KR20160105860A - Radiation-sensitive composition, manufacturing method therefor, cured film, color filter, manufacturing method therefor, patterning method, solid-state imaging element, and image display device - Google Patents

Abstract

A radiation-sensitive composition capable of suppressing the generation of foreign matter and residues while improving long-term retardation and retention, a process for producing a radiation-sensitive composition, a cured film, a color filter and a process for producing the same, A solid-state image pickup device, and an image display device. CI Pigment Green 36, CI Pigment Yellow 150 and CI Pigment Yellow 185, and the content of the CI Pigment Green 36 relative to 100 parts by mass of the pigment is 80 to 86 parts by mass, Wherein the resin has a mass ratio of from 20 to 50 mg KOH / g and an amine value to acid value of from 0.85 to 1.45, wherein the mass ratio of CI Pigment Yellow 150 to CI Pigment Yellow 185 is in the range of 65.4: 35.6 to 79.0: 21.0. ≪ / RTI >

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation sensitive composition, a radiation sensitive composition, a cured film, a color filter and a manufacturing method thereof, a pattern forming method, a solid state imaging device, PATTERNING METHOD, SOLID-STATE IMAGING ELEMENT, AND IMAGE DISPLAY DEVICE}

The present invention relates to a radiation-sensitive composition. More particularly, the present invention relates to a radiation-sensitive composition which is preferably used for forming a colored layer of a color filter. The present invention also relates to a method for producing a radiation sensitive composition, a cured film, a color filter and a method for manufacturing the same, a pattern forming method, a solid-state imaging device and an image display device.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, there is a tendency that the demand of liquid crystal displays (LCDs), especially color liquid crystal displays, increases. And the spread of organic EL displays is also demanded from the demand for further high image quality. On the other hand, demand for solid-state image pickup devices such as CCD image sensors has been greatly increased owing to the spread of digital cameras and mobile phones equipped with cameras.

Color filters are used as key devices for these displays and optical elements, and there is an increasing demand for cost reduction with the demand for further high image quality. Such a color filter usually has coloring patterns of three primary colors of red (R), green (G), and blue (B), and in a display device or an imaging device, It plays a role.

Colorants used in color filters generally require the following characteristics. That is, there should be no optical disturbance such as non-uniformity of optical density which causes favorable spectral characteristics on color reproducibility, light scattering which is a cause of lowering contrast of liquid crystal display, color irregularity of solid-state image sensor, roughness, It is required to have good fastness under environmental conditions such as heat resistance, light resistance, humidity resistance, etc., a molar extinction coefficient is large and a thin film is possible.

As the composition for forming the coloring region of the color filter, the compositions described in Patent Documents 1 to 6 are known.

Patent Document 1: JP-A-2012-198408 Patent Document 2: JP-A-2009-086375 Patent Document 3: JP-A-2009-086089 Patent Document 4: JP-A-2004-287298 Patent Document 5: JP-A-2009-151026 Patent Document 6: JP-A-2012-211968

Here, as a composition for forming the coloring region of the color filter, after the cured film is formed by using the composition, fluctuation of the line width of the pattern due to long-term exposure until exposure is suppressed (hereinafter referred to as "long- Quot; property "), it is required to suppress the generation of foreign matter when the prepared composition is stored for a long time, and to suppress the generation of residues after exposure and development.

The present invention solves these problems and provides a radiation-sensitive composition capable of suppressing the generation of foreign matter and residues while improving long-term retardation and retention, a process for producing the same, a cured film, a color filter, A pattern forming method, a solid-state image pickup device and an image display device.

As a result of a detailed investigation by the present inventors, it has been found that a pigment containing CI Pigment Green 36, CI Pigment Yellow 150, CI Pigment Yellow 185, and a resin having an amine value and an acid value and containing CI Pigment The content of green 36 is 80 to 86 parts by mass, the mass ratio of CI Pigment Yellow 150 and CI Pigment Yellow 185 is in the range of 65.4: 35.6 to 79.0: 21.0, and the ratio of the acid value of the resin and the amine value to the acid value of the resin It has been found that the above problems can be solved by using a radiation sensitive composition in a specific range, and the present invention has been accomplished.

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

&Lt; 1 > A pigment containing a pigment comprising CI Pigment Green 36, CI Pigment Yellow 150, CI Pigment Yellow 185,

The content of C.I. Pigment Green 36 relative to 100 parts by mass of the pigment is 80 to 86 parts by mass, the mass ratio of C.I. Pigment Yellow 150 to C.I. Pigment Yellow 185 is in the range of 65.4: 35.6 to 79.0: 21.0,

Wherein the resin has an acid value of 20 to 50 mg KOH / g and an amine value to acid value of 0.85 to 1.45.

<2> The radiation-sensitive composition according to <1>, further comprising at least one of an acid derivative, an amine salt of an acid derivative, and a metal salt of an acid derivative.

<3> The radiation-sensitive composition according to <1> or <2>, further comprising an ultraviolet absorber.

<4> The radiation sensitive composition according to any one of <1> to <3>, wherein the mass ratio of the resin to the pigment is 0.2 to 0.4.

<5> The radiation sensitive composition according to any one of <1> to <4>, further comprising a polymerizable compound and a polymerization initiator.

<6> The radiation sensitive composition according to any one of <1> to <5>, which is used for forming a colored layer of a color filter.

&Lt; 7 > a pigment containing C.I. Pigment Green 36, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185 and a resin,

The content of C.I. Pigment Green 36 relative to 100 parts by mass of the pigment is 80 to 86 parts by mass, the mass ratio of C.I. Pigment Yellow 150 to C.I. Pigment Yellow 185 is in the range of 65.4: 35.6 to 79.0: 21.0,

Wherein the resin has an acid value of 20 to 50 mgKOH / g and an amine value to acid value of from 0.85 to 1.45.

<8> A method for producing a radiation sensitive composition according to <7>, which comprises covalently covalently dispersing a pigment including CI Pigment Green 36, CI Pigment Yellow 150, and CI Pigment Yellow 185 using the resin .

<9> A cured film obtained by curing the radiation sensitive composition according to any one of <1> to <6>.

&Lt; 10 > A color filter having a cured film according to < 9 >.

<11> A method for producing a radiation sensitive composition, comprising the steps of: applying a radiation sensitive composition according to any one of <1> to <6> on a support to form a radiation sensitive composition layer; , And removing the unexposed portions to form a pattern.

<12> A process for producing a radiation sensitive composition, comprising the steps of: applying a radiation sensitive composition according to any one of <1> to <6> on a support to form a radiation sensitive composition layer; And removing the unexposed portions to form a pattern.

&Lt; 13 > A solid-state image pickup device having a color filter obtained by the method of manufacturing a color filter according to < 10 > or a color filter according to < 10 >.

&Lt; 14 > A color filter according to < 10 > or an image display device having a color filter obtained by the method of manufacturing a color filter according to < 12 >.

According to the present invention, it becomes possible to provide a radiation-sensitive composition capable of suppressing the generation of foreign matters and the formation of residues, while maintaining a good long-term delay and retention. It is also possible to provide a method for producing a radiation sensitive composition, a cured film, a color filter and a manufacturing method thereof, a pattern forming method, a solid-state imaging device and an image display device.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "" is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

In the present specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the composition. It also refers to the solid content at 25 占 폚.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes a group (atomic group) having a substituent group together with a group (atomic group) having no 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 the present 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 beams 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.

In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers 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.

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, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and TSKgel Super AWM-H , 6.0 mm ID x 15 cm) can be obtained by using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

<Radiation-sensitive composition>

The radiation sensitive composition of the present invention (hereinafter also referred to as "the composition of the present invention") comprises a pigment including CI Pigment Green 36, CI Pigment Yellow 150, CI Pigment Yellow 185, and a resin having an amine value and an acid value , The content of CI Pigment Green 36 to 100 parts by mass of the pigment is 80 to 86 parts by mass and the mass ratio of CI Pigment Yellow 150 to CI Pigment Yellow 185, that is, (mass of CI Pigment Yellow 150: CI (Mass of Pigment Yellow 185) of 65.4: 35.6 to 79.0: 21.0 and the resin has an acid value of 20 to 50 (mgKOH / g) and an amine value to acid value of 0.85 to 1.45 (mgKOH / g) .

According to the present invention, it is possible to suppress generation of foreign matter and residues while improving long-time delay and retention. Further, according to the present invention, the filtration property of the composition can be improved, and the surface roughness of the cured film can be suppressed.

The composition of the present invention is preferably used for forming a colored layer of a color filter. The composition of the present invention may further comprise a pigment including CI Pigment Green 36, CI Pigment Yellow 150, and CI Pigment Yellow 185, and a resin having an amine value and an acid value, as well as a polymerizable compound, a polymerization initiator, and the like .

For example, in the case of forming a colored layer by photoresist, the composition of the present invention includes a pigment including CI Pigment Green 36, CI Pigment Yellow 150, CI Pigment Yellow 185, and a resin having an amine value and an acid value , A polymerizable compound, a polymerization initiator and an alkali-soluble resin. It may also contain a surfactant, a solvent, and the like.

In addition, in the case of forming a colored layer by dry etching, the composition of the present invention may contain, in addition to a pigment including CI Pigment Green 36, CI Pigment Yellow 150, and CI Pigment Yellow 185 and a resin having an amine value and an acid value , And a polymerizable compound. In addition, it may contain components such as a surfactant and a solvent.

Hereinafter, the composition of the present invention will be described in detail.

<< Pigment >>

The composition of the present invention contains at least CI Pigment Green 36, CI Pigment Yellow 150 and CI Pigment Yellow 185 as pigments.

In the composition of the present invention, the content of CI Pigment Green 36 relative to 100 parts by mass of the total pigment including CI Pigment Green 36, CI Pigment Yellow 150 and CI Pigment Yellow 185 is 80 to 86 parts by mass, 85 parts by mass is preferable, and 82 parts by mass to 84 parts by mass is more preferable. By setting the content of C.I. Pigment Green 36 to 80 parts by mass or more with respect to 100 parts by mass of the pigment, the roughness of the reproduced image can be further reduced when the color filter is formed. Further, by controlling the content of C.I. Pigment Green 36 to 86 parts by mass or less based on 100 parts by mass of the pigment, occurrence of foreign matter and residue can be suppressed.

In the composition of the present invention, the content of CI Pigment Yellow 185 in 100 parts by mass of the total pigment is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass.

In the composition of the present invention, the content of CI Pigment Yellow 150 in 100 parts by mass of the total pigment is preferably 1 to 40 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 8 to 15 parts by mass.

In the composition of the present invention, the mass ratio of CI Pigment Yellow 150 and CI Pigment Yellow 185 is in the range of 65.4: 35.6 to 79.0: 21.0, preferably in the range of 65.4: 35.6 to 75.0: 25.0, and 68.0: 32.0 to 72.0: A range of 28.0 is more preferable.

The average primary particle size of the pigment used in the composition of the present invention is practically 10 nm or more. The upper limit is preferably 1 占 퐉 or less, more preferably 500 nm or less, more preferably 200 nm or less, further preferably 100 nm or less, particularly preferably 50 nm or less, from the viewpoint of obtaining a better contrast. In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used as an index showing the monodispersibility of the particles unless otherwise specified. The monodispersibility (Mv / Mn) of the pigment fine particles (primary particles) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, particularly preferably 1.0 to 1.5. In the present invention, the average primary particle diameter of the particles is determined from an image observed by a transmission electron microscope, and the average diameter of 500 particles is determined.

The pigment particles may be prepared by a conventional method, for example, by pulverization by milling (breakdown method), or by precipitation using a good solvent and a poor solvent (build-up method). For the former (break-down method), the pigment particles can be made finer by a regular method using a bead mill or the like. For example, reference may be made to the description given in the section entitled " mechanical cracking "on page 12-21 of the Journal of the Japanese Chemical Society, vol. 45, No. 5 (2006) The latter (build-up method) is also referred to as a re-impregnation method and is disclosed in, for example, Japanese Laid-Open Patent Publication No. 2011-026452, Japanese Laid-Open Patent Publication No. 2011-012214, Japanese Laid-Open Patent Publication No. 2011-001501, 235895, JP-A-2010-2091, JP-A-2010-209160, and the like.

For adjusting the spectral transmittance of the composition of the present invention, a colorant such as an inorganic pigment, an organic pigment other than CI Pigment Green 36, CI Pigment Yellow 150, and CI Pigment Yellow 185 may be appropriately added.

Examples of the inorganic pigments that can be appropriately added to the composition of the present invention include metal compounds represented by metal oxides and metal complex salts and specifically include iron, cobalt, aluminum, silicon, cadmium, lead, copper, titanium, zirconium , Metal oxides such as magnesium, chromium, zinc, antimony and the like, and composite oxides of the above metals, black pigments such as carbon black and titanium black.

As the organic pigments that can be appropriately added to the composition of the present invention, for example,

CI pigment yellow 1, 2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 1, 36, 36, 37, 37, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 147, 148, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 182, 187, 188, 193, 194, 199, 213, 214, etc.,

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 73,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 175, 176, 178, 179, 184, 185, 172, 179, 170, 176, 168, 169, 170, 187, 188, 190, 200, 208, 210, 220, 226, 242, 246, 279

C. I. Pigment Green 10, 37

C. I. Pigment Violet 1, 19, 23, 27, 32, 37

15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80

C. I. Pigment Black 1

C. I. Pigment Brown 25, 28

C. I. Pigment Black 1

And the like.

Examples of the known dyes that can be appropriately added to the composition of the present invention include dyes disclosed in Japanese Unexamined Patent Application Publication No. 64-90403, Japanese Unexamined Patent Publication No. 64-91102, Japanese Unexamined Patent Publication No. 1-94301, Patent Documents 6-11614, 2592207, 4808501, 5667920, 505950, 5667920, 5-333207, and 593307 And JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828 can be used. As a chemical structure, it is possible to use a pyrazole compound, a pyromethene compound, an anilino compound, a triphenylmethane compound, an anthraquinone compound, a benzilidene compound, an oxolin compound, a pyrazolotriazoazo compound, A cyanine compound, a phenothiazine compound, a pyrrolopyrazolequamethane compound, and the like can be used. As the dye, a dye multimer may be used. Examples of the pigment multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097.

The blending amount of the pigment contained in the composition of the present invention may be 10% by mass or more, 20% by mass or more, and 30% by mass or more of the total solid content of the radiation sensitive composition. The upper limit is not particularly limited, but may be 80% by mass or less, 70% by mass or less, and 65% by mass or less.

The total amount of C. I. Pigment Green 36, C. I. Pigment Yellow 150 and C. I. Pigment Yellow 185 in the composition of the present invention is preferably 95% by mass or more based on the total amount of the colorant. Here, the total amount of the coloring agent means the total amount of the coloring agent including the dye in the case of including the dye in addition to the pigment.

The content of the coloring agent other than CI Pigment Green 36, CI Pigment Yellow 150 and CI Pigment Yellow 185 in the total amount of colorants contained in the composition of the present invention may be 10% by mass or less, 5% by mass or less , And may be 1% by mass or less, or 0% by mass.

<< Resin with amine and acid value >>

The specific dispersion resin (hereinafter also referred to as "specific dispersion resin") used in the present invention has an amine value and an acid value, an acid value of 20 to 50, and an amine value to acid value of 0.85 to 1.45.

In the specific dispersion resin, the ratio of the amine value to the acid value (amine value / acid value) is 0.85 to 1.45, preferably 0.85 to 1.45, more preferably 0.90 to 1.42, and further preferably 1.00 to 1.40. By setting this range, the effect of the present invention can be more effectively exhibited. The acid value of the specific dispersion resin is 20 to 50 mgKOH / g, preferably 25 to 45 mgKOH / g, more preferably 30 to 40 mgKOH / g.

The amine value of the specific dispersion resin is preferably 17 to 72.5 mgKOH / g, more preferably 20 to 70 mgKOH / g, and even more preferably 30 to 60 mgKOH / g.

The mass ratio of the specific dispersion resin to the pigment, that is, the mass ratio of the specific dispersion resin / pigment is preferably 0.2 to 0.4, more preferably 0.25 to 0.35.

Here, the amine value and the acid value of the specific dispersion resin used in the present invention refer to the values measured by the following methods.

The amine value of the specific dispersion resin is expressed in terms of the weight of potassium hydroxide (KOH) equivalent to the basic component per 1 g of the solid content. The measurement sample was dissolved in acetic acid, and the resulting solution was subjected to neutralization titration with 0.1 M perchloric acid / acetic acid solution using a potentiometric titration apparatus (trade name: AT-510, manufactured by Kyoto Denshi Kogyo). Using the inflection point of the appropriate pH curve as an appropriate end point, the amine value was calculated by the following formula.

B = 56.11 x Vs x 0.1 x f / w

B: Amine value (mgKOH / g)

Vs: Amount of 0.1 M perchloric acid / acetic acid solution (mL) required for titration

f: Potency of 0.1 M perchloric acid / acetic acid solution

w: Weight of the sample to be measured (g) (in terms of solid content)

The acid value of the specific dispersion resin represents the weight of potassium hydroxide required to neutralize the acidic component per 1 g of the solid content. The measurement sample was dissolved in tetrahydrofuran / water = 9/1 mixed solvent, and the obtained solution was neutralized with a 0.1 M sodium hydroxide aqueous solution using a potentiometric titration apparatus (trade name: AT-510, manufactured by Kyoto Denshi Kogyo). Using the inflection point of the appropriate pH curve as an appropriate end point, the acid value was calculated by the following formula.

A = 56.11 x Vs x 0.5 x f / w

A: acid value (mgKOH / g)

Vs: Amount of 0.1 M sodium hydroxide aqueous solution required for titration (mL)

f: Potency of 0.1 M aqueous sodium hydroxide solution

w: Weight of the sample to be measured (g) (in terms of solid content)

The specific dispersion resin used in the present invention preferably has a main chain portion composed of a known amino group, more preferably an oligomer or polymer containing a primary or secondary amino group. Specific examples of the oligomer or polymer containing an amino group include poly (lower alkyleneimine), polyallylamine, polydiallylamine, metaxylene diamine-epichlorohydrine polycondensate, polyvinylamine, 3- (Meth) acrylic acid amide copolymer, a dialkylaminopropyl (meth) acrylamide copolymer, a (meth) acrylic acid 2-dialkylaminoethyl copolymer, and the like, And more preferably a backbone structure selected from a 2-dialkylaminoethyl acrylate copolymer.

The poly (lower alkyleneimine) may be in the form of a chain or a network, preferably a network.

The number-average molecular weight of the main chain portion in the specific dispersion resin is preferably 100 to 10,000, more preferably 200 to 5,000, still more preferably 300 to 2,000, still more preferably 500 to 1,500.

The main chain portion of the specific dispersion resin is preferably composed of a poly (lower alkyleneimine), or polyallylamine skeleton in particular. The lower level in the poly (lower alkyleneimine) means that the number of carbon atoms is 1 to 5, and the lower alkyleneimine means an alkyleneimine having 1 to 5 carbon atoms.

The specific dispersion resin is a resin having a repeating unit represented by the general formula (I-1) and a repeating unit represented by the general formula (I-2), or a repeating unit represented by the general formula (II- 2). &Lt; / RTI &gt;

(A repeating unit represented by the general formula (I-1) and a repeating unit represented by the general formula (I-2)

The repeating unit represented by formula (I-1) and the repeating unit represented by formula (I-2) will be described in detail.

[Chemical Formula 1]

In the general formulas (I-1) and (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group. a independently represents an integer of 1 to 5; * Represents the connection between repeating units.

X represents a group having a functional group having a pKa of 14 or less. And Y represents an oligomer chain or polymer chain having 40 to 10,000 atoms.

The specific dispersion resin preferably has, as a copolymerization component, a repeating unit represented by the general formula (I-3) in addition to the repeating unit represented by the general formula (I-1) and the general formula (I-2).

(2)

In the general formula ^{(I-3), R 1} , R 2 , and a is R ^1, R ² and a and agreed in the formula (I-1). Y 'represents an oligomer chain or polymer chain having 40 to 10,000 atoms having an anionic group. The repeating unit represented by the general formula (I-3) can be formed by reacting a resin having a primary or secondary amino group in the main chain portion with an oligomer or polymer having a group capable of reacting with an amine to form a salt .

In the general formulas (I-1), (I-2) and (I-3), R ¹ and R ² are preferably hydrogen atoms. a is preferably 2 from the viewpoint of raw material availability.

The specific dispersion resin may contain, in addition to the repeating units represented by the general formula (I-1), the general formulas (I-2) and (I-3), a lower alkyleneimine containing a primary or tertiary amino group It may be included as a repeating unit. The nitrogen atom in such a lower alkyleneimine repeating unit may also be bonded with a group represented by X, Y or Y '. A resin containing both a repeating unit bonded with a group represented by X and a repeating unit combined with Y in such a main chain structure is also included in the specific dispersion resin.

The repeating unit represented by the general formula (I-1) is a repeating unit having a basic nitrogen atom to which a partial structure X having a functional group having a pKa of 14 or less is bonded. Such a repeating unit having a basic nitrogen atom has a storage stability, From the viewpoint of dispersibility, the content of the repeating units is preferably 1 to 80 mol%, more preferably 3 to 50 mol%.

The repeating unit represented by the general formula (I-2) is a repeating unit having an oligomer chain or a polymer chain having 40 to 10,000 atoms, and from the viewpoint of storage stability, Is preferably contained in an amount of 10 to 90 mol%, particularly preferably 30 to 70 mol%.

The content ratio [(I-1) :( I-2)] of the repeating unit (I-1) and the repeating unit (I-2) 1: 100, and more preferably in the range of 1: 1 to 1:10.

The repeating unit represented by the general formula (I-3) which is used in combination according to purposes has a structure in which a partial structure containing an oligomer chain or a polymer chain Y 'having 40 to 10,000 atoms is ionically bonded to the nitrogen atom of the main chain And is preferably contained in an amount of 0.5 to 20 mol%, more preferably 1 to 10 mol%, of all the repeating units contained in the specific dispersion resin.

The fact that the polymer chain Y 'is ionically bonded can be confirmed by infrared spectroscopy or base titration.

(A repeating unit represented by formula (II-1) and a repeating unit represented by (II-2)

The repeating unit represented by formula (II-1) and the repeating unit represented by formula (II-2) will be described in detail.

(3)

In the general formulas (II-1) and (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. *, X and Y are synonymous with *, X and Y in the general formulas (I-1) and (I-2).

The specific dispersion resin further contains, as a copolymerization component, a repeating unit represented by the following general formula (II-3) in addition to the repeating unit represented by the general formula (II-1) .

[Chemical Formula 4]

In the general formula ^{(II-3), R 3} , R 4, R 5 and R ⁶ is a R ^3, R ^4, R ⁵ and R ⁶ and copper in the formula (II-1). Y 'agrees with Y' in the general formula (I-3).

In the general formulas (II-1), (II-2) and (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of raw materials.

The general formula (II-1) is a repeating unit having a basic nitrogen atom to which a partial structure X having a functional group having a pKa of 14 or less is bonded. Such a repeating unit having a basic nitrogen atom has, in view of storage stability and developability, Is preferably contained in an amount of 1 to 80 mol%, more preferably 3 to 50 mol%, of the total repeating units contained in the specific dispersion resin.

The repeating unit represented by formula (II-2) is a repeating unit having an oligomer chain or a polymer chain Y of 40 to 10,000 atoms. From the standpoint of storage stability, Is preferably contained in an amount of 10 to 90 mol%, particularly preferably 30 to 70 mol%.

(II-1) :( II-2) of the repeating unit (II-1) and the repeating unit (II-2) 1: 100, and more preferably in the range of 1: 1 to 1:10.

The repeating unit represented by the general formula (II-3) used together with the purpose is preferably contained in an amount of 0.5 to 20 mol%, more preferably 1 to 10 mol%, of the total repeating units of the specific dispersion resin.

From the viewpoint of dispersibility, it is particularly preferable that the specific dispersion resin contains both of the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2).

< Partial structure X having a functional group of pKa 14 or less >

A partial structure X having a functional group having a pKa of 14 or less will be described.

X has a functional group having a pKa of 14 or less at a water temperature of 25 占 폚. The term "pKa" used herein is a definition described in the Chemical Manual (II) (revised edition 4, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.).

The "functional group having a pKa of 14 or less" is not particularly limited as far as the physical properties satisfy this condition, and the pKa satisfies the above range with a known functional group. Particularly, And a functional group having a pKa of 11 or less is particularly preferable. Specific examples of the partial structure X include a carboxylic acid group (pKa: about 3 to 5), a sulfonic acid (pKa: about -3 to -2), -COCH ₂ CO- (pKa: about 8 to 10) COCH ₂ CN (pKa: about 8 to 11), -CONHCO-, a phenolic hydroxyl group, -R _F CH ₂ OH or - (R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group, (PKa: about 3 to about 5), a sulfonic acid group (about pKa: about 3 to about 2), -COCH ₂ CO- (pKa: about 8 to 10).

When the pKa of the functional group of the partial structure X is 14 or less, interaction with the titanium dioxide particles can be achieved.

The partial structure X having a functional group having a pKa of 14 or less is preferably bonded directly to a basic nitrogen atom in the repeating unit having a basic nitrogen atom. The nitrogen atom and the partial structure X of the repeating unit having a basic nitrogen atom may be connected not only to a covalent bond but also to an ionic bond to form a salt.

The partial structure X containing a functional group having a pKa of 14 or less is preferably a structure represented by the following general formula (V-1), general formula (V-2) or general formula (V-3)

[Chemical Formula 5]

In the formulas (V-1) and (V-2), U represents a single bond or a divalent linking group. d and e independently represent 0 or 1; In the general formula (V-3), Q represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include alkylene (more specifically, for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CHMe-, - (CH ₂ ) ₅ -, -CH ₂ CH (nC ₁₀ H ₂₁ ) -, etc.), an oxygen-containing alkylene group (more specifically, -CH ₂ OCH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ -, etc.), an arylene group (E.g., phenylene, tolylene, biphenylene, naphthylene, furanylene, pyrrolylene and the like), alkyleneoxy (for example, ethyleneoxy, propyleneoxy, phenyleneoxy) An alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 20 carbon atoms is preferable, and an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms is particularly preferable. From the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents an acyl group or an alkoxycarbonyl group. As the acyl group in Q, an acyl group having 1 to 30 carbon atoms (for example, formyl, acetyl, n-propane oil, benzoyl and the like) is preferable, and acetyl is particularly preferable. As the alkoxycarbonyl group for Q, Q is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoints of ease of production and availability of a starting material (precursor X 'of X).

The partial structure X is preferably bonded to a basic nitrogen atom in the repeating unit having a basic nitrogen atom. Thereby, the dispersibility and the dispersion stability of the titanium dioxide particles can be further improved.

Since the partial structure X contains a functional group having a pKa of 14 or less, it also functions as an alkali-soluble group. Thus, when the coating film formed by the composition of the present invention is energized and partially cured to dissolve and remove the unexposed portion to form a pattern, the developability of the uncured region in an alkali developing solution is improved, The stability and developability can be improved.

The content of the functional group having a pKa of 14 or less in the partial structure X is not particularly limited, but is preferably 0.01 to 5 mmol, particularly preferably 0.05 to 1 mmol, per g of the specific dispersion resin. Within this range, the dispersibility and dispersion stability of the titanium dioxide particles are improved, and when the cured film is formed by the composition of the present invention, the developability of the uncured portions is excellent. From the viewpoint of the acid value, it is preferable that the acid value of the specific dispersion resin is included in an amount of about 5 to 50 mgKOH / g.

(Oligomer chain or polymer chain Y having 40 to 10,000 atoms)

The oligomer chain or polymer chain Y of 40 to 10,000 atoms will be described. Examples of Y include known polymer chains such as polyester, polyamide, polyimide and poly (meth) acrylic acid ester which can be connected to the main chain portion of a specific dispersion resin. It is preferable that the binding site with Y for the specific dispersing resin is the oligomer chain or the terminal of the polymer chain Y. [

Y is at least one repeating unit selected from the group consisting of a poly (lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a repeating unit of a meta xylene diamine-epichlorohydrin polycondensate, Is preferably bonded to the nitrogen atom of the repeating unit having at least one kind of nitrogen atom selected from repeating units. A repeating unit derived from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a poly (diallylamine) -based repeating unit, a meta-xylene-diamine-epichlorohydrin- The bonding form of the main chain portion and Y of the repeating unit having at least one kind of basic nitrogen atom to be selected is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the bonding form of Y to the main chain portion is preferably from 95: 5 to 5:95, and particularly preferably from 90:10 to 10:90, in the ratio of covalent bond: ion bond = 100: 0 to 0: Outside this range, the dispersibility and dispersion stability are deteriorated and the solvent solubility is lowered.

Y is preferably ion-bonded to the nitrogen atom of the repeating unit having a basic nitrogen atom as an amide bond or a carboxylic acid salt.

The number of atoms of the oligomer chain or the polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000 from the viewpoints of dispersibility, dispersion stability, and developability.

The number average molecular weight of Y is preferably 1,000 to 50,000, particularly 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability.

The branched chain structure represented by Y is preferably linked to two or more of the main chain chain in one molecule of the resin, particularly preferably 5 or more.

In particular, it is also preferable that Y has a structure represented by the general formula (III-1).

[Chemical Formula 6]

In the general formula (III-1), Z represents a polymer or oligomer having a polyester chain as a partial structure, and is a group in which a carboxyl group is removed from a polyester having a free (free) carboxylic acid represented by the following general formula (IV).

(7)

In the general formula (IV), Z is synonymous with Z in the general formula (III-1). When the specific dispersion resin contains the repeating unit represented by the general formula (I-3) or (II-3), it is also preferable that Y 'is the general formula (III-2).

[Chemical Formula 8]

In the general formula (III-2), Z is synonymous with Z in the general formula (III-1).

(IV-1) a polycondensation of a carboxylic acid and a lactone, (IV-2) a polycondensation of a carboxylic acid containing a hydroxyl group, (IV- 3) polycondensation of divalent alcohol and divalent carboxylic acid (or cyclic acid anhydride).

(IV-1) The carboxylic acid used in the polycondensation reaction of the carboxylic acid and the lactone is preferably an aliphatic carboxylic acid (preferably a linear or branched carboxylic acid having 1 to 30 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid and cyclohexanoic acid), hydroxyl group-containing carboxylic acids (linear or branched Hydroxy group-containing carboxylic acids are preferred, and examples thereof include glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12- Decanoic acid, 12-hydroxystearic acid, 2,2-bis (hydroxymethyl) butyric acid, and the like. In particular, a straight chain aliphatic carboxylic acid having 6 to 20 carbon atoms or a hydroxyl group-containing carboxylic acid having 1 to 20 carbon atoms . These carboxylic acids may be mixed and used. The lactone may be any of known lactones and may be, for example,? -Propiolactone,? -Butyrolactone,? -Butyrolactone,? -Hexanolactone,? -Octanolactone,? -Valerolactone, ? -caprolactone,? -dopedanolactone,? -caprolactone,? -caprolactone,? -dodecanolactone and? -methyl- -butyrolactone, and in particular,? -caprolactone is preferable from the viewpoints of reactivity and availability desirable.

These lactones may be used by mixing a plurality of kinds. The introduction ratio of the carboxylic acid and the lactone in the reaction is not uniquely determined because it depends on the molecular weight of the objective polyester chain. The ratio of carboxylic acid: lactone is preferably 1: 1 to 1: 1,000, more preferably 1: 3 to 1: 500 is particularly preferable.

(IV-2) The hydroxyl group-containing carboxylic acid in the polycondensation of the hydroxyl group-containing carboxylic acid is the same as the hydroxyl group-containing carboxylic acid in the above (IV-1), and the preferable range is also the same.

The dihydric alcohol in the polycondensation reaction of (IV-3) a dihydric alcohol and a dicarboxylic acid (or cyclic acid anhydride) is preferably a straight chain or branched aliphatic diol (diol having 2 to 30 carbon atoms, For example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5- 1,6-hexanediol, 1,8-octanediol, and the like), and an aliphatic diol having 2 to 20 carbon atoms is particularly preferred.

As the dicarboxylic acid, a straight or branched divalent aliphatic carboxylic acid (a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms is preferable, and examples thereof include succinic acid, maleic acid, adipic acid, sebacic acid, dodecane diacid, glutaric acid Succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, tartaric acid, malic acid and the like). In addition, acid anhydrides equivalent to these divalent carboxylic acids (for example, succinic anhydride, anhydroglutaric acid, etc.) may be used.

The divalent carboxylic acid and the dihydric alcohol are preferably introduced in a molar ratio of 1: 1. This makes it possible to introduce a carboxylic acid at the terminal.

The polycondensation in the production of the polyester is preferably carried out by adding a catalyst. As the catalyst, a catalyst functioning as a Lewis acid is preferable. For example, a Ti compound (for example, Ti (OBu) ₄ , Ti (O-Pr) ₄ or the like), a Sn compound (for example, Dibutyltin oxide, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutoxide, stannic chloride, etc.), protonic acid (e.g., sulfuric acid, para toluenesulfonic acid and the like). The amount of the catalyst is preferably from 0.01 mol% to 10 mol%, and particularly preferably from 0.1 mol% to 5 mol%, based on the molar amount of all the monomers. The reaction temperature is preferably 80 ° C to 250 ° C, and particularly preferably 100 ° C to 180 ° C. The reaction time varies depending on the reaction conditions, but is generally from 1 hour to 24 hours.

The number average molecular weight of the polyester can be measured as a polystyrene reduced value by the GPC method. The number average molecular weight of the polyester is 1,000 to 1,000,000, preferably 2,000 to 100,000, and particularly preferably 3,000 to 50,000. When the molecular weight is within this range, both dispersibility and developability can be achieved.

Y is a polyester obtained by polycondensation of (IV-1) a carboxylic acid and a lactone, and (IV-2) a polycondensation of a hydroxyl group-containing carboxylic acid , From the viewpoint of ease of manufacture.

Specific examples of the specific dispersing resin [(A-1) to (A-60)] are shown below by the specific structure of the repeating unit of the resin and the combination thereof, but the present invention is not limited thereto. K is from 1 to 80, l is from 10 to 90, m is from 0 to 80, n is from 0 to 70, and k + 1, m and n are each a polymerization molar ratio of repeating units, l + m + n = 100. p and q represent the number of connected chains of the polyester chain, and independently represent 5 to 100,000. R 'represents a hydrogen atom or an alkoxycarbonyl group.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

As a method of synthesizing a specific dispersion resin, reference can be made to the description of paragraphs 0081 to 0089 of Japanese Laid-Open Patent Publication No. 2009-203462, the contents of which are incorporated herein by reference.

The specific dispersion resin preferably has a weight average molecular weight of 3,000 to 100,000, more preferably 5,000 to 55,000, and even more preferably 7,000 to 20,000. The presence of a nitrogen atom in the repeating unit (i) having a nitrogen atom in a specific dispersion resin can be confirmed by a method such as acid titration and the presence of a functional group having a pKa of 14 or less and the presence of a functional group The bonding of the repeating unit with the nitrogen atom can be confirmed by a method such as base titration, nuclear magnetic resonance spectroscopy or infrared spectroscopy. The point (ii) having the oligomer chain or the polymer chain Y of 40 to 10,000 atoms in the side chain can be confirmed by a nuclear magnetic resonance spectroscopy or GPC method.

Specific examples of the specific dispersion resin are as follows. In a specific dispersion resin of the following structure, k: l: m: n = 25: 40: 5: 30 ( polymerization molar ratio), shows the p = 60, q = 60, R is _{C (= O) C 7 H} 15 . The weight average molecular weight of the specific dispersion resin is 10,000. The amine value of the specific dispersion resin is 45 (mgKOH / g) and the acid value is 32.3 (mgKOH / g). The specific dispersion resin may be contained in only one kind of the composition of the present invention, or may contain two or more kinds thereof.

[Chemical Formula 14]

<< Pigment Derivatives >>

The composition of the present invention may further contain a pigment derivative. The pigment derivative is a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group or a phthalimide methyl group. The pigment derivative preferably contains a pigment derivative (acid derivative) having an acidic group or a pigment derivative (basic derivative) having a basic group from the viewpoints of dispersibility and stability of the pigment, and the pigment derivative preferably contains at least one acidic derivative Is more preferable. Also preferred are amine salts or metal salts of acidic derivatives (for example, salts of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and the like).

Examples of the organic pigments for constituting the pigment derivative include pigments such as diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perynone pigments, , Thioindigo-based pigments, isoindoline-based pigments, isoindoline-based pigments, quinophthalone-based pigments, and metal complex system pigments.

The acid group of the pigment derivative is preferably a sulfonic acid, a carboxylic acid or a salt thereof (a salt is preferably a quaternary ammonium salt such as tetramethylammonium salt or tetrabutylammonium salt), more preferably a carboxylic acid group or a sulfonic acid group , And a sulfonic acid group is particularly preferable. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.

As the pigment derivative, a quinoline-based, benzimidazolone-based, and isoindoline-based pigment derivative is particularly preferable, and a quinoline-based and benzimidazolone-based pigment derivative is more preferable. Particularly, a pigment derivative having the following structure is preferable.

[Chemical Formula 15]

In the general formula (P), A represents a partial structure selected from the following general formulas (PA-1) to (PA-3). B represents a single bond, or a (t + 1) -configured linking group. C represents a single bond, -NH-, -CONH-, -CO ₂ -, -SO ₂ NH-, -O-, -S- or SO ₂ -. D represents a single bond, an alkylene group, a cycloalkylene group or an arylene group. E represents -SO ₃ H, -SO ₃ M (M represents an alkali metal atom), -CO ₂ H or N (Rpa) (Rpb). Rpa and Rpb each independently represent an alkyl group or an aryl group, and Rpa and Rpb may be connected to each other to form a ring. t represents an integer of 1 to 5;

[Chemical Formula 16]

In the formulas (PA-1) and (PA-2), Rp1 represents an alkyl group or an aryl group having 1 to 5 carbon atoms. In the general formula (PA-3), Rp2 represents a hydrogen atom, a halogen atom, an alkyl group, or a hydroxyl group. s represents an integer of 1 to 4; When s is 2 or more, a plurality of Rp2 may be the same or different. In formula (PA-1) and the general formula (PA-3), Rp3 is a single _{bond, -NH-, -CONH-, -CO 2 -} , -SO 2 NH-, -O-, -S- or SO ₂ -. * Denotes the connection with B

In the formula (P), Rp1 is preferably a methyl group or a phenyl group, and most preferably a methyl group. In the general formula (PA-3), Rp2 is preferably a hydrogen atom or a halogen atom, and most preferably a hydrogen atom or a chlorine atom.

In the general formula (P), the linking group of (t + 1) represented by B includes, for example, an alkylene group, a cycloalkylene group, an arylene group and a heteroarylene group. Among them, a linking group represented by the following structural formulas (PA-4) to (PA-9) is particularly preferable.

[Chemical Formula 17]

Among the structural formulas (PA-4) to (PA-9), a pigment derivative having a linking group represented by the structural formula (PA-5) or (PA-8) as B is preferable because of better dispersibility.

Examples of the alkylene group, cycloalkylene group and arylene group represented by D in the general formula (P) include methylene, ethylene, propylene, butylene, pentylene, hexylene, decylene, cyclopropylene, cyclobutylene, Pentylene, cyclohexylene, cyclooctylene, cyclodecylene, phenylene, naphthylene and the like. Among them, D is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms.

In the general formula (P), when E represents -N (Rpa) (Rpb), examples of the alkyl group and the aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, an octyl group, a decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group , A cyclodecyl group, a phenyl group, and a naphthyl group. As Rpa and Rpb, an alkyl group is particularly preferable, and an alkyl group having 1 to 5 carbon atoms is most preferable. T is preferably 1 or 2.

Specific examples of the pigment derivative are shown below, but the present invention is not limited thereto. As other pigment derivatives, reference can be made to paragraphs 0162 to 0183 of Japanese Laid-Open Patent Publication No. 2011-252065 and paragraphs 0019 to 0035 of Japanese Laid-Open Patent Publication No. 2004-217842, the contents of which are incorporated herein by reference.

[Chemical Formula 18]

When the pigment derivative is contained in the composition of the present invention, the content of the pigment derivative is preferably from 1 to 30 mass%, more preferably from 3 to 20 mass%, based on the total mass of the pigment in the composition. The pigment derivative may be used alone or in combination of two or more.

<< Polymerizable compound >>

The composition of the present invention may further contain a polymerizable compound. As the polymerizable compound, a known polymerizable compound which can be crosslinked by radicals, acids and heat can be used. For example, a polymerizable compound containing an ethylenic unsaturated bond, cyclic ether (epoxy, oxetane) . The polymerizable compound is suitably selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds from the viewpoint of sensitivity. Of these, polyfunctional polymerizable compounds having four or more functionalities are preferable, and polyfunctional polymerizable compounds having five or more functionalities are more preferable.

Such a group of compounds is well known in the art and can be used in the present invention without any particular limitation. These may be, for example, monomers, prepolymers, that is, any of a dimer, a trimer and an oligomer or a mixture thereof and a chemical form thereof such as 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 and an aliphatic polyhydric alcohol compound, and an amide 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 epoxy, or a monofunctional or polyfunctional carboxylic acid And a dehydration condensation reaction product with a water-soluble organic solvent are suitably used. In addition, 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 a monofunctional or polyfunctional alcohol, an amine or a thiol, Unsaturated carboxylic acid esters or amides having a cleavable substituent, and mono- or polyfunctional alcohols, amines and thiol substitution reactions are also suitable. As another example, a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like may be used in place of the above unsaturated carboxylic acid.

As specific compounds of these compounds, compounds described in paragraphs [0095] to [0108] of JP-A No. 2009-288705 can be suitably used in the present invention.

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 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, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, and (meth) acrylate, Japanese Examined Patent Publication 48 (Meth) acrylates described in JP-A-41708, JP-A-50-6034, JP-A-51-37193, Polyester acrylates described in JP-A-48-64183, JP-A-49-43191, JP-A-52-30490, epoxies which are reaction products of epoxy resin and (meth) acrylic acid And polyfunctional acrylates and methacrylates such as acrylates, 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 an ethylenic unsaturated group as a bifunctional group, such as those described in JP-A-2010-160418, JP-A-2010-129825 and JP-B-4364216, Or more, and a carboxy resin can also be used.

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, the compounds described in paragraphs [0254] to [0257] of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

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

[Chemical Formula 19]

[Chemical Formula 20]

In the above general formula, 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 plural Rs present in each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) is -OC (= O) CH = CH ₂ or -OC ) C (CH ₃₎ represents a group represented by = CH _2.

Specific examples of the polymerizable compounds represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-269779 Can be used.

Further, in JP-A 10-62986, ethylene oxide or propylene oxide is added to the polyfunctional alcohol represented by the general formulas (1) and (2) together with the specific examples thereof and then (meth) acrylated The compound may 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) (Trade name: A-DPH-12E, manufactured by Shin-Nakamura Kagaku K. K.) and ethylene glycol-modified diethylene glycol diacrylate (ethylene glycol diacrylate) , And a structure in which a propylene glycol residue is interposed. These oligomer types can also be used. As a commercially available product, M-305 manufactured by Toagosei Co., Ltd. may be used.

The polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, it can be used as it is. If necessary, the nonylromatic carboxylic acid anhydride is reacted with the hydroxyl group of the above- . 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.

The monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid and a multifunctional monomer having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride, Preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd.

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 preferable acid value of the polyfunctional monomer having an acid group is 0.1 mg KOH / g to 40 mg KOH / g, particularly preferably 5 mg KOH / g 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 deteriorates, resulting in poor curability such as surface smoothness of the pixel. Therefore, when two or more kinds of 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 groups as the entire polyfunctional monomer to fall within the above range.

It is also preferable that the polymerizable compound contains a polyfunctional monomer having a caprolactone structure.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, (Meth) acrylic acid and? -Caprolactone obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine and the like with (meth) acrylic acid and? -Caprolactone, Modified polyfunctional (meth) acrylate. Among them, a polyfunctional monomer having a caprolactone structure represented by the following general formula (Z-1) is preferable.

[Chemical Formula 21]

In the general formula (Z-1), all six R's are groups represented by the following general formula (Z-2), or one to five of the six R's are groups represented by the general formula (Z-2) And the remainder is a group represented by the following general formula (Z-3).

[Chemical Formula 22]

In the general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

(23)

In the general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (in the formulas (Z-1) to (Z-3) = 1, the number of groups represented by formula (2) = 2 and R ¹ are all hydrogen atoms), DPCA-30 (number of groups represented by the same formula, m = 1 and formula (Z- (Wherein R ¹ is a hydrogen atom), DPCA-60 (the compound represented by the formula: m = 1, the number of groups represented by the formula (Z-2) = 6 and R ¹ are all hydrogen atoms), DPCA-120 M = 2 in the formula, the number of groups represented by the formula (Z-2) = 6, and R ¹ are all hydrogen atoms).

In the present invention, the polyfunctional monomers having a caprolactone structure may be used alone or in combination of two or more.

It is also preferable that the specific monomer in the present invention is at least one member selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

&Lt; EMI ID =

E in the general formulas (Z-4) and (Z-5) each independently represents - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) , Y represents independently 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 (Z-4), 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 0 to 40 It is an integer. 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, 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 (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the general formula (Z-5), 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.

The - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) O) - in the general formula (Z-4) or the general formula A form in which the terminal is bonded to X is preferable.

The compounds represented by the above general formula (Z-4) or (Z-5) 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 formula (Z-4) or (Z-5) 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 (Z-4) or the general formula (Z-5) can be produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to ring opening skeleton And (meth) acryloyl groups are introduced into the terminal hydroxyl groups of the ring-opening skeleton by reaction 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 (Z-4) or the general formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

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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(26)

Examples of commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include 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 curable composition having an extremely 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.).

JER-827, JER-834, JER-1001, JER-1002, JER-1003, and JER-823 as the bisphenol A type epoxy resin having an epoxy group, as the cyclic ether (epoxy, oxetane) EPICLON1051, EPICLON1051, and EPICLON1055 (manufactured by DIC Corporation), and the like, and bisphenol F type epoxy resin (trade name: JER-1055, JER- (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation), and JER-806, JER-807, JER-4004, JER-4005, JER- JER-152, JER-157S70, and JER-157S65 (above, Japan Epoxy Resin Co., Ltd.) as phenol novolak type epoxy resin, EPICLON N-760, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation)) and EPICLON N-660 and EPICLON N-760 EPICLON N-670, EPICLON N-670, EPICLON N-680, EPICLON N-690, ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (manufactured by ADEKA Corporation) as the aliphatic epoxy resin, Celloxide 2021P , 2-epoxy-4- (2-oxiranyl) cyclohexyl of 2,2-bis (hydroxymethyl) -1-butanol, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE- EX-214L, EX-216L, EX-321L, EX-321L, EX-321L, EX-321L, EX- NC-2000 (manufactured by Nippon Oil &amp; Chemical Co., Ltd.), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP- , NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA) and JER-1031S (manufactured by Japan Epoxy Resin Co., Ltd.). Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

Details of the structure, the use of the polymerizable compound, whether it is used singly or in combination, and the amount of the polymerizable compound can be arbitrarily set in accordance with the final performance design of the coloring 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 formed by the coloring composition, it is preferable to use trifunctional or more functional groups and the number of functional groups different from each other (e.g., acrylic acid ester, methacrylic acid ester, styrene series compound, vinyl ether group compound) A method of controlling both sensitivity and strength 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 from the viewpoint that the developability of the colored composition can be controlled and an excellent pattern forming ability can be obtained.

The compatibility and dispersibility with other components (for example, a photopolymerization initiator, a dispersant, an alkali-soluble resin, etc.) contained in the coloring composition is also an important factor in 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.

The content of the polymerizable compound in the composition of the present invention is preferably from 0.1% by mass to 90% by mass, more preferably from 1.0% by mass to 60% by mass, more preferably from 2.0% by mass to 40% by mass relative to the total solid content in the colorant composition % Is particularly preferable.

The composition of the present invention may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more kinds are included, the total amount is preferably in the above range.

<Polyfunctional thiol compound>

The 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 and the like. 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 particularly preferably an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (II) to (IV), and compounds represented by (II) are particularly preferable. These polyfunctional thiols can be used singly or in combination.

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The content of the polyfunctional thiol compound in the 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 in the composition.

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.

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

<Polymerization Initiator>

The composition of the present invention may further contain a polymerization initiator. By containing a polymerization initiator, the sensitivity can be further improved.

As the polymerization initiator, a photopolymerization initiator is preferable. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. In addition, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of the monomer.

The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, (Such as hexaarylbaiimidazole), oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, And an oxime compound is preferable.

As the biimidazole-based compound, reference can be made, for example, to the description of paragraphs 0067 to 0076 of Japanese Laid-Open Patent Publication No. 2013-209623, the contents of which are incorporated herein by reference.

From the viewpoint of exposure sensitivity, it is also possible to use a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, Oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3 -Aryl-substituted coumarin compound is preferable.

More preferably, a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, a triarylimidazole compound, a benzimidazole compound , An onium compound, a benzophenone compound, and an acetophenone compound, and is a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, And at least one compound selected from the group consisting of a thiol compound and a thiol compound is particularly preferable. The triarylimidazole compound may be a mixture with benzimidazole.

Specifically, as the trihalomethyltriazine compound, the following compounds are exemplified. Ph is a phenyl group.

[Chemical Formula 29]

As the triarylimidazole compound and the benzimidazole compound, the following compounds are exemplified.

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As the trihalomethyltriazine compound, a commercially available product may be used, and for example, TAZ-107 (Midori Kagaku) may be used.

Particularly, when the composition of the present invention is used in the production of a color filter provided in a solid-state imaging device, it is important to form a fine pattern in a sharp shape, so that it is cured and developed with no residue on the unexposed portion . From this viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. Particularly, in the case of forming a fine pattern in a solid-state image pickup device, stepper exposure is used for curing exposure. Since this exposure device may be damaged by halogen, and the addition amount of the polymerization initiator should also be suppressed to a low level, Taking this into consideration, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern such as a solid-state imaging element.

As the halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Japanese Patent Publication No. 53-133428, the compound described in German Patent Publication No. 3337024, the compound described in JP-A-3337024 by FC Schaefer et al. Org. Chem .; 29, 1527 (1964), compounds described in Japanese Laid-Open Patent Publication No. 62-58241, compounds described in Japanese Laid-Open Patent Publication No. 5-281728, compounds described in Japanese Laid-Open Patent Publication No. 5-34920, A compound described in Japanese Patent Publication No. 4212976, particularly a compound described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph No. 0075, and the like.

As other photopolymerization initiators other than the above, acridine derivatives are exemplified. Specific examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph number 0076, and the contents thereof are incorporated herein by reference.

Examples of the ketone compound include compounds described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph number 0077, and the contents thereof are incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969 or the acylphosphine oxide-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm may be used. As the acylphosphine-based initiator, commercially available IRGACURE-819 and DAROCUR-TPO (trade names, all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound. As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used.

Examples of the oxime compounds such as oxime derivatives suitably used as the photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan- 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

As oxime compounds, see J. C. S. Perkin II (1979) pp. Pp. 1653-1660, J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797, JP-A 2006-342166, etc. .

IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF) and TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) .

As oxime compounds other than the above-mentioned materials, compounds described in Japanese Unexamined Patent Publication No. 2009-519904 in which oxime is linked to carbazole N, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in Japanese Unexamined Patent Application Publication Nos. 2002-15025 and 2009-292039 where nitro groups are introduced, ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton in the same molecule The compound described in U.S. Patent Publication No. 7556910, the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, or the like may be used.

Preferably, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can be suitably used. Of the cyclic oxime compounds, cyclic oxime compounds which are covalently bound to the carbazole dyes described in JP-A-2010-32985 and JP-A-2010-185072 are preferred from the viewpoint of high sensitivity due to their high light absorption.

The compound described in Japanese Unexamined Patent Application Publication No. 2009-242469 having an unsaturated bond at a specific site of an oxime compound can also be suitably used because high sensitivity can be achieved by regenerating active radicals from polymerization inert radicals.

Particularly preferred are oxime compounds having a specific substituent group as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

Specifically, as the oxime compound which is a photopolymerization initiator, a compound represented by the following general formula (OX-1) is preferable. Further, the N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the form (E) and the form (Z).

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In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

Examples of the monovalent non-metallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. In addition, the substituent described above may be further substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

Specific examples of the general formula (OX-1) are shown below, but it is needless to say that the present invention is not limited thereto.

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

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000 from the viewpoint of sensitivity.

Specific examples of the molar extinction coefficient of the compound include an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), an ethyl acetate solvent at a concentration of 0.01 g / L It is preferable to measure it.

When the composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass relative to the total solid content of the composition desirable. By setting to such a range, more excellent sensitivity and pattern formability can be obtained.

The composition of the present invention may contain only one type of photopolymerization initiator or two or more types of photopolymerization initiators. When two or more kinds are included, the total amount is preferably in the above range.

<< Alkali-soluble resin >>

The composition of the present invention may further contain an alkali-soluble resin.

As the alkali-soluble resin, a linear organic polymer may 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 capable of promoting alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, preferably soluble in an organic solvent and capable of being developed by a weakly alkaline aqueous solution , And (meth) acrylic acid are particularly preferable. These acid groups may be only one kind, or two or more kinds.

Examples of the monomer capable of imparting an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And monomers having an isocyanate group such as cyanatoethyl (meth) acrylate. The monomers for introducing these acid groups may be one kind or two or more kinds. In order to introduce an acid group into the alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization (hereinafter sometimes referred to as " monomer for introducing an acid group ") is used as a monomer component The polymerization may be carried out.

When an acid group is introduced as a monomer component capable of imparting an acid group after polymerization, a treatment for imparting an acid group as described later, for example, is required after polymerization.

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, a monomer component essentially comprising a compound represented by the following formula (ED) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as " (A).

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

(ED2)

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In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2010-168539.

Thus, the composition of the present invention can form a cured coating film having excellent heat resistance as well as excellent transparency. Of the above-mentioned ether dimer represented by 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 includes, for example, methyl, ethyl, , Straight-chain or branched alkyl groups such as isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; 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 (methylene)] bis- (Isopropyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (n-propyl) ] Bis-2-propenoate, di (n-butyl) -2,2 '- [oxybis (Methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '- [oxybis Di (lauryl) -2,2'- [oxybis (methylene)] bis-2-propenoate, di (lauryl) Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di- Methoxyethyl) -2,2 '- [oxybis Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, dibenzyl- Bis (2-propenyl) bis [2-propenyl] biphenyl-2, 2 '- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- (Methylene)] bis-2-propenoate, di (tert-butylcyclohexyl) -2,2 '- [oxybis Di (tricyclodecanyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, diadamanthyl- Di (2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- 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.

The alkali-soluble resin may contain a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).

In general 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.

In order to improve the crosslinking efficiency of the coloring composition of the present invention, an alkali-soluble resin having a polymerizable group may be used. When such an alkali-soluble resin is used, the effect of the present invention tends to further improve the solvent resistance. In addition, light resistance and heat resistance tend to be improved. 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 An unsaturated group-containing acrylic resin obtained by reaction of an urethane-modified polymerizable double bond-containing acrylic resin obtained by the reaction of an acrylic resin, an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the 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 207 and JP-A No. 2003-335814, a resin obtained by basic treatment of a resin having on its side chain 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 a (meth) acrylic acid benzyl / (meth) acrylic acid copolymer and a (meth) benzyl acrylate / (meth) acrylic acid / other monomer is suitable. (Meth) acrylic acid benzylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate copolymer disclosed in Japanese Patent Application Laid-open No. 7-140654 (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic 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 copolymers and the like, and particularly preferred are copolymers of benzyl methacrylate / methacrylic acid and the like.

As the alkali-soluble resin, reference may be made to Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to [0685] to [0700] of US Patent Application Publication No. 2012/0235099) Which is incorporated herein by reference.

In addition, the copolymer (B) described in paragraphs Nos. 0029 to 0063 described in JP-A-2012-32767 and the alkali-soluble resin used in the examples, and the copolymer described in paragraphs 0088 to 0098 of JP-A- The binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Laid-Open Patent Publication No. 2012-137531 and the binder resin used in the examples, and the binder resin used in the examples of Japanese Laid-Open Patent Publication No. 2013-024934 To 0143 and binder resins used in the examples, paragraphs 0092 to 0098 of Japanese Laid-Open Patent Publication No. 2011-242752 and binder resins used in the examples, and Japanese Laid-Open Patent Publication No. 2012-032770, paragraph No. 0030 It is preferable to use the binder resin as described in [0072]. The contents of which are incorporated herein by reference. More specifically, the following resins are preferable.

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The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and even more preferably 70 mgKOH / g 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 particularly preferably 7,000 to 20,000.

When the alkali-soluble resin is contained in the coloring composition, the content of the alkali-soluble resin is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 12% by mass relative to the total solid content of the coloring composition , And particularly preferably 3% by mass to 10% by mass.

The composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds of alkali-soluble resins. When two or more kinds are included, the total amount is preferably in the above range.

<< Solvent >>

The composition of the present invention may further contain a solvent. The solvent is not particularly limited so far as it satisfies solubility of each component and applicability of the composition. The solvent is preferably an organic solvent.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, cyclohexyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate , Butyl butyrate, methyl lactate, ethyl lactate, alkyloxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (for example, methyl methoxyacetate, methoxyacetate, methoxyacetate, ethoxy Ethoxyacetic acid and the like), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, 3-methoxypropionate Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and the like), 2-oxypropionic acid alkyl esters such as 2-oxypropyl Propyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- (2-methoxypropionate), 2- Methyl 2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol Diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, di Ethylene glycol mono Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, Toluene, xylene, and the like as the aromatic hydrocarbon, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, have.

The content of the solvent in the composition of the present invention is preferably from 50 to 95% by mass, more preferably from 60 to 90% by mass. The composition of the present invention may contain only one kind of solvent, or two or more types of the solvent. When two or more kinds are included, the total amount is preferably in the above range.

<< UV absorber >>

The composition of the present invention may further contain an ultraviolet absorber. With such a constitution, the occurrence of residue can be further suppressed.

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 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.

(38)

[Chemical Formula 39]

(40)

(41)

When the 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%, and preferably 2 to 6 mass%, based on the total solid content of the composition More preferable. The composition of the present invention may contain only one kind of ultraviolet absorber, or two or more kinds of ultraviolet absorbers. When two or more kinds are included, the total amount is preferably in the above range.

<< Adhesion improver >>

The composition of the present invention may further contain an adhesion improver. As the adhesion improver, for example, the adhesion improver described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638 may suitably be used. Specific examples include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-phenyl Thiazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, And 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like. As the adhesion improver, a silane coupling agent is preferable.

The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group chemically bondable to an inorganic material. (Meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group is preferable as the group having such a group Among them, those having a (meth) acryloyl group or a glycidyl group are preferable.

The silane coupling agent is also preferably a silane compound having at least two functional groups having different reactivity in one molecule, particularly preferably having an amino group and an alkoxy group as a functional group. Examples of such a silane coupling agent include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name: KBM-602 manufactured by Shin-Etsu Chemical Co., -Aminopropyl-trimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd.), N -? - aminoethyl -? - aminopropyltriethoxysilane Aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyltriethoxysilane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE- KBE-903) and 3-methacryloxypropyltrimethoxysilane (trade name KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.).

Specific examples of the silane coupling agent include, but are not limited to, the following compounds.

(42)

The content of the adhesion improver is preferably from 0.001% by mass to 20% by mass, more preferably from 0.01% by mass to 10% by mass, and particularly preferably from 0.1% by mass to 5% by mass, based on the solid content of the composition of the present invention.

<< Surfactant >>

The composition of the present invention may contain various surfactants 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.

Particularly, since the composition of the present invention contains a fluorine-containing surfactant, the uniformity of liquid coating thickness and the liquid-repellency (liquid-repellency) can be improved by improving the liquid property Can be 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.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, and SC-101 (manufactured by Sumitomo 3M Limited), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Glass Co., Ltd.) have.

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

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 silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," Tory Silicone SH8400 "and" TSF-4440 "manufactured by Momentive Performance Materials "KF341", "KF6001", and "KF6002" manufactured by Shin-Etsu Silicones Co., Ltd., "BYK307", "BYK323", and "BYK330" manufactured by Big Chemie.

When the surfactant is contained in the composition of the present invention, the addition amount of the surfactant is preferably from 0.001 mass% to 2.0 mass%, more preferably from 0.005 mass% to 1.0 mass%, based on the total mass of the composition.

The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more kinds are included, the total amount is preferably in the above range.

<< Polymerization inhibitor >>

The composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cerium salt.

The content of the polymerization inhibitor is preferably 0.001 to 1% by mass, more preferably 0.005 to 0.1% by mass, based on the total solid content of the composition of the present invention. The polymerization inhibitor may be used alone or in combination of two or more.

The composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cerium salt.

The content of the polymerization inhibitor is preferably 0.001 to 1% by mass, more preferably 0.005 to 0.1% by mass, based on the total solid content of the composition of the present invention. The polymerization inhibitor may be used alone or in combination of two or more.

&Lt; Method for producing radiation sensitive composition &gt;

The process for producing the composition of the present invention comprises a CI Pigment Green 36, a CI Pigment Yellow 150, a CI Pigment Yellow 185 and a resin, wherein the content of CI Pigment Green 36 to 100 parts by mass of the total pigment is 80 to 86 Wherein the mass ratio of CI Pigment Yellow 150 to CI Pigment Yellow 185 is in the range of 65.4: 35.6 to 79.0: 21.0, the acid value of the resin is 20 to 50, and the ratio of the amine value to the acid value is 0.85 to 1.45. Liquid is used.

The method for producing a composition of the present invention includes a step of covalently curing a pigment including CI Pigment Green 36, CI Pigment Yellow 150 and CI Pigment Yellow 185 using the resin having the amine value and the acid value . With this configuration, the effect of the present invention can be more effectively exhibited. In particular, the filterability of the composition after preparation can be improved.

&Lt; Cured Film, Pattern Forming Method, Color Filter, and Manufacturing Method of Color Filter >

Next, the cured film, the pattern forming method and the color filter according to the present invention will be described in detail with reference to its manufacturing method.

The cured film of the present invention is formed by curing the composition of the present invention. Such a cured film is preferably used for a color filter.

In the pattern forming method of the present invention, the composition of the present invention is applied on a support to form a radiation-sensitive composition layer, and unnecessary portions are removed to form a coloring pattern.

The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) of a color filter.

In the composition of the present invention, a pattern may be formed by a so-called photolithography method to produce a color filter, or a pattern may be formed by a dry etching method.

That is, in a first method of producing a color filter of the present invention, a step of forming a radiation-sensitive composition layer by applying a coloring composition on a support, a step of exposing the radiation-sensitive composition layer in a pattern form, To form a coloring pattern, is exemplified as an example of a method of manufacturing a color filter.

A second manufacturing method of the color filter of the present invention is a method of manufacturing a color filter comprising the steps of applying a coloring composition on a support to form a radiation-sensitive composition layer and curing to form a colored layer; forming a photoresist layer on the colored layer , A step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the colored layer using the resist pattern as an etching mask.

In the present invention, a photolithography method is more preferable.

The details of these will be described below.

Hereinafter, each step in the pattern forming method of the present invention will be described in detail with reference to a method of manufacturing a color filter for a solid-state imaging device, but the present invention is not limited to this method. Hereinafter, a color filter for a solid-state imaging device may be simply referred to as a "color filter ".

<< Process of forming a radiation-sensitive composition layer >>

In the step of forming the radiation sensitive composition layer, the composition of the present invention is applied on a support to form a radiation sensitive composition layer.

Examples of the support that can be used in the present step include a solid-state imaging device (solid-state imaging device) 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 a device can be used.

The coloring 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 formation surface side (back surface).

The color pattern of the solid-state imaging element or the back surface of the substrate for a solid-state imaging element may be provided with a light-shielding film.

If necessary, an undercoat layer may be provided on the support in order to improve adhesion with the upper layer, prevent diffusion of the substance, or planarize the surface of the substrate. The undercoat layer may contain a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like, and these components may be appropriately selected from the components to be incorporated in the composition of the present invention desirable.

As a method of applying the composition of the present invention onto a support, various coating methods such as slit coating, inkjet coating, spin coating, flex coating, roll coating, screen printing and the like can be applied.

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

<Step of forming a pattern by photolithography method>

<< Process of Exposure >>

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, for example, using an exposure apparatus such as a stepper. Thus, a cured film is obtained.

As the radiation (light) usable at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). Irradiation dose (exposure dose) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2 is preferably 50mJ / cm ² ~ 1000mJ / cm ^2, and more ^{preferably, 80mJ / cm 2 ~ 500mJ /} cm 2 in particular.

The thickness of the cured film (colored film) is preferably 1.0 占 퐉 or less, more preferably 0.1 占 퐉 to 0.9 占 퐉, and still more preferably 0.2 占 퐉 to 0.8 占 퐉.

When the film thickness is 1.0 mu m or less, high resolution and high adhesion can be obtained, which is preferable.

In the present step, a cured film having a thin film thickness of 0.7 m or less can be suitably formed, and the obtained cured film is subjected to development processing in a pattern forming step described later to improve the developability, surface roughness , And a colored pattern excellent in the pattern shape can be obtained.

<< Development Process >>

Subsequently, the alkali developing treatment is performed so that the radiation-sensitive composition layer in the unexamined portion in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured portion.

As the developing solution, an organic alkali developing solution which does not cause damage to the imaging element, circuit, etc. on the ground (base) is preferable. The developing temperature is usually 20 to 30 DEG C, and the developing 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 newly supplying the developing solution may be repeated several times.

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene, and these alkaline agents An alkaline aqueous solution diluted with pure water to a concentration of 0.001 mass% to 10 mass%, preferably 0.01 mass% to 1 mass% is preferably used as the developer.

As the developing solution, an 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 purified water after development.

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

In this post-baking treatment, the coated film after development 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.

&Lt; Case where pattern is formed by dry etching >

In the case of forming a pattern by dry etching, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2013-64993, the contents of which are incorporated herein by reference.

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 image pickup device, as the other process, if necessary. For example, it may include a curing step of curing the formed color 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 forming a pattern.

In addition, when the coloring composition of the present invention is used, for example, clogging of nozzles and piping in the dispenser discharge portion, contamination due to deposition, sedimentation and drying of the coloring composition or pigment into the coater may occur. Therefore, in order to efficiently clean the contamination caused by the composition of the present invention, it is preferable to use the solvent relating to the present composition described above as a cleaning liquid. Also, 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 and JP-A-2007-281523 are also suitable for cleaning and removing the coloring composition of the present invention Can be used to make.

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. It is particularly preferable that the mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) has a ratio of 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 uses the composition of the present invention, it is possible to perform exposure with excellent exposure margin, and the colored pattern (colored pixel) formed is excellent in pattern shape, The color characteristic is excellent because the residue in the developing portion is suppressed.

The color filter 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 CCD or a CMOS of high resolution exceeding one million pixels. The color filter for a solid-state imaging device 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 of the present invention is preferably 2.0 占 퐉 or less, more preferably 1.0 占 퐉 or less, and even more preferably 0.7 占 퐉 or less.

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.

An oxygen barrier film may be formed on the color filter. The oxygen barrier film is preferably provided on the surface of the color filter layer made of the composition of the present invention. As the oxygen shielding film used in the present invention, for example, an oxygen shielding film having an oxygen permeability of 200 ml / m ² · day · atm or more is exemplified. As to the oxygen barrier film, for example, reference may be made to the description of paragraphs 0217 to 0221 of Japanese Laid-Open Patent Publication No. 2011-248197, which is incorporated herein by reference.

<Solid-state image sensor>

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.

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 light-shielding surface and the photodiode light-receiving portion. The device protective film is provided with a light- And a color filter.

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

<Image Display Device>

The color filter of the present invention can be used not only for the solid-state image pickup device but also for an image display apparatus such as a liquid crystal display apparatus and an organic EL display apparatus, and is particularly suitable for use in a liquid crystal display apparatus. The liquid crystal display device provided with the color filter of the present invention is capable of displaying a high-quality image with good display tones and excellent display characteristics.

For the definition of the display device and the details of each display device, refer to, for example, "Electronic display device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued by Sakai Corporation)", "Display device (Ibukisumi Akira, ) Published in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the "next generation liquid crystal display technology ".

The color filter of the present invention may be used in a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Shootpan Co., Ltd., 1996) ". The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

Further, the color filter in the present invention can be used for a bright, high definition COA (Color-filter On Array) method. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. The color filter of the present invention is excellent in color purity, light transmittance and the like and excellent in color tone of a colored pattern (pixel) in that a coloring matter multifunctional material excellent in hue is used. Therefore, a COA type liquid crystal display Device can be provided. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer. In addition, the present invention can be suitably used for the display of the micro-OLED system (micro OLED). These image display methods are described in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (published by Toray Research Center Research Division, 2001).

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. These members are described in, for example, "Market of Liquid Crystal Display Materials and Chemicals, 1994 (published by Shimaguchi Co., Ltd., CMC)", "2003 Current Status and Future Prospects of LCD Related Markets Published by Fuji Chimera Soken Co., Ltd., 2003).

Regarding the backlight, it is described in the SID meeting Digest 1380 (2005) (A. Konno et al.) And in the monthly display December 2005, pages 18-24 (Yamazaki Shimaya), 25-30 pages (Yagi Takaaki) .

When the color filter according to the present invention is used for a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and LED light sources (RGB-LEDs) of red, As the light, it is possible to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

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.

[Example 1]

<Preparation of Pigment Dispersion Composition G-1>

83 parts of CI Pigment Green 36 (PG 36), 5 parts of CI Pigment Yellow 185 (PY 185), 12 parts of CI Pigment Yellow 150 (PY 150) and 30 parts of a specific dispersion resin (A) , 10 parts of the pigment derivative (A), 10 parts of benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (= 60/22/18 [molar ratio], weight average molecular weight: 530 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA ") was added to 10 parts of polyvinyl alcohol (molecular weight: 8,000) to obtain 670 parts of a mixed solution. Using a 0.3 mm diameter zirconia beads, (Manufactured by Nippon Express Co., Ltd.) for 3 hours to prepare a pigment dispersion composition G-1.

The specific dispersing resin (A)

Wherein q represents 60, q represents 60, and R represents C (= O) C (= O) in a specific dispersion resin (A) having the following structures: k: l: m: n = 25: ₇ H ₁₅ . The weight average molecular weight of the specific dispersion resin (A) is 10,000. The amine value of the specific dispersion resin (A) is 45 (mgKOH / g) and the acid value is 32.3 (mgKOH / g). The amine value and the acid value of the specific dispersion resin (A) were measured by the above-mentioned method.

(43)

Pigment dispersion compositions G-2 to G-18 were obtained in the same manner as in the above-mentioned Pigment dispersion composition G-1 except for changing the components as shown in the following table.

[Table 6]

In the table, the specific dispersing resins (B) to (G) were prepared by adjusting the ratios of k, l, m and n of the specific dispersing resin (A). Details are as follows.

Specific dispersion resin (B): Weight average molecular weight (10,000)

Specific dispersion resin (C): Weight average molecular weight (11,000)

Specific dispersion resin (D): Weight average molecular weight (10,000)

Specific dispersion resin (E): Weight average molecular weight (10,000)

Specific dispersion resin (F): Weight average molecular weight (12,000)

Specific dispersion resin (G): Weight average molecular weight (9,000)

Specific dispersion resin (H): Weight average molecular weight (10,000)

Specific dispersion resin (I): Weight average molecular weight (11,000)

Specific dispersion resin (J): Weight average molecular weight (10,000)

&Lt; Pigment Derivative (A) >

Fuming sulfuric acid (25 mass% SO ₃ ) and 450 parts of 101 mass% sulfuric acid adjusted from sulfuric acid were introduced, 45 parts of CI Pigment Yellow 138 was added little by little, and the mixture was reacted at 80 캜 for 3 hours. The reaction solution was added with stirring to 5000 parts of ice water to precipitate sulfone. Subsequently, the resultant was separated by filtration, washed with 2000 parts of 0.1 mass% hydrochloric acid, and further washed with 2000 parts of purified water to obtain a paste of sulfonated CI Pigment Yellow 138. The obtained sulfonated paste was redispersed in 5000 parts of water (pH of the slurry after redispersing was 2.3), and a 25 mass% caustic soda solution was added with stirring to adjust the pH to 11.5. During the pH adjustment, the reaction solution changed from a yellow slurry state to a red solution state. The pH was finely adjusted every 5 minutes and continued for 1 hour. Further, the mixture was heated from pH 11.5 to 60 占 폚 and stirred for 3 hours. To this red solution, an aqueous solution containing 47 parts of aluminum chloride (hexahydrate) was added dropwise little by little to obtain a yellow precipitate. The pH after addition of the total amount was 3.5. Filtered, washed with water and dried to obtain 40 parts of the pigment derivative (A).

&Lt; Pigment Derivative (B) >

20 parts of 5-aminobenzimidazolone and 25 parts of cyanuric chloride were introduced into 300 parts of methanol and reacted at 20 ° C or lower for 2 hours. Subsequently, 34 parts of aminoethane sulfonic acid, 27 parts of sodium hydroxide and 700 parts of water were introduced , Reflux for 4 hours. Subsequently, the mixture was cooled to 60 deg. C and 170 parts of a 10 mass% aluminum sulfate aqueous solution was introduced. After stirring at 60 deg. C for 1 hour, the mixture was filtered, washed with water and dried to obtain 60 parts of a pigment dispersant (B).

&Lt; Pigment Derivative (C) >

40 parts of 5-aminobenzimidazolone and 25 parts of cyanuric chloride were introduced into 500 parts of methanol and reacted at 50 DEG C for 2 hours. Subsequently, 18 parts of 6-aminocaproic acid, 22 parts of sodium hydroxide and 1000 parts of water were introduced , And the mixture was refluxed for 4 hours. Subsequently, the mixture was cooled to 60 deg. C, 450 parts of a 10 mass% stearylamine acetic acid aqueous solution was introduced, stirred at 60 deg. C for 1 hour, filtered, washed with water and dried to obtain 94 parts of a pigment dispersant (C).

&Lt; Pigment Derivative (D) >

(44)

&Lt; Preparation of radiation sensitive composition of Example 1 >

Using the pigment dispersion composition G-1, the following composition was mixed and stirred and filtered to prepare a radiation-sensitive composition of Example 1. The solid content of the radiation sensitive composition of Example 1 was 25 mass%, and the content of the pigment to the total solid content of the radiation sensitive composition was 42%.

<Composition>

Pigment dispersion composition G-1; 70 parts

A photopolymerization initiator (IRGACURE OXE01 [2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione], manufactured by BASF); 1.2 part

Polymerizable compound (A) (trade name: KAYARAD DPHA (manufactured by Nippon Kayaku)); 1.56 part

Polymerizable compound (B) (trade name: A-DPH-12E (Shin-Nakamura Kagaku)); 3.64 part

Alkali-soluble resin (resin 1 below); 2.72 part

Fluorine surfactant (trade name: F-475 (manufactured by DIC)); 0.01 part

The following additive 1 (trade name: UV-503, manufactured by Daitogakugaku); 0.9 part

The following additive 2 (paramethoxy phenol); 0.002 part

Organic solvents: propylene glycol methyl ether acetate (PGMEA); 20 copies

The radiation sensitive compositions of Examples 2 to 13 and Comparative Examples 1 to 8 were obtained in the same manner as in Example 1 except that the components in the radiation sensitive compositions of Example 1 were changed as shown in Table 7 below.

Further, the radiation sensitive compositions of Example 3 were prepared by mixing the aforementioned pigment dispersion compositions G-3, G-4 and G-5 at a mass ratio of 83: 12: 5.

The following evaluations were carried out on the radiation-sensitive compositions obtained in Examples and Comparative Examples.

<Evaluation of Filterability>

For the radiation sensitive compositions obtained in Examples and Comparative Examples, the filtration rate was evaluated by measuring the filtration flow rate using CWOHOS1S3 manufactured by Entegris. The results are shown in the following table.

5: 0.50 L / min or more

4: 0.40 L / min or more, less than 0.50 L / min

3: 0.20 L / min or more, 0.40 L / min or less

2: not less than 0.05 L / min, not more than 0.20 L / min

1: less than 0.05 L / min

&Lt; Evaluation of retardation &

Each of the radiation sensitive compositions of the examples and the comparative examples was applied on a silicone 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 To obtain a radiation-sensitive composition layer.

Then, a checkerboard pattern having a square of 1.4 mu m was exposed through a mask (exposure dose: 300 mJ / cm 2) using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) ² ). After the formation of the radiation-sensitive composition layer using the radiation-sensitive composition, the post-coating delay (PCD (post coating delay) was set to 0 or 24 hours until the radiation-sensitive composition layer was exposed.

Subsequently, the exposed layer of the radiation-sensitive composition was subjected to a puddle 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 water was further washed with pure water to obtain a pattern.

For each of the patterns obtained by PCD 0 hour and PCD 24 hours, the line width of the pattern of one pixel was measured at arbitrary 10 points in the wafer, and an average value was obtained. 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.

5: Difference in linewidth of each pattern within ± 0.025 μm

4: Difference in linewidth of each pattern exceeds ± 0.025 μm, within 0.06 μm

3: Difference in linewidth of each pattern exceeds ± 0.06 μm, within 0.10 μm

2: Difference in line width of each pattern exceeds ± 0.10 μm, within 0.15 μm

1: Difference in linewidth of each pattern exceeds ± 0.15 μm

<Evaluation of preservation stability (evaluation of foreign matter increase rate)>

Each of the radiation sensitive compositions obtained above was applied onto 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 to obtain a radiation sensitive composition layer.

Foreign matter having a size of 1.0 탆 or more was counted on the substrate on which the radiation sensitive composition layer was formed using a defect evaluation device ComPLUS.

This evaluation was carried out immediately after the preparation of the radiation sensitive composition and after 3 months from the time of refrigerating (5 캜) to evaluate the foreign matter increase rate by the following criterion.

The foreign matter increase rate was calculated as (number of foreign matter after 3 months of refrigeration / number of foreign matter immediately after preparation). A criterion of 3 or more is practically preferable.

5: Foreign matter increase rate <1.1

4: 1.1 &lt;

3: 1.3 &lt;

2: 1.5 &lt;

1: 3.0? Foreign object increase rate

<Evaluation of Residual Amount>

Each of the radiation sensitive compositions of the examples and the comparative examples was applied on a silicone 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 To obtain a radiation-sensitive composition layer.

Then, a checkerboard pattern having a square of 1.4 mu m was exposed through a mask (exposure dose: 300 mJ / cm 2) using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) ² ). Subsequently, the exposed layer of the radiation-sensitive composition was subjected to a puddle 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 water was further washed with pure water to obtain a pattern. Subsequently, the resultant was heated on a hot plate at 200 DEG C for 5 minutes to obtain a color filter.

The pixel pattern of the obtained color filter was observed from the upper side of the color filter on the silicon wafer at a magnification of 30,000 times by using a measuring SEM (S-7800H, manufactured by Hitachi Seisakusho Co., Ltd.) And evaluated by stitching.

The smaller the development residue, the better the resolution of the pattern. The results are shown in the following table.

5: Less than 0.5% of residue

4: Residual amount is 0.5% or more and less than 0.9%

3: Residual amount is 0.9% or more, less than 1.3%

2: Residual amount is 1.3% or more and less than 2.0%

1: Residual amount is 2.0% or more

<Image sensor application characteristics>

Each of the radiation sensitive compositions of the Examples and Comparative Examples was applied on a glass plate 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 to form a radiation sensitive composition layer &Lt; / RTI &gt;

Subsequently, the obtained radiation-sensitive composition layer was exposed to light (exposure dose: 1000 mJ / cm ² ) and then heated on a hot plate at 200 ° C for 5 minutes to obtain a colored resin film for a color filter.

The degree of roughness was measured on the resulting colored resin film for a color filter, and the image sensor application characteristics were evaluated.

First, the obtained colored resin film for a color filter was provided between an observation lens of an optical microscope and a light source, the light was irradiated toward the observation lens, and the state of the transmitted light was observed by an optical microscope equipped with a digital camera having a magnification of 1000 times. The digital camera installed in the optical microscope was equipped with a CCD of 128 megapixels, and the surface of the film in the transmitted light state was photographed. The photographed image was saved as data (digital image) digitally converted into an 8-bit bitmap format. The film surface was photographed on arbitrarily selected 20 regions.

The digitally converted data was obtained by digitizing the photographed image as the density distribution of 256 gradations ranging from 0 to 255 for each of the three primary colors of RGB.

Then, with respect to the stored digital image, one grid size was divided into a grid shape so as to correspond to a square of 2 mu m on the actual plate, and the brightness in one compartment was averaged. In the present embodiment, since an image of 1000 times the optical size was photographed with a digital camera of 1280000 pixels, 2 mu m on the actual plane became 2 mm on the photographed image, and the image size on the display was 452 mm x 352 mm, The total number of compartments in one area was 39776.

The average luminance of one arbitrary section and all adjacent sections adjacent thereto was measured for the whole section of each area. A section having a difference of 5 or more from the average luminance of the adjacent sections was regarded as a significant difference section and the ratio of the average total number of the significant difference sections in the total area to the total number of sections (39776) in each section was calculated. The results are shown in the following table.

Also, the smaller the ratio of the average total number of the significant subdivisions of the entire area to the total number of subdivisions of each area, the less roughness of the reproduced image, which is suitable for use in image sensors.

5: Within 0.3% of compartment ratio

4: Compartment ratio exceeding 0.3%, within 0.6%

3: Division ratio exceeding 0.6%, within 1.2%

2: Compartment ratio exceeding 1.2%, within 2.0%

1: Breaking ratio exceeding 2.0%

[Table 7]

In Table 7, each symbol means the following compound.

XAN: Short for cyclohexanone

Resin 1: Weight average molecular weight 11,000

[Chemical Formula 45]

Resin 2: Weight average molecular weight 14,000

(46)

Resin 3: weight average molecular weight 12,000

(47)

Resin 4: Weight average molecular weight 11,000

(48)

Polymerizable compound (C): M-305 manufactured by Toagosei Co., Ltd.

Polymerizable compound (D): Nippon Kayakusa DPCA-20

Additive 1: UV-503, manufactured by Daitogagakusha

(49)

Additive 2: p-methoxyphenol

(50)

Additive 3: (trade name: SM-1, manufactured by Kobe Dendenbutsuga Chemical Co., Ltd.)

(51)

From the results shown in Table 7, it was found that, when the radiation sensitive compositions of the Examples were used, generation of foreign matters and generation of residues can be suppressed while satisfactorily delaying and leaving for a long period of time. In addition, when the radiation sensitive compositions of the Examples were used, it was found that the filterability and image sensor characteristics were also good. On the other hand, in the case of using the radiation sensitive compositions of the comparative examples, it was found that it is difficult to suppress generation of foreign matter and residues while improving long-term delay and retention.

Claims (14)

CI Pigment Green 36, CI Pigment Yellow 150, CI Pigment Yellow 185,
The content of CI Pigment Green 36 to 100 parts by mass of the pigment is 80 to 86 parts by mass, the mass ratio of CI Pigment Yellow 150 and CI Pigment Yellow 185 is in the range of 65.4: 35.6 to 79.0: 21.0,
Wherein the resin has an acid value of 20 to 50 mg KOH / g and an amine value to acid value of 0.85 to 1.45. The method according to claim 1,
An acid derivative, an amine salt of an acid derivative, and a metal salt of an acid derivative. The method according to claim 1 or 2,
Further comprising an ultraviolet absorber. The method according to any one of claims 1 to 3,
Wherein the mass ratio of the resin to the pigment is 0.2 to 0.4. The method according to any one of claims 1 to 4,
A radiation-sensitive composition further comprising a polymerizable compound and a polymerization initiator. The method according to any one of claims 1 to 5,
A radiation sensitive composition for use in forming a colored layer of a color filter. CI Pigment Green 36, CI Pigment Yellow 150, CI Pigment Yellow 185,
The content of CI Pigment Green 36 to 100 parts by mass of the pigment is 80 to 86 parts by mass, the mass ratio of CI Pigment Yellow 150 and CI Pigment Yellow 185 is in the range of 65.4: 35.6 to 79.0: 21.0,
Wherein the resin has an acid value of 20 to 50 mgKOH / g and an amine value to acid value of from 0.85 to 1.45. The method of claim 7,
Covalently bonding the pigment comprising CI Pigment Green 36, CI Pigment Yellow 150 and CI Pigment Yellow 185 with the resin. A cured film obtained by curing the radiation sensitive composition according to any one of claims 1 to 6. A color filter having the cured film according to claim 9. A step of applying the radiation sensitive composition described in any one of claims 1 to 6 on a support to form a radiation sensitive composition layer; a step of exposing the radiation sensitive composition layer in a pattern shape; And removing the development to form a pattern. A step of applying the radiation sensitive composition described in any one of claims 1 to 6 on a support to form a radiation sensitive composition layer; a step of exposing the radiation sensitive composition layer in a pattern shape; And removing the development to form a pattern. A solid-state image pickup element having the color filter obtained by the color filter according to claim 10 or the method for manufacturing a color filter according to claim 12. An image display apparatus having the color filter obtained by the color filter according to claim 10 or the method of manufacturing a color filter according to claim 12.