KR20160015381A - Radiation sensitive composition, color filter, method for producing color filter, and solid-state imaging element - Google Patents

Abstract

The present invention provides a radiation sensitive composition, a color filter, a manufacturing method thereof, and a solid-state imaging device having high transmittance in a visible light range, good heat resistance, and good exposure latitude. The radiation-sensitive composition of the present invention comprises particles having a refractive index of 1.80 to 2.80, a polymerizable compound, an oxime-based photopolymerization initiator, an? -Aminoketone-based photopolymerization initiator and an organic solvent, wherein the oxime-based photopolymerization initiator and the? And the mass ratio of the photopolymerization initiator is 1: 1.5 to 1: 4.

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation sensitive composition, a color filter, a manufacturing method thereof, and a solid-state imaging device,

The present invention relates to a radiation sensitive composition, a color filter, a manufacturing method thereof, and a solid-state imaging device.

In recent years, miniaturization of pixels has progressed with an increase in the number of pixels of an image sensor for the purpose of improving the resolution of image sensors (CCD, CMOS). On the other hand, Therefore, for the purpose of improving the sensitivity, one color of a plurality of color filters may be white (transparent).

Regarding the white (transparent) pixel (hereinafter referred to as "white filter pixel" as appropriate) of such a color filter, the oxime-based photopolymerization initiator, the ultraviolet absorber, and a monomer having an aromatic ring or a monomer having a hydrogen bond Based on the total weight of the photosensitive resin composition.

Further, a photosensitive resin composition which can be applied to a solid-state imaging element and contains a titanium dioxide particle, a graft copolymer having a specific structure, a polymerizable compound, a polymerization initiator, and a solvent has been proposed (see Patent Document 1).

The present invention also provides a photosensitive transparent composition for a color filter of a solid-state imaging element, which comprises a photopolymerization initiator, a polymerizable compound, and an alkali-soluble resin as a color filter transparent composition for a color filter, wherein the curable film obtained from the photosensitive transparent composition has a wavelength of 633 nm And a refractive index of 1.60 to 1.90 (see Patent Document 2).

Also, as a radiation sensitive composition, there has been proposed a photosensitive resin composition comprising a titanium dioxide particle, an oligimine resin, a polymerizable compound, a photopolymerization initiator, and an organic solvent (see Patent Document 3).

Patent Document 1: JP-A-2011-127096 Patent Document 2: JP-A-2012-137564 Patent Document 3: JP-A-2013-64979

However, recently, compositions having higher transmittance in the visible light range than the compositions described in Patent Documents 1 to 3 and having good heat resistance and good exposure latitude are required.

An object of the present invention is to provide a radiation sensitive composition having a high transmittance in a visible region and a good heat resistance and exposure latitude.

The present inventors have found that a photocatalyst comprising a high refractive index particle composed of a substance having a refractive index of 1.80 to 2.80, a polymerizable compound, a photopolymerization initiator and an organic solvent, wherein the mass ratio of the oxime-based photopolymerization initiator and the? : 4, it was found that the above problems can be solved.

More specifically, the above-mentioned problem is solved by the following means <1>, preferably by <2> to <14>.

A photothermographic material comprising a particulate material having a refractive index of 1.80 to 2.80, a polymerizable compound, an oxime-based photopolymerization initiator, an? -Aminoketone-based photopolymerization initiator and an organic solvent, wherein the mass ratio of the oxime-based photopolymerization initiator and? : 1.5 to 1: 4.

<2> The radiation-sensitive composition according to <1>, wherein the oxime-based photopolymerization initiator is represented by the following general formula (I).

The compound of formula (I)

[Chemical Formula 1]

(In the 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, may form a condensed ring with Ar ¹ , R ³ represents any one 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 m 1 is an integer of 0 to 4 When m1 is 2 or more, R ³ may be the same or different. Ar ¹ represents a group formed by a combination of an arylene group or an arylene group and -C (= O) -.

<3> The radiation-sensitive composition according to <1> or <2>, wherein the oxime-based photopolymerization initiator is represented by the following general formula (I-1).

In general formula (I-1)

(2)

(In the general formula (I-1), R ⁴ represents any one of a hydrogen atom, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group which may have a substituent, and R ⁵ represents a halogen atom, an alkyl group, An alkylthio group, an arylthio group, an amino group, an alkylthio 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 1 ring or 2 Each of the rings represents any one of a 4, 5, 6, and 7-membered ring.) The condensed ring in which the condensed ring is condensed with the adjacent benzene ring is shown.

<4> The radiation-sensitive composition according to any one of <1> to <3>, wherein the? -Aminoketone photopolymerization initiator is represented by the following general formula (II-1).

In general formula (II-1)

(3)

(In the general formula (II-1), R ¹¹ represents a hydrogen atom or an alkyl group; R ¹² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, Import, dimethyl amino group or represents a morpholinyl group, Ar ² is an aryl represents an alkylene, X ³ and X ⁴ are, each independently, a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, having a carbon number of 3-5 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.)

<5> The radiation sensitive composition according to any one of <1> to <4>, further containing 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 amino butadiene 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>, wherein the radiation sensitive composition contains 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 forming a pixel of a color filter.

<11> A color filter obtained by using the radiation sensitive composition according to any one of <1> to <9>.

<12> A process for producing a radiation sensitive composition, comprising the steps of: forming a radiation sensitive composition layer on a support using a radiation sensitive composition according to any one of <1> to <9>; And a step of forming a pattern by developing the color filter

&Lt; 13 > A color filter produced by the method of manufacturing a color filter according to < 12 >.

<14> A solid-state imaging device having a color filter according to <11> or a color filter according to <13>.

According to the present invention, it becomes possible to provide a radiation-sensitive composition having a high transmittance in a visible light range and good heat resistance and good exposure latitude.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "radiation " in this specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray. In the present invention, light means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle lines such as electron beams and ion beams .

In the present specification, the term " (meth) acrylate "refers to both or either acrylate and methacrylate, and" (meth) acrylate "refers to both acrylate and methacrylate, The term "(meth) acryloyl" refers to both acryloyl and methacryloyl.

Also, in this specification, the terms "monomer" and "monomer" are synonyms. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds 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 involved in the polymerization reaction.

The weight average molecular weight and number average molecular weight can be determined by gel permeation chromatography (GPC).

In the present specification, Me in the formula represents a methyl group, Et represents an ethyl group, Pr indicates a propyl group, Bu indicates a butyl group, and Ph indicates a phenyl group.

In the present specification, the term " process "is included in this term as well as an independent process, even if the desired action of the process can not be clearly distinguished from other processes.

<Radiation-sensitive composition>

The radiation sensitive composition of the present invention comprises a high refractive index particle composed of a substance having a refractive index of 1.80 to 2.80, a polymerizable compound, a photopolymerization initiator and an organic solvent, wherein the mass ratio of the oxime-based photopolymerization initiator to the? 1: 1.5 to 1: 4.

The radiation sensitive composition of the present invention has a high transmittance in the visible light range, and is excellent in heat resistance and exposure latitude. Although this mechanism is presumed, by setting the mass ratio of the oxime-based photopolymerization initiator and the? -Aminoketone-based photopolymerization initiator in the radiation-sensitive composition to the range of 1: 1.5 to 1: 4, even if the amount of the oxime-based photopolymerization initiator used is relatively small, The polymerization of the polymerizable compound can be initiated. As a result, since the decomposition product of the oxime-based photopolymerization initiator can be reduced, it is considered that by decreasing by-products causing coloration, the transmittance in the visible region can be increased and the heat resistance is also improved.

In the radiation sensitive composition of the present invention, it is preferable that the cured film obtained from the radiation sensitive composition has a refractive index of 1.80 to 2.80 with respect to light having a wavelength of 500 nm.

Further, when the radiation sensitive composition of the present invention is used to form a cured film having a film thickness of 0.6 占 퐉, for example, by using an i-line stepper exposure apparatus and exposing the pattern under a condition of exposure dose of 300 mJ / cm ² through a mask, The light transmittance in the thickness direction of the cured film is preferably 85% or more, more preferably 88% or more, more preferably 89% or more, and particularly preferably 90% or more over the entire wavelength range of 400 nm to 700 nm. A white filter pixel included in the color filter is preferable from the viewpoint of satisfying a sufficient function as a white filter pixel that the light transmittance is 85% or more over the entire wavelength range of 400 nm to 700 nm.

Further, it is preferable that the radiation sensitive composition of the present invention contains substantially no coloring agent. The content of the colorant is preferably 0.1% by mass or less based on the total solid content of the composition. Further, the colorant does not include the respective components described later (for example, high refractive index particles or ultraviolet absorber).

The radiation sensitive composition of the present invention can be preferably used as a radiation sensitive composition for a solid state imaging element and more preferably used for forming a pixel of a color filter of a solid state imaging element, It is more preferable to use it as a white filter for use in the present invention.

<< Particles with a refractive index of 1.80 to 2.80 >>

The refractive index of the constituent material (material) of the particles having a refractive index of 1.80 to 2.80 (hereinafter also referred to as high refractive index particles) is 1.80 or more, preferably 1.90 or more, and more preferably 2.0 or more. The upper limit is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 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 maintaining the transmittance of the cured film within a specific range by the fluctuation amount. On the other hand, by setting the lower limit value to 1.80 or more, it is possible to suppress and prevent interference with other pixels due to the waveguide effect when the color filter is formed using the radiation sensitive composition of the present invention. The refractive index of the high refractive index particles is determined by obtaining the arithmetic average value of the corresponding circle equivalent diameters by respectively obtaining projection areas of the titanium dioxide particles using a transmission electron microscope unless otherwise specified.

The weight average particle diameter of the primary particles of the high refractive index particles is preferably 150 nm or less, more preferably 100 nm or less, particularly preferably 80 nm or less. There is no particular lower limit, but it is practically at least 1 nm. The weight average particle diameter of the high refractive index particles in the layer is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, particularly preferably 80 nm or less. The lower limit is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and more preferably 10 nm or more. With respect to the weight average particle diameter of the high refractive index particles, unless otherwise specified, the mixed liquid 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 . This measurement is carried out using a microtrack (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd., and the weight average particle diameter is obtained.

The specific surface area of the high refractive index particles is preferably from 10 m ² / g to 400 m ² / g, more preferably from 20 m ² / g to 200 m ² / g, still more preferably from 30 m ² / g to 150 m ² / g Do.

Examples of the high refractive index particles include at least one kind of element selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, And a metal oxide. Specific examples thereof include particles of titanium dioxide, tin oxide, indium oxide, zinc oxide, or zirconium oxide. Among them, particles of titanium oxide, tin oxide, indium oxide, or zirconium oxide are particularly preferable. The metal oxide particles may contain another element mainly composed of an oxide of these metals. 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 mainly composed of titanium dioxide is preferably a main component of a mixed crystal of rutile, rutile / anatase, anatase, and amorphous structure, and it is particularly preferable that the rutile structure is a main component.

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

As a preferred embodiment of the present invention, inorganic fine particles mainly composed of titanium dioxide may contain at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium). Thereby, the photocatalytic activity of the titanium dioxide can be suppressed, and the weather resistance of the high refractive index layer can be improved.

The high refractive index particles may be treated in combination of two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a fine particle shape, a spherical shape, a cubic shape, a spindle shape or an irregular shape. Two or more kinds of metal oxide particles may be used in combination with the high refractive index layer and the medium refractive index layer.

As the titanium dioxide, a commercially available product may be used. Specific examples of commercially available products include TTO series (TTO-51 (A), TTO-51 (C), TTO-55 (Trade name, manufactured by Ishihara Sangyo Co., Ltd.), MT series (MT-01, MT-05, etc.) (trade name, manufactured by DAIKA CO., LTD. .

The high refractive index particles may be used alone or in combination of two or more.

The content of the high refractive index particles in the composition is preferably 10 mass% or more, more preferably 15 mass% or more, and most preferably 20 mass% or more, in the total solid content. The upper limit is preferably 65 mass% or less, more preferably 60 mass% or less, and particularly preferably 55 mass% or less.

<< Dispersant >>

The composition of the present invention preferably uses a dispersant containing a structural unit represented by any one of the following general formulas (1) and (2) as a dispersant for high refractive index particles.

[Chemical Formula 4]

(1) and (2), R ¹ to R ⁶ each represent a hydrogen atom or a monovalent organic group, X ¹ and X ² each represent -CO-, -C (= O) L ¹ and L ² each represent a single bond or a divalent organic linking group; A ¹ and A ² each represent a single bond or a divalent organic linking group; M and n each represent an integer of 2 to 8, and p and q represent an integer of 1 to 100, respectively.

In the 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. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

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, and more preferably 1 to 3 carbon atoms), a methoxy group, Hexyloxy group and the like.

Specific examples of the preferable alkyl group include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, -Hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group.

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 preferably hydrogen atoms or methyl groups, .

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 phenylene groups are preferable from the viewpoint of adsorption to pigments, and -C (= O) O- is most preferable.

In the general formulas (1) and (2), L ¹ and L ² each represent a single bond or a divalent organic linking group. As the divalent organic linking group, a substituted or unsubstituted alkylene group or a divalent organic linking group having a partial structure including the alkylene group and a hetero atom or a hetero atom is preferable. 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. The hetero atom in the partial structure containing a hetero atom includes, for example, an oxygen atom, a nitrogen atom and a sulfur atom, and among these, an oxygen atom and a nitrogen atom are preferable.

Specific examples of the preferable alkylene group 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 hydroxyl group and the like.

Examples of the divalent organic linking group include a partial structure containing a hetero atom or a hetero atom selected from -C (═O) -, -OC (═O) -, -NHC (═O) - at the terminal of the aforementioned alkylene group And is bonded to the adjacent oxygen atom through a partial structure containing the hetero atom or the hetero atom in view of the adsorption property to the pigment. Here, the adjacent oxygen atom means an oxygen atom bonded to the side chain terminal side with respect to L ¹ in the general formula (1) and L ² in the general formula (2).

In the 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 preferred alkyl groups include straight chain, branched and cyclic alkyl groups having 1 to 20 carbon atoms and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, An isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an iso-butyl group, an iso-butyl group, an iso-butyl group, an isobutyl group, Pentyl 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 group of a monovalent non-metal atom group other than hydrogen is used, and preferable examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, An N, N-dialkylamino group, an N, N-diarylamino group, an N, N-dialkylamino group, an N- Alkylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, an N, N-diarylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, An alkylsulfinyl group, an alkylsulfinyl group, an alkylsulfinyl group, an alkylsulfinyl group, an alkylsulfinyl group, an alkylsulfinyl group, an alkylsulfinyl group, an alkylsulfinyl group, an alkylsulfinyl group, A naphthyl group, a naphthyl group, a lauryl group, an N ', N'-dialkyl ester group, a N'-aryl group, Alkyl-N-alkylureido group, an N'-alkyl-N-alkylureido group, an N'-alkylureido group, N'-dialkyl-N-alkylureido groups, N'-dialkyl-N-alkylureido groups, N'- N'-diaryl-N-alkylureido groups, N'-diaryl-N-arylureido groups, N'-alkyl-N'-aryl- Alkyl-N-aryloxycarbonyl group, an N-alkyl-N'-aryl-N-aryl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, Aryloxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N- Alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, an N-arylcarbamoyl group, an N, N-diarylcarbamoyl group, an N-alkyl- , An arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and a conjugate salt thereof (hereinafter referred to as a sulfonate group), an alkoxysulfonyl group, an aryloxaphonyl group, An N, N-dialysulfanamoyl group, an N-alkylsulfinomoyl group, a sulfamoyl group, a N, N-dialkylsulfamoyl group, An alkylsulfamoyl group, an N, N-dialkylsulfamoyl group, an N-arylsulfamoyl group, an N, N-diarylsulfamoyl group, an N-alkyl- ₃ H ₂ ) and its conjugate salt (hereinafter referred to as a phosphonate group), a dialkylphosphono group (-PO ₃ (alkyl) ₂ ), a diarylphosphono group (-PO ₃ (aryl) ₂ ) Alkylarylphosphono groups (-PO ₃ (alkyl) (aryl)), monoalkylphosphono groups (-PO ₃ H (alkyl)) and their conjugate salts (hereinafter referred to as alkylphosphonato groups) a phosphono group (-PO ₃ H (aryl)) and its conjugated salts device (hereinafter, aryl phosphine Ney earthenware called quot;), phosphono oxy group (-OPO ₃ H ₂₎ and its conjugated salts device (hereinafter, referred to as phosphonate Ney took group), dialkyl phosphono oxy group _{(-OPO 3 (alkyl) 2)} , (-OPO ₃ (aryl) ₂ ), an alkylarylphosphonooxy group (-OPO ₃ (alkyl) (aryl)), a monoalkylphosphonooxy group (-OPO ₃ H (Hereinafter referred to as an alkylphosphonatooxy group), a monoarylphosphonooxy group (-OPO ₃ H (aryl)) and a conjugate salt thereof (hereinafter referred to as an arylphosphonatooxy group) A cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group and a silyl group.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and they may further have a substituent.

Examples of the substituent include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N, N-dialkylamino group, an N, N-diarylamino group, A heteroaryl group, an alkenyl group, an alkynyl group and a silyl group are preferable in terms of dispersion stability.

Specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesyl group, a cumene group, a chlorophenyl group, a bromophenyl group, a chloromethylphenyl group, a hydroxyphenyl group, a methoxyphenyl group, A phenoxyphenyl group, a methylthiophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, a methoxycarbonylphenyl group, an ethoxyphenylcarbonyl group, a phenoxycarbonyl group, a phenoxyphenyl group, a phenoxyphenyl group, A naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group,

Examples of A ¹ and A ² include linear, branched, or cyclic alkyl groups of 3 to 20 carbon atoms and cyclic alkyl groups of 5 to 20 carbon atoms in terms of dispersion stability and developability More preferably a linear chain of 4 to 15 carbon atoms, a branched chain of 4 to 15 carbon atoms, and a cyclic alkyl group of 6 to 10 carbon atoms, more preferably an alkyl group of 6 to 10 carbon atoms More preferred are straight-chain, branched alkyl groups of 6 to 12 carbon atoms.

In the general formulas (1) and (2), m and n each represent an integer of 2 to 8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

In the general formulas (1) and (2), p and q each represent an integer of 1 to 100. p may be different, and q may be different, or two or more kinds may be mixed. p and q are preferably from 5 to 60, more preferably from 5 to 40, and still more preferably from 5 to 20, from the viewpoints of dispersion stability and developability.

The copolymer comprising a structural unit represented by any one of the general formulas (1) and (2) preferably contains a repeating unit represented by the general formula (1) from the viewpoint of dispersion stability.

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

(1) -2

[Chemical Formula 5]

In the 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, 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 units represented by the general formula (1), (2), or (1) -2 may be obtained by polymerizing or copolymerizing the monomers represented by the following general formula (i), (ii) , As a repeating unit of a polymer compound.

[Chemical Formula 6]

In the general formulas (i), (ii) and (i) -2, R ¹ to R ⁶ each represent a hydrogen atom or a monovalent organic group; X ¹ and X ² each represent -CO- , -C (= O) O-, -CONH-, -OC (= O) - or a phenylene group, L ¹ and L ² each represent a single bond or a divalent organic linking group, (= O) - or NHC (= O) -, A ¹ and A ² each represent 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.

Specific preferred examples of the monomer represented by the general formula (i), (ii), or (i) -2 are the monomers (XA-1) to (XA-1) described in paragraphs 0081 to 0084 of Japanese Patent Application Laid- XA-23) are exemplified, but the present invention is not limited thereto.

The copolymer comprising a structural unit represented by any one of the general formula (1) and the following general formula (2) is a copolymer comprising at least one repeating unit selected from the repeating units represented by any one of formulas (1) and (2) And may include only one species or two or more species.

In the copolymer containing the structural unit represented by any one of the general formulas (1) and (2), the content of the repeating unit represented by any one of formulas (1) and (2) However, when the total amount of the repeating units contained in the polymer is 100% by weight, the amount of the repeating units represented by any one of formulas (1) and (2) is preferably 5% by weight or more, more preferably 50% , More preferably from 50% by mass to 80% by mass.

The copolymer containing the structural unit represented by any one of the general formulas (1) and (2) is preferably a copolymer comprising a monomer having a functional group capable of adsorbing to a pigment and a monomer having a functional group capable of adsorbing to the pigment, Is preferably a polymer compound obtained by copolymerizing monomers represented by 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 a monomer having an ionic group. Among them, monomers having an acidic group, monomers having an organic dye structure or a heterocyclic structure are preferable from the viewpoint of adsorption ability to a 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 with a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, ω-carboxy-poly Caprolactone mono (meth) acrylate, and the like. In addition, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as a precursor of the carboxyl group. Among these, from the viewpoint of developmentability of the unexposed portion, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a monomer having a cyclic structure such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride Additional reactants with anhydrides are preferred.

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

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

The copolymer comprising a structural unit represented by any one of the general formulas (1) and (2) may contain only one type of repeating unit derived from a monomer having an acidic group, do.

Examples of the monomer having an organic dye structure or a heterocyclic structure include a monomer comprising a specific monomer, a maleimide and a maleimide derivative described in paragraphs 0048 to 0070 of JP-A No. 2009-256572 And the like.

Examples of the monomer having a basic nitrogen atom include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 1- (meth) N, N-dimethylaminoethyl) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, N, N-diethylaminoethyl (meth) (Meth) acrylic acid, N, N-di-n-butylaminoethyl (meth) acrylate, Pyrrolidinoethyl (meth) acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate and N, N-methylphenylaminoethyl (Meth) acrylamides such as N- (N ', N'-dimethylaminoethyl) acrylamide, N- (N', N'-dimethylaminoethyl) (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- ) Acrylamide, N- (N ', N'-dimethylaminopropyl) methacrylamide, N- (N', N'-diethylaminopropyl) 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 3- (N, N- 1- (dimethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (Meth) acrylamides, piperidino (meth) acrylamides, N-methyl-2-pyrrolidyl Methacrylamide, and the like. There may be mentioned N, N- dimethylamino styrene, N, N- dimethylamino-methyl styrene.

It is also possible to use monomers having a urea group, a urethane group, a saturated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group. Specific examples thereof include the monomers described in paragraph [0095] of Japanese Laid-Open Patent Publication No. 2012-173356, the contents of which are incorporated herein by reference.

Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers, cationic vinyl monomers). Examples of the anionic vinyl monomer include an alkali metal salt of a vinyl monomer having an acidic group and a salt of an organic amine (for example, a tertiary amine such as triethylamine or dimethylaminoethanol) As the vinyl monomer, the nitrogen-containing vinyl monomer may be a halogenated alkyl (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); Benzyl halides such as benzyl chloride, benzyl bromide and the like; Alkyl sulfonic acid esters such as methanesulfonic acid (alkyl group: C1-18); Arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1-18); Dialkylsulfate dialkyl (alkyl group: C1-4), dialkyldiallylammonium salts, and the like.

The copolymer comprising a structural unit represented by any one of the general formula (1) and the following general formula (2) may further contain a repeating unit derived from a copolymerizable vinyl monomer in a range not inhibiting the effect .

Examples of the vinyl monomers usable herein include, but are not limited to, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (Meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrene, and (meth) acrylonitrile. Specific examples of such vinyl monomers include the following compounds. In the present specification, the term "(meth) acrylic" may be sometimes referred to as " acrylic or methacrylic "

Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy- Methacrylic acid benzyl acrylate, (meth) acrylic acid diethylene glycol monomethyl ether, ( (Meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol mono (Meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid? -Phenoxyethoxyethyl, (meth) acrylate nonylphenoxypolyethylene glycol, (meth) acrylic acid dicyclopentenyl, (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, triflouroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl ) Acrylic acid tribromobiphenyl, (meth) acrylic acid tribromobiphenyloxyethyl, and the like.

Examples of the crotonic acid esters include butyl crotonate, hexyl crotonate, and the like.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butylate, vinyl methoxy acetate, and vinyl benzoate.

Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, .

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

Examples of styrene include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, (For example, t-butyl), acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group capable of being deprotected by an acidic substance Methyl benzoate, and? -Methyl styrene.

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

As the other dispersant, it is also preferable to use a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / other monomer. Further, a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate and the copolymer of 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / Acrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

In the present invention, as the dispersant, those shown below are particularly preferable.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

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

The molecular weight of the dispersant used in the present invention is preferably 2,000 to 50,000, more preferably 5,000 to 30,000 in terms of weight average molecular weight (Mw).

The content of the dispersant is preferably 5 to 60 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the high refractive index particles.

The dispersant may be contained in only one kind of the composition of the present invention, or may contain two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

<< Photopolymerization initiator >>

The radiation sensitive composition of the present invention comprises a photopolymerization initiator which comprises a oxime-based photopolymerization initiator and an? -Aminoketone-based photopolymerization initiator, wherein the mass ratio of the oxime-based photopolymerization initiator to the? -Aminoketone- 4. When the mass ratio of the oxime-based photopolymerization initiator to the? -Aminoketone-based photopolymerization initiator is less than 1.5, the amount of the oxime-based photopolymerization initiator is relatively increased and the decomposition product due to the oxime-based photopolymerization initiator is apt to occur, The transmittance at the surface of the substrate becomes low. In addition, heat resistance and exposure latitude are also inferior.

When the mass ratio of the? -Aminoketone-based photopolymerization initiator to the oxime-based photopolymerization initiator is more than 4, the amount of the oxime-based photopolymerization initiator in the photopolymerization initiator becomes relatively small, resulting in a problem of sensitivity deterioration.

The mass ratio of the oxime-based photopolymerization initiator and the? -Aminoketone-based photopolymerization initiator is preferably 1: 1.8 to 1: 1.35, more preferably 1: 2.0 to 1: 3.0. By setting this range, the effect of the present invention can be achieved more effectively.

The total content of the photopolymerization initiator in the total solid content of the radiation sensitive composition of the present invention is preferably 0.1 to 10 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1.0 to 5 mass% .

<<< Oxime-based photopolymerization initiator >>>

The oxime-based photopolymerization initiator used in the present invention may be used singly or in combination of two or more.

The oxime-based photopolymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a high absorbance at 365 nm.

The oxime-based photopolymerization initiator preferably has a molar extinction coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000.

The molar extinction coefficient of the oxime-based photopolymerization initiator can be measured by a known method. For example, a molar extinction coefficient of 0.01 g / L or less can be measured with an ultraviolet visible spectrophotometer (Varian Carry-5 spectrophotometer) By weight.

The oxime-based photopolymerization initiator used in the present invention is preferably represented by the following general formula (I).

The compound of formula (I)

[Chemical Formula 12]

(In the 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, may form a condensed ring with Ar ¹ , R ³ represents any one 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 m 1 is an integer of 0 to 4 When m1 is 2 or more, R ³ may be the same or different. Ar ¹ represents a group formed by a combination of an arylene group or an arylene group and -C (= O) -.

In the general formula (I), R ¹ represents any one of a hydrogen atom, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group.

As the acyl group, any of aliphatic, aromatic, and heterocyclic groups may be used. More preferably 2 to 30 carbon atoms in total, more preferably 2 to 20 carbon atoms in total, and particularly preferably 2 to 16 carbon atoms in total. Examples of the substituent which the acyl group may have include 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, A benzoyl group, a benzoyl group, a benzoyl group, a benzoyl group, a benzoyl group, a benzoyl group, a benzoyl group, a benzoyl group, a benzoyl group, A 2-naphthoyl group, a pyridylcarbonyl group, a methacryloyl group, an acryloyl group, and the like can be given.

The alkyloxycarbonyl group preferably has 2 to 30 carbon atoms in total, more preferably 2 to 20 carbon atoms in total, and particularly preferably 2 to 16 carbon atoms in total. Examples of such an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonylbutoxycarbonyl group, an isobutyloxycarbonyl group, an allyloxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group , And ethoxyethoxycarbonyl group.

The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 30 carbon atoms in total, more preferably 7 to 20 carbon atoms in total, and particularly preferably 7 to 16 carbon atoms in total. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 2-naphthoxycarbonyl group, a paramethoxyphenoxycarbonyl group, a 2,5-diethoxyphenoxycarbonyl group, a para-chlorophenoxycarbonyl group, A paranitrophenoxycarbonyl group, and a para-cyanophenoxycarbonyl group.

The acyl group, alkyloxycarbonyl group and aryloxycarbonyl group may further have a substituent, but are preferably amorphous. As the substituent, any one of an alkoxy group, an aryloxy group, and a halogen atom is preferable.

In the general formula (I), R ² represents a substituent. R ² is preferably a group consisting of a combination of an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms and -O-. It is preferable that R ² forms a ring. When R ² forms a ring, any one of 4, 5, 6, and 7-membered rings is preferred, and a 5-membered or 6-membered ring is preferred. When R ² forms a ring, it may form a condensed ring with Ar ¹ . The condensed ring formed by combining with Ar &lt; ¹ &gt; is preferably a condensed ring condensed with two or three rings. When R ² forms a ring, it is preferably a hetero ring, more preferably one to three of oxygen atoms and sulfur atoms in the ring structure, more preferably one oxygen atom Do.

In the general formula (I), R ³ independently represents 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 m1 is 2 or more, in the case of forming a ring by connecting with each other, it is forming a ring as independent R ³ to each other is preferable, more preferably that forms an aryl group having a carbon number of 6-12, respectively between independent R ³ desirable.

In the general formula (I), m1 represents an integer of 0 to 4, preferably 0 or 1.

In the general formula (I), Ar ¹ represents a group formed by a combination of an arylene group or an arylene group and -C (= O) -. The carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 12. Particularly, a group comprising a phenylene group or a combination of a phenylene group and -C (= O) - is preferable, and a phenylene group is more preferable.

The oxime-based photopolymerization initiator used in the present invention is more preferably represented by the following general formula (I-1).

In general formula (I-1)

[Chemical Formula 13]

(In the general formula (I-1), R ⁴ represents any one of a hydrogen atom, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group which may have a substituent, and R ⁵ represents a halogen atom, an alkyl group, An alkylthio group, an arylthio group, an amino group, an alkylthio 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 1 ring or 2 Each of the rings represents any one of a 4, 5, 6, and 7-membered ring.) The condensed ring in which the condensed ring is condensed with the adjacent benzene ring is shown.

In the general formula (I-1), R ⁴ is synonymous with R ¹ in the above-mentioned general formula (I), and the preferable range is also the same.

In the general formula (I-1), R ⁵ is synonymous with R ³ in the general formula (I), and preferable ranges are also the same.

In the general formula (I-1), m2 agrees with m1 in the above-mentioned general formula (I), and the preferable range is also the same.

In the general formula (I-1), A represents a condensed ring in which one ring or two rings are condensed with an adjacent benzene ring, and each ring may be any one of 4, 5, 6, and 7 member rings . Each ring is preferably a 5- or 6-membered ring. A is preferably a heterocyclic ring, more preferably one to three of oxygen atom and sulfur atom in the ring structure, more preferably one oxygen atom.

The oxime-based photopolymerization initiator used in the present invention is more preferably represented by the following general formula (I-2) or (I-3).

In general formula (I-2)

[Chemical Formula 14]

(In the general formula (I-2), R ⁴ represents any one of a hydrogen atom, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group which may have a substituent, and R ⁵ represents a halogen atom, an alkyl group, . group, an alkyloxy group, represents an aryloxy group, an aryloxy carbonyl group, an alkylthio come, either coming aryl Im, and an amino group m2 is an integer of 0 ~ 4 X is -CH ₂ -, An oxygen atom and a sulfur atom, and 1 represents an integer of 1 to 3.)

In general formula (I-3)

[Chemical Formula 15]

(In the general formula (I-3), R ⁴ represents any one of a hydrogen atom, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group which may have a substituent, and R ⁵ represents a halogen atom, an alkyl group, . group, an alkyloxy group, represents an aryloxy group, an aryloxy carbonyl group, an alkylthio come, either coming aryl Im, and an amino group m2 is an integer of 0 ~ 4 X is -CH ₂ -, An oxygen atom and a sulfur atom, and 1 represents an integer of 1 to 3.)

In the general formulas (I-2) and (I-3), R ⁴ is the same as R ¹ in the above-mentioned general formula (I), and preferable ranges are also the same.

In the general formulas (I-2) and (I-3), R ⁵ is the same as R ³ in the above-mentioned general formula (I), and preferable ranges are also the same.

In the general formulas (I-2) and (I-3), m2 is the same as m1 in the above general formula (I), and preferable ranges are also the same.

In the general formulas (I-2) and (I-3), X represents -CH ₂ -, an oxygen atom or a sulfur atom, and an oxygen atom is preferable.

In the general formulas (I-2) and (I-3), 1 represents an integer of 1 to 3, preferably 1.

Examples of the oxime-based photopolymerization initiator usable in the present invention include 3-benzoyloxyiminobutain-2-one, 3-acetoxyiminobutain-2-one, 3-propionyloxyiminobutain- 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- Sulfonyloxy) iminobutaine-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

PBG-309, TRONLY TR-PBG-305 (manufactured by BASF Corporation), IRGACURE-OXE01 (trade name, manufactured by BASF), IRGACURE-OXE02 Adeka's NCI-831 and Adeka's NCI-930 (manufactured by ADEKA) are also suitably used.

Specific examples of the oxime-based photopolymerization initiator usable in the present invention are shown below, but the present invention is not limited thereto.

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

The total content of the oxime type polymerization initiator relative to the total solid content of the radiation sensitive composition of the present invention is preferably 0.05 to 8 mass%, more preferably 0.1 to 5 mass%, and more preferably 0.2 to 4 mass% desirable.

<<< α-Aminoketone Photopolymerization Initiator >>>

The? -Aminoketone photopolymerization initiator used in the present invention may be used singly or in combination of two or more.

The? -aminoketone-based photopolymerization initiator preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably an absorption wavelength in a wavelength region of 360 nm to 480 nm, more preferably an ultraviolet region having a high absorbance at 365 nm and 455 nm Is particularly preferable.

The? -aminoketone photopolymerization initiator preferably has a molar extinction coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000.

As the? -aminoketone-based photopolymerization initiator, compounds represented by the following formula (II) can be preferably used.

In general formula (II)

[Chemical Formula 21]

(In formula (II), X ¹ and X ² each independently represent an alkyl group, an aryl group, or a group formed by a combination of an alkylene group and an aryl group, X ³ and X ⁴ each independently represent a hydrogen atom , an alkyl group of 1 to 12 carbon atoms, represents a phenyl alkyl group having 3-5 alkenyl group or a carbon number of 7-9 of the X ³ and X ⁴ may form a ring by combining with each other. X ⁵ is 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 Formula (II), X ¹ and X ² each independently represent an alkyl group, an aryl group, or a group formed by a combination of an alkylene group and an aryl group, and any of X ¹ and X ² represents an alkylene group or an aryl group And the other is an alkyl group. The number of carbon atoms of the alkyl group is preferably from 1 to 3, more preferably 1 or 2. The carbon number of the aryl group is preferably 6 to 12, and more preferably 6. The number of carbon atoms of the alkylene group is preferably from 1 to 6, more preferably from 1 to 3, and still more preferably, a methylene group. The aryl group may or may not have a substituent, but preferably does not have a substituent.

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, and X ³ and X ⁴ may be bonded to each other to form a ring. The alkyl group may be any of linear, branched and 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 is preferably a dimethylamino group, a diethylamino group or a morpholino group, more preferably a dimethylamino group or a morpholino group, and more preferably a dimethylamino group.

In 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 a morpholino group, It is preferable that it is an anger.

The? -aminoketone-based photopolymerization initiator is more preferably represented by the following general formula (II-1).

In general formula (II-1)

[Chemical Formula 22]

(In the general formula (II-1), R ¹¹ represents a hydrogen atom or an alkyl group; R ¹² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, Import, dimethyl amino group or represents a morpholinyl group, Ar ² is an aryl represents an alkylene, X ³ and X ⁴ are, each independently, a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, having a carbon number of 3-5 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.)

In the general formula (II-1), R ¹¹ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. When R ¹¹ represents an alkyl group, the alkyl group preferably has 1 to 3 carbon atoms, more preferably 1 or 2.

In the general formula (II-1), R ¹² is synonymous with X ⁵ in the general formula (II), and the preferable range is also the same.

In the general formula (II-1), Ar ² represents an arylene group. The carbon number of the arylene group is preferably from 6 to 12, and more preferably 6. [

In the general formula (II-1), X ³ and X ⁴ are the same as those of X ³ and X ⁴ in the above-mentioned general formula (II), and preferable ranges are also the same.

As the? -Amino ketone-based photopolymerization initiator usable in the present invention, commercially available products IRGACURE-819 and DAROCUR-TPO (all trade names, all manufactured by BASF) can be used.

As the? -aminoketone-based photopolymerization initiator, specifically, the following compounds can be exemplified. Methyl-1-phenylpropane-1-one, 2-diethylamino-2-methyl-1-phenylpropane- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- 1- (4-isopropylphenyl) -2- methylpropane-1-one, 1- (4-butylphenyl) -2- Dimethylamino-2-methylpropane-1-one, 2-dimethylamino-1- (4-methoxyphenyl) 1-one (IRGACURE 907), 2- (4-methylthiophenyl) propan- 2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one (IRGACURE 369) (4-morpholinyl) phenyl] -1-butanone (IRGACURE 37 9).

<< 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 ethylenic unsaturated bond is usually used as the polymerizable compound as the polymerizable compound.

On the other hand, when the active compound is an acid such as sulfonic acid, phosphoric acid, sulfinic acid, carboxylic acid, sulfuric acid or sulfuric acid monoester, examples of the polymerizable compound include cyclic ethers such as an epoxy group, oxetanyl group and tetrahydrofuranyl group, Or a compound having a vinylbenzene group is used.

When the active compound is a base such as an amino compound, a compound having a cyclic group such as an epoxy group, oxetane group, or tetrahydrofuranyl group or a vinylbenzene group is used as the polymerizable compound.

The polymerizable compound is preferably selected from compounds having at least one terminal ethylenic unsaturated bond, more preferably two or more terminal ethylenic unsaturated bonds. Such a group of compounds is well known in the industrial field and can be used in the present invention without any particular limitation. These may be, for example, any of a monomer, a prepolymer, that is, a chemical form such as a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. The polymerizable compounds in the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, An amide of an unsaturated carboxylic acid with an aliphatic polyhydric alcohol compound, and an oligomer of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and a multimer thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. Further, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a leaving group substituent and mono- or polyfunctional alcohols, amines and thiol substituents are also suitable. As another example, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like instead of the above unsaturated carboxylic acid.

As specific compounds of these compounds, compounds described in paragraphs 0095 to 0108 of Japanese Laid-Open Patent Publication No. 2009-288705 can be suitably used in the present invention.

The polymerizable compound is also preferably a polymerizable monomer having at least one addition-polymerizable ethylene group and having an ethylenic unsaturated group having a boiling point of 100 캜 or higher at normal pressure. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ethyleneoxy modified dipentaerythritol hexaacrylate (A-DPH-12E commercially available from Shin Nakamura, (Acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, and the like can be used. [0040] The polyoxyethylene (meth) acrylate (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols, Japanese Patent Publication No. 48-41708 (Meth) acrylates described in respective publications, Japanese Unexamined Patent Publication (Kokai) No. 48-64183, Japanese Unexamined Patent Publication (Kokai) No. Sho 50-6034, Japanese Unexamined Patent Publication Polyfunctional acrylates such as epoxy acrylates, which are reaction products of an epoxy resin with (meth) acrylic acid, and the like, which are described in each of Japanese Patent Application Laid-Open No. 49-43191 and Japanese Patent Publication Methacrylate, and mixtures thereof.

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

As other preferable polymerizable compounds, those having a fluorene ring and having two or more functional ethylenic polymerizable groups, such as those described in JP-A-2010-160418, JP-A-2010-129825 and JP- It is also possible to use a compound, a cadmium resin.

As the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 占 폚 or higher at normal pressure, compounds according to paragraphs <0254> to <0257> of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

Suitable polymerizable compounds in the present invention include polymerizable compounds having two or more terminal ethylenic unsaturated bonds.

As examples of such a polymerizable compound, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

(23)

In the general formulas (MO-1) to (MO-5), n is 0 to 14, and m is 1 to 8. R and T present in plural in one molecule may be the same or different.

At least one of the plurality of Rs is -OC (= O) CH = CH ₂ or -OC (= O) in each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO- represents a group represented by _{C (CH 3) = CH 2} .

As specific examples of the radically polymerizable monomer represented by the formulas (MO-1) to (MO-5), compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779 are also suitable Can be used to make.

In addition, in JP-A 10-62986, ethylene oxide or propylene oxide is added to the polyfunctional alcohol described together with specific examples of the general formulas (1) and (2), and then (meth) acrylate One compound can also be used as a polymerizable compound.

Among them, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (commercially available products such as KAYARAD D-320; Nippon Kayaku Co., (KAYARAD D-310 manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) (Manufactured by Kayaku K.K.), and a structure in which the (meth) acryloyl group intervenes between ethylene glycol and propylene glycol moieties. These oligomer types can also be used.

As the polymerizable compound, an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group may be contained, and for example, an ethylenic unsaturated compound having an acid group is suitably used. The ethylenically unsaturated compounds having an acid group are obtained by (meth) acrylating a part of the hydroxyl groups of the polyfunctional alcohol and adding an acid anhydride to the remaining hydroxyl groups to form a carboxy group.

If the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, the ethylenic compound can be used as it is. If necessary, the hydroxyl group of the above-mentioned ethylenic compound is reacted with a nonaromatic carboxylic acid anhydride, . In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

In the present invention, examples of the monomer having an acid group include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which are obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride to give an acid group . Especially preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd., M-510 and M-520.

These monomers may be used singly or in combination of two or more in view of difficulty in using a single compound in the production process. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer.

The acid value of the polyfunctional monomer having an acid group is preferably from 0.1 to 40 mg-KOH / g, particularly preferably from 5 to 30 mg-KOH / g. If the acid value of the multifunctional monomer is too low, the development and dissolution characteristics are deteriorated. If the acid value is too high, the production and handling become difficult and the photopolymerization performance tends to be lowered and the curability such as surface smoothness of the pixel tends to be poor. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination or when polyfunctional monomers having no acid group are used in combination, it is preferable to adjust the acid value as the total polyfunctional monomer to fall within the above range.

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).

&Lt; EMI ID =

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

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

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

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

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

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

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

The total content of the compound represented by the general formula (i) or (ii) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the general formula (i) or (ii) can be produced by a process known in the art such as a step of binding an open-chain skeleton to pentaerythritol or dipentaerythritol by ring-opening addition reaction of ethylene oxide or propylene oxide, Can be synthesized from a step of introducing a (meth) acryloyl group by reacting a terminal hydroxyl group of the (meth) acryloyl chloride with, for example, (meth) acryloyl chloride. Each process is a well-known process, and one skilled in the art can easily synthesize the compound represented by the general formula (i) or (ii).

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

Specifically, the compounds (a) to (f) below (hereinafter also referred to as "exemplified compounds (a) to (f)") , (e) and (f) are preferable.

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Examples of commercially available products of the polymerizable compounds represented by the general formula (i) or (ii) include SR-494, a tetrafunctional acrylate having four ethylene oxy chains of Satomar Co., Ltd., a pen of Nippon Kayaku K.K. DPCA-60, which is a hexafunctional acrylate having six tyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

As the polymerizable compound, there can be mentioned, for example, those described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293 and JP-A-2-16765 And the ethylene oxide described in JP-A-62-39418, JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, Also suitable are urethane compounds having a skeleton. Examples of the polymerizable compound include compounds having an amino or sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 By using the polymerizable compounds, a radiation sensitive composition having a very high photosensitive speed can be obtained.

UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyowa Chemical Industry Co., Ltd.).

The details of the structure of the polymerizable compound, whether or not the polymerizable compound is used alone, whether or not the polymerizable compound is used alone, and the amount of the polymerizable compound to be added can be arbitrarily set according to the final performance design of the radiation sensitive composition. For example, from the viewpoint of sensitivity, a structure having a large number of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. Further, from the viewpoint of enhancing the strength of the cured film, those having three or more functional groups and having different functionalities and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene-based compound and vinyl ether-based compound) A method of adjusting both the sensitivity and the intensity is also effective. It is also preferable to use a polymerizable compound having three or more functional groups and having different ethylene oxide chain lengths in combination from the viewpoint that the developability of the radiation sensitive composition can be controlled and an excellent pattern can be obtained. Also, the compatibility and dispersibility with other components (for example, a photopolymerization initiator, an alkali-soluble resin, etc.) contained in the radiation sensitive composition is also an important factor for selecting and using a polymerizable compound. For example, The compatibility may be improved by the use of the purity compound or by the combined use of two or more species. In addition, a specific structure may be selected from the viewpoint of improving adhesion with a hard surface such as a support.

Specific examples of the polymerizable compound are given below, but the present invention is not limited thereto.

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The polymerizable compound may be used singly or in combination of two or more.

The content of the polymerizable compound in the radiation sensitive composition of the present invention is preferably 0.1 to 90% by mass, more preferably 1.0 to 80% by mass, more preferably 10 to 40% by mass relative to the total solid content in the radiation sensitive composition. % By mass is particularly preferable.

<Polyfunctional 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 promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkane thiol compound, particularly preferably a compound having a structure represented by the following general formula (I).

The compound of formula (I)

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(Wherein n represents an integer of 2 to 4, and L represents a linking group having 2 to 4 valences.)

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

[Chemical Formula 29]

The compounding amount of the polyfunctional thiol compound in the radiation sensitive composition of the present invention is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass, based on the total solid content excluding the solvent.

The polyfunctional thiol compound may contain only one kind or two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

Further, the polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability and adhesion.

<< Organic solvents >>

The radiation-sensitive composition of the present invention contains an organic solvent.

The organic solvent is not particularly limited so far as it satisfies solubility of each component and applicability of the radiation-sensitive composition. Particularly, in the case of containing an alkali-soluble resin to be described later, it is preferably selected in consideration of its solubility, coatability, and safety.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl acetate, methyl lactate, ethyl lactate, alkyloxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Ethoxyacetic acid ethyl, etc.), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionate Propyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) , Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- Examples of the ethers include diethyleneglycol dimethylether, diethyleneglycol dimethylether, diethyleneglycol dimethylether, diethyleneglycol dimethylether, diethyleneglycol dimethylether, diethyleneglycol dimethylether, diethyleneglycol dimethylether, But are not limited to, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Examples of the aromatic hydrocarbon include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, and examples thereof include toluene, xylene, cyclopentanone and the like.

From the viewpoints of the solubility of the alkali-soluble resin and the shape of the coated surface, these organic solvents are preferably mixed with two or more kinds. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- A mixed solvent composed of two or more kinds selected from methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate to be.

As the mixed solvent in which two or more kinds of organic solvents are mixed, a mixed solvent of ethers and ketones is preferable from the viewpoint of preventing precipitation precipitates from aging with time. As a mixed solution of ethers and ketones, particularly preferred is a mixed solvent composed of propylene glycol monomethyl ether acetate and cyclohexanone.

When the mixed solvent containing two or more kinds of organic solvents contains cyclohexanone, the content of cyclohexanone in the mixed solvent contained in the radiation sensitive composition is preferably 5 to 90% by mass , More preferably 10 to 85 mass%, and still more preferably 15 to 80 mass%.

The total content of the organic solvent in the radiation-sensitive composition is preferably 5% to 80% by mass, more preferably 5% to 60% by mass, and most preferably 10% To 50% by mass is particularly 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 (more precise).

As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine ultraviolet absorbers can be used. In the present invention, it is particularly preferable to use an ultraviolet absorber having an amino butadiene skeleton.

Examples of the salicylate ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and examples of the benzophenone ultraviolet absorber include 2,2'-dihydro 4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and the like. Examples of the benzotriazole based ultraviolet absorber include 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5- chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- Azole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethyl) phenyl] benzotriazole and the like.

Examples of substituted acrylonitrile ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Examples of the triazine-based ultraviolet absorber include 2- [4 - [(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] Methylphenyl) -1,3,5-triazine, 2- [4- [(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -Dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5- Of a mono (hydroxyphenyl) triazine compound; Bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4- -Methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis - (2,4-dimethylphenyl) -1,3,5-triazine; bis (hydroxyphenyl) triazine compounds; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2,4,6- Hydroxy-4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine, 2,4,6-tris [ And tris (hydroxyphenyl) triazine compounds such as 1,3,5-triazine.

Specific examples of the ultraviolet absorber are given below, but the present invention is not limited thereto.

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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%, more preferably 1 to 8 mass%, based on the total solid content of the radiation sensitive composition And more preferably 2 to 6% by mass. When the amount of the ultraviolet absorber is in this range, the transmittance and heat resistance in the visible light range can be further improved.

<< Binder Polymer >>

The radiation sensitive composition of the present invention may further contain a binder polymer.

As the binder polymer, a linear organic polymer can be appropriately selected from an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably, an acrylic copolymer, a molecule having a styrene-based copolymer as a main chain). From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable.

Examples of the group promoting the alkali solubility include an acid group, an alcoholic hydroxyl group, a pyrrolidone group, and an alkylene oxide group, and more preferably an acid group.

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, a carboxylic acid anhydride group and the like, preferably soluble in an organic solvent and developable by a weakly alkaline aqueous solution And a carboxyl group is particularly preferable. These acid groups may be only one kind, or two or more kinds.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of solvent at the time of producing the alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally .

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic anhydride copolymers, maleic acid copolymers and novolac resins, and acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to the polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl , And cyclohexyl (meth) acrylate. Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, Furfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like as the N-substituted maleimide monomer described in JP-A No. 10-300922 , N-phenylmaleimide, N-cyclohexylmaleimide and the like. In addition, these monomers copolymerizable with (meth) acrylic acid may be either one type alone or two or more types.

As the alkali-soluble resin, an alkali-soluble resin having as a monomer component a compound represented by the following general formula (ED) (hereinafter sometimes referred to as "ether dimer") is also preferable.

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In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group. 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.

Thus, the radiation sensitive composition of the present invention can form a cured coating film having excellent 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, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n Straight or branched chain alkyl groups such as butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to desorb by heat are preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2' - [oxybis (Isopropyl) -2,2 '- [oxybis (methylene)] -2-propenoate, di (n-propyl) )] Bis-2-propenoate, di (n-butyl) -2,2 '- [oxybis (methylene)] bis- (Methylene)] bis-2-propenoate, di (tert-butyl) -2,2'- Di (stearyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) -2 Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di -Methoxyethyl) -2,2 ' - [oxybis ( 2-propenoate, dibenzyl-2, 2 '- [oxy (2-methoxyphenyl) Bis (methylene)] bis-2-propenoate, diphenyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- (Dicyclopentadienyl) -2, 2 '- [oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) , 2 '- [oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2' Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, diadamantyl- 2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be either one kind or two or more kinds. The structure derived from the compound represented by the formula (ED) may be copolymerized with another monomer.

In addition to the above, it is preferable to include the ethylenically unsaturated monomer (a) represented by the following formula (X) as a monomer to be copolymerized with the alkali-soluble resin.

The formula (X)

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(In the 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, Alkyl group, and n represents an integer of 1 to 15.)

In the formula (X), the number of carbon atoms of the alkylene group of R ² is preferably 2 to 3. The alkyl group of R ³ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the 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 (isopropyl) group.

Examples of the ethylenically unsaturated monomer (a) include ethylene oxide (EO) modified (meth) acrylate of phenol, EO or propylene oxide (PO) modified (meth) acrylate of paracylphenol, EO- (Meth) acrylate of nonylphenol, and the like. Among these compounds, EO or PO-modified (meth) acrylate of para-cumylphenol has a higher dispersing effect.

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-mentioned polymer containing a polymerizable group include DYNAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (manufactured by Diamond Shamrock Co., Ltd., containing COOH), BisCot R-264, 106 (all manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series, Flackcell CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) . As the alkali-soluble resin containing these polymerizable groups, it is preferable that an isocyanate group and an OH group are previously reacted to leave an unreacted isocyanate group, and a compound containing a (meth) acryloyl group and a Acrylic resin containing an unsaturated group obtained by the reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in a molecule, Acid pendant epoxy acrylate resin, a polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group, an isocyanate and a polymerizable group , A resin obtained by reacting a compound having an epoxy group-containing compound 9207 and Japanese Unexamined Patent Application Publication No. 2003-335814, or resins obtained by subjecting a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group on?

As the alkali-soluble resin, a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomer is particularly suitable. In addition, a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate and a copolymer of 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylate described in JP-A No. 7-140654 Acid copolymer, 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, and the like.

As the alkali-soluble resin, the polymeric compounds C-1 to C-57 described in paragraphs 0317 to 0348 of Japanese Patent Application Laid-Open No. 2007-277514 may be used, and the content is incorporated herein. These polymer compounds C-1 to C-57 may be used as the above-mentioned dispersant.

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, most preferably 70 to 120 mgKOH / g.

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 molecular weight of the compound used in the present invention can be measured by Gel Permeation Chromatography (GPC) and is defined as a polystyrene reduced value measured by GPC. For example, TSKgel Super AWM-H (6.0 mm ID × 15.0 cm, manufactured by TOSOH CORPORATION) was used as a column, 10 mmol / L lithium bromide NMP (N -Methylpyrrolidinone) solution.

The content of the binder polymer in the radiation sensitive composition is preferably from 1 to 60 mass%, more preferably from 2 to 40 mass%, and particularly preferably from 3 to 15 mass%, based on the total solid content of the composition %to be.

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 the unit mole fraction of each unit in the resin molecule.

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<< Polymerization inhibitor >>

It is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during the production of the composition of the present invention. As the polymerization inhibitor, known thermal polymerization inhibitors can be used. Specific examples thereof include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t- , 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl- Primary cerium salts, and the like.

The addition amount of the thermal polymerization inhibitor is preferably about 0.001 to about 5 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 the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

In particular, since the composition according to the preferred embodiment of the present invention contains a fluorine-based surfactant, the liquid properties (particularly, fluidity) when the composition is prepared as a coating liquid can be further improved, Saving property) can be further improved.

That is, in the case of forming a film by using a coating liquid to which a composition containing a fluorine-containing surfactant is applied, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, . Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

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

As the fluorine-based surfactant, those containing at least one of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II) may be used as the copolymer component.

[Chemical Formula 39]

In the general formula (I), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and plural R ^{01 s} present may be the same or different. 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 is an integer of 1 to 10, m is an integer of 2 to 14, and 1 is an integer of 0 to 10. a represents a mole percentage which represents a polymerization ratio of the structural unit, and represents an integer of 0 to 100;

In the general formula (II), R ⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and plural R ^{01 s} present may be the same or different. 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 represents a mass percentage representing a polymerization ratio of the structural unit, and represents an integer of 0 to 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), see paragraphs 0016 to 0037 of JP-A-2010-032698, the contents of which are incorporated herein by reference.

Examples of the fluorochemical surfactant include Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101 (manufactured by Sumitomo 3M Co., Ltd.), F- , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Glass Co., 20000 (manufactured by Nippon Rubrizon Co., Ltd.). The following compounds may also be used. In the following structures, EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

(40)

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Diestearate and consumptive fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 manufactured by BASF).

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.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

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

Examples of silicone based surfactants include fluorine-based surfactants such as TORAY Silicon DC3PA, TORAY Silicone SH7PA, TORAY Silicon DC11PA, TORAY Silicone SH21PA, TORAY Silicone SH28PA, TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4440 "," TSF- KP341 ", " KF6001 ", "KF6002 ", manufactured by Shin-Etsu Silicone Co., Ltd., BYK307, BYK323 and BYK330 manufactured by Big Chemie.

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

The amount of the surfactant to be added is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.0% by mass, based on the total solid content of the composition.

The method for producing the radiation-sensitive composition is not particularly limited and can be obtained, for example, by adding each component contained in the composition to an organic solvent and stirring.

The radiation sensitive composition is preferably filtered with a filter for the purpose of eliminating foreign matter or reducing defects.

The filter used for the filtration of the filter is not particularly limited as far as it is a filter conventionally used for filtration and the like.

Examples of the material of the filter include fluororesins such as PTFE (polytetrafluoroethylene); Polyamide based resins such as nylon-6, nylon-6,6 and the like; Polyolefin resins (including high density, ultra high molecular weight) such as polyethylene and polypropylene (PP); And the like. Of these materials, polypropylene (including high-density polypropylene) is preferable.

The pore diameter 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 within the above-mentioned range, fine particles can be removed more effectively, and turbidity can be further reduced.

Here, the hole diameter of the filter can refer to the nominal value of the filter maker. Examples of commercially available filters include filters available from Nippon Polyurethane Industry Co., Ltd., Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nippon Micrel Co., Ltd.) or Kitsch Microfilter, You can choose.

In filter filtration, two or more kinds of filters may be used in combination.

For example, filtration may first be performed using a first filter, and then filtration may be performed using a second filter having a different pore diameter from the first filter.

At this time, the filtering in the first filter and the filtering in the second filter may be performed only once or two or more times, respectively.

The second filter may be formed of the same material as the first filter described above.

[Pattern formation method, color filter and method for manufacturing the same]

A pattern forming method, a color filter, and a manufacturing method thereof according to the present invention will be described.

In the method of forming a pattern of the present invention, the above-described radiation-sensitive composition of the present invention is applied on a support to form a coating layer (radiation-sensitive composition layer) (hereinafter also referred to as a "radiation- (Hereinafter also referred to as a " development step ") to obtain a patterned cured film by exposing a coating layer (hereinafter also referred to as" exposure step "

The pattern forming method of the present invention can be suitably applied to the pixel formation of the color filter included in the solid-state imaging element.

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 which can be applied to pattern formation in addition to a plate-like member such as a substrate.

Each step in the pattern forming method of the present invention will be described in detail below with reference to a method for producing a color filter of the present invention.

The method for manufacturing a color filter of the present invention is to apply the pattern forming method of the present invention and includes forming a patterned cured film on a substrate by using the pattern forming method of the present invention.

A method of manufacturing a color filter (hereinafter, also referred to as a color filter for a solid-state imaging element) of the solid-state image sensor of the present invention includes the steps of applying the above-described radiation-sensitive composition of the present invention to form a coating layer (Hereinafter also referred to as a " radiation-sensitive composition layer forming step "), a coating layer is exposed (hereinafter also referred to as an" exposure step & To obtain a cured film as a pixel.

That is, the method for manufacturing a color filter of the present invention (hereinafter also referred to as the production method of the present invention) (the step of forming a radiation-sensitive composition layer) comprises the steps of applying the radiation- Forming composition layer), exposing the coating layer to light (exposure step), and developing it to form a pattern (developing step) to obtain a patterned cured film.

The color filter of the present invention is obtained by the above production method.

The color filter of the present invention may have at least a transparent (white) pattern (white filter pixel) which is a pixel formed using the radiation sensitive composition of the present invention.

Specific examples of the color filter of the present invention include a form of a multicolor color filter (for example, a transparent pattern, a red pattern, a blue pattern, and a green pattern) in which a transparent pattern A color filter of four or more colors having at least a pattern) is suitable.

Hereinafter, the color filter of the present invention may be simply referred to as a "color filter ".

<Step of forming a radiation-sensitive composition layer>

In the step of forming the radiation-sensitive composition layer, it is preferable to form the radiation-sensitive composition layer on the substrate using the radiation-sensitive composition of the present invention.

As the substrate that can be used in the present process, for example, a substrate (for example, a silicon substrate) is provided with a solid substrate (e.g., a silicon substrate) provided with an imaging element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) A substrate for an imaging device can be used.

The transparent pattern in the present invention may be formed on the imaging element formation surface side (surface) of the substrate for the solid-state imaging element, or on the imaging element non-formation surface side (back surface). A light shielding film may be provided between each imaging element in the substrate for the solid-state imaging element or on the back surface of the substrate for the solid-state imaging element.

If necessary, an undercoat layer may be provided on the substrate for improving adhesion with the upper layer, preventing diffusion of the material, or planarizing the surface of the substrate.

Examples of the method of forming the layer of the radiation sensitive composition of the present invention on a substrate include a method of applying or printing, and various methods such as slit coating, inkjet method, rotary coating, flexible coating, roll coating, Method can be used.

The film thickness of the radiation-sensitive composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and further preferably 0.2 to 3 μm.

Drying (prebaking) of the layer of the radiation-sensitive composition applied on the substrate can be performed at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds in a hot plate, an oven or the like.

<Exposure Step>

In the exposure step, the radiation-sensitive composition layer formed in the step of forming the radiation-sensitive composition layer is subjected to pattern exposure through a mask having a predetermined mask pattern using, for example, an exposure apparatus such as a stepper.

As the radiation (light) which can be used at the time of exposure, it is meant to include visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like. Particularly, ultraviolet rays such as g- i line). Irradiation dose (exposure dose), and has 30 ~ 1500mJ / cm ² are preferred, and more preferred ^{50 ~ 1000mJ / cm 2, 80} ~ 500mJ / cm 2 is most preferred.

<Development Process>

Subsequently, by carrying out the alkali developing treatment, the radiation-sensitive composition layer in the unexposed area in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured portion.

As the developer, an organic alkali developing solution which does not cause damage to the underlying imaging element or circuit is preferable. The development temperature is usually 20 to 30 DEG C, and the development time is conventionally 20 to 90 seconds. In order to remove the residues, it is sometimes carried out 120 to 180 seconds in recent years. Further, in order to further improve the removability of the residue, the step of removing the developing solution every 60 seconds and supplying a new developing solution may be repeated a number of times.

Examples of the alkaline agent to be used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide And organic alkaline compounds such as benzene trimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene. These alkaline compounds Is diluted with pure water to a concentration of 0.001 to 10 mass%, preferably 0.01 to 1 mass%, is preferably used as the developing solution.

As the developing solution, inorganic alkali may be used. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.

When a developer comprising such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with pure water after development.

Subsequently, it is preferable to carry out a heat treatment (post-baking) after drying. If a multi-colored pattern is to be formed, the cured film can be produced by repeating the above steps in order for each color. As a result, a color filter is obtained.

The post-baking is a post-development heat treatment for making the curing to be complete, and is generally subjected to a heat curing treatment at 100 캜 to 240 캜, preferably at 200 캜 to 240 캜.

The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), or a high-frequency heater so as to satisfy the above conditions.

Further, the manufacturing method of the present invention may have a known process as a manufacturing method of a color filter for a solid-state imaging device as a process other than the above, if necessary. For example, it may include a curing step of curing the formed transparent pattern by heating and / or exposure, if necessary, after the step of forming the radiation sensitive composition layer, the step of exposing, and the step of developing.

In addition, when the radiation sensitive composition of the present invention is used, for example, the clogging of nozzles and piping of the discharging portion of the coating device and the contamination by deposition, sedimentation and drying of the radiation sensitive composition or inorganic particles into the applicator . 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 composition described above as a cleaning liquid. Further, Japanese Patent Application Laid-Open Nos. 7-128867, 7-146562, 8-278637, 2000-273370, 2006-85140, The cleaning liquids described in JP-A-2006-291191, JP-A-2007-2101, JP-A-2007-2102, JP-A-2007-281523, etc., It can be suitably used as a cleaning liquid.

Among these, 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 two or more species, it is preferable to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) is particularly preferably 60/40. Further, in order to improve the permeability of the cleaning liquid to the contaminants, the surfactant relating to the present composition described above may be added to the cleaning liquid.

Since the color filter of the present invention is mounted on the image sensor, the image pickup in the image sensor can be performed with high sensitivity and high quality.

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

The 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 m or less, more preferably 1.0 m or less. Here, the "coloring" of a coloring pattern (coloring pixel) is a concept including transparent (white).

The size (pattern width) of the coloring pattern (coloring pixel) is preferably 2.5 占 퐉 or less, more preferably 2.0 占 퐉 or less, and particularly preferably 1.7 占 퐉 or less.

[Solid-state image pickup device]

The solid-state image pickup 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 not particularly limited as long as the configuration includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode composed of polysilicon or the like are formed on a support, and on the photodiode and the transfer electrode, And a device shielding 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. The device protective film is provided with the color filter for solid- Filter.

Further, it may be a structure having the light-converging means (for example, a microlens or the like, hereinafter the same) on the device protective layer and below the color filter (near the support) or a structure having the condensing means on the color filter.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In addition, "%" and "part" are on a mass basis unless otherwise specified.

&Lt; Example 1 >

(1) Preparation of high refractive index particle dispersion 1-1

A dispersion liquid of the following composition A was subjected to a dispersion treatment under the following conditions by using Ultra Apex Mill (trade name) manufactured by Gotobu Kogyo K.K. as a circulation type dispersion apparatus (bead mill) to prepare a high refractive index particle To obtain a dispersion liquid 1-1.

<Composition A>

High refractive index particles (titanium dioxide, rutile type, refractive index: 2.71, trade name: TTO-51 (C) manufactured by Ishihara Sangyo Co., Ltd.): 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, weight average molecular weight: 10,000.

(41)

The dispersion apparatus was operated under the following conditions.

· Bead diameter: φ0.05mm

· Beads filling rate: 75 volume%

· Speed: 8m / sec

· Pump feed rate: 10Kg / hour

· Cooling water: Tap water

· Beads Mill Circumcontent Volume: 0.15L

· Mixed liquid volume to be dispersed: 0.44 kg

For each of 300 titanium dioxide particles contained in the resulting high refractive index Particle Dispersion 1-1, the projected areas of the titanium dioxide particles were determined using a transmission electron microscope, and the arithmetic average value of the corresponding circle equivalent diameters was found to be 40 nm .

(2) Preparation of a radiation-sensitive composition

The high refractive index Particle Dispersion 1-1 (dispersion composition) obtained above was used to mix the respective components so as to obtain the following composition to obtain a radiation-sensitive composition.

&Lt; Composition of radiation sensitive composition >

High dispersion index particle dispersion (dispersion composition) prepared above: 68.6 mass% of the total solid content

Polymerizable compound (A) (trade name: M305, manufactured by Toagosei Co., Ltd.) having the following structure: 21.3 mass%

Oxime-based photopolymerization initiator (A) (oxime compound of the following structure, synthesized by the method of Synthesis Example 7 of JP-A-2007-316451): 0.4 mass%

(A) (compound of the following structure, trade name: IRGACURE 369, manufactured by BASF): 1.0% by mass of the total solids content

Resin (A) (20% PGMEA solution) having the following structure: 4.5 mass%

Ultraviolet absorber (A) having the following structure: 4.0 mass%

Polymerization inhibitor (para-methoxyphenol): 0.01% by mass in total solids

Surfactant (fluorinated surfactant, 1% PGMEA solution, synthesized by the method shown in Synthesis Examples below): 0.2 mass%

Organic solvent (mixed solvent of propylene glycol methyl ether acetate (PGMEA) and cyclohexanone (XAN) (ratio by mass of 58:42): 28% by mass based on the total solid content of the radiation-

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

(42)

The oxime-based photopolymerization initiator (A)

(43)

The? -aminoketone photopolymerization initiator (A)

(44)

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

[Chemical Formula 45]

Ultraviolet absorber (A): An ultraviolet absorber having a butadiene skeleton (UV-503, manufactured by Daito Kagaku)

(46)

Surfactant: Megapac F-781F, manufactured by DIC Corporation EO represents ethyleneoxy group and PO represents 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.

(47)

High-Refractive Index Particle Dispersions 1-2 to 3 were obtained in the same manner as in the above-described Example 1 except that the specific dispersion resin of the high-refractive index Particle Dispersion 1-1 was changed as shown in the following table.

Except that the high refractive index particles of the high refractive index particle dispersion 1-1 of Example 1 were changed to zirconium oxide (UEP-100 made by Daiichi Kigenso Kagaku Kogyo Co., Ltd., refractive index: 2.20), a high refractive index particle dispersion 1-4.

Except that the ingredients in the composition of the radiation sensitive composition of Example 1 were changed to the equivalent weight as shown in the following table and that the total amount of the photopolymerization initiator was kept constant and only the ratio was changed, 2 to 13 and Comparative Examples 1 to 3 were obtained.

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

(48)

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

(49)

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

(50)

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

(51)

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

(52)

The oxime-based photopolymerization initiator (D)

(53)

alpha -aminoketone photopolymerization initiator (B): trade name: IRGACURE 907, manufactured by BASF)

(54)

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

(55)

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

(56)

[evaluation]

The following evaluations were carried out using each of the radiation sensitive compositions of the examples and comparative examples obtained as described above.

<Spectral Evaluation>

Each of the radiation sensitive compositions of the examples and comparative examples obtained above was coated on a glass wafer by a spin coat method so that the film thickness after coating was 0.6 占 퐉 and then heated on a hot plate at 100 占 폚 for 2 minutes. Further, the substrate was heated on a hot plate at 200 DEG C for 8 minutes to form a radiation-sensitive composition layer. The spectral transmittance of the substrate on which the radiation sensitive composition layer was formed was measured using a spectrophotometer MCPD-3000 (manufactured by OTSUKA DENKI CO., LTD.). The results are shown in the following table.

&Lt; Evaluation of heat resistance &

In the spectral evaluation, the spectral transmittance of the radiation-sensitive composition layer obtained by heating at 200 ° C for 8 minutes and the rate of change of the spectral transmittance after heating the layer of the radiation-sensitive composition on a hot plate at 260 ° C for 5 minutes [ / 5 minutes before heating at 260 占 폚 for 5 minutes) × 100]. The results are shown in the following table.

Criteria

3: The variation of transmittance is within ± 1.5%

2: Variation of transmittance exceeds ± 1.5% and within 3%

1: Variation of transmittance exceeds ± 3%

&Lt; Evaluation of exposure latitude &

Each of the radiation sensitive compositions of the examples and comparative examples obtained above was applied to a silicon wafer with an undercoat layer by a spin coat method so that the film thickness after coating was 0.6 mu m and then heated on a hot plate at 100 DEG C for 2 minutes Followed by heating to obtain a radiation-sensitive composition layer.

Subsequently, a Bayer pattern having a square of 1.1 mu m was exposed (exposure amount: 300 mJ / cm &lt; ² &gt;) through a mask to the obtained radiation-sensitive composition layer using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) .

Subsequently, the exposed layer of the radiation-sensitive composition was subjected to paddle development at 23 DEG C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, rinsing was carried out with a spin shower, and further washed with pure water to obtain a pattern.

Further, the radiation-sensitive composition layer separately obtained from the above was exposed at an exposure amount higher than the above exposure dose by 200 mJ / cm ² . Subsequently, development was carried out in the same manner as described above to obtain a pattern.

For each pattern obtained at an exposure dose of 300 mJ / cm ² and at a higher exposure dose, 10 lines of the line width in one pixel were measured to obtain an average value. The line width of the pattern was observed using a measurement SEM (trade name: S-7800H, manufactured by Hitachi, Ltd.). Then, the difference between the average values of the line widths of the respective patterns was obtained. The results are shown in the following table.

3: Difference in linewidth of each pattern within ± 0.1μm

2: Difference in line width of each pattern exceeds ± 0.1 μm, within 0.2 μm

1: Difference in linewidth of each pattern exceeds ± 0.2 μm

&Lt; Evaluation of residue degree &

Each of the radiation sensitive compositions of the examples and comparative examples obtained above was applied to a silicon wafer with an undercoat layer by a spin coat method so that the film thickness after coating was 0.6 mu m and then heated on a hot plate at 100 DEG C for 2 minutes Followed by heating to obtain a radiation-sensitive composition layer.

Subsequently, a Bayer pattern having a square of 1.1 mu m was exposed (exposure amount: 300 mJ / cm &lt; ² &gt;) through a mask to the obtained radiation-sensitive composition layer using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) .

Subsequently, the exposed layer of the radiation-sensitive composition was subjected to paddle development at 23 DEG C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, rinsing was carried out with a spin shower, and further washed with pure water to obtain a pattern.

The amount of the residue remaining on the base of the obtained pattern was evaluated by image binarization. The results are shown in the following table.

3: Less than 1% of total area of residue

2: the amount of residue is not less than 1% and not more than 3%

1: Residue amount exceeds 3% of total area of foundation

<Evaluation of Pattern Distortion>

Each of the radiation sensitive compositions of the examples and comparative examples obtained above was applied to a silicon wafer with an undercoat layer by a spin coat method so that the film thickness after coating was 0.6 mu m and then heated on a hot plate at 100 DEG C for 2 minutes Followed by heating to obtain a radiation-sensitive composition layer.

Subsequently, the resulting radiation-sensitive composition layer was allowed to stand for a predetermined time, and then a 1.1 μm square Bayer pattern was exposed through a mask (exposure amount: 300 mJ) using an i-line stepper exposure apparatus FPA-3000i5 + / cm ² ). After the formation of the radiation-sensitive composition layer using the radiation-sensitive composition, the time (PCD (post coating delay)) for leaving the radiation-sensitive composition layer until exposure was 24 hours.

Subsequently, the exposed layer of the radiation-sensitive composition was subjected to paddle development at 23 DEG C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, rinsing was carried out with a spin shower, and further washed with pure water to obtain a pattern.

The distortion of the obtained pattern was evaluated by an optical microscope observation. The results are shown in the following table.

3: No foreign matter

2: slight pattern distortion

1: Full surface pattern distortion

&Lt; Evaluation of refractive index &

Each of the radiation sensitive compositions of the examples and comparative examples obtained above was coated on a silicon wafer so that the film thickness after coating was 0.6 占 퐉 and then heated on a hot plate at 100 占 폚 for 2 minutes. Further, the substrate was heated on a hot plate at 200 DEG C for 8 minutes to form a radiation-sensitive composition layer. The refractive index of the substrate on which the radiation sensitive composition layer was formed was measured by using ellipsometry VUV-VASE (JA Woollam Japan). The results are shown in the following table.

[Table 1]

The total content of the photopolymerization initiator is 1.4% by mass of the total solid content.

As is apparent from the above evaluation, in the examples in which the mass ratio of the oxime-based photopolymerization initiator and the? -Aminoketone-based photopolymerization initiator was 1: 1.5 to 1: 4, the transmittance in the visible region was high and the heat resistance and the exposure latitude were good Could know.

Especially, when the oxime-based photopolymerization initiator represented by the general formula (I) was used, it was found that the effect of the present invention was better. Further, when the oxime-based photopolymerization initiator represented by the general formula (I-1) was used, it was found that the effect of the present invention was better.

Further, when the? -Aminoketone photopolymerization initiator represented by the general formula (II-1) was used, it was found that the effect of the present invention was better.

It was also found that when the composition contains an ultraviolet absorber having an amino butadiene skeleton, the effect of the present invention is better.

Further, when a dispersant having an acid value of 40 to 70 mgKOH / g was contained in the composition, it was found that the pattern residual and pattern distortion were smaller.

On the other hand, it is preferable that the mass ratio of the oxime-based photopolymerization initiator to the α-aminoketone-based photopolymerization initiator does not satisfy 1: 1.5 to 1: 4 It was found that at least one of the transmittance, the heat resistance and the exposure latitude in the visible light range was not good.

Claims (14)

A particle having a refractive index of 1.80 to 2.80, a polymerizable compound, an oxime-based photopolymerization initiator, an? -Aminoketone-based photopolymerization initiator and an organic solvent,
Wherein the mass ratio of the oxime-based photopolymerization initiator and the? -Aminoketone-based photopolymerization initiator is 1: 1.5 to 1: 4. The method according to claim 1,
Wherein the oxime-based photopolymerization initiator is represented by the following general formula (I).
The compound of formula (I)
[Chemical Formula 1]

In 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, may form a condensed ring with Ar ¹ , R ³ represents any one 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 a group formed by a combination of an arylene group or an arylene group and -C (= O) -. The method according to claim 1 or 2,
Wherein the oxime-based photopolymerization initiator is represented by the following general formula (I-1).
In general formula (I-1)
(2)

In the general formula (I-1), R ⁴ represents any one of a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group and an aryloxycarbonyl group, R ⁵ represents a halogen atom, an alkyl 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 condensed ring in which one ring or two rings are condensed with an adjacent benzene ring, and each ring represents any one of 4, 5, 6 and 7 member rings. The method according to any one of claims 1 to 3,
Wherein the? -Aminoketone photopolymerization initiator is represented by the following general formula (II-1).
In general formula (II-1)
(3)

In the general formula (II-1), R ¹¹ represents a hydrogen atom or an alkyl group, R ¹² represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, , represents a dimethyl-amino group, or morpholinyl group, Ar ² is and represents an arylene, X ³ and X ⁴ are, each independently, a hydrogen atom, an alkenyl group or the carbon atoms of the alkyl group having 1 to 12 carbon atoms, having a carbon number of 3 to 5 7 to 9, and X ³ and X ⁴ may be bonded to each other to form a ring. The method according to any one of claims 1 to 4,
Wherein the ultraviolet absorber further comprises 1 to 8% by mass of the ultraviolet absorber relative to the total solid content of the radiation sensitive composition. The method of claim 5,
Wherein the ultraviolet absorber has an amino butadiene skeleton. The method according to any one of claims 1 to 6,
Wherein the particle having the refractive index of 1.80 to 2.80 is a titanium dioxide particle. The method according to any one of claims 1 to 7,
Wherein the polymerizable compound is (meth) acrylate. The method according to any one of claims 1 to 8,
And a dispersant having an acid value of 40 to 70 mg KOH / g. The method according to any one of claims 1 to 9,
A radiation sensitive composition for forming a pixel of a color filter. A color filter obtained by using the radiation sensitive composition according to any one of claims 1 to 9. 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 9; and a step of exposing the radiation-sensitive composition layer to a pattern- And then forming a pattern by developing the color filter. A color filter produced by the method of manufacturing a color filter according to claim 12. A color filter according to Claim 11, or a solid-state image pickup device having the color filter according to Claim 13.