JP2012208374A - Radiation-sensitive composition, pattern formation method, color filter and manufacturing method thereof, and solid state imaging device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition being used for pixel formation of a solid state imaging device, allowing a pixel excellent in resolution, and enabling suppression of occurrence of release defect in a pixel after post-bake carried out in pixel formation.SOLUTION: A radiation-sensitive composition used for pixel formation of a solid state imaging device contains a resin, an ultraviolet absorber and a pigment, where the pigment contains at least one kind or more of each of a pigment (A) having the maximum absorption wavelength at 400 nm or more and less than 500 nm, a pigment (B) having the maximum absorption wavelength at 500 nm or more and less than 600 nm and a pigment (C) having the maximum absorption wavelength at 600 nm or more and 700 nm or less, and the total content of all the pigments is 0.1 mass% or more and 20 mass% or less relative to the total solid.

Description

  The present invention relates to a radiation-sensitive composition, a pattern forming method, a color filter and a method for producing the same, and a solid-state imaging device.

In a color filter used in an image sensor (CCD, CMOS, etc.), there is a case where one color of a plurality of color filters is set to white (transparent) for the purpose of increasing sensitivity (for example, see Patent Document 1). As a background, for the purpose of improving the resolution, pixel miniaturization has been progressed with the increase in the number of pixels. However, on the other hand, the opening becomes small, leading to a decrease in sensitivity. Therefore, in order to compensate for the decrease in sensitivity, one color of the color filter is made white (transparent) to increase the sensitivity. For example, Patent Document 2 discloses a technique related to improvement of pattern rectangularity in pixels included in such a color filter.
On the other hand, a transparent material may be used also for the protective film use of a liquid crystal display device (for example, refer patent documents 3-4).

JP 2007-53153 A JP 2010-49029 A JP 2008-52250 A JP 2007-271994 A

However, when forming a pixel included in a color filter for an image sensor (hereinafter also referred to as a “solid-state image pickup device” as appropriate), if a pigment in which a pigment is completely removed from a general color filter photosensitive composition is used, the post Pixel peeling may occur after baking, which is a problem.
In addition to the above problems, in a solid-state imaging device, since a pixel pattern is formed on a wafer, pattern resolution often becomes a problem due to exposure halation.

This invention is made | formed in view of said situation, and makes it a subject to achieve the following objectives.
That is, the present invention is suitably used for pixel formation of a solid-state imaging device, can form a pixel with excellent resolution, and suppress the occurrence of pixel peeling defects after post-baking performed at the time of pixel formation. It is an object to provide a radiation-sensitive composition.
The present invention also provides a color filter capable of displaying a fine and high-quality image, a pattern forming method suitably used for manufacturing the color filter, and a method for manufacturing a color filter to which the pattern forming method is applied. For the purpose.
Another object of the present invention is to provide a solid-state imaging device having excellent sensitivity characteristics.

  Means for solving the above problems are as follows.

<1> A resin, an ultraviolet absorber, and a pigment, and as the pigment, a pigment (A) having a maximum absorption wavelength at 400 nm to less than 500 nm, and a pigment having a maximum absorption wavelength at 500 nm to less than 600 nm (B ) And a pigment (C) having a maximum absorption wavelength at 600 nm or more and 700 nm or less, and the total content of all pigments is 0.1% by mass or more and 20% by mass or less with respect to the total solid content. A radiation-sensitive composition used for pixel formation of a solid-state imaging device.

<2> The pigment (A) having a maximum absorption wavelength at 400 to 500 nm, the pigment (B) having a maximum absorption wavelength at 500 to less than 600 nm, and the pigment having a maximum absorption wavelength at 600 to 700 nm ( The radiation-sensitive composition according to <1>, wherein the content of C) is 0.2% by mass or more and 10% by mass or less with respect to the total solid content.

<3> The total content of the pigment (B) having a maximum absorption wavelength in the range of 500 nm to less than 600 nm and the pigment (C) having a maximum absorption wavelength in the range of 600 nm to 700 nm is 1% by mass or more based on the total solid content. <1> or <2>, wherein the content ratio of the pigment (B) and the pigment (C) [(B) :( C)] is 1: 2 to 2: 1. Radiation sensitive composition.

<4> The radiation-sensitive composition according to <1> to <3>, wherein the content of the ultraviolet absorber is 2% by mass or more and 10% by mass or less based on the total solid content.

<5> Furthermore, the radiation sensitive composition as described in any one of <1>-<4> containing a polymeric compound.

<6> The radiation-sensitive composition according to any one of <1> to <5>, wherein the polymerizable compound is a polymerizable monomer having a hydrogen bonding group.

<7> The radiation-sensitive composition according to <1> to <6>, wherein the content of the polymerizable monomer having a hydrogen bonding group is 20% by mass or more based on the total solid content.

<8> The radiation-sensitive composition according to <6> or <7>, wherein the hydrogen bonding group is at least one selected from a carboxyl group, an alkoxycarbonylamino group, and a ureido group.

<9> The radiation-sensitive composition according to any one of <1> to <8>, wherein the ultraviolet absorber is a conjugated diene compound.

<10> The radiation-sensitive composition according to any one of <1> to <8>, wherein the conjugated diene compound is a compound represented by the following general formula (I).

[In General Formula (I), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² may be the same as or different from each other, but both R ¹ and R ² do not represent a hydrogen atom. R ¹ and R ² may be bonded to each other to form a cyclic amino group together with the adjacent nitrogen atom. R ³ and R ⁴ each independently represents an electron withdrawing group. ]

<11> The radiation-sensitive composition according to any one of <6> to <10>, wherein the monomer having a hydrogen bonding group is a polyfunctional monomer.

<12> The radiation-sensitive composition according to any one of <1> to <11>, further containing a photopolymerization initiator.

<13> The colored radiation-sensitive composition according to <12>, wherein the photopolymerization initiator is an oxime compound.

<14> A step of applying the radiation-sensitive composition according to any one of <1> to <13> onto a support plate to form a radiation-sensitive composition layer, and the formed radiation-sensitive property Forming a pattern by exposing the composition layer to ultraviolet rays through a mask and developing the composition layer.

<15> A method for producing a color filter, comprising: a step of forming a pattern on a substrate using the pattern forming method according to <14>; and a step of post-baking the formed pattern.

<16> A color filter produced by the method for producing a color filter according to <15>.

<17> A solid-state imaging device comprising the color filter according to <16>.

According to the present invention, it is suitably used for pixel formation of a solid-state imaging device, can form a pixel with excellent resolution, and suppress the occurrence of pixel peeling defects after post-baking performed at the time of pixel formation. Radiation-sensitive compositions can be provided.
Further, according to the present invention, there are provided a color filter capable of displaying a fine and high-quality image, a pattern forming method suitably used for manufacturing the color filter, and a method for manufacturing a color filter to which the pattern forming method is applied. Can be provided.
In addition, according to the present invention, it is possible to provide a solid-state imaging device having excellent sensitivity characteristics.

42 is a diagram illustrating a layout of pixels included in a color filter formed in Example 36. FIG. 38 is a diagram illustrating a layout of pixels included in a color filter used for comparison with a color filter formed in Example 36. FIG.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below is made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the radiation-sensitive composition of the present invention, the total solid content means the total mass of components excluding the organic solvent from the total composition of the radiation-sensitive composition.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

In the present specification, the “alkyl group” refers to a “straight chain, branched, and cyclic” alkyl group, and may be substituted or unsubstituted.
Further, in this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “meth”. ") Acryloyl" represents both and / or acryloyl and methacryloyl, and (meth) acrylamide represents both or either acrylamide or methacrylamide.

  In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

  In addition, in the description of groups (atomic groups) in the present specification, the description that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .

≪Radiosensitive composition≫
The radiation-sensitive composition of the present invention contains a resin, an ultraviolet absorber, and a pigment. As the pigment, a pigment (A) having a maximum absorption wavelength at 400 nm to less than 500 nm, and a maximum at 500 nm to less than 600 nm. Each pigment contains at least one pigment (B) having an absorption wavelength and at least one pigment (C) having a maximum absorption wavelength at 600 nm to 700 nm, and the total content of all pigments is 0.1% by mass with respect to the total solid content. The content is 20% by mass or less and is used for pixel formation of the solid-state imaging device.

The radiation-sensitive composition of the present invention has the above-described configuration, so that a pixel having excellent resolution can be formed, and the occurrence of pixel peeling defects after post-baking performed at the time of pixel formation is suppressed. can do. In addition, since the radiation-sensitive composition of the present invention contains an appropriate amount of pigment that is neither too high nor too low, an appropriate amount of light can be adjusted by using a color filter using this as a pixel. A device with good sensitivity characteristics can be obtained.
Hereafter, each component contained in the radiation sensitive composition of this invention is demonstrated sequentially.

[1] Resin The radiation-sensitive composition of the present invention contains at least one resin.
As the resin, an alkali-soluble resin is suitable.
The alkali-soluble resin is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. 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. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. 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, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  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 the conditions are determined experimentally. 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. 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, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as monomers and polymethylmethacrylate macromonomers include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  The alkali-soluble resin preferably includes a polymer obtained by polymerizing a monomer component having a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”) as an essential component. Thereby, the radiation sensitive composition of this invention can form the cured coating film which was extremely excellent also in heat resistance and transparency.

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

In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, A linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; an aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

  Moreover, in order to improve the crosslinking efficiency of the radiation sensitive composition in this invention, you may use the alkali-soluble resin which has a polymeric group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include: Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., manufactured by), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, Japanese Patent Application Laid-Open No. 2002-229207 And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl 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 / methacrylic acid copolymer.

  The alkali-soluble resin is preferably an alkali-soluble resin having a polymerizable group in the side chain among the alkali-soluble resins described above.

The acid value of the alkali-soluble resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 20 mgKOH / g to 150 mgKOH / g, and most preferably 30 mgKOH / g to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  In this invention, 10-90 mass% is preferable with respect to the total solid of a radiation sensitive composition from viewpoints of developability etc., and, as for content of resin in a radiation sensitive composition, 20-60 mass%. Is more preferable, and 30 to 50% by mass is particularly preferable.

  When the radiation-sensitive composition of the present invention contains a polymerizable compound, the ratio of the mass of the resin to the mass of the total polymerizable compound [total mass of the resin / total mass of the polymerizable compound] is the developability. From the viewpoint of coexistence of pattern rectangularity, 0.5 or more and 1.5 or less are preferable, 0.6 or more and 1.4 or less are more preferable, and 0.8 or more and 1.3 or less are most preferable.

[2] Ultraviolet absorber The radiation-sensitive composition of the present invention contains at least one ultraviolet absorber. Thereby, the line width thickening at the time of exposure is suppressed. As the ultraviolet absorber, for example, a compound having an absorption maximum between 250 nm and 400 nm can be used.

  More specifically, as the ultraviolet absorber, for example, Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Yongkou Chemical Industry), Tomissorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, Benzophenone compounds such as SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Sipro Kasei);

Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry), TINUVIN PS, TINUVIN99-2, TINUVIN1092, TINUVIN384-2, TINUVIN900-2 , TINUVIN928, TINUVIN1130 (manufactured by Ciba Specialty Chemicals), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORBVER234, EVERSORB234 Benzotriazole compounds, such as 100, Tomissorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, and SEESORB709 (made by Cypro Kasei);

Benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate;
Hydroxyphenyltriazine compounds such as TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477DW, TINUVIN479 (manufactured by Ciba Specialty Chemicals);
And so on.

  As the ultraviolet absorber, a conjugated diene compound is more preferable, and a compound represented by the following general formula (I) is particularly preferable. By using this conjugated diene compound, it is possible to suppress subsequent development performance fluctuations especially when low-illuminance exposure is performed. Therefore, exposure illuminance dependence related to pattern formability such as pattern line width, film thickness, and spectral spectrum. Can be suppressed.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² May be the same as or different from each other, but R ¹ and R ² do not represent a hydrogen atom.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ or R ² include methyl group, ethyl group, propyl group, n-butyl group, n-hexyl group, cyclohexyl group, n- Decyl group, n-dodecyl group, n-octadecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N, N-diethylaminopropyl group, cyanoethyl group, Phenethyl group, benzyl group, pt-butylphenethyl group, pt-octylphenoxyethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, ethoxycarbonylmethyl group, 2- (2-hydroxy An ethoxy) ethyl group, a 2-furylethyl group, and the like.

The aryl group having 6 to 20 carbon atoms represented by R ¹ or R ² may be a single ring or a condensed ring, and may be any of a substituted aryl group having a substituent or an unsubstituted aryl group. It may be. For example, the substituent of the substituted aryl group having a substituent includes an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, a hydroxy group, and a cyano group. Group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group and the like. Of these, a substituted or unsubstituted phenyl group, 1-naphthyl group, and 2-naphthyl group are preferable.

R ¹ and R ² may be bonded to each other to form a cyclic amino group together with the adjacent nitrogen atom. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.

Among the above, R ¹ and R ² are each a lower alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl). , 2-ethylhexyl, tert-octyl, etc.) or a substituted or unsubstituted phenyl group (for example, tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-t-amylphenyl group, etc.) preferable. It is also preferable that R ¹ and R ² are bonded to each other to form a cyclic amino group (for example, a piperidine ring, a pyrrolidine ring, or a morpholine ring) together with the adjacent nitrogen atom.

In the general formula (I), R ³ and R ⁴ represent an electron withdrawing group. Here, the electron-withdrawing group is an electron-withdrawing group having a Hammett's substituent constant σ _p value (hereinafter simply referred to as “σ _p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less.
Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. . Substituent constants obtained by Hammett's rule include a σ _p value and a σ _m value, and these values are described in many general books. For example, the JA Dean edition “Lange's Handbook of Chemistry” "Twelfth edition, 1979 (Mc Graw-Hill)" and "Chemical domain special issue", 122, 96-103, 1979 (Nanedo), Chemical Reviews, 91, 165-195, 1991 detailed. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.

Specific examples of the electron-withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, at least An alkyl group substituted with two or more halogen atoms, an alkoxy group substituted with at least two halogen atoms, an aryloxy group substituted with at least two halogen atoms, or at least two halogen atoms Substituted alkyl Amino group, at least two an alkylthio group substituted with a halogen atom, sigma _p value of 0.20 or more other electron-withdrawing aryl group substituted with group, a heterocyclic group, a chlorine atom, a bromine atom, an azo group Or a selenocyanate group. Of these substituents, the group that can further have a substituent may further have a substituent as described above.

Among the above, in the present invention, R ³ is preferably a group selected from a cyano group, —COOR ⁵ , —CONHR ⁵ , —COR ⁵ , —SO ₂ R ⁵ , and R ⁴ is a cyano group. A group selected from the group, —COOR ⁶ , —CONHR ⁶ , —COR ⁶ , —SO ₂ R ⁶ is preferred. R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ or R ⁶ are the same as those in R ¹ or R ² , and the preferred embodiments are also the same.
Among these, as R ³ and R ⁴ , an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable. In particular, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable.

Moreover, at least one of the above R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group.

  Hereinafter, preferred specific examples of the compound represented by the general formula (I) [Exemplary compounds (1) to (14)] are shown. However, the present invention is not limited to these.

  The compounds represented by the general formula (I) are disclosed in JP-B 44-29620, JP-A 53-128333, JP-A 61-169831, JP-A 63-53543, JP-A 63-53544, JP It can synthesize | combine by referring the method described in each gazette of 63-56651.

Hereinafter, specific synthetic methods of typical compounds among the compounds represented by the general formula (I) will be described.
-Synthesis Method of Exemplary Compound (1)-
3-Anilinoacrolein anil (13.3 g) and ethylphenylsulfonylacetate (14.3 g) are heated in acetic anhydride (40 ml) to 85-90 ° C. for 2 hours. Acetic anhydride is removed under reduced pressure, ethanol (40 ml) and gen-hexylamine (24.1 g) are added, and the mixture is refluxed for 2 hours. Ethanol is removed, the residue is subjected to column chromatography, purified, and recrystallized from ethanol to obtain the desired product. Mp 95-96 ° C.

The content of the ultraviolet absorber described above (for example, the compound represented by the general formula (I)) in the radiation-sensitive composition of the present invention is 0. 0 relative to the total solid content of the composition. 01 mass%-30 mass% are preferable, 0.01 mass%-20 mass% are more preferable, 0.01 mass%-15 mass% are especially preferable, 2 mass%-10 mass% are the most preferable.
When the content of this ultraviolet absorber is 0.01% by mass or more, the light shielding ability at the time of exposure is good and the pattern line width due to excessive progress of polymerization is prevented, and the desired line width is easily obtained. Further, the generation of peripheral residues (development residues) is further suppressed. On the other hand, when it is 30% by mass or less, the light shielding ability at the time of exposure is not too strong, and the polymerization proceeds better.

  The change in the pattern line width as described above becomes conspicuous in a transparent photocurable composition with little light absorption with respect to ultraviolet rays such as g-line, h-line and i-line as exposure light sources. Therefore, the compound represented by the general formula (I) (conjugated diene compound) is particularly effective when constituting a transparent radiation-sensitive composition.

[3] Pigment The radiation-sensitive composition of the present invention contains a pigment, and the pigment has a maximum absorption wavelength at 400 nm or more and less than 500 nm (hereinafter referred to as “pigment (A)” as appropriate). ), A pigment (B) having a maximum absorption wavelength at 500 nm or more and less than 600 nm (hereinafter abbreviated as “pigment (B)” as appropriate), and a pigment (C) having a maximum absorption wavelength at 600 nm or more and 700 nm or less (C) ( Hereinafter, it is necessary to appropriately contain at least one of each of “pigment (B)”. The total content of all pigments including the pigments (A) to (C) contained in the radiation-sensitive composition is 0.1% by mass or more and 20% by mass or less based on the total solid content of the radiation-sensitive composition. .

  As a kind of the pigment contained in the radiation-sensitive composition of the present invention, a pigment (A), a pigment (B), and a pigment (C) each selected from a specific absorption maximum wavelength range are essential. There is no restriction | limiting in particular, A conventionally well-known various pigment can be mixed and used.

As the pigment in the radiation-sensitive composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment that is as fine as possible. In consideration of handling properties, the average particle size of the pigment is preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.05 μm.
In addition, the average particle diameter of the pigment in this specification is a volume average particle diameter measured using a Nanotrac UPA particle size analyzer (product name: UPA-EX150, manufactured by Nikkiso Co., Ltd.).

  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, An oxide of a metal such as silver and a composite oxide of the metal can be given. Titanium nitrides, silver tin compounds, silver compounds, carbon black, and the like can also be used.

As an organic pigment, for example,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , Etc. 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81, 81: 1, 81: 2, 81: 3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc.
C. I. Pigment Green 7, 10, 36, 37, 58, etc.
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 39, 42, etc.
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc.
C. I. Pigment Brown 25, 28, etc.
C. I. Pigment Black 1, etc.
Can be mentioned.

<Pigment (A)>
As the pigment (A), a pigment having a maximum absorption wavelength at 400 nm or more and less than 500 nm is selected from the known pigments including the above-mentioned pigments. Only one type of pigment (A) may be used, or two or more types may be used in combination.
Specific examples of pigments that can be preferably used as the pigment (A) include Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 150, and Pigment Yellow 185.

<Pigment (B)>
As the pigment (B), a pigment having a maximum absorption wavelength at 500 nm or more and less than 600 nm is selected from the known pigments including the above-mentioned pigments. Only one type of pigment (B) may be used, or two or more types may be used in combination.
Specific examples of pigments that can be preferably used as the pigment (B) include PigmentRed 81, PigmentRed 122, PigmentRed 177, PigmentRed 209, PigmentRed 242 and PigmentRed 254, PigmentViolet 23.

<Pigment (C)>
As the pigment (C), a pigment having a maximum absorption wavelength of 600 nm to 700 nm is selected from the known pigments including the above-mentioned pigments. Only one type of pigment (C) may be used, or two or more types may be used in combination.
Specific examples of pigments that can be preferably used as the pigment (C) include Pigment Green 7, Pigment Green 36, Pigment Green 58, Pigment Blue 15: 3, and Pigment Blue 15: 6.

As a preferable combination of the pigment (A), the pigment (B) and the pigment (C), for example,
Pigment (A) is Pigment Yellow 139, Pigment (B) is Pigment Red 254 and Pigment Violet 23, and Pigment (C) is Pigment Blue 15: 6,
Pigment (A) is Pigment Yellow 150, Pigment (B) is PigmentRed 177 and Pigment Violet 23, and Pigment (C) is Pigment Blue 15: 6,
Pigment (A) is Pigment Yellow 139, Pigment (B) is PigmentRed 254 and Pigment Violet 23, and Pigment (C) is Pigment Blue 15: 3,
Examples include a combination in which the pigment (A) is Pigment Yellow 185, the pigment (B) is PigmentRed 254 and Pigment Violet 23, and the pigment (C) is Pigment Blue 15: 6.

  The total content of all pigments contained in the radiation-sensitive composition is 0.1% by mass or more and 20% by mass or less, preferably 0.5% by mass, based on the total solid content of the radiation-sensitive composition. It is 10 mass% or less, More preferably, it is 1.0 mass% or more and 5.0% mass or less.

The content of the pigment (A), the pigment (B) and the pigment (C) is preferably 0.2% by mass or more and 10% by mass or less, respectively, with respect to the total solid content of the radiation-sensitive composition. Each of them is more preferably 0.3% by mass or more and 5.0% by mass or less, and further preferably 0.5% by mass or more and 3.0% by mass or less, respectively.
However, the content of the pigment (A), the pigment (B) and the pigment (C) is the total content of all pigments contained in the radiation-sensitive composition (0.1% by mass or more to 20% by mass with respect to the total solid content). It is necessary to adjust within the range of (mass% or less).

  The content ratio of the pigment (A), the pigment (B), and the pigment (C) is preferably 5 times or less of the pigment (B) and the pigment (C) with respect to the pigment (A). The pigment (B) and the pigment (C) are more preferably 4 times or less, and the pigment (B) and the pigment (C) are more preferably 3 times or less of the pigment (A).

The total content of the pigment (B) and the pigment (C) is preferably 1% by mass or more and 18% by mass or less, and 1.5% by mass or more and 10% by mass from the viewpoint of suppressing peeling after post-baking. The mass is more preferably no greater than 2.0%, and even more preferably no less than 2.0% and no greater than 5.0%.
The mass ratio [(B) :( C)] of the pigment (B) and the pigment (C) is preferably 1: 2 to 2: 1, and preferably 1.75: 1 to 1: 1. More preferably, it is 75, and it is still more preferable that it is 1.5: 1 to 1: 1.5.
The pigment (B) and the pigment (C) preferably satisfy both the total content and the content mass ratio.

-Pigment dispersant-
The radiation sensitive composition of the present invention may contain a pigment dispersant.
Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalene sulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives, etc. Can do.
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.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, and the like. Examples thereof include a polymer having a sulfonic acid group at the terminal end described in JP-A-273191, and a polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the pigment surface include poly (lower alkyleneimine) described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like. ) And a polyester reaction product, a reaction product of polyallylamine and polyester described in JP-A-9-169821, etc., a macromonomer described in JP-A-10-339949, JP-A-2004-37986, and the like, Copolymers with nitrogen atom monomers, graft-type polymers having partial skeletons or heterocyclic rings of organic dyes described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc. A copolymer of a macromonomer and an acid group-containing monomer described in JP 2010-106268 A, etc. It is below. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 exhibits the dispersibility of the pigment dispersion, the dispersion stability, and the radiation-sensitive composition using the pigment dispersion. Particularly preferred from the viewpoint of developability.

  As the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries, Ltd. (5 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (2-hydroxyethyl acrylate) ε-caprolactone 10 molar equivalent addition product), and JP-A-2-2720 Polyester macromonomer described in No. 09 publication. Among these, the polyester-based macromonomer particularly excellent in flexibility and solvophilicity is particularly preferable from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the radiation-sensitive composition using the pigment dispersion. The polyester macromonomer represented by the polyester macromonomer described in JP-A-2-272009 is most preferable.

  As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  The pigment dispersant that can be used in the present invention is also available as a commercial product, and specific examples thereof include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)”, 110 (by BYK Chemie). Copolymer containing acid groups), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ) "EFKA 4047, 4050-4010-4165 (polyurethane)", EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid) Salt), 6220 (fatty acid polyester), 6745 Phthalocyanine derivatives), 6750 (azo pigment derivatives) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, manufactured by Enomoto Kasei Co., Ltd. DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation," Homogenol L- 18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935, 85 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) ”manufactured by Nippon Lubrizol Co., Ltd. , 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate) ”manufactured by Nikko Chemicals, MYS-IEX (Polyoxyethylene monostearate), Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd. “W001: Cationic System Surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Nonionic surfactants such as, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, manufactured by Morishita Sangyo Co., Ltd.” EFKA Polymer 401, EFKA Polymer 450 ”,“ Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid manufactured by San Nopco Corporation Polymeric dispersants such as “100”, manufactured by ADEKA Corporation “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 , P-123 ", Sanyo Chemical Co., Ltd." Ionet (trade name) S-20 ", and the like.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The pigment dispersant may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.

  Below, the dispersing agent described in Unexamined-Japanese-Patent No. 2010-106268 preferably used in this invention is demonstrated.

  A preferred dispersant is a graft copolymer having a graft chain selected from a polyester structure, a polyether structure, and a polyacrylate structure in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000 in the molecule. And a graft copolymer containing at least a structural unit represented by any one of the following formulas (1) to (4) is preferable, and at least the following formula (1A), the following formula (2A), and the following formula (3A). A graft copolymer containing a structural unit represented by any one of the following formula (3B) and the following (4) is more preferable.

In the formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and particularly preferably an oxygen atom.
In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ and X ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and are a hydrogen atom or a methyl group, from the viewpoint of synthesis constraints. Are more preferable, and a methyl group is particularly preferable.
In the formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a divalent linking group and are not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following (Y-1) to (Y-21) linking groups. In the following structures, A and B each represent a bond with the left terminal group and the right terminal group in formulas (1) to (4). Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a monovalent organic group, and the structure is not particularly limited, but specifically, an alkyl group Hydroxyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, amino group, and the like. Among these, the monovalent organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ preferably has a steric repulsion effect particularly from the viewpoint of improving dispersibility, and is represented by Z ^{1 to} Z ³ . As the organic group, each independently an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms is preferable, and among them, particularly an alkoxy group having each independently a branched alkyl group having 5 to 24 carbon atoms. Or the alkoxy group which has a C5-C24 cyclic alkyl group is preferable. The organic group represented by Z ⁴ each preferably an alkyl group having 5 to 24 carbon atoms independently, among them, each independently of 5 to 24 carbon atoms branched alkyl group or cyclic carbon atoms 5-24 Alkyl groups are preferred.
In Formula (1)-Formula (4), n, m, p, and q are integers of 1 to 500, respectively.
Moreover, in Formula (1) and Formula (2), j and k represent the integer of 2-8 each independently. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoints of dispersion stability and developability.

R ³ in the formula (3) represents a branched or straight chain alkylene group. R ³ in Formula (3) is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
R ⁴ in the formula (4) represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ in formula (4) is preferably a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ in Formula (4) is an alkyl group, the alkyl group includes a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a carbon number having 5 to 20 carbon atoms. Are preferable, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. In addition, as R ⁴ in formula (4), two or more types of R ⁴ having different structures may be mixed and used in the graft copolymer.

  In the graft copolymer, the structural unit represented by the formula (1) to the formula (4) is preferably contained in a range of 10% to 90% in terms of mass with respect to the total mass of the graft copolymer. More preferably, it is contained in the range of 30% to 70%. When the structural units represented by the formulas (1) to (4) are included within this range, the dispersibility of the pigment is high and the developability when forming the light-shielding film is good.

  Moreover, in the graft copolymer, the graft copolymer from which 2 or more types of structures differ can be contained.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same.
Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.
The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or the following formula (3B) from the viewpoints of dispersion stability and developability.

Wherein (3A) or ^{(3B), X 3, Y} 3, Z 3 and p, the formula ^{(3) X 3, Y 3} , have the same meaning as ^{Z 3} and p in, preferred ranges are also the same.

  The graft copolymer is more preferably one having a structural unit represented by the formula (1A).

  Specific examples of the graft copolymer include the following compounds. In addition, in the following exemplary compounds, the numerical value written together with each structural unit represents the content of the structural unit [mass%: appropriately described as (wt%)].

  The pigment dispersant in the present invention is preferably a compound having a polyester chain.

As content of the pigment dispersant in a radiation sensitive composition, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments, 5-70 mass parts is more preferable, and it is 10-60 mass parts. More preferably.
Specifically, if a polymer dispersant is used, the content thereof is preferably in the range of 5 to 100 parts, and in the range of 10 to 80 parts in terms of mass, with respect to 100 parts by mass of the pigment. It is more preferable.
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1-30 parts in conversion of mass as a content of a pigment derivative with respect to 100 mass parts of pigments, and it exists in the range of 3-20 parts more. A range of 5 to 15 parts is particularly preferable.

  When a pigment dispersant is further used in the radiation-sensitive composition, the total content of the pigment and the dispersant is 30 with respect to the total solid content constituting the radiation-sensitive composition from the viewpoint of curing sensitivity and color density. The mass is preferably from 90% by mass to 90% by mass, more preferably from 40% by mass to 85% by mass, and still more preferably from 50% by mass to 80% by mass.

[4] Polymerizable compound The radiation-sensitive composition of the present invention preferably contains a polymerizable compound.
Specifically, the polymerizable compound is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.
Specifically, the polymerizable compound is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

  As the polymerizable compound, polymerizable monomers described in detail below can be suitably used. As the polymerizable monomer, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable.

Examples of polymerizable monomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Methylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxy) (Methyl) acrylate after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as chill) isocyanurate, glycerin and trimethylolethane; JP-B-48-41708, JP-B-50-6034, JP Urethane acrylates as described in JP-A-51-37193; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be mentioned.
The monomer preferably contains a monomer having a hydrogen bonding group (hereinafter also referred to as “hydrogen bonding group-containing monomer”).
This effectively forms a hydrogen bond between the hydrogen-bonding group-containing monomers (or a hydrogen bond between the hydrogen-bonding group-containing monomer and another monomer described later), thereby suppressing thermal sagging due to post-baking. Deterioration of the pattern rectangularity is suppressed.

Specifically, examples of the hydrogen bonding group include a hydroxyl group, a carboxyl group, an amino group, a ureido group, an alkoxycarbonylamino group, a sulfo group, a sulfonamide group, and an amide group. Among these, those having both hydrogen donating to the hydrogen bond and substituents accepting the hydrogen bond are preferable.
From the viewpoint of the rectangular shape of the pattern, the hydrogen bonding group is more preferably at least one selected from a carboxyl group, an alkoxycarbonylamino group, and a ureido group.

The hydrogen bonding group-containing monomer is preferably a polyfunctional monomer (hereinafter also referred to as “polyfunctional polymerizable monomer”).
Hereinafter, specific examples of the polyfunctional polymerizable monomer containing a hydrogen bonding group will be described.

  Examples of the polyfunctional polymerizable monomer containing a hydroxyl group include pentaerythritol triacrylate, ECH-modified ethylene glycol diacrylate, ECH-modified glycerol triacrylate, ECH-modified phthalic acid diacrylate, triglycerol diacrylate, ECH-modified trimethylolpropane triacrylate. Etc.

Examples of the polyfunctional polymerizable monomer containing a carboxyl group include compounds represented by the following general formula (III-1) or general formula (III-2). However, the present invention is not limited to these.
In the following general formula, when T or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X and W.

  In general formula (III-1), n is 0-14 and m is 1-8. In the general formula (III-2), W is R or X as defined in the general formula (III-1), and 3 to 5 Ws are R among the 6 Ws. p is 0-14 and q is 1-8. A plurality of R, X, T, and G present in one molecule may be the same or different.

  Specific examples of the compound represented by the general formula (III-1) or the general formula (III-2) are shown below. However, the present invention is not limited to these.

  As a combination of the polyfunctional polymerizable monomer containing a carboxyl group described above and another monomer described later, TO-2359, TO-2360, TO-2348, or TO manufactured by Toa Synthetic Chemical Co., Ltd. -756 is commercially available.

Examples of the polyfunctional monomer having an alkoxycarbonylamino group include U-6LHA, U-6LYXA, U-12LMA manufactured by Shin-Nakamura Chemical Co., Ltd.
Examples of the polyfunctional monomer having an amide group include Toa Gosei monomers M-315 and M-215. In addition, a polyfunctional monomer containing an amino group can also be suitably used.
Specific examples of the polyfunctional monomer containing a hydrogen bonding group include the following compounds.

Among the above hydrogen bonding group-containing monomers, preferred are carboxyl group-containing monomers, alkoxycarbonylamino group-containing monomers, and ureido group-containing monomers, and most preferred are carboxyl group-containing monomers.
Furthermore, it is more preferable to use a carboxyl group-containing monomer and an amino group-containing polyfunctional monomer in combination.

  The radiation-sensitive composition of the present invention preferably contains 30% by mass or more of the above-mentioned hydrogen bonding group-containing monomer in the total solid content, so that deterioration of pattern rectangularity due to post-baking can be suppressed. The content of the hydrogen bonding group-containing monomer in the total solid content of the radiation-sensitive composition of the present invention is more preferably 33% by mass or more, and most preferably 35% by mass or more.

In the present invention, the content of the total polymerizable compound (the total polymerizable compound component containing at least a hydrogen bonding group-containing monomer and further containing another polymerizable compound as necessary) in the radiation-sensitive composition is determined by the composition The total solid content is preferably 10 to 80% by mass, more preferably 10 to 70% by mass, and most preferably 10 to 60%. When the content of the total polymerizable compound is 10% by mass or more, a good cured film can be obtained, and when it is 80% by mass or less, generation of development residue can be more effectively suppressed.
Moreover, when it contains a hydrogen bonding group containing monomer, it is preferable to contain the content so that it may become 20 mass% or more with respect to the total solid of a composition.

As a combination of a hydrogen-bonding group-containing monomer and a UV absorber, which are suitable polymerizable compounds in the radiation-sensitive composition of the present invention, from the viewpoint of coexistence of development residue reduction and pattern rectangularity improvement, A combination is preferred.
That is, the hydrogen-bonding group-containing monomer is a polyfunctional monomer containing at least one hydrogen-bonding group selected from a carboxyl group, an alkoxycarbonylamino group, and a ureido group, and the ultraviolet absorber is represented by the general formula ( A combination form which is a compound represented by I) is preferred.
Among the above forms, the radiation-sensitive composition of the present invention is particularly preferably a form containing a polyfunctional (meth) acrylate having no hydrogen bonding group as the polymerizable compound.

[5] Photopolymerization initiator The radiation-sensitive composition of the present invention preferably contains a photopolymerization initiator.
As the photopolymerization initiator in the present invention (hereinafter sometimes simply referred to as “polymerization initiator”), those known as photopolymerization initiators as described below can be used.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, from the ultraviolet region to visible light. An initiator that preferably has photosensitivity, may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization according to the type of monomer. It may be.
The photopolymerization 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 photopolymerization 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, and 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 compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  In addition, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbo Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphite Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the photopolymerization 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 photopolymerization 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 photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-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.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used as commercial products.

  Examples of oxime compounds other than those described above include compounds described in JP-T 2009-519904, in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule The compound described in U.S. Pat. No. 7,556,910, the compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A. Among the cyclic oxime compounds, the cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A are particularly preferable in terms of high light absorption and high sensitivity.
In addition, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can achieve high sensitivity by regenerating an active radical from a polymerization inert radical, and can be suitably used. .

Most preferably, the oxime compound includes an oxime compound having a specific substituent as disclosed in JP 2007-26979 A and an oxime compound having a thioaryl group as disclosed in JP 2009-191061 A.
Specifically, the oxime photopolymerization initiator is preferably a compound represented by the following formula (1). 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. .

In general formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the optionally substituted alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

In the general formula (1), examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A in the general formula (1) is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. ) -Substituted alkylene group, alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group) An alkylene group substituted with a phenanthryl group or a styryl group.

In general formula (1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the general formula (1), the structure of “SAr” formed by Ar and the adjacent S in the general formula (1) is preferably the following structure from the viewpoint of sensitivity. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following general formula (2).

In general formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. It is an integer.
R, A, and Ar in the general formula (2) have the same meanings as R, A, and Ar in the general formula (1), and preferred examples thereof are also the same.

  In the general formula (2), as the monovalent substituent represented by X, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, A halogen atom is mentioned. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X in the general formula (2) is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in General formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  In the general formula (2), examples of the divalent organic group represented by Y include the structures shown below. In the group shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the general formula (2).

  Among these, as the divalent organic group, the following structures are preferable from the viewpoint of sensitivity.

  Furthermore, the osym compound is preferably a compound represented by the following general formula (3).

In General Formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.
R, X, A, Ar, and n in the general formula (3) have the same meanings as R, X, A, Ar, and n in the general formula (2), and preferred examples are also the same.

  Although the specific example of the oxime compound used suitably below is shown, this invention is not limited to these.

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

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

  You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

  The content of the photopolymerization initiator in the radiation-sensitive composition (the total content in the case of two or more) is in the range of 0.1 to 20% by mass with respect to the total solid content of the radiation-sensitive composition. Is preferable, more preferably in the range of 0.5 to 10% by mass, and particularly preferably in the range of 1 to 8% by mass. Within this range, good sensitivity and pattern formability can be obtained.

  The radiation-sensitive composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, a photopolymerization initiator that is sensitized by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer that can be contained in the radiation-sensitive composition include compounds described in paragraph numbers [0101] to [0154] of JP-A-2008-32803.
The content of the sensitizer in the radiation-sensitive composition is preferably 0.1% by mass to 20% by mass in terms of solid content from the viewpoints of light absorption efficiency to the deep part and initiation decomposition efficiency, and 0 More preferably, it is 5 mass%-15 mass%.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

[5] Organic Solvent The radiation sensitive composition of the present invention can generally be constituted using an organic solvent.
The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the radiation-sensitive composition are satisfied, but particularly considering the solubility, coating property, and safety of the UV absorber and the binder. Are preferably selected. Moreover, when preparing the radiation sensitive composition of this invention, it is preferable that at least 2 type of organic solvent is included.

  Examples of the organic 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, alkyl esters, and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 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, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  As described above, these organic solvents may be used in combination of two or more from the viewpoints of the solubility of the ultraviolet absorber and the alkali-soluble resin, the improvement of the coated surface, and the like, in particular, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene A mixed solution composed of two or more selected from glycol methyl ether acetate is preferably used.

  The content of the organic solvent in the radiation-sensitive composition is preferably such that the total solid content of the composition is 5 to 90% by mass, more preferably 5 to 87% by mass, from the viewpoint of applicability. 10 to 85% by mass is particularly preferable.

[6] Other additives In the radiation-sensitive composition of the present invention, various additives, for example, a filler, a polymer compound other than the above, a surfactant, an organic carboxylic acid, an organic carboxylic acid are included as necessary. An anhydride, a polymerization inhibitor, an adhesion promoter, an antioxidant, an aggregation inhibitor, and the like can be blended.

<Surfactant>
Various surfactants may be added to the radiation-sensitive composition of the present invention 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. Of these, fluorine surfactants are preferred.

In particular, since the radiation-sensitive composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, when a film is formed using a coating liquid to which a radiation-sensitive composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coating surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the radiation-sensitive composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. It is.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

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

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.

Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant to the radiation-sensitive composition is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to the total mass of the radiation-sensitive composition. 1.0% by mass.

<Organic carboxylic acid, organic carboxylic anhydride>
The radiation-sensitive composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.

  Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaryl acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

The addition amount of these organic carboxylic acids and / or organic carboxylic acid anhydrides is generally 0.01 to 10% by mass, preferably 0.03 to 5% by mass, more preferably in the total solid content of the radiation-sensitive composition. Is in the range of 0.05 to 3 mass%.
By adding these organic carboxylic acids and / or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the residual undissolved material of the radiation-sensitive composition while maintaining high pattern adhesion. It is.

<Polymerization inhibitor>
In the radiation-sensitive composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the radiation-sensitive composition. .
Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Of these, p-methoxyphenol is preferred.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the total mass of the radiation-sensitive composition.

  Specific examples of adhesion promoters, antioxidants, and anti-agglomeration agents include fillers such as glass and alumina; binder resins other than polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate and the like Polymer compound: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropi Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol) And antioxidants such as 2,6-di-t-butylphenol; and aggregation inhibitors such as sodium polyacrylate.

In addition, the radiation-sensitive composition of the present invention is an organic carboxylic acid, preferably a molecular weight of 1000, when the alkali-solubility of the radiation-sensitive composition in the ultraviolet-irradiated part is promoted and the developability is further improved. The following low molecular weight organic carboxylic acids can be contained.
Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid Aliphatic dicarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid Acid; Aliphatic tricarboxylic acid such as tricarballylic acid, aconitic acid, and camphoronic acid; Aromatic monocarboxylic acid such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellito Aromatic polycarboxylic acids such as acids, trimesic acid, merophanoic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid It is done.

The radiation-sensitive composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. Examples of filters include, for example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (high density, super A high molecular weight filter). Among these filters, filters made of polyamide resins such as nylon-6 and nylon-6,6, and polypropylene (including high density polypropylene) are preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 2.5 μm, and more preferably about 0.01 to 2.0 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth coloring composition in a post process.

When using filters, two different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

≪Pattern forming method, color filter and manufacturing method thereof≫
The pattern forming method, color filter, and manufacturing method thereof of the present invention will be described.
The pattern forming method of the present invention includes a step of applying the radiation-sensitive composition of the present invention on a support to form a radiation-sensitive composition layer, and the formed radiation-sensitive composition layer through a mask. And a step of forming a pattern by exposing to ultraviolet light and developing.
The pattern forming method of the present invention can be suitably applied to the formation of pixels and the like that the color filter has.

  The support for forming a pattern by the pattern forming method of the present invention is not particularly limited as long as it is a support applicable to pattern formation in addition to a plate-like object such as a substrate.

  Each step in the pattern forming method of the present invention will be described in detail below through the color filter manufacturing method of the present invention.

The color filter manufacturing method of the present invention applies the pattern forming method of the present invention. Using the pattern forming method of the present invention, a step of forming a pattern on a substrate, and post-baking the formed pattern. And a step of performing.
That is, the method for producing a color filter of the present invention (hereinafter also referred to as the production method of the present invention) includes a step of applying the radiation-sensitive composition of the present invention on a substrate to form a radiation-sensitive composition layer. And a step of forming a pattern by exposing the developed radiation-sensitive composition layer to ultraviolet rays through a mask and developing the layer, and a step of post-baking the formed pattern.
The color filter of the present invention is obtained by the above production method.

  In the method for producing a color filter of the present invention, since the radiation-sensitive composition of the present invention is used, a pixel (pattern) having excellent rectangularity can be formed, and the occurrence of peeling of the pixel (pattern) after post-baking is suppressed. Therefore, a color filter capable of displaying a fine and high-quality image can be obtained.

Hereinafter, the manufacturing method of the color filter of this invention is demonstrated in detail.
More specifically, in the production method of the present invention, the radiation-sensitive composition of the present invention is applied directly or via another layer onto a silicon wafer as a substrate, and then dried to form a radiation-sensitive composition layer. A step of forming (coating film) (radiation-sensitive composition layer forming step), a step of pattern-exposing the radiation-sensitive composition layer with ultraviolet rays through a mask (exposure step), and the exposed radiation-sensitive radiation. A step of developing the composition layer with an alkaline developer to form a pattern (development step), and a step of subjecting the pattern obtained by the development treatment to a heat treatment (post-bake step). Moreover, the process of hardening the said radiation sensitive composition layer or pattern by heating and exposure as needed may be included.

  As a method for applying the radiation-sensitive composition, various methods such as a spray method, an ink jet method, a roll coating method, and a spin coating method can be used.

As ultraviolet rays used at least in the exposure, at least one of g-line, h-line and i-line is preferable, and i-line is more preferable.
As the exposure machine, for example, a stepper can be suitably used.

  Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine; alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; pyrrole, piperidine, N- Cyclic tertiary amines such as methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene; pyridine , Collidine, Cytidine, aromatic tertiary amines such as quinoline; tetramethylammonium hydroxide, the aqueous solution of quaternary ammonium salts such as tetraethyl ammonium hydroxide may be used.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the alkali developer.

  As a developing method, any of a liquid filling method, a dipping method, a shower method and the like may be used, and the developing time is usually 30 to 180 seconds.

  After alkali development, for example, washing with running water is performed for 30 to 90 seconds, and the pattern is formed by drying with compressed air or compressed nitrogen, for example.

  Next, after exposing the pattern after alkali development again with the radiation, it is preferably performed at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, on the hot plate with a heating device such as a hot plate or an oven. Then, a predetermined transparent pattern can be formed by performing post-baking for 5 to 30 minutes and in an oven for 30 to 90 minutes.

  The transparent pattern thus formed has an array of a plurality of rectangular pixels on the substrate. One side (maximum side) of the pixel is generally 1.0 μm to 20 μm or less. Among them, effective use of a substrate such as a silicon wafer, miniaturization of a device using a solid-state image sensor, and solid-state image sensor From the viewpoint of high-speed operation, it is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less.

  Further, the thickness of the pixel in the color filter of the present invention is not particularly limited, but it tends to be thin from the viewpoint of effective use of a substrate such as a silicon wafer and shading of a device using a solid-state imaging device, and is 2 μm or less. Is preferable, 1.5 μm or less is more preferable, and 1.0 μm or less is particularly preferable.

≪Solid-state imaging device≫
The solid-state imaging device of the present invention is configured to include the color filter of the present invention described above.
The solid-state imaging device of the present invention is excellent in sensitivity characteristics because the pixel (pattern) peeling is suppressed and the color filter of the present invention having excellent pixel (pattern) rectangularity and high resolution is provided.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .
A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (for example, a CCD image sensor, a CMOS image sensor) 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, the color filter of the present invention 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.

  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]: Formation of pattern of color filter for solid-state imaging device-Preparation of pigment dispersion composition P1-
A mixed liquid having the following composition was mixed and dispersed by a bead mill for 2 hours to prepare a pigment dispersion composition P-1.
-Composition-
Pigment Yellow 139 [Pigment (A)] ... 2.14 parts Pigment Red 254 [Pigment (B)] ... 4.81 parts Pigment Violet 23 [Pigment (B)] ... 1.18 parts Pigment Blue 15: 6 [Pigment (C)] ... 4.73 parts · Compound 1 below · 0.64 parts · Dispersant 1 below · 1.71 parts · Cyclomer P-ACA (compound having the following structure, solid content 50 mass%, (Weight average molecular weight 30000, manufactured by Daicel Corporation)
... 9.86 parts · Propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA" as appropriate) ... 66.50 parts · Cyclohexanone ... 8.43 parts

  In addition, the said dispersing agent 1 is compoundable according to the synthesis example described in paragraph number [0245]-[0247] of Unexamined-Japanese-Patent No. 2009-203462.

  With respect to the obtained pigment dispersion composition P1, the volume average particle size was measured using a Nanotrac UPA particle size analyzer (product name: UPA-EX150, manufactured by Nikkiso Co., Ltd.), and it was 10 nm.

~ Preparation of radiation sensitive composition ~
The following components were stirred and mixed to prepare the radiation sensitive composition of Example 1.
-Composition of radiation sensitive composition-
Pigment dispersion composition P-1 5.13 parts PGMEA 69.36 parts Monomer A (compound having the following structure) 0.57 parts TO-2349 (manufactured by Toagosei Co., Ltd., monomer B below) And 7: 3 mixture of dipentaerythritol hexaacrylate) ... 4.39 parts · Cyclomer P-ACA (solid content 50 mass%, weight average molecular weight 30000, manufactured by Daicel Corporation) ... 18.73 parts · initiator (Compound II, manufactured by BASF, product name IRGACURE OXE01) 1.06 parts UV absorber (III) (compound having the following structure) 0.71 parts Surfactant 0.04 parts (fluorine-based) Surfactant; manufactured by DIC Corporation, product name MegaFuck F-781F)
・ Polymerization inhibitor: 0.01 parts (p-methoxyphenol; manufactured by Kanto Chemical Co., Ltd., product name: p-methoxyphenol)

  The radiation-sensitive composition obtained above was filtered with a nylon filter “Membrane Disc NX047100” (manufactured by Nippon Pole) to remove coarse particles.

<Preparation of coating film (radiation-sensitive composition layer)>
The radiation-sensitive composition obtained above was applied by spin coating on a silicon wafer treated with hexamethyldisilazane (HMDS), and then heated on a hot plate at a surface temperature of the coating film surface of 100 ° C. for 120 seconds. Then, a coating film having a thickness of about 0.8 μm after drying was formed.

<Formation of color filter pattern for solid-state image sensor>
Next, an i-line stepper (product name: FPA-3000i5 +, Canon (through a mask pattern in which 1.2 μm square pixels are arranged in a 4 mm × 3 mm region on the substrate) is applied to the dried coating film. The product was exposed at an exposure amount of 150 mJ / cm ² .

The pattern-exposed coating film is subjected to paddle development at room temperature for 60 seconds using an organic alkaline developer CD-2060 (manufactured by Fuji Film Electronics Materials Co., Ltd.), and then further subjected to pure water in a spin shower for 20 seconds. I did a rinse. Thereafter, it was further washed with pure water. Thereafter, the substrate was dried by high speed rotation and post-baked with a hot plate at 220 ° C. for 300 seconds to form a pattern (pixel) on the silicon wafer.
As described above, a 1.2 μm square pattern was produced on a silicon wafer to obtain a color filter for a solid-state imaging device.

<Evaluation>
The following evaluation and measurement were performed on the 1.2 μm square pattern of the obtained color filter. The results of evaluation and measurement are shown in Table 1 below.

(1) Defect evaluation by pattern peeling The obtained silicon wafer with a color filter was inspected by a defect inspection apparatus ComPLUS3 manufactured by Applied Materials technology, a defective portion was detected, and the number of defects due to peeling was extracted from these defective portions. Based on the number of peeling defects extracted, the evaluation was made according to the following evaluation criteria.
~Evaluation criteria~
Good: The number of peeling defects is 0 or more and 10 or less Possible: The number of peeling defects is 11 or more and 20 or less (practically acceptable)
Impossible: More than 21 peeling defects

(2) Cross-sectional shape of pattern The 1.2 μm square pattern of the obtained color filter is cut along a plane perpendicular to the color filter surface (silicon wafer surface), and the shape of the cut surface is SEM (product name: S -4800 (manufactured by Hitachi High-Technologies Corporation) at a magnification of 30,000, and the pattern rectangularity index (the length of the upper side of the pattern / the length of the lower side of the pattern) is calculated from the shape of the cut surface. Evaluation was performed according to the evaluation criteria.
~Evaluation criteria~
Good: The pattern rectangularity index was 0.9 or more and 1.1 or less, that is, a rectangular shape and a good shape was obtained.
Possible: The pattern rectangularity index was 0.8 or more and less than 0.9, or greater than 1.1 and less than or equal to 1.3, which was practically acceptable.
Impossible: The pattern rectangularity index was less than 0.8 or greater than 1.3, and a rectangular pattern was not obtained.

[Examples 2 to 35]: Formation of pattern of color filter for solid-state imaging device Pigment dispersion composition prepared by changing pigment composition of pigment dispersion composition P-1 in Example 1 as shown in Table 2 below The radiation properties of Examples 2 to 35 were the same as Example 1 except that the composition of the radiation sensitive composition was changed as shown in Table 1 below instead of any of P-2 to P-13. A composition was prepared to produce a color filter. Moreover, the same evaluation as Example 1 was performed. The results of evaluation and measurement are shown in Table 1 below.

[Comparative Examples 1 and 2]: Formation of color filter pattern for solid-state imaging device Same as Example 1 except that the composition of the radiation-sensitive composition in Example 1 was changed as shown in Table 2 below. Thus, Comparative Examples 1 and 2 were prepared, and a color filter was prepared. Moreover, the same evaluation as Example 1 was performed. The results of evaluation and measurement are shown in Table 1 below.

The structures of M-13 and M-14 used in Example 24 and Example 25 are shown below.

The structure of TINUVIN 479, which is an ultraviolet absorber used in Example 27, is shown below.

  As shown in Table 1, it contains a resin, an ultraviolet absorber, and a pigment. As the pigment, a pigment having a maximum absorption wavelength at 400 to 500 nm (pigment (A)), and a maximum absorption wavelength at 500 to 600 nm. Each having at least one pigment having a maximum absorption wavelength at 600 to 700 nm (pigment (B)), and the total content of all pigments is 0.00. In the radiation-sensitive composition of each example that was 1% or more and 20% or less, pattern peeling was suppressed and the pattern had excellent rectangularity.

  Even in the case where the radiation-sensitive composition in which the monomer A used in each of the above examples was changed to the above-described compounds as specific examples of the polyfunctional monomer containing a hydrogen bonding group was used, each Example Similarly to the above, pattern peeling can be suppressed and a pattern having excellent rectangularity can be formed.

In the above embodiment, an example in which a pixel pattern of a color filter is formed on a silicon wafer has been described. However, when a solid-state imaging device is manufactured, the silicon wafer is formed using a photodiode, a light shielding film, a device protection film, and the like. What is necessary is just to substitute for the board | substrate for solid-state image sensors with formed.
For example, on a silicon wafer on which a photodiode and a transfer electrode are formed, a light shielding film made of tungsten having an opening only in the light receiving portion of the photodiode is formed, and the entire surface of the formed light shielding film and the photodiode light receiving portion (openings in the light shielding film). A device protective layer made of silicon nitride is formed so as to cover the portion. Next, on the formed device protection layer, a pattern is formed by the same method as in the above embodiment, and a red pixel, a blue pixel, and a green pixel are formed by a known method to form a color filter. Next, by forming a microlens as a light condensing means on the obtained color filter, a solid-state imaging device (CCD, CMOS, etc.) having good color reproducibility can be produced.

[Example 36]
On the device formed by a known method (for example, the method described in JP-A No. 2001-267544), the same pattern as the pattern (pixel) of the color filter produced in Example 1 was formed as the first color. . Next, each colored pixel was formed in the same manner as the green, blue, and red colored pixels described in JP2010-244028A.
As described above, the color filter A1 was manufactured so as to repeat the layout shown in FIG.
Next, a microlens was formed by a known method to produce an image sensor A1.
Color filters A2 to A36 were prepared in the same manner as the color filter A1, except that the pattern formed for the first color was changed to any of the patterns of the color filters prepared in Examples 2 to 35 and Comparative Example 1. Image sensors A2 to A36 provided with this were manufactured.
In FIG. 1, regions indicated by R, G, and B symbols are regions composed of colored pixels of Green, Blue, and Red, and regions indicated by halftone dots without symbols are examples or This is an area composed of the same pattern as the pattern (pixel) formed in the comparative example.

When actually performing an imaging test using each of the obtained image sensors A1 to A36, the image sensors including the color filters A1 to A35 having the patterns obtained in Examples 1 to 35 are all in a bright place. Images could be formed with good sensitivity and color reproducibility even in dark places.
On the other hand, the image obtained by the image sensor A36 provided with the color filter having the pattern obtained in Comparative Example 1 was a whitish image in a bright room, and a good image could not be formed.
In addition, the general color filter having the layout shown in FIG. 2 is dark when shooting in a dark place, and a good image cannot be obtained. In FIG. 2, regions indicated by symbols R, G, and B are regions made up of green, blue, and red colored pixels.

Claims (17)

  A resin, an ultraviolet absorber, and a pigment, and as the pigment, a pigment (A) having a maximum absorption wavelength at 400 nm to less than 500 nm, and a pigment (B) having a maximum absorption wavelength at 500 nm to less than 600 nm, A solid-state imaging device containing at least one pigment (C) having a maximum absorption wavelength at 600 nm to 700 nm and having a total content of all pigments of 0.1% by mass to 20% by mass with respect to the total solid content A radiation-sensitive composition used for forming pixels.   The pigment (A) having a maximum absorption wavelength at 400 to 500 nm, the pigment (B) having a maximum absorption wavelength at 500 to 600 nm, and the pigment (C) having a maximum absorption wavelength at 600 to 700 nm. The radiation-sensitive composition according to claim 1, wherein the content is 0.2% by mass or more and 10% by mass or less with respect to the total solid content.   The total content of the pigment (B) having a maximum absorption wavelength at 500 nm to less than 600 nm and the pigment (C) having a maximum absorption wavelength at 600 nm to 700 nm is 1% by mass to 18% by mass in the total solid content. The radiation-sensitive material according to claim 1 or 2, wherein the content mass ratio [(B) :( C)] of the pigment (B) and the pigment (C) is 1: 2 to 2: 1. Sex composition.   4. The radiation-sensitive composition according to claim 1, wherein the content of the ultraviolet absorber is 2% by mass or more and 10% by mass or less based on the total solid content.   Furthermore, the radiation sensitive composition of any one of Claims 1-4 containing a polymeric compound.   The radiation-sensitive composition according to any one of claims 1 to 5, wherein the polymerizable compound is a monomer having a hydrogen bonding group.   The radiation-sensitive composition according to any one of claims 1 to 6, wherein the content of the monomer having a hydrogen bonding group is 20% by mass or more based on the total solid content.   The radiation-sensitive composition according to claim 6 or 7, wherein the hydrogen bonding group is at least one selected from a carboxyl group, an alkoxycarbonylamino group, and a ureido group.   The radiation sensitive composition according to any one of claims 1 to 8, wherein the ultraviolet absorber is a conjugated diene compound. The radiation-sensitive composition according to any one of claims 1 to 8, wherein the conjugated diene compound is a compound represented by the following general formula (I).

[In General Formula (I), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² may be the same as or different from each other, but both R ¹ and R ² do not represent a hydrogen atom. R ¹ and R ² may be bonded to each other to form a cyclic amino group together with the adjacent nitrogen atom. R ³ and R ⁴ each independently represents an electron withdrawing group. ]   The radiation-sensitive composition according to any one of claims 6 to 10, wherein the monomer having a hydrogen bonding group is a polyfunctional monomer.   Furthermore, the radiation sensitive composition of any one of Claims 1-11 containing a photoinitiator.   The colored radiation-sensitive composition according to claim 12, wherein the photopolymerization initiator is an oxime compound.   The process of providing the radiation sensitive composition of any one of Claims 1-13 on a support body, and forming the radiation sensitive composition layer, and the formed radiation sensitive composition layer Forming a pattern by exposing to ultraviolet light through a mask and developing the pattern.   A method for producing a color filter, comprising: a step of forming a pattern on a substrate using the pattern forming method according to claim 14; and a step of post-baking the formed pattern.   A color filter produced by the method for producing a color filter according to claim 15.   A solid-state imaging device comprising the color filter according to claim 16.