JP6158765B2 - Radiation-sensitive composition, color filter and method for producing the same, and solid-state imaging device - Google Patents

Description

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

Recently, for the purpose of improving the resolution of image sensors (CCD, CMOS), pixel miniaturization has been progressed with the increase in the number of pixels of the image sensor. . Thus, for the purpose of improving sensitivity, one color of a plurality of color filters may be white (transparent).
With respect to white (transparent) pixels (hereinafter referred to as “white filter pixels” as appropriate) of such color filters, an oxime-based photopolymerization initiator, an ultraviolet absorber, a monomer having an aromatic ring, or a hydrogen bond. A technique of applying a photosensitive resin composition containing a specific monomer such as a monomer having been proposed has been proposed.
Further, a photosensitive resin composition that can be applied to a solid-state imaging device and includes titanium dioxide particles, a graft copolymer having a specific structure, a polymerizable compound, a polymerization initiator, and a solvent has been proposed (see Patent Document 1). .
A photosensitive transparent composition for a color filter of a solid-state imaging device, comprising a photopolymerization initiator, a polymerizable compound, and an alkali-soluble resin as the photosensitive transparent composition for a color filter, the photosensitive transparent composition The photosensitive transparent composition whose refractive index with respect to the light of wavelength 633nm of the cured film obtained from 1.60-1.90 is proposed (refer patent document 2).
Further, as a radiation-sensitive composition, a photosensitive resin composition containing titanium dioxide particles, oligoimine resin, a polymerizable compound, a photopolymerization initiator, and an organic solvent has been proposed (Patent Document 3). See).

JP 2011-127096 A JP 2012-137564 A JP 2013-64979 A

However, in recent years, there has been a demand for a radiation-sensitive composition having a higher transmittance in the visible light region and better heat resistance and exposure latitude than the compositions described in Patent Documents 1 to 3.
The present invention solves such a problem, and an object of the present invention is to provide a radiation-sensitive composition having high transmittance in the visible light region and good heat resistance and exposure latitude.

The inventor includes high refractive index particles composed of a material having a refractive index of 1.80 to 2.80, a polymerizable compound, a photopolymerization initiator, and an organic solvent, and an oxime photopolymerization initiator and an α-aminoketone system. It has been found that the above problem can be solved by setting the mass ratio of the photopolymerization initiator to 1: 1.5 to 1: 4.
Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <14>.
<1> particles having a refractive index of 1.80 to 2.80, a polymerizable compound, an oxime photopolymerization initiator, an α-aminoketone photopolymerization initiator, and an organic solvent,
A radiation-sensitive composition having a mass ratio of an oxime photopolymerization initiator and an α-aminoketone photopolymerization initiator of 1: 1.5 to 1: 4.
<2> The radiation-sensitive composition according to <1>, wherein the oxime photopolymerization initiator is represented by the following general formula (I).
Formula (I)
(In general formula (I), R ¹ represents any ^one of a hydrogen atom, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, R ² represents a substituent, and forms a condensed ring with Ar ^1. R ³ represents any of a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group, and m1 is 0 to 4. When m1 is 2 or more, R ^{3 s} may be the same or different, and Ar ¹ is an arylene group or a combination of an arylene group and —C (═O) —. Represents a group.)
<3> The radiation-sensitive composition according to <1> or <2>, wherein the oxime photopolymerization initiator is represented by the following general formula (I-1).
Formula (I-1)
(In the general formula (I-1), R ⁴ represents a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ⁵ represents a halogen atom or an alkyl group. Represents any one of a group, an aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group, m2 represents an integer of 0 to 4. A represents one ring. Or, a condensed ring in which two rings are condensed represents a structure in which an adjacent benzene ring is condensed, and each ring represents any of 4, 5, 6 and 7-membered rings.)
<4> The radiation-sensitive composition according to any one of <1> to <3>, wherein the α-aminoketone photopolymerization initiator is represented by the following general formula (II-1).
Formula (II-1)
(In General Formula (II-1), R ¹¹ represents a hydrogen atom or an alkyl group, and R ¹² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 1 carbon atom. -8 represents an alkylthio group, dimethylamino group or morpholino group, Ar ² represents an arylene group, X ³ and X ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 3 carbon atoms. Represents an alkenyl group of ˜5 or a phenylalkyl group of 7 to 9 carbon atoms, and X ³ and X ⁴ may be bonded to each other to form a ring.)
<5> The radiation-sensitive composition according to any one of <1> to <4>, further comprising 1 to 8% by mass of an ultraviolet absorber based on the total solid content of the radiation-sensitive composition.
<6> The radiation-sensitive composition according to <5>, wherein the ultraviolet absorber has an aminobutadiene skeleton.
<7> The radiation-sensitive composition according to any one of <1> to <6>, wherein the particles having a refractive index of 1.80 to 2.80 are titanium dioxide particles.
<8> The radiation-sensitive composition according to any one of <1> to <7>, wherein the polymerizable compound is (meth) acrylate.
<9> The radiation-sensitive composition according to any one of <1> to <8>, containing a dispersant having an acid value of 40 to 70 mgKOH / g.
<10> The radiation-sensitive composition according to any one of <1> to <9>, which is used for pixel formation of a color filter.
<11> A color filter obtained using the radiation-sensitive composition according to any one of <1> to <9>.
<12> In order to obtain a patterned cured film, a step of forming a radiation-sensitive composition layer on a support using the radiation-sensitive composition according to any one of <1> to <9> A color filter produced by the color filter production method according to <13><12>, wherein the radiation sensitive composition layer is exposed and developed to form a pattern. . <14> A solid-state imaging device having the color filter according to <11> or the color filter according to <13>.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the radiation sensitive composition with the high transmittance | permeability in visible light region, and favorable heat resistance and exposure latitude.

In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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 addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
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.
The weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl 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. .

<Radiation sensitive composition>
The radiation-sensitive composition of the present invention comprises high refractive index particles composed of a material having a refractive index of 1.80 to 2.80, a polymerizable compound, a photopolymerization initiator, and an organic solvent, and comprises an oxime photopolymerization initiator. The mass ratio of the α-aminoketone photopolymerization initiator is 1: 1.5 to 1: 4.
The radiation-sensitive composition of the present invention has high transmittance in the visible light region, and good heat resistance and exposure latitude. Although this mechanism is presumed, by setting the mass ratio of the oxime photopolymerization initiator and the α-aminoketone photopolymerization initiator in the radiation-sensitive composition to a range of 1: 1.5 to 1: 4. Even if the amount of the oxime photopolymerization initiator used is relatively small, the polymerization of the polymerizable compound can be initiated. As a result, the decomposition product of the oxime-based photopolymerization initiator can be reduced, so that the transmittance in the visible light region can be increased and the heat resistance can be improved by reducing by-products that cause coloring. It is done.

  It is preferable that the refractive index with respect to the light with a wavelength of 500 nm of the cured film obtained from a radiation sensitive composition of the radiation sensitive composition of this invention is 1.80-2.80.

The radiation-sensitive composition of the present invention forms a cured film having a thickness of 0.6 μm by, for example, using an i-line stepper exposure apparatus and exposing a pattern through a mask under an exposure amount of 300 mJ / cm ^2. The light transmittance in the thickness direction of the cured film is preferably 85% or more over the entire wavelength region of 400 nm to 700 nm, more preferably 88% or more, and 89% or more. More preferably, it is particularly preferably 90% or more. It is preferable that the light transmittance is 85% or more over the entire wavelength region of 400 nm to 700 nm from the viewpoint that the white filter pixel included in the color filter performs a sufficient function as the white filter pixel.

  Moreover, it is preferable that the radiation sensitive composition of this invention does not contain a coloring agent substantially. The content of the colorant is preferably 0.1% by mass or less with respect to the total solid content of the composition. In addition, each component (for example, high refractive index particle | grains and an ultraviolet absorber) mentioned later is not included in the said coloring agent.

  The radiation-sensitive composition of the present invention can be preferably used as a radiation-sensitive composition for a solid-state image sensor, more preferably used for forming a pixel of a color filter included in the solid-state image sensor, and the color of the solid-state image sensor. More preferably, the filter is used for white filter pixels.

<< particles having a refractive index of 1.80 to 2.80 >>
Particles having a refractive index of 1.80 to 2.80 (hereinafter also referred to as high refractive index particles) have a refractive index of a constituent material (substance) of 1.80 or more and 1.90 or more. Preferably, it is 2.0 or more. As an upper limit, it is 3.0 or less, it is preferable that it is 2.9 or less, and it is more preferable that it is 2.8 or less. By setting the refractive index of the high refractive index particles to 2.8 or less, it is possible to increase the refractive index while keeping the transmittance of the cured film within a specific range by the amount of variation. On the other hand, by setting the lower limit value to 1.80 or more, when a color filter is formed using the radiation-sensitive composition of the present invention, interference with other pixels due to the waveguide effect is suppressed and prevented. Can do. The refractive index measurement method of the high refractive index particles, unless otherwise specified, each obtained the projected area of the titanium dioxide particles using a transmission electron microscope, the value obtained by calculating the arithmetic mean value of the corresponding equivalent circle diameter To do.
The weight average diameter of the primary particles of the high refractive index particles is preferably 150 nm or less, more preferably 100 nm or less, and particularly preferably 80 nm or less. Although there is no lower limit in particular, it is practical that it is 1 nm or more. The weight average diameter of the high refractive index particles in the layer is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less, and particularly preferably 80 nm or less. Although there is no lower limit in particular, 1 nm or more is preferable, 5 nm or more is more preferable, and 10 nm or more is further more preferable. As for the weight average diameter of the high refractive index particles, unless otherwise specified, the liquid mixture or dispersion containing the particles is diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted solution is subjected to dynamic light scattering. It is obtained by measuring using the method. This measurement shall be the weight average particle diameter obtained by using Microtrack (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd.
The specific surface area of the high refractive index particles is preferably 10 m ² / g to 400 m ² / g, more preferably 20 m ² / g to 200 m ² / g, and 30 m ² / g to 150 m ² / g. More preferably it is.

  Examples of the high refractive index particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. And particles containing a metal oxide having the above element. Specific examples include titanium dioxide, tin oxide, indium oxide, zinc oxide, or zirconium oxide particles. Among these, particles of titanium oxide, tin oxide, indium oxide, or zirconium oxide are particularly preferable. The metal oxide particles can contain oxides of these metals as main components and further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. The crystal structure of the inorganic fine particles containing titanium dioxide as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase or amorphous structure, particularly preferably a rutile structure.

  The high refractive index particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide, and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents.

As a preferred embodiment of the present invention, one containing at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in inorganic fine particles mainly composed of titanium dioxide can be mentioned. Thereby, the photocatalytic activity which titanium dioxide has can be suppressed, and the weather resistance of a high refractive index layer can be improved.
The high refractive index particles may be treated by combining two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.

Commercially available products may be used as titanium dioxide. Specifically as a commercial item, TTO series (TTO-51 (A), TTO-51 (C), TTO-55 (C) etc.), TTO-S, V series (TTO-S-1, TTO), for example -S-2, TTO-V-3, etc.)
Product name, manufactured by Ishihara Sangyo Co., Ltd.), MT series (MT-01, MT-05, etc.) (manufactured by Teika Co., Ltd., product name) and the like.

High refractive index particles may be used singly or in combination of two or more.
The content of the high refractive index particles in the composition is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more in the total solid content. As an upper limit, 65 mass% or less is preferable, 60 mass% or less is more preferable, and 55 mass% or less is especially preferable.

<< dispersant >>
In the composition of the present invention, a dispersant containing a structural unit represented by any of the following general formula (1) and the following general formula (2) is preferably used as a dispersant for high refractive index particles.

In the general formulas (1) and (2), R ^{1 to} R ⁶ each represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² are each —CO—, —C (= O) represents O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² each represent a single bond or a divalent organic linking group, and A ¹ and A ² Represents a monovalent organic group, m and n each represent an integer of 2 to 8, and p and q each represent an integer of 1 to 100.

In general formulas (1) and (2), R ^{1 to} R ⁶ each represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, A 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group are exemplified.
In the general formulas (1) and (2), R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are each a hydrogen atom or a methyl group on the pigment surface. It is most preferable from the viewpoint of adsorption efficiency.

In the general formulas (1) and (2), X ¹ and X ² each represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. . Among them, —C (═O) O—, —CONH—, and a phenylene group are preferable from the viewpoint of adsorptivity to the pigment, and —C (═O) O— is most preferable.

In general formulas (1) and (2), L ¹ and L ² each represent a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising the alkylene group and a heteroatom or a partial structure containing a heteroatom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Among these, an oxygen atom and a nitrogen atom are preferable.
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
The divalent organic linking group includes a heteroatom or a heteroatom selected from —C (═O) —, —OC (═O) —, and —NHC (═O) — at the end of the above alkylene group. Those having a partial structure and linked to an adjacent oxygen atom via the heteroatom or a partial structure containing a heteroatom are preferred from the viewpoint of adsorptivity to the pigment. Here, the adjacent oxygen atom means an oxygen atom that binds to L ¹ in the general formula (1) and L ² in the general formula (2) on the side chain end side.

In general formulas (1) and (2), A ¹ and A ² each represent a monovalent organic group. As the monovalent organic group, a hydroxyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is preferable.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), Alkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate) Group), a phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (— OPO ₃ (aryl) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoaruki Phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups, which may further have a substituent.

  Examples of the substituent include an alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.

  Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group It can be exemplified phosphonophenyl phenyl group.

As A ¹ and A ² , from the viewpoint of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a number having 5 to 20 carbon atoms Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. A linear alkyl group having 6 to 10 and a branched alkyl group having 6 to 12 carbon atoms is more preferable.

  In general formula (1) and (2), m and n represent the integer of 2-8, respectively. In view of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

  In general formula (1) and (2), p and q represent the integer of 1-100, respectively. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

  The copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) includes the repeating unit represented by the general formula (1) from the viewpoint of dispersion stability. Those are preferred.

  The repeating unit represented by the general formula (1) is more preferably a repeating unit represented by the following general formula (1) -2.

General formula (1) -2

In General Formula (1) -2, R ^{1 to} R ³ each represent a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents —C (= O)-or NHC (= O)-, A ¹ represents a monovalent organic group, m represents an integer of 2 to 8, and p represents an integer of 1 to 100.

  The repeating unit represented by the general formula (1), (2), or (1) -2 is a simple unit represented by the following general formula (i), (ii), or (i) -2, respectively. The polymer is introduced as a repeating unit of the polymer compound by polymerization or copolymerization.

In the general formulas (i), (ii), and (i) -2, R ^{1 to} R ⁶ each represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each represent — CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² represent a single bond or a divalent organic linking group, respectively. La represents an alkylene group having 2 to 10 carbon atoms, Lb represents —C (═O) — or NHC (═O) —, and A ¹ and A ² are each a monovalent organic group. And m and n each represent an integer of 2 to 8, and p and q each represent an integer of 1 to 100.

  In the following, preferred specific examples of the monomer represented by the general formula (i), (ii), or (i) -2 are those described in paragraphs 0081 to 0084 of JP2012-173356A. Although the isomers (XA-1) to (XA-23) are exemplified, the present invention is not limited to these.

  The copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) is selected from the repeating units represented by either the general formula (1) or (2). It is sufficient that at least one type of repeating unit is included, and only one type may be included, or two or more types may be included.

  Moreover, in the copolymer containing the structural unit represented by either the general formula (1) or the following general formula (2), the inclusion of the repeating unit represented by any of the general formulas (1) and (2) The amount is not particularly limited, but when the total repeating unit contained in the polymer is 100% by mass, the repeating unit represented by any one of the general formulas (1) and (2) is 5% by mass or more. It is preferable to contain, it is more preferable to contain 50 mass%, and it is further more preferable to contain 50 mass%-80 mass%.

The copolymer containing the structural unit represented by any one of the above general formula (1) and the following general formula (2) is a monomer having a functional group capable of adsorbing to the pigment for the purpose of enhancing adsorption to the pigment And a polymer compound obtained by copolymerizing the above-described monomers represented by the general formulas (i), (ii), and (i) -2.
Specific examples of the monomer having a functional group capable of adsorbing to the pigment include a monomer having an acidic group, a monomer having an organic dye structure or a heterocyclic structure, a monomer having a basic nitrogen atom, and an ionic group. A monomer etc. can be mentioned. Of these, monomers having an acidic group, and monomers having an organic dye structure or a heterocyclic structure are preferable from the viewpoint of adsorption to the pigment.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, ω- Carboxy-polycaprolactone mono (meth) acrylate can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, maleic anhydride, phthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic anhydride from the viewpoint of developing removability of unexposed areas. An addition reaction product with a cyclic anhydride such as

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  The copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) preferably contains a repeating unit derived from a monomer having an acidic group as described above.

  The copolymer containing the structural unit represented by any of the general formula (1) and the following general formula (2) may contain only one type of repeating unit derived from a monomer having an acidic group. And two or more types may be included.

  Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, specific monomers, maleimides, and maleimide derivatives described in paragraph Nos. 0048 to 0070 of JP-A-2009-256572. 1 type selected from a group is mentioned.

  Examples of the monomer having a basic nitrogen atom include (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, and (meth) acrylic acid. 1- (N, N-dimethylamino) -1,1-dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N (meth) acrylic acid, N-diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth ) Piperidinoethyl acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrole (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N ′), and the like. -Dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) Acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- ( N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) Acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (Meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and the like, styrenes N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene and the like.

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include the monomers described in paragraph No. 0095 of JP2012-173356A, the contents of which are incorporated herein.

  Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers and cationic vinyl monomers). Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having the above acidic groups, salts with organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and the like. As the vinyl monomer, the above nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride and benzyl bromide; Alkylsulfonic acid esters such as acids (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1-18); dialkyl sulfates (alkyl groups: C1-4), etc. Quaternized with dialkyl diallyla Such as Moniumu salts.

  The copolymer including the structural unit represented by any one of the general formula (1) and the following general formula (2) further includes a repeating unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired. May be included.

  Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, phenyl (meth) acrylate, ( 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , 2- (ethoxy) ethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, (meta ) Acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (Meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β-phenoxyethoxyethyl, (meth) acrylic acid nonylphenoxypolyethylene glycol, (meth) acrylic acid disi Clopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid trifluoroethyl, (meth) acrylic acid octafluoropentyl, (meth) acrylic acid perfluorooctyl ethyl, (meth) acrylic acid dicyclopenta Nyl, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl. Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  A preferred embodiment of the copolymer containing the structural unit represented by any one of the general formula (1) and the following general formula (2) is represented by at least the general formula (i), (ii), or (i) -2. And a monomer having an acidic group, or a monomer having an organic dye structure or a heterocyclic structure, and more preferably represented by the general formula (i) -2 described above. And a monomer having an acid group are copolymerized.

  As other dispersants, it is also preferable to use a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers. Further, 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 / Examples thereof include benzyl methacrylate / methacrylic acid copolymer.

  In the present invention, the dispersants shown below are particularly preferable.

  The acid value of the dispersant is preferably 10 to 400 mgKOH / g, more preferably 20 to 200 mgKOH / g, and still more preferably 40 to 70 mgKOH / g. By setting the acid value of the dispersant to 40 mgKOH / g or more, the residue remaining on the ground of the pattern can be further reduced when the pattern is formed. In addition, by setting the acid value of the dispersant to 70 mgKOH / g or less, even when the radiation-sensitive composition layer is left for a long time before the exposure after the formation of the radiation-sensitive composition layer, pattern distortion is generated. It can suppress more effectively. The acid value of the dispersant can be calculated, for example, from the average content of acid groups in the dispersant.

The molecular weight of the dispersant used in the present invention is 2,000 to 50,000 in terms of weight average molecular weight (Mw).
0 is preferable, and 5,000 to 30,000 is more preferable.
The content of the dispersant is preferably 5 to 60 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the high refractive index particles.
Only 1 type of dispersing agent may be contained in the composition of this invention, and may be contained 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<< photopolymerization initiator >>
The radiation-sensitive composition of the present invention contains, as a photopolymerization initiator, an oxime photopolymerization initiator and an α-aminoketone photopolymerization initiator, and an oxime photopolymerization initiator and an α-aminoketone photopolymerization initiator, Is a mass ratio of 1: 1.5 to 1: 4. When the mass ratio of the α-aminoketone photopolymerization initiator to the oxime photopolymerization initiator is less than 1.5, the amount of the oxime photopolymerization initiator is relatively increased, resulting from the oxime photopolymerization initiator. Decomposition products are easily generated, and the transmittance in the visible light region is reduced. Moreover, heat resistance and exposure latitude are also inferior.
Moreover, when the mass ratio of the α-aminoketone photopolymerization initiator to the oxime photopolymerization initiator exceeds 4, the amount of the oxime photopolymerization initiator in the photopolymerization initiator is relatively small, and the sensitivity is reduced. Problems arise.
The mass ratio of the oxime photopolymerization initiator and the α-aminoketone photopolymerization initiator is preferably 1: 1.8 to 1: 1.35, and is 1: 2.0 to 1: 3.0. More preferably. By setting it as such a range, the effect of this invention can be achieved more effectively.
The total content of the photopolymerization initiator based on the total solid content of the radiation-sensitive composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, More preferably, it is 1.0-5 mass%.

<<< oxime photopolymerization initiator >>>
The oxime photopolymerization initiator used in the present invention may be used alone or in combination of two or more.
The oxime photopolymerization initiator preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and has a high absorbance at 365 nm. Particularly preferred.
The oxime photopolymerization initiator has a molar extinction coefficient at 365 nm or 405 nm of preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200,000. 000 is particularly preferred.
The molar extinction coefficient of the oxime-based photopolymerization initiator can be measured using a known method. For example, an ultraviolet-visible spectrophotometer (Varian's Cary-5 spctroph) is used.
It is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent.

The oxime photopolymerization initiator used in the present invention is preferably represented by the following general formula (I). Formula (I)
(In general formula (I), R ¹ represents any ^one of a hydrogen atom, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, R ² represents a substituent, and forms a condensed ring with Ar ^1. R ³ represents any of a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group, and m1 is 0 to 4. When m1 is 2 or more, R ^{3 s} may be the same or different, and Ar ¹ is an arylene group or a combination of an arylene group and —C (═O) —. Represents a group.)

In general formula (I), R ¹ represents any of a hydrogen atom, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
The acyl group may be any of aliphatic, aromatic and heterocyclic rings. Those having 2 to 30 carbon atoms are preferred, those having 2 to 20 carbon atoms are more preferred, and those having 2 to 16 carbon atoms are particularly preferred. Examples of the substituent which the acyl group may have include, for example, an acetyl group, an n-propanoyl group, an i-propanoyl group, a methylpropanoyl group, a butanoyl group, a pivaloyl group, a hexanoyl group, a cyclohexanecarbonyl group, an octanoyl group, and decanoyl. Group, dodecanoyl group, octadecanoyl group, benzylcarbonyl group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, toluenecarbonyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, Examples include 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, methacryloyl group, acryloyl group and the like.
The alkyloxycarbonyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 16 carbon atoms. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. Is mentioned.
The aryloxycarbonyl group is preferably an alkoxycarbonyl group having a total carbon number of 7 to 30, more preferably a total carbon number of 7 to 20, and particularly preferably a total carbon number of 7 to 16.
Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.
The acyl group, alkyloxycarbonyl group and aryloxycarbonyl group may further have a substituent, but are preferably unsubstituted. As the substituent, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable.

In general formula (I), R ² represents a substituent. R ² is preferably a C 1-10 alkyl group or a group consisting of a combination of a C 1-10 alkyl group and —O—. R ² preferably forms a ring. When R ² forms a ring, any of 4, 5, 6, and 7-membered rings are preferred, and 5- or 6-membered rings are preferred. In addition, when R ² forms a ring, Ar ¹ may form a condensed ring. Further, the condensed ring formed by bonding to Ar ¹ is preferably a condensed ring in which two or three rings are condensed. In addition, when R ² forms a ring, it is preferably a heterocyclic ring, more preferably 1 to 3 oxygen atoms or sulfur atoms in the ring structure, and one oxygen atom. More preferably, it has.

In general formula (I), each R ³ independently represents a halogen atom, an alkyl group, an aryl group,
It represents any of an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group. When m1 is 2 or more and are connected to each other to form a ring, it is preferable that each R ³ independently forms a ring,
It is more preferable that each R ³ independently forms an aryl group having 6 to 12 carbon atoms.

In general formula (I), m1 represents the integer of 0-4, and 0 or 1 is preferable.
In general formula (I), Ar ¹ represents an arylene group or a group composed of a combination of an arylene group and —C (═O) —. 6-24 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable. In particular, a phenylene group or a group comprising a combination of a phenylene group and —C (═O) — is preferable, and a phenylene group is more preferable.

The oxime photopolymerization initiator used in the present invention is more preferably represented by the following general formula (I-1).
Formula (I-1)
(In the general formula (I-1), R ⁴ represents a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ⁵ represents a halogen atom or an alkyl group. Represents any one of a group, an aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group, m2 represents an integer of 0 to 4. A represents one ring. Or, a condensed ring in which two rings are condensed represents a structure in which an adjacent benzene ring is condensed, and each ring represents any of 4, 5, 6 and 7-membered rings.)

In the general formula (I-1), R ⁴ has the same meaning as R ¹ in the above-mentioned formula (I), and preferred ranges are also the same.
In the general formula (I-1), R ⁵ has the same meaning as R ³ in the above-mentioned formula (I), and preferred ranges are also the same.
In general formula (I-1), m2 is synonymous with m1 in general formula (I) mentioned above, and its preferable range is also the same.
In the general formula (I-1), A represents a structure in which a condensed ring in which one ring or two rings are condensed with an adjacent benzene ring, and each ring has 4, 5, 6 and 7 members. Represents one of the rings. Each ring is preferably a 5- or 6-membered ring. A is preferably a heterocyclic ring, more preferably 1 to 3 of oxygen atoms and sulfur atoms in the ring structure, and still more preferably 1 of oxygen atoms.

The oxime photopolymerization initiator used in the present invention is more preferably represented by the following general formula (I-2) or (I-3).
Formula (I-2)
(In the general formula (I-2), R ⁴ represents a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ⁵ represents a halogen atom or an alkyl group. Represents any one of a group, an aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group, m2 represents an integer of 0 to 4. X represents —CH _2. -Represents one of an oxygen atom and a sulfur atom, and l represents an integer of 1 to 3.)

Formula (I-3)
(In the general formula (I-3), R ⁴ represents a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ⁵ represents a halogen atom or an alkyl group. Represents any one of a group, an aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group, m2 represents an integer of 0 to 4. X represents —CH _2. -Represents one of an oxygen atom and a sulfur atom, and l represents an integer of 1 to 3.)

In general formulas (I-2) and (I-3), R ⁴ has the same meaning as R ¹ in general formula (I) described above, and the preferred range is also the same.
In general formulas (I-2) and (I-3), R ⁵ has the same meaning as R ³ in general formula (I) described above, and the preferred range is also the same.
In general formulas (I-2) and (I-3), m2 has the same meaning as m1 in general formula (I) described above, and the preferred range is also the same.
In general formulas (I-2) and (I-3), X represents —CH ₂ —, an oxygen atom, or a sulfur atom,
An oxygen atom is preferred.
In general formulas (I-2) and (I-3), l represents an integer of 1 to 3, and 1 is preferable.

Examples of the oxime-based photopolymerization initiator that can be used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimibutan-2-one, 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane- 2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.
Examples of commercially available oxime compounds include IRGACURE-OXE01 (trade name: manufactured by BASF), IRGACURE-OXE02 (trade name: manufactured by BASF), TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG. −305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arkles NCI-831, Adeka Arkles NCI-930 (made by ADEKA) are also preferably used.

  Hereinafter, although the specific example of the oxime type photoinitiator which can be used in this invention is shown, this invention is not limited to these.

  The total content of the oxime polymerization initiator based on the total solid content of the radiation-sensitive composition of the present invention is preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass. More preferably, the content is 0.2 to 4% by mass.

<<< α-aminoketone photopolymerization initiator >>>
The α-aminoketone photopolymerization initiator used in the present invention is:
The α-aminoketone photopolymerization initiator may be used alone or in combination of two or more.
The α-aminoketone photopolymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and absorbances of 365 nm and 455 nm. Particularly high are preferred.
The α-aminoketone photopolymerization initiator has a molar extinction coefficient at 365 nm or 405 nm of preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to Particularly preferred is 200,000.

As the α-aminoketone photopolymerization initiator, a compound represented by the following general formula (II) can be preferably used.
Formula (II)
(In general formula (II), X ¹ and X ² each independently represent an alkyl group, an aryl group, or a group comprising a combination of an alkylene group and an aryl group. X ³ and X ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms, and X ³ and X ⁴ are bonded to each other to form a ring. X ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a dimethylamino group, or a morpholino group.

In general formula (II), X ¹ and X ² each independently represents an alkyl group, an aryl group, or a group comprising a combination of an alkylene group and an aryl group, and any ^one of X ¹ and X ² represents an alkylene group It is a group consisting of a combination with an aryl group, and the other is preferably an alkyl group. 1-3 are preferable and, as for carbon number of an alkyl group, 1 or 2 is more preferable. 6-12 are preferable and, as for carbon number of an aryl group, 6 is more preferable. 1-6 are preferable, as for carbon number of an alkylene group, 1-3 are more preferable, and a methylene group is further more preferable. The aryl group may have a substituent, but preferably does not have a substituent.
In general formula (II), X ³ and X ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms. X ³ and X ⁴ may be bonded to each other to form a ring. The alkyl group may be linear, branched or cyclic. The alkyl group, alkenyl group and phenylalkyl group may have a substituent. Examples of the substituent include an OH group, an alkoxy group having 1 to 4 carbon atoms, -CN or -COOR (R represents an alkyl group having 1 to 4 carbon atoms). In particular, —NX ³ X ⁴ preferably represents a dimethylamino group, a diethylamino group or a morpholino group, more preferably a dimethylamino group or a morpholino group, and even more preferably a dimethylamino group.
In the general formula (II), X ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a dimethylamino group or morpholino group, A morpholino group is preferred.

The α-aminoketone photopolymerization initiator is more preferably represented by the following general formula (II-1).
Formula (II-1)
(In General Formula (II-1), R ¹¹ represents a hydrogen atom or an alkyl group, and R ¹² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 1 carbon atom. -8 represents an alkylthio group, dimethylamino group or morpholino group, Ar ² represents an arylene group, X ³ and X ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 3 carbon atoms. Represents an alkenyl group of ˜5 or a phenylalkyl group of 7 to 9 carbon atoms, and X ³ and X ⁴ may be bonded to each other to form a ring.)

In General Formula (II-1), R ¹¹ represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom. When R ¹¹ represents an alkyl group, the alkyl group preferably has 1 to 3 carbon atoms, and more preferably 1 or 2.
In general formula (II-1), R < ¹² > is synonymous with X < ⁵ > in general formula (II), and its preferable range is also the same.
In General Formula (II-1), Ar ² represents an arylene group. 6-12 are preferable and, as for carbon number of an arylene group, 6 is preferable.
In the general formula (II-1), X ³ and X ⁴ has the same meaning as X ³ and X ⁴ in the above-mentioned formula (II), and preferred ranges are also the same.

Specific examples of the α-aminoketone photopolymerization initiator include the following compounds. For example, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropane- 1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- (4-ethylphenyl) -2-methylpropan-1-one, 2-dimethylamino-1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino -1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propane- -One, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1-one (IRGACURE 369), 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (IRGACURE 379).

<< polymerizable compound >>
The radiation sensitive composition of the present invention contains a polymerizable compound. Here, the polymerizable compound is a compound that causes polymerization by an active species. Examples of the active species include radicals, acids, and bases.
When the radical is an active species, a compound having a terminal ethylenically unsaturated bond as a polymerizable group is usually used as the polymerizable compound.
On the other hand, when the active species is an acid such as sulfonic acid, phosphoric acid, sulfinic acid, carboxylic acid, sulfuric acid, and sulfuric monoester, examples of the polymerizable compound include cyclic groups such as an epoxy group, an oxetanyl group, and a tetrahydrofuranyl group. A compound having an ether group or a vinylbenzene group is used.
When the active species is a base such as an amino compound, the polymerizable compound is, for example, a compound having a cyclic ether group such as an epoxy group, oxetanyl group or tetrahydrofuranyl group, or a vinylbenzene group. The
The polymerizable compound is preferably selected from compounds having at least one terminal ethylenically unsaturated bond, more preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any 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. Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxies, 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 substituted 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.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethyleneoxy Modified dipentaerythritol hexaacrylate (A-DPH-12E as a commercial product; manufactured by Shin-Nakamura Chemical Co., Ltd.), hexanediol (medium ) After adding ethylene oxide or propylene oxide to polyfunctional alcohols such as acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, (meth) acrylated Urethane (meth) acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, Nos. 49-43191 and 52-30490, polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and the like. Mixing these It can be mentioned.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
As other preferable polymerizable compounds, compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and cardo resins. Can also be used.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

Suitable polymerizable compounds in the present invention include polymerizable compounds having two or more terminal ethylenically unsaturated bonds.
As examples of such polymerizable compounds, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In general formula (MO-1)-(MO-5), n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or — represents a OC (= O) C (CH 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. It can be suitably used in the present invention.

  In addition, compounds that are (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof are also included. Can be used as a polymerizable compound.

  Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

As a polymeric compound, you may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, For example, the ethylenically unsaturated compounds which have an acid group can be mentioned suitably. Ethylenically unsaturated compounds having an acid group can be obtained by, for example, converting a part of hydroxy groups of the polyfunctional alcohol into (meth) acrylate and adding an acid anhydride to the remaining hydroxy group to form a carboxy group. can get.
If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In addition, the polymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or ((CH ₂ ) _y CH (CH ₃ ) O) —, and y Each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (i), the sum total of an acryloyl group and a methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (ii), the sum total of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{((CH 2) y CH (} CH 3) O) - , the oxygen atom side terminal A form bonded to X is preferred.

  The compound represented by general formula (i) or (ii) may be used individually by 1 type, and may be used together 2 or more types. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as total content in the polymeric compound of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (i) or (ii) has a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from the step of bonding and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (i) or (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  As a commercial item of the polymerizable compound represented by the general formula (i) or (ii), for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a radiation-sensitive composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a radiation sensitive composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In addition, from the viewpoint of increasing the strength of the cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using them together is also effective. Furthermore, it is preferable to use a trifunctional or higher functional polymerizable compound having a different ethylene oxide chain length in that the developability of the radiation-sensitive composition can be adjusted and excellent pattern formation can be obtained. In addition, selection and use of polymerizable compounds are important for compatibility and dispersibility with other components (eg, photopolymerization initiator, alkali-soluble resin, etc.) contained in the radiation-sensitive composition. For example, compatibility may be improved by the use of a low-purity compound or a combination of two or more. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

Hereinafter, although the specific example of a polymeric compound is given, it is not limited to this.

A polymeric compound may be used by 1 type, or may be used in combination of 2 or more type.
As for content of the polymeric compound in the radiation sensitive composition of this invention, 0.1-90 mass% is preferable with respect to the total solid in a radiation sensitive composition, and 1.0-80 mass% is further. Preferably, 10% by mass to 40% by mass is particularly preferable.

<Multifunctional thiol compound>
The radiation sensitive composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of accelerating the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (I).

Formula (I)
(In the formula, n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

  In the general formula (I), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (II) to (IV), and a compound represented by (II) is particularly preferable. These polyfunctional thiols can be used alone or in combination.

About the compounding quantity of the polyfunctional thiol compound in the radiation sensitive composition of this invention, 0.3-8.9 mass% is preferable with respect to the total solid content except a solvent, and 0.8-6.4 mass. % Is more preferable.
The polyfunctional thiol compound may contain only 1 type, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.
Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.

<< Organic solvent >>
The radiation sensitive composition of the present invention contains 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. In particular, if it contains an alkali-soluble resin described later, its solubility,
It is preferably selected in consideration of applicability and safety.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. As well as ethers For example, 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., and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc., and aromatic hydrocarbons such as, for example, Preferred examples include ruene, xylene, cyclopentanone and the like.

These organic solvents are also preferably in the form of a mixture of two or more thereof from the viewpoints of solubility of the alkali-soluble resin, improvement of the coated surface state, and the like. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solvent composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
As the mixed solvent obtained by mixing two or more organic solvents, a mixed solvent of ethers and ketones is preferable from the viewpoint of preventing the precipitation of the radiation-sensitive composition during refrigeration. Particularly preferred as a mixed solution of ethers and ketones is a mixed solvent composed of propylene glycol monomethyl ether acetate and cyclohexanone.
Moreover, when the mixed solvent formed by mixing two or more organic solvents contains cyclohexanone, the content ratio of cyclohexanone in the mixed solvent contained in the radiation-sensitive composition is preferably 5 to 90% by mass. -85 mass% is more preferable, and 15-80 mass% is further more preferable.

  From the viewpoint of applicability, the total content of the organic solvent in the radiation-sensitive composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, and further 5 to 60% by mass is further provided. 10 to 50% by mass is preferable.

<Ultraviolet absorber>
The radiation-sensitive composition of the present invention preferably contains an ultraviolet absorber, whereby the shape of the pattern to be formed can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. In the present invention, it is particularly preferable to use an ultraviolet absorber having an aminobutadiene skeleton.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. Examples of benzophenone-based UV absorbers include 2,2′-dihydroxy-4- Methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- And hydroxy-4-octoxybenzophenone. Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3). '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzoto Azole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole and the like.

  Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, and the like. Furthermore, as an example of a triazine ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as 1,3,5-triazine and 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy); 3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6 Bis (hydroxyphenyl) triazine compounds such as-(2,4-dimethylphenyl) -1,3,5-triazine; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4- Dibutoxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2- And tris (hydroxyphenyl) triazine compounds such as hydroxy-4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine.

  Hereinafter, although the specific example of a ultraviolet absorber is given, it is not limited to this.

The ultraviolet absorber may be used alone or in combination of two or more.
When the radiation-sensitive composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 to 15 mass% with respect to the total solid content of the radiation-sensitive composition, It is more preferably 1 to 8% by mass, and further preferably 2 to 6% by mass. By setting the amount of the ultraviolet absorber in such a range, the transmittance and heat resistance in the visible light region can be improved.

<< Binder polymer >>
The radiation sensitive composition of the present invention may further contain a binder polymer.
The binder polymer is a linear organic polymer, and is a group that 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 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 include an acid group, an alcoholic hydroxyl group, a pyrrolidone group, and an alkylene oxide group, and an acid group is more preferable.
The acid group is not particularly limited, and examples thereof include a carboxyl group, an active methylene group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and a carboxylic acid anhydride group. Those that can be developed with an aqueous solution are preferred, and carboxyl groups are particularly preferred. These acid groups may be used alone or in combination of two or more.

  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,
Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like 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 is preferably an alkali-soluble resin having a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”) as a monomer component.

In general formula (ED), R < ¹ > and R < ² > represent a hydrogen atom or a hydrocarbon group each independently. The hydrocarbon group as R ₁ and R ₂ is preferably a hydrocarbon group having 1 to 25 carbon atoms, and may further have a substituent.

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 the general formula (ED), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, but for example, methyl, ethyl, n Linear or branched alkyl groups such as -propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl , Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; 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, for example, 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-propenoate, 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-butylcyclohexyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 '-[oxybis (Methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like. 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.

In addition to the above, it is preferable to include an ethylenically unsaturated monomer (a) represented by the following formula (X) as a monomer to be copolymerized with the alkali-soluble resin.
Formula (X)
(In Formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group of 20. n represents an integer of 1 to 15.)

In the formula (X), the number of carbon atoms of the alkylene group R ² is preferably 2-3. Although the carbon number of the alkyl group of R ³ is 1 to 20, more preferably 1 to 10, alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (iso) propyl group.

  Examples of the ethylenically unsaturated monomer (a) include phenol ethylene oxide (EO) modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) modified (meth) acrylate, and nonylphenol EO modified (meth). Examples thereof include acrylate, PO-modified (meth) acrylate of nonylphenol, and the like. Of these compounds, EO or PO-modified (meth) acrylate of paracumylphenol has a higher dispersion effect.

Moreover, in order to improve the crosslinking efficiency of the radiation sensitive composition of the present invention, an alkali-soluble resin having a polymerizable group may be used.
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-described polymer containing a polymerizable group include: NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Viscoat R-264, Examples thereof include KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, 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, JP 2002-229207 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.
In addition, as the alkali-soluble resin, polymer compounds C-1 to C-57 described in paragraphs 0317 to 0348 of JP-A-2007-277514 can be used, the contents of which are incorporated herein. Further, these polymer compounds C-1 to C-57 may be used as the dispersant described above.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 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.
The method for measuring the molecular weight of the compound used in the present invention can be measured by gel permeation chromatography (GPC), and is defined as a polystyrene equivalent value by GPC measurement. For example, HLC-8220 (manufactured by Tosoh Corporation) is used, TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) is used as a column, and 10 mmol / L lithium bromide NMP (N— It can be determined by using a methylpyrrolidinone) solution.

  As content in the radiation sensitive composition of a binder polymer, 1-60 mass% is preferable with respect to the total solid of a composition, More preferably, it is 2-40 mass%, Especially preferably, 3 ˜15 mass%.

  Specific examples of the alkali-soluble resin used as the binder polymer include the following compounds, but the present invention is not particularly limited thereto. The numerical value shown in each unit represents each unit molar fraction in the resin molecule.

<< Polymerization inhibitor >>
During the production or storage of the 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. As the polymerization inhibitor, known thermal polymerization inhibitors can be used. Specifically, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the thermal polymerization inhibitor is preferably about 0.001 to about 5% by mass with respect to the total solid content of the composition.

<< Surfactant >>
Various surfactants may be added to the 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.

In particular, the composition according to a preferred embodiment of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved. Uniformity and liquid-saving properties can be further improved.
That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. 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 within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

  Further, as the fluorosurfactant, those containing at least one of a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II) as a copolymerization component may be used. .

In general formula (I), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of R ⁰¹ may be the same as or different from each other. R ¹ represents a single bond or a linking group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom. n represents an integer of 1 to 10, m represents an integer of 2 to 14, and l represents an integer of 0 to 10. a shows the mole percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100.
In general formula (II), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a plurality of R ⁰¹ may be the same as or different from each other. p is an integer of 0 to 20, q is an integer of 0 to 20, r is an integer of 0 to 20, and p, q, and r are not 0 at the same time. b shows the mass percentage showing the polymerization ratio of this structural unit, and shows the integer of 0-100. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.
For details of the compound represented by the general formula (I) or the general formula (II), paragraphs 0016 to 0037 of JP2010-032698A can be referred to, and the contents thereof are incorporated herein.

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, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Japan Rouble) Zole Co., Ltd.). Also, the following compounds can be used. In the following structure, EO represents an ethyleneoxy group and PO represents a propyleneoxy group.

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 octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distea Rate, sorbitan fatty acid ester (BASF's Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc.).

  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.
0.001-2.0 mass% is preferable with respect to the total solid content mass of a composition, and, as for the addition amount of surfactant, 0.01-1.0 mass% is more preferable.

  The manufacturing method of a radiation sensitive composition is not specifically limited, For example, it adds by each component contained in a composition to an organic solvent, and is obtained by stirring.

The radiation-sensitive composition is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of the filter material include: a fluororesin such as PTFE (polytetrafluoroethylene); a polyamide resin such as nylon-6 and nylon-6, 6; a polyolefin resin such as polyethylene and polypropylene (PP) (high density, Including ultra high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore diameter of the filter in the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter 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., Ltd. .
In filter filtration, two or more filters may be used in combination.
For example, filtration can be performed first using a first filter, and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or may be performed twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.

[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.
In the pattern forming method of the present invention, the radiation-sensitive composition of the present invention described above is applied on a support to form a coating layer (radiation-sensitive composition layer) (hereinafter referred to as “radiation-sensitive composition”). The layer is also referred to as a “layer forming step”, and the coating layer is exposed (hereinafter also referred to as “exposure step”) and developed to form a pattern (hereinafter also referred to as “development step”). Including getting.
The pattern forming method of the present invention can be suitably applied to pixel formation included in a color filter included in a solid-state imaging device.

  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, and includes forming a patterned cured film on a substrate using the pattern forming method of the present invention.
The method for producing a color filter for a solid-state image sensor of the present invention (hereinafter also referred to as a color filter for a solid-state image sensor) is obtained by applying the radiation-sensitive composition of the present invention described above and applying a coating layer (radiation-sensitive composition layer). ) (Hereinafter also referred to as “radiation-sensitive composition layer forming step”), the coating layer is exposed (hereinafter also referred to as “exposure step”), and developed to form a pattern, whereby a solid-state imaging device Obtaining a cured film as a white filter pixel in the color filter.
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) (radiation-sensitive composition layer forming step) is applied by applying the radiation-sensitive composition of the present invention onto a substrate. Forming a layer (radiation-sensitive composition layer), exposing the coating layer (exposure process), and developing to form a pattern (development process) to obtain a patterned cured film.
The color filter of the present invention is obtained by the above production method.

The color filter of this invention should just have at least the transparent (white) pattern (white filter pixel) which is a pixel formed using the radiation sensitive composition of this invention.
As a specific form of the color filter of the present invention, for example, a form of a multicolored color filter (for example, a transparent pattern, a red pattern, a blue pattern, and a combination of a transparent pattern (white filter pixel) and another colored pattern) A color filter having four or more colors having at least a green pattern is preferable.
Hereinafter, the color filter of the present invention may be simply referred to as “color filter”.

<Radiation sensitive composition layer formation process>
In the radiation sensitive composition layer forming step, it is preferable to form a radiation sensitive composition layer on the substrate using the radiation sensitive composition of the present invention.
As a substrate that can be used in this step, for example, a solid-state imaging device in which an imaging device (light receiving device) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). A substrate can be used.
The transparent pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface). A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate.
Further, if necessary, an undercoat layer may be provided on the substrate in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate surface.

  Examples of the method for forming the radiation-sensitive composition layer of the present invention on a substrate include a method by coating or printing, and various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like. The coating method can be used.

  As a film thickness of a radiation sensitive composition layer, 0.1 micrometer-10 micrometers are preferable, 0.2 micrometer-5 micrometers are more preferable, 0.2 micrometer-3 micrometers are still more preferable.

  The radiation-sensitive composition layer applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

<Exposure process>
In the exposure step, the radiation-sensitive composition layer formed in the radiation-sensitive composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper, for example.
The radiation (light) that can be used for the exposure means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like, and ultraviolet rays such as g rays and i rays are particularly preferred (particularly preferred). i line). Irradiation dose (exposure amount) is more preferably preferably ^{50~1000mJ / cm 2 30~1500mJ / cm 2} , 80~500mJ / cm 2 being most preferred.

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

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001 to 10% by mass, preferably An alkaline aqueous solution diluted with pure water so as to be 0.01 to 1% by mass is preferably used as the developer.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate and the like are preferable.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  Next, it is preferable to perform heat treatment (post-bake) after drying. If a multicolor pattern is formed, a cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained.

Post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coated film after development is in the above-described condition be able to.

  In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as processes other than the above as needed. For example, after performing the above-mentioned radiation-sensitive composition layer forming step, exposure step, and development step, a curing step of curing the formed transparent pattern by heating and / or exposure may be included as necessary. .

In addition, when using the radiation-sensitive composition of the present invention, for example, clogging of nozzles and piping parts of the coating apparatus discharge unit, contamination due to the deposition, sedimentation, and drying of the radiation-sensitive composition and inorganic particles in the coating machine, etc. May occur. Therefore, in order to efficiently clean the contamination caused by the radiation-sensitive composition of the present invention, it is preferable to use the solvent relating to the present composition as the cleaning liquid. JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP-A 2007-2101, JP-A 2007-2102, JP-A 2007-281523 and the like can also be suitably used as cleaning liquids for cleaning and removing the radiation-sensitive composition of the present invention.
Of the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid with respect to contaminants, a surfactant related to the present composition may be added to the cleaning liquid.

By mounting the color filter of the present invention on the image sensor, it is possible to perform imaging with the image sensor with high sensitivity and high quality.
The color filter for a solid-state imaging device of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixel) in the color filter for a solid-state imaging device of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less. Here, “coloring” of the coloring pattern (colored pixel) is a concept including transparency (white).
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes the above-described color filter of the present invention.
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 (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. A light-shielding film made of tungsten or the like having an opening only in the light-receiving portion of the photodiode, and a device protection 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 portion. It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter Etc.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

<Example 1>
(1) Preparation of High Refractive Index Particle Dispersion 1-1 For a mixed solution having the following composition A, as a circulation type dispersion device (bead mill), an ultra apex mill (trade name) manufactured by Kotobuki Industries Co., Ltd. is used. Dispersion treatment was performed under the conditions to obtain a high refractive index particle dispersion 1-1 as a dispersion composition.
<Composition A>
-High refractive index particles (titanium dioxide, rutile type, refractive index: 2.71, manufactured by Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C)): 212.5 parts-The following specific dispersion resin (A) ( 20% propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”) solution): 286.9 parts, PGMEA: 350.6 parts

Specific dispersion resin (A): Acid value: 50 mg / KOH, The weight average molecular weight is 10,000.

The dispersing device was operated under the following conditions.
・ Bead diameter: φ0.05mm
・ Bead filling rate: 75% by volume
・ Peripheral speed: 8m / sec
・ Pump supply amount: 10Kg / hour
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Amount of liquid mixture to be dispersed: 0.44 kg

  About 300 titanium dioxide particles contained in the obtained high refractive index particle dispersion 1-1, the projected area of the titanium dioxide particles is obtained using a transmission electron microscope, and the arithmetic mean value of the corresponding equivalent circle diameter is obtained. When determined, it was 40 nm.

(2) Preparation of radiation-sensitive composition Using the high-refractive-index particle dispersion 1-1 (dispersion composition) obtained above, each component is mixed so as to have the following composition, and the radiation-sensitive composition. I got a thing.
<Composition of radiation sensitive composition>
-High refractive index particle dispersion prepared above (dispersion composition): 68.6% by mass in the total solid content
Polymerizable compound (A) having the following structure (manufactured by Toa Gosei Co., Ltd., trade name: M305): 21.3% by mass in the total solid content
Oxime-based photopolymerization initiator (A) (oxime compound having the following structure, synthesized by the method of Synthesis Example 7 of JP-A-2007-316451): 0.4% by mass in the total solid content
Α-aminoketone photoinitiator (A) (compound with the following structure, trade name: IRGACURE 369, manufactured by BASF): 1.0% by mass in the total solid content
Resin (A) having the following structure (20% PGMEA solution): 4.5% by mass in the total solid content
-UV absorber (A) having the following structure: 4.0% by mass in the total solid content
Polymerization inhibitor (paramethoxyphenol): 0.01% by mass in the total solid content
-Surfactant (Fluorosurfactant, 1% PGMEA solution, synthesized by the method shown in the following synthesis example): 0.2% by mass in the total solid content
Organic solvent (Propylene glycol methyl ether acetate (PGMEA) and cyclohexanone (XAN) mixed solvent (mass ratio 58:42): 28% by mass with respect to the total solid content of the radiation-sensitive composition

Polymerizable compound (A): 55 to 63% by mass of triacrylate

Oxime-based photopolymerization initiator (A)

α-Aminoketone photopolymerization initiator (A)

Resin (A): Weight average molecular weight 11,000

Ultraviolet absorber (A): Ultraviolet absorber having a butadiene skeleton (UV-503, manufactured by Daito Chemical Co., Ltd.)

Surfactant: Megafac F-781F, manufactured by DIC Corporation In the following structure, EO represents an ethyleneoxy group and PO represents a propyleneoxy group. p is an integer of 0 to 20, q is an integer of 0 to 20, r is an integer of 0 to 20, and p, q, and r are not 0 at the same time.

  High refractive index particle dispersions 1-2 to 3 were obtained in the same manner except that the specific dispersion resin of the high refractive index particle dispersion 1-1 of Example 1 described above was changed as described in the table. .

  Except that the high refractive index particles of the high refractive index particle dispersion 1-1 of Example 1 described above were changed to zirconium oxide (UEP-100 manufactured by Daiichi Rare Element Chemical Industry, refractive index: 2.20). Thus, a high refractive index particle dispersion 1-4 was obtained.

  Same as above except that the components in the composition of the radiation-sensitive composition of Example 1 described above were changed by equal weight as described in the following table, and that the total amount of the photopolymerization initiator was constant and only the ratio was changed. Thus, the radiation sensitive compositions of Examples 2 to 13 and Comparative Examples 1 to 3 were obtained.

Polymerizable compound (B): (Nippon Kayaku Co., Ltd., brand name: KAYARAD DPHA, a: b = 3: 7 (molar ratio) in the following structure)

Specific dispersion resin (B): acid value: 37 mg / KOH, weight average molecular weight 13,500

Specific dispersion resin (C): acid value: 106 mg / KOH, weight average molecular weight 38,900

Oxime-based photopolymerization initiator (B): manufactured by BASF, trade name: IRGACURE OXE-01

Oxime-based photopolymerization initiator (C): manufactured by BASF, trade name: IRGACURE OXE-02
Oxime-based photopolymerization initiator (D)

α-Aminoketone photopolymerization initiator (B): trade name: IIRGACURE 907, manufactured by BASF)

Resin (B): Weight average molecular weight 14,000

Ultraviolet absorber (B): 4-tert-butyl-4′-methoxydibenzoylmethane (Avobenzone), Parsol (registered trademark) 1789 (manufactured by DSM Nutrition)

[Evaluation]
The following evaluations were performed using the radiation-sensitive compositions of Examples and Comparative Examples obtained above.
<Spectroscopic evaluation>
Each of the radiation-sensitive compositions of Examples and Comparative Examples obtained above was applied by spin coating on a glass wafer so that the film thickness after application was 0.6 μm, and then on a hot plate, Heated at 100 ° C. for 2 minutes. Furthermore, it heated at 200 degreeC on the hotplate for 8 minutes, and formed the radiation sensitive composition layer. With respect to the substrate on which this radiation-sensitive composition layer was formed, the spectral transmittance was measured using a spectrophotometer MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The results are shown in the table below.

<Heat resistance evaluation>
In the above spectral evaluation, the spectral transmittance of the radiation-sensitive composition layer obtained by heating at 200 ° C. for 8 minutes and the spectral transmission after heating the radiation-sensitive composition layer on a hot plate at 260 ° C. for 5 minutes. The rate of change in the rate [(after adding at 260 ° C. for 5 minutes / before heating at 260 ° C. for 5 minutes) × 100] was measured. The results are shown in the table below.
Criteria 3: Transmission fluctuation is within ± 1.5% 2: Transmission fluctuation is over ± 1.5% within 3% 1: Transmission fluctuation is over ± 3%

<Evaluation of exposure latitude>
Each of the radiation-sensitive compositions of Examples and Comparative Examples obtained above was applied by spin coating onto a silicon wafer with an undercoat layer so that the film thickness after application was 0.6 μm, and then hot plate Above, it heated at 100 degreeC for 2 minute (s), and the radiation sensitive composition layer was obtained.
Next, using the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the 1.1 μm square Bayer pattern was exposed to the obtained radiation-sensitive composition layer through a mask (exposure amount 300 mJ). / Cm ² ).
Next, paddle development was performed on the radiation-sensitive composition layer after exposure using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water, and the pattern was obtained.
In addition, the radiation-sensitive composition layer obtained separately from the above was exposed at an exposure amount 200 mJ / cm ² higher than the exposure amount. Next, development was performed in the same manner as described above to obtain a pattern.
For each of the patterns obtained with an exposure amount of 300 mJ / cm ² and a higher exposure amount, the line width within one pixel was measured at any 10 points within the wafer, and the average value was obtained. The line width of the pattern was observed using a length measurement SEM (trade name: S-7800H, manufactured by Hitachi, Ltd.). And the difference of the average value of the line width of each pattern was calculated | required. The results are shown in the table below.
3: Difference in line width of each pattern is within ± 0.1 μm 2: Difference in line width of each pattern is more than ± 0.1 μm, Within 0.2 μm 1: Difference in line width of each pattern is more than ± 0.2 μm

<Residual residue evaluation>
Each of the radiation-sensitive compositions of Examples and Comparative Examples obtained above was applied by spin coating onto a silicon wafer with an undercoat layer so that the film thickness after application was 0.6 μm, and then hot plate Above, it heated at 100 degreeC for 2 minute (s), and the radiation sensitive composition layer was obtained.
Next, using the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the 1.1 μm square Bayer pattern was exposed to the obtained radiation-sensitive composition layer through a mask (exposure amount 300 mJ). / Cm ² ).
Next, paddle development was performed on the radiation-sensitive composition layer after exposure using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water, and the pattern was obtained.
The amount of residue remaining on the ground surface of the obtained pattern was evaluated by binarizing the image. The results are shown in the table below.
3: Residue amount is less than 1% of the total ground area 2: Residue amount is 1 to 3% of the total ground area
1: Residue amount is more than 3% of the total area of the substrate

<Evaluation of pattern distortion>
Each of the radiation-sensitive compositions of Examples and Comparative Examples obtained above was applied by spin coating onto a silicon wafer with an undercoat layer so that the film thickness after application was 0.6 μm, and then hot plate Above, it heated at 100 degreeC for 2 minute (s), and the radiation sensitive composition layer was obtained.
Next, after leaving the obtained radiation-sensitive composition layer for a certain period of time, an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) was used, and a 1.1 μm square Bayer pattern was passed through a mask. It exposed (exposure amount 300mJ / cm < ² >). After the radiation-sensitive composition layer was formed using the radiation-sensitive composition, the time for which the radiation-sensitive composition layer was allowed to stand before exposure (PCD (post coating delay)) was 24 hours.
Next, paddle development was performed on the radiation-sensitive composition layer after exposure using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water, and the pattern was obtained.
The distortion of the obtained pattern was evaluated by observation with an optical microscope. The results are shown in the table below.
3: No foreign matter 2: Slight pattern distortion 1: Full pattern distortion

<Refractive index evaluation>
Each of the radiation-sensitive compositions of Examples and Comparative Examples obtained above was applied on a silicon wafer so that the film thickness after application was 0.6 μm, and then on a hot plate at 100 ° C. for 2 minutes. Heated. Furthermore, it heated at 200 degreeC on the hotplate for 8 minutes, and formed the radiation sensitive composition layer. Ellipsometry V is applied to the substrate on which the radiation-sensitive composition layer is formed.
The refractive index was measured using UV-VASE (manufactured by JA Woollam Japan). The results are shown in the table below.

The total content of the photopolymerization initiator is 1.4% by mass of the total solid content.
As is clear from the above evaluation, in the examples in which the mass ratio of the oxime photopolymerization initiator and the α-aminoketone photopolymerization initiator is 1: 1.5 to 1: 4, the transmittance in the visible light region. It was found that the heat resistance and the exposure latitude were good.
In particular, it was found that the effect of the present invention was better when the oxime photopolymerization initiator represented by the general formula (I) was used. Moreover, when the oxime type photoinitiator represented by the said general formula (I-1) was used, it turned out that the effect of this invention is still more favorable.
Moreover, when the alpha-aminoketone type photoinitiator represented by the said general formula (II-1) was used, it turned out that the effect of this invention is more favorable.
Moreover, when the ultraviolet absorber which has aminobutadiene frame | skeleton was contained in the composition, it turned out that the effect of this invention is more favorable.
Moreover, when a dispersing agent with an acid value of 40-70 mgKOH / g was contained in the composition, it turned out that a pattern residual and a pattern distortion become smaller.
On the other hand, a comparative example not containing at least one of an oxime photopolymerization initiator and an α-aminoketone photopolymerization initiator, and a mass ratio of the oxime photopolymerization initiator and the α-aminoketone photopolymerization initiator is 1: In the comparative example not satisfying 1.5 to 1: 4, it was found that at least one of the transmittance in the visible light region, the heat resistance and the exposure latitude was not good.

Claims (16)

Including a titanium oxide having a weight average diameter of primary particles of 80 nm or less and a refractive index of 1.80 to 2.80, a polymerizable compound, a photopolymerization initiator, and an organic solvent,
The photopolymerization initiator includes an oxime photopolymerization initiator and an α-aminoketone photopolymerization initiator,
A radiation-sensitive composition, wherein a mass ratio of the oxime photopolymerization initiator and the α-aminoketone photopolymerization initiator is 1: 1.5 to 1: 4. The radiation-sensitive composition according to claim 1, wherein the oxime photopolymerization initiator is represented by the following general formula (I).
Formula (I)
In general formula (I), R ¹ represents any ^one of a hydrogen atom, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, R ² represents a substituent, and Ar ¹ may form a condensed ring. Often, R ³ represents any of a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group. m1 represents an integer of 0 to 4. When m1 is 2 or more, R ³ may be the same or different. Ar ¹ represents an arylene group or a group composed of a combination of an arylene group and —C (═O) —. The radiation-sensitive composition according to claim 1 or 2, wherein the oxime photopolymerization initiator is represented by the following general formula (I-1).
Formula (I-1)
In general formula (I-1), R ⁴ represents a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ⁵ represents a halogen atom or an alkyl group. , An aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group. m2 represents an integer of 0 to 4. A represents a structure in which a condensed ring in which one ring or two rings are condensed is condensed with an adjacent benzene ring, and each ring represents any of 4, 5, 6 and 7-membered rings. The radiation-sensitive composition according to any one of claims 1 to 3, wherein the α-aminoketone photopolymerization initiator is represented by the following general formula (II-1).
Formula (II-1)
In General Formula (II-1), R ¹¹ represents a hydrogen atom or an alkyl group, and R ¹² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 1 to 1 carbon atoms. 8 represents an alkylthio group, dimethylamino group or morpholino group, Ar ² represents an arylene group, X ³ and X ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 3 to 3 carbon atoms. 5 represents an alkenyl group or a phenylalkyl group having 7 to 9 carbon atoms, and X ³ and X ⁴ may be bonded to each other to form a ring.   Furthermore, the radiation sensitive composition of any one of Claims 1-4 which contains a ultraviolet absorber 1-8 mass% with respect to the total solid of a radiation sensitive composition.   The radiation-sensitive composition according to claim 5, wherein the ultraviolet absorber has an aminobutadiene skeleton. The radiation-sensitive composition according to any one of claims 1 to 6 , wherein the polymerizable compound is (meth) acrylate. Acid value contains a dispersant 40~70mgKOH / g, the radiation-sensitive composition according to any one of claims 1-7. The radiation sensitive composition of any one of Claims 1-8 whose weight average diameter of the primary particle of the said titanium oxide is 10-80 nm. The light transmittance with respect to the thickness direction of a cured film is 85% or more over the whole wavelength range of 400 nm-700 nm, when a cured film with a film thickness of 0.6 micrometer is formed, The any one of Claims 1-9 The radiation-sensitive composition as described in 1. The radiation-sensitive composition according to any one of claims 1 to 10, wherein the oxime photopolymerization initiator is represented by the following general formula (I-2) or (I-3).
Formula (I-2)
In general formula (I-2), R ⁴ represents a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ⁵ represents a halogen atom or an alkyl group. , An aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group. m2 represents an integer of 0 to 4. X is, -CH ₂ - represents any of an oxygen atom and a sulfur atom. l represents an integer of 1 to 3.
Formula (I-3)
In general formula (I-3), R ⁴ represents a hydrogen atom, an acyl group that may have a substituent, an alkoxycarbonyl group, or an aryloxycarbonyl group, and R ⁵ represents a halogen atom or an alkyl group. , An aryl group, an alkyloxy group, an aryloxy group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and an amino group. m2 represents an integer of 0 to 4. X is, -CH ₂ - represents any of an oxygen atom and a sulfur atom. l represents an integer of 1 to 3. The radiation-sensitive composition according to any one of claims 1 to 11, wherein the photopolymerization initiator comprises only an oxime photopolymerization initiator and an α-aminoketone photopolymerization initiator. The radiation-sensitive composition according to any one of claims 1 to 12 used in a pixel forming the color filter. The color filter obtained by using a radiation-sensitive composition according to any one of claims 1 to 13. A step of forming a radiation-sensitive composition layer on a support using the radiation-sensitive composition according to any one of claims 1 to 13 , and the radiation-sensitive composition for obtaining a patterned cured film. Forming a pattern by exposing the functional composition layer and then developing the composition layer, and a method for producing a color filter. A solid-state imaging device having the color filter according to claim 14 .