure energy: Exposure swing was performed in steps of 30 mJ to 10 mJ.
Optimum exposure energy was examined. )
Oxygen concentration (volume%) See Table 1 below (21% is atmospheric conditions)

The film thickness of the cured resin (color filter pixel portion) is an optical film thickness measuring device: Filmetrics F50 (manufactured by Filmetrics), and an average value of 5 points in an 8 inch plane is set as a film thickness setting value. did.
The line width measurement after patterning was performed by observing with a line width measuring electron microscope S9260 (manufactured by Hitachi High-Technologies Corporation). The average value of 5 points in the 8 inch plane was set as the line width setting value.

The more detailed process conditions for the above examples are as follows.
(1) Substrate: 8 "Siwafer
(2) under layer: CT4000L
(Postbake 200 ° C. × 300 sec, FT 0.1 μm
@Postbake)
(3) GREEN: GREEN
(4) FT: 0.6um@prebake
(5) Prebake: 100 ° C. × 120 sec
(6) Exp: ***** (Exposure swing is performed under the above conditions)
(7) Dev: CD-2060 60 sec Puddle / Rinse
200rpm × 30sec DIW
(8) Postbake: 200 ° C. × 300 sec
(9) Pattern observation: HV 0.8 kV, Ip 8 pA, magnification x 30.0 k
Microscope and CD-SEM
(2), (3), (4), (5), (7), (8) used a clean truck ACT8 manufactured by Tokyo Electron. (9) used S9260A manufactured by Hitachi High-Technologies Corporation.
This apparatus was set so that the oxygen concentration in the apparatus room could be controlled. Specifically, a measuring instrument capable of monitoring the oxygen concentration was set in the chamber, provided with a line for introducing oxygen gas and dilution gas. The oxygen concentration in the room during exposure was constantly confirmed using this measuring instrument.

The photosensitive resin composition was irradiated with exposure energy under the above conditions, and the pattern resolution (separability) was evaluated. Examples corresponding to the following evaluations are shown in FIG.
A: The pattern is separated and the shape is good. The target dimensions can be obtained with a margin.
B: The pattern is separated and a target dimension is obtained.
C: The pattern is separated. However, the target dimensions cannot be obtained.
D: The pattern is separated. However, the target dimension cannot be obtained and the shape is round.
E: The pattern was not resolved (separated).
F: Image formation could not be performed.

A double line shows a preferable range.

  From the above results, it can be seen that according to the production method of the present invention, in forming a cured resin of a radical polymerization type photosensitive resin composition, a remarkable effect is exhibited in improving the pattern resolution.

(Comparative Example 2)
Development evaluation was performed in the same manner as in Example 1 except that the oxygen concentration was changed to 18% by volume and 15% by volume, respectively. As a result, pattern resolution (separation) was not performed (E).

(Reference example)
Let us use ML-501C / B manufactured by USHIO INC. As a sealed space. Further, as in the stepper described above, the oxygen / nitrogen flow rate was adjusted while checking the oxygen / nitrogen supply system with a self-made / oxygen concentration meter. The same exposure and development test as in Example 1 was performed. This apparatus had an oxygen gas input system and a dilution gas input system, and a measuring instrument for confirming the oxygen concentration was installed in the chamber. By using this exposure machine, a Bayer pattern with the width of the color filter pixel portion as shown in Table 2 was produced. The exposure illuminance at this time was 1000 W / m ² . The exposure energy was changed from 30 mJ to 10 mJ. Optimum exposure energy was examined. The evaluation of the exposure development pattern was the same as in Example 1.

  As described above, in proximity exposure, even if the oxygen concentration is increased, the effect is limited, and in particular, the pattern cannot be separated at a pixel width of 3.0 μm or less. On the contrary, according to the present invention, it can be seen that, in the formation of a fine pattern of less than 3.0 μm □, a remarkable effect is exhibited in improving the resolution.

(Example 2)
Furthermore, the same evaluation as Example 1 was performed by changing the monomer A-1 and the polymerization initiator B-1 used in the photosensitive resin composition to the following ones. At this time, the illuminance was 7500 W / m ² and the oxygen concentration was 30% by volume. As a result, it was found that the use of a monomer having a larger number of functional groups has a higher effect on resolution. In addition, the polymerization initiator was confirmed to be particularly effective when an oxime compound (B1 and B2 below) was used, and it was confirmed that the improvement effect was observed even under conditions where the corners of the pixel portion were scratched. .

(Example 3)
Evaluation in Example 1 was performed in the same manner except that the setting of the optical system of the stepper was changed as shown in Table 3 below. The descriptions in the table show the evaluation results in the order of shape / DOF characteristics.

Judgment criteria Shape (planar shape of color filter pixel part)
A: The shape of the Bayer pattern is very sharp.
B: The shape of the Bayer pattern is inferior to A but sharp.
C: The shape of the Bayer pattern is not sharp, but the manufacturing suitability is secured.
D: The shape is not sharp but is observed in a round shape. There is no manufacturing suitability.
In addition, the example of A determination and the example of D determination were shown in FIG. 3 as a schematic diagram.

DOF characteristics (Line width fluctuation range is within ± 10%)
A: The DOF margin is 1.2 μm or more.
B: The DOF margin is 1.0 or more and less than 1.2 μm.
C: The DOF margin is 0.8 or more and less than 1.0 μm.
D: The DOF margin is less than 0.8 μm.

  From the above results, it can be seen that better patterning can be achieved by optimizing the numerical aperture (NA) and coherence factor (σ) when performing exposure under the high oxygen concentration condition of the present invention. .

1 Condenser lens 2 Projection lens 4 Substrate (work)
5 Reticle 10 Solid-state Image Sensor 11 Upper Flattening Film 12 Lower Flattened Film 15 Microlens 20 Color Filter 20B, 20G, 20R Color Filter Pixel Unit

Claims (14)

  A method of forming a patterned resin cured product by irradiating a radical polymerization type photosensitive resin composition with exposure energy and then developing an exposed portion, wherein the exposure energy is irradiated with an oxygen concentration of 21% by volume. A method for producing a cured resin, which is performed in a super atmosphere so as to form a pattern having a width of 5 μm or less.   The method for producing a cured resin product according to claim 1, wherein the oxygen concentration is 55% by volume or less.   The method for producing a cured resin product according to claim 1 or 2, wherein the exposure energy is irradiated by an active energy ray selected from g-line, h-line, i-line, KrF excimer laser line, and ArF excimer laser line. The illuminance of the exposure energy is 5000 W / m ^{2 to} 18000 W / m ^{2. The} method for producing a cured resin according to claim 1.   The method for producing a cured resin according to claim 1, wherein the exposure energy is irradiated by reduced projection exposure.   The method for producing a cured resin according to any one of claims 1 to 5, wherein the radical polymerization type photosensitive resin composition is a colored photosensitive composition comprising an organic pigment and / or an inorganic pigment.   The resin cured product according to any one of claims 1 to 6, wherein the exposure energy irradiation is performed by a projection optical system having a coherence factor (σ) of 0.5 or less and a lens aperture ratio (NA) of 0.5 or more. Manufacturing method.   The method for producing a cured resin product according to claim 1, wherein the radical polymerization type photosensitive resin composition is a photocurable composition.   The resin cured product according to any one of claims 1 to 8, wherein the radical polymerization type photosensitive resin composition contains a specific polymer, a monomer having an ethylenically unsaturated double bond, a polymerization initiator, and a colorant. Manufacturing method. The method for producing a cured resin according to claim 9, wherein the monomer is a monomer represented by any of the following formulas (MO-1) to (MO-7).
(In the formula, R is a group having a hydroxy group or a vinyl group at the terminal. However, it has at least one vinyl group in the molecule. T, Z ² and Z are linking groups. N is an integer. )   The method for producing a cured resin according to any one of claims 1 to 10, wherein the cured resin is a pixel portion of a color filter.   The method for producing a cured resin product according to claim 11, wherein a plurality of pixel portions of different colors are adjacent to each other for the pixel portion of the color filter.   The manufacturing method of the solid-state image sensor which produces the solid-state image sensor which has a color filter through the manufacturing method of Claim 11 or 12.   A method for manufacturing a liquid crystal display device, wherein a liquid crystal display device having a color filter is produced through the manufacturing method according to claim 11.