TWI653503B - Radiation-sensitive composition, cured film, display element, and toner dispersion liquid - Google Patents

Abstract

An object of the present invention is to provide a radiation-sensitive composition that has good storage stability and can form a cured film having excellent solvent resistance.

The solution of the present invention is a radiation-sensitive composition containing (A) a polymer, (B) a polymerizable compound, and (C) a radiation-sensitive polymerization initiator, and the (A) polymer is selected from the group consisting of the following polymers Of polymer (A1), polymer (A2), and polymer (A3), and is polymer (A1) or a combination of polymer (A2) and polymer (A3), polymer (A1): has Polymer of ethylene oxide and propylene oxide, polymer (A2): polymer having ethylene oxide (excluding the above polymer (A1)), polymer (A3): having propylene oxide Polymer (wherein the polymer (A1) is not included), and the ratio of the ethylene oxide (oxi) to the propylene oxide (oxe) in the polymer (A) is expressed in molar ratio (oxi / oxe ) Is calculated as 3/97 ~ 50/50.

Description

Radiation-sensitive composition, cured film, display element, and toner dispersion liquid

The present invention relates to a radiation-sensitive composition, a cured film, and a display element. More specifically, the present invention relates to a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, and the like. A radiation-sensitive composition of a cured film used in the method, a cured film formed using the radiation-sensitive composition, and a display element including the cured film.

When manufacturing a color filter using a color-sensitive radiation composition, a method is known in which a pigment-dispersed color-sensitive radiation composition is coated on a substrate and dried, and then the dried coating film is patterned in a desired pattern. The shape is irradiated with radiation (hereinafter referred to as "exposure") and developed to obtain pixels of each color (for example, refer to Patent Documents 1 to 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, refer to Patent Document 3). In addition, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (for example, refer to Patent Document 4).

In addition, in the technical field of color filters in recent years, the performance requirements of the formed cured film and the composition for forming the cured film are becoming more and more strict. For example, from the aspect of solvent resistance, it has been proposed A composition having a polymer having an ethylene oxide group and a propylene oxide group is used as a material capable of forming a cured film having good solvent resistance (for example, refer to Patent Documents 5 to 8).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2-144502

[Patent Document 2] Japanese Unexamined Patent Publication No. 3-52201

[Patent Document 3] Japanese Unexamined Patent Publication No. 6-35188

[Patent Document 4] Japanese Patent Laid-Open No. 2000-310706

[Patent Document 5] Japanese Patent Laid-Open No. 2007-052147

[Patent Document 6] Japanese Patent Laid-Open No. 2007-333847

[Patent Document 7] Japanese Patent Laid-Open No. 2010-009033

[Patent Document 8] Japanese Patent Laid-Open No. 2010-262259

However, the radiation-sensitive composition described in Patent Documents 5 to 8 is not necessarily satisfactory in terms of solvent resistance, and there is a problem that the storage stability of the radiation-sensitive composition is poor. Therefore, an object of the present invention is to provide a radiation-sensitive composition that has good storage stability and can form a cured film that is also excellent in solvent resistance.

In view of the above-mentioned actual situation, the present inventors conducted intensive studies, and as a result, found that by using a radiation-sensitive composition containing a polymer obtained by controlling the ethylene oxide and propylene oxide groups at a specific ratio, The solvent resistance of the formed film is surprisingly greatly improved, and the storage stability is also excellent, thereby completing the present invention.

That is, the present invention provides a radiation-sensitive composition containing (A) a polymer, (B) a polymerizable compound, and (C) a radiation-sensitive polymerization initiator, and the (A) polymer is selected from the group consisting of In the group of polymer (A1), polymer (A2) and polymer (A3), it is polymer (A1), or a combination of polymer (A2) and polymer (A3). Polymer (A1): Polymer polymer (A2) having ethylene oxide and propylene oxide group: polymer having ethylene oxide (excluding the above polymer (A1)) polymer (A3): having propylene oxide group Polymers (wherein the polymer (A1) is not included), and the ratio of the ethylene oxide (oxi) to the propylene oxide (oxe) in the polymer (A) is expressed in mole ratio (oxi / oxe) Counted as 3/97 ~ 50/50.

The present invention also provides a cured film formed using the radiation-sensitive composition and a display element including the cured film. Here, the “cured film” refers to pixels of various colors, a protective film, a black matrix, a spacer, an insulating film, and the like used in display elements and solid-state imaging elements.

The composition of the present invention has good storage stability and can form a cured film that is also excellent in solvent resistance.

Therefore, the radiation-sensitive composition of the present invention is extremely suitable for producing color filters for color separation of color liquid crystal display elements, solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. Various color filters are represented by light filters. It is also extremely useful as a protective film material, a spacer material, and an insulating film material.

[Form of Implementing Invention]

Hereinafter, the present invention will be described in detail.

(Radiosensitive composition)

Hereinafter, the constituent components of the radiation-sensitive composition of the present invention will be described in detail.

-(A) Polymer-

The component (A) in the present invention is a component that causes a crosslinking reaction during the exposure and / or post-baking step to improve the hardenability of the coating film.

The radiation-sensitive composition of the present invention must contain the following polymer (A1), polymer (A2), and polymer (A1) among polymers (A3), or polymer (A2) and polymer (A3) Combination as component (A). As the component (A), as long as the polymer (A1) or a combination of the polymer (A2) and the polymer (A3) is contained, the polymer (A1), the polymer (A2), and the polymer (A3) can be used. A polymer other than these is appropriately selected and contained. For example, when the polymer (A1) is used as the component (A), in addition to the polymer (A1), at least one selected from the polymer (A2) and the polymer (A3) may be contained. (A) As a component, it is preferable to contain a polymer (A1) at least from a viewpoint of solvent resistance.

Polymer (A1): A polymer having an ethylene oxide group and a propylene oxide group.

Polymer (A2): a polymer having an ethylene oxide group (wherein the polymer (A1) is not included).

Polymer (A3): A polymer having a propylene oxide group (excluding the polymer (A1)).

Furthermore, the present inventors have conducted intensive studies and found that by controlling the ratio of the ethylene oxide group to the propylene oxide group in the (A) polymer within a predetermined range, the storage stability is surprisingly excellent. In addition, a cured film having excellent solvent resistance can be formed.

That is, the ratio of oxiethylene (oxi) to propylene oxide (oxe) in the polymer (A) is 3/97 to 50/50 in terms of molar ratio (oxi / oxe), which further improves the solvent resistance. From the viewpoint of sex, it is preferably 4/96 ~ 30/70, more preferably 5/95 ~ 23/77, even more preferably 6/94 ~ 20/80, and particularly preferably 7/93 ~ 16/84.

The polymer (A1) may be, for example, a copolymer including a monomer containing an ethylenically unsaturated monomer (a1) having an epoxy ethyl group and an ethylenically unsaturated monomer (a2) having a propylene oxide group. As the polymer (A2), for example, a polymer including a monomer having an ethylenically unsaturated monomer (a1) having an epoxyethyl group (excluding the polymer (A1)) may be used as the polymer The polymer (A3) may be, for example, a polymer containing a monomer having an propylene oxide-containing ethylenically unsaturated monomer (a2) (excluding the polymer (A1) described above).

At this time, the content of the ethylenically unsaturated monomer (a1) having an epoxyethyl group in the polymer (A), w _oxi and the content of the ethylenically unsaturated monomer (a2) having an propylene oxide group, w _oxe The mass ratio (w _oxi / w _oxe ) is preferably _3/97 ~ 50/50. From the viewpoint of further improving the solvent resistance, it is preferably _4/96 ~ 40/60, and more preferably 5/95 ~ 28 / 72, further more preferably 6/94 ~ 21/79, and particularly preferably 7/93 ~ 16/84.

Here, the molar ratio (oxi / oxe) is a ratio of the total molar number of the ethylene oxide groups to the total molar number of the propylene oxide groups in all the polymers constituting the component (A), and the mass ratio (w _oxi / w _oxe ) is the total mass of the ethylenically unsaturated monomer (a1) having an epoxy ethyl group in all the monomers constituting the polymer (A) w _oxi and the ethylenically unsaturated monomer having a propylene oxide group The proportion of the total mass _woxe of the saturated monomer (a2) in all the monomers constituting the polymer (A). For example, when the component (A) contains, in addition to the polymer (A1), at least one polymer selected from the polymer (A2) and the polymer (A3), the molar ratio (oxi / oxe) is polymerized. (A1) and at least one polymer selected from polymer (A2) and polymer (A3) have a total mole number of oxirane (oxi) and a total mole of propylene oxide (oxe) The ratio of ear number and mass ratio (w _oxi / w _oxe ) is occupied by all monomers constituting polymer (A1) and at least one polymer selected from polymer (A2) and polymer (A3) _w oxe mass ratio of the total ethylenically unsaturated epoxy ethyl monomer (a1) and the total mass of w _oxi propylene oxide group having ethylenic unsaturated monomer (a2) a.

Examples of the ethylenically unsaturated monomer (a1) having an epoxyethyl group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and β (meth) acrylic acid. -Ethyl glycidyl ester, vinyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl o-vinyl benzyl glycidyl Glyceryl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) Styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) ) Styrene, 2,3,4-ginseng (glycidyloxymethyl) styrene, 2,3,5-ginseng (glycidyloxymethyl) styrene, 2,3,6-ginseng ( Glycidyloxymethyl) styrene, 3,4,5-gins (glycidyloxymethyl) styrene, 2,4,6-gins (glycidyloxymethyl) styrene, etc. Glycidyl ether-based ethylenically unsaturated monomer; 1,2-epoxy-4-vinylcyclohexane, a compound represented by the following general formula (1), a compound represented by the following general formula (2), An ethylenically unsaturated monomer having an alicyclic group obtained by epoxidizing a carbon-carbon double bond, such as a compound represented by the following general formula (3).

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms which may contain a hetero atom].

[In formulas (2) and (3), R ² independently represents a hydrogen atom or a methyl group, and X ² independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms that may contain a hetero atom] .

The alkanediyl group having 1 to 6 carbon atoms in X ¹ and X ² may be linear or branched. Specific examples include methylene, ethylidene, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, and propane-1,3- Diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,4-diyl Base, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, and the like. Among them, an alkanediyl group having 1 to 4 carbon atoms is preferred, and an alkanediyl group having 1 or 2 carbon atoms is more preferred.

The alkanediyl group having 1 to 6 carbon atoms may contain a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the hetero atom-containing alkanediyl group include (*)-CH ₂ CH ₂ -O- and (*)-CH. ₂ -O-CH _2- , (*)-CH ₂ CH ₂ -S-, (*)-CH ₂ -S-CH _2- , (*)-CH ₂ CH ₂ -NH-, (*)-CH ₂ -NH-CH ₂ -etc. Here, (*) represents a bond with -COO-.

Examples of the compound represented by the formula (1) include 3,4-epoxycyclohexyl methyl methacrylate (trade name Cyclomer M100, manufactured by DAICEL Chemical Industry Co., Ltd .; in the formula (1), R ¹ is a methyl group, X ¹ is a methylene compound), 3,4-epoxycyclohexyl methyl acrylate (trade name Cyclomer A400, manufactured by DAICEL Chemical Industry Co., Ltd .; in formula (1), R ¹ is a hydrogen atom, and X ¹ is a methylene group compound of).

Examples of the compound represented by the formula (2) include compounds represented by the formulae (2-1) to (2-8).

Examples of the compound represented by the formula (3) include compounds represented by the formulae (3-1) to (3-8).

Among these ethylenically unsaturated monomers (a1) having an epoxy ethyl group, among the ethylenically unsaturated monomers having a glycidyl ether group, glycidyl (meth) acrylate and (meth) acrylic acid are preferred. β-methyl glycidyl ester. Among ethylenically unsaturated monomers having an alicyclic group obtained by epoxidizing a carbon-carbon double bond, a compound represented by formula (1), a compound represented by formula (2), and formula (3) are preferred. Represented compounds. Among the compounds represented by the formula (2), compounds represented by the formulae (2-1), (2-4), (2-5), and (2-8) are more preferable. Among the compounds represented by formula (3), compounds represented by formulas (3-1), (3-4), (3-5), and (3-8) are more preferred.

The ethylenically unsaturated monomer (a1) having an epoxyethyl group can be used alone or in combination of two or more kinds.

Examples of the ethylenically unsaturated monomer (a2) having a propylene oxide group include a compound represented by the following general formula (4), a compound represented by the following general formula (5), and a following general formula (6) Represented compounds.

[In the formula (4), R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group, and Y ¹ represents a single bond or An alkanediyl group having 1 to 6 carbon atoms which may contain one or more heteroatoms].

[In the formula (5), R ²¹ represents a hydrogen atom or a methyl group, and R ²² to R ²⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted An aryl group, Y ² represents a single bond or an alkanediyl group having 1 to 6 carbon atoms which may contain one or more heteroatoms].

[In formula (6), R ³¹ represents a hydrogen atom or a methyl group, and R ³² to R ³⁶ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted An aryl group, Y ³ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms which may contain one or more heteroatoms].

The alkyl group having 1 to 6 carbon atoms may be linear or branched. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, secondary pentyl, neo Amyl, n-hexyl, etc. Among them, an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group and an ethyl group are more preferred.

Aryl refers to a monocyclic to tricyclic aromatic hydrocarbon group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specific examples include phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, 9-fluorenyl, and the like. Among them, phenyl is preferred.

Examples of the substituent of the alkyl group and the aryl group include a halogen atom, a hydroxyl group, and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferred. The alkoxy group may be linear or branched, and the number of carbon atoms is preferably 1 to 6. Specific examples include methoxy, ethoxy, propoxy, isopropoxy, and butoxy. In addition, the position and number of the substituents are arbitrary. For example, when a fluorine atom is used as the substituent, it may be a perfluoroalkyl group. When there are two or more substituents, the substituents may be the same or different.

The alkanediyl group having 1 to 6 carbon atoms may be linear or branched. As a specific example, the same alkanediyl group as described above may be mentioned. Among them, an alkanediyl group having 1 to 4 carbon atoms is preferred, and an alkanediyl group having 1 or 2 carbon atoms is more preferred. The alkanediyl group having 1 to 6 carbon atoms may contain one or more heteroatoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom which are the same as those described above. Specific examples of the alkanediyl group containing one or more heteroatoms include, for example, -O-CH ₂ CH ₂ CH ₂ -O-CH _2- , and -CH in addition to the same alkanediyl group as described above. ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH _2- , -O-CH ₂ CH ₂ CH ₂ -S-CH _2- , -CH ₂ -O-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -Wait.

Examples of the compound represented by the formula (4) include 3- (vinyloxymethyl) -2-methylpropylene oxide, and 3- (vinyloxy (Methyl) -3-methylpropylene oxide, 3- (vinyloxymethyl) -2-ethylpropylene oxide, 3- (vinyloxymethyl) -3-ethylpropylene oxide, 3- (Vinyloxyethyl) -2-methylpropylene oxide, 3- (vinyloxyethyl) -3-methylpropylene oxide, 3- (vinyloxyethyl) -2-ethyl epoxy Propane, 3- (vinyloxyethyl) -3-ethylpropylene oxide, 2- (vinyloxymethyl) -2-methylpropylene oxide, 2- (vinyloxymethyl) -3- Methyl propylene oxide, 2- (vinyloxymethyl) -2-ethyl propylene oxide, 2- (vinyloxymethyl) -3-ethyl propylene oxide, 2- (vinyloxyethyl ) -2-methyl propylene oxide, 2- (ethyleneoxyethyl) -3-methyl propylene oxide, 2- (ethyleneoxyethyl) -2-ethyl propylene oxide, 2- (ethylene (Ethoxyethyl) -3-ethoxypropane (vinyloxyalkyl) alkyl propylene oxide.

Examples of the compound represented by the formula (5) include, for example, 3-[(meth) acrylic acidoxymethyl] propylene oxide, and 3- [2- (meth) acrylic acidoxyethyl] propylene oxide. (Meth) acryloxyalkylene epoxy such as 2-[(meth) acryloxymethyl] propylene oxide, 2- [2- (meth) acryloxyethyl] propylene oxide Propane; such as 3-[(meth) acrylic oxomethyl] -2-methyl propylene oxide, 3-[(meth) propylene oxomethyl] 3-methyl propylene oxide, 3-[( (Meth) acrylic acid oxymethyl] -2-ethylpropylene oxide, 3-[(meth) acrylic acid oxymethyl] -3-ethylpropylene oxide, 3- [2- (meth) propylene Ethoxyethyl] -2-methylpropylene oxide, 3- [2- (meth) propylene ethoxyethyl] 3-methylpropylene oxide, 3- [2- (meth) propylene ethoxyethyl Yl] -2-ethyl propylene oxide, 3- [2- (meth) acryloxyethyl] -3-ethyl propylene oxide, 2-[(meth) acryloxymethyl] -2 -Methyl propylene oxide, 2-[(meth) acrylic oxomethyl] -3-methyl propylene oxide, 2-[(meth) propylene oxomethyl] 4-methyl propylene oxide, 2-[(A Propyl) propenyloxymethyl] -2-ethylpropylene oxide, 2-[(meth) propenyloxymethyl] -3-ethylpropylene oxide, 2-[(meth) acrylic acid oxymethyl Yl] -4-ethylpropylene oxide, 2- [2- (meth) acryloxyethyl] -2-methylpropylene oxide, 2- [2- (meth) acryloxyethyl] -3-methyl propylene oxide, 2- [2- (meth) acryloxyethyl] -4-methylpropylene oxide, 2- [2- (meth) acryloxyethyl] -2 -Ethyl propylene oxide, 2- [2- (meth) acryloxyethyl] -3-ethylpropylene oxide, 2- [2- (meth) acryloxyethyl] -4-ethyl [(Meth) acrylic alkoxyalkyl] alkyl propylene oxide such as propylene oxide; such as 3-[(meth) acrylic ethoxymethyl] -2-trifluoromethyl propylene oxide, 3 -[(Meth) acrylic acid oxymethyl] -2-pentafluoroethyl propylene oxide, 3-[(meth) acrylic acid oxymethyl] -2-fluoropropylene oxide, 3-[(methyl ) Acryloxymethyl] -2,2-difluoropropylene oxide, 3-[(meth) acryloxymethyl] -2,2,4-trifluoropropylene oxide, 3-[(methyl ) Acrylic acid oxymethyl] -2,2,4,4-tetrafluoropropylene oxide, 3- [2- (meth) acrylic acid oxyethyl] -2-trifluoromethyl propylene oxide, 3- [2- (Meth) acryloxyethyl] -2-pentafluoroethyl Propylene oxide, 3- [2- (meth) acryloxyethyl] -2-fluoropropylene oxide, 3- [2- (meth) acryloxyethyl] -2,2-difluoro Propylene oxide, 3- [2- (meth) acryloxyethyl] -2,2,4-trifluoropropylene oxide, 3- [2- (meth) acryloxyethyl] -2, 2,4,4-tetrafluoropropylene oxide, 2-[(meth) acryloxymethyl] -2-trifluoromethylpropylene oxide, 2-[(meth) acryloxymethyl]- 3-trifluoromethyl propylene oxide, 2-[(meth) acrylic acid oxymethyl] -4-trifluoromethyl propylene oxide, 2-[(meth) acrylic acid oxymethyl] -2- Pentafluoroethyl propylene oxide, 2-[(meth) acryloxymethyl] -3-pentafluoroethyl propylene oxide, 2-[(meth) acryloxymethyl] -4-pentafluoro Ethyl propylene oxide, 2-[(meth) acryloxymethyl] -2,3-difluoropropylene oxide , 2-[(meth) acrylic acid oxymethyl] -2,4-difluoropropylene oxide, 2-[(meth) acrylic acid oxymethyl] -3,3-difluoropropylene oxide, 2 -[(Meth) acrylic acid oxymethyl] -3,4-difluoropropylene oxide, 2-[(meth) acrylic acid oxymethyl] -4,4-difluoropropylene oxide, 2- [ (Meth) acrylic acid oxymethyl] -3,3,4-trifluoropropylene oxide, 2-[(meth) acrylic acid oxymethyl] -3,4,4-trifluoropropylene oxide, 2 -[(Meth) acrylic acid oxymethyl] -3,3,4,4-tetrafluoropropylene oxide, 2- [2- (meth) acrylic acid oxyethyl] -2-trifluoromethyl ring Oxypropane, 2- [2- (meth) acrylic acid oxyethyl] -3-trifluoromethyl propylene oxide, 2- [2- (meth) acrylic acid oxyethyl] -4-trifluoromethyl Propylene oxide, 2- [2- (meth) acryloxyethyl] -2-pentafluoroethyl propylene oxide, 2- [2- (meth) acryloxyethyl] -3-penta Fluoroethyl propylene oxide, 2- [2- (Meth) acryloxyethyl] -4-pentafluoroethyl propylene oxide, 2- [2- (Meth) acryloxyethyl] -2 , 3-difluoropropylene oxide, 2- [2- (meth) acryloxyethyl] -2,4-difluoropropylene oxide, 2- [2- (meth) acryloxyethyl] -3,3-difluoropropylene oxide, 2- [2- (meth) propenyloxyethyl] -3,4-difluoroepoxy Alkane, 2- [2- (meth) propenyloxyethyl] -4,4-difluoropropylene oxide, 2- [2- (meth) propenyloxyethyl] -3,3,4- Trifluoropropylene oxide, 2- [2- (meth) acryloxyethyl] -3,4,4-trifluoropropylene oxide, 2- [2- (meth) acryloxyethyl]- [(Meth) acryloxyalkyl] fluoropropylene oxide or [(meth) acryloxyalkyl] fluoroalkylpropylene oxide, such as 3,3,4,4-tetrafluoropropylene oxide; For example, 2-[(meth) acryloxymethyl] -2-phenylpropylene oxide, 2-[(meth) acryloxymethyl] -3-phenylpropylene oxide, 2-[(methyl Propyl) propenyloxymethyl] -4-phenylpropylene oxide, 2- [2- (meth) propenyloxyethyl] -2-phenylpropylene oxide, 2- [2- (methyl) Propylene ethoxyethyl] -3-phenylpropylene oxide, 2- [2- (meth) propylene ethoxyethyl] -4-phenylpropylene oxide [(Meth) acryloxyalkyl] phenyl propylene oxide and the like.

Examples of the compound represented by the formula (6) include, for example, 4- [3- (3-ethyloxypropane-3-ylmethoxy) propoxy] styrene, 4- [4- (3 -Ethyloxypropane-3-ylmethoxy) butoxy] styrene, 4- [5- (3-ethyloxypropane-3-ylmethoxy) pentoxy] styrene, 4 -[6- (3-Ethoxypropane-3-ylmethoxy) hexyloxy] styrene, 4- [7- (3-Ethoxypropane-3-ylmethoxy) heptyloxy Group] aromatic vinyl compounds having a propylene oxide group such as styrene.

Among these unsaturated monomers (a2), a compound represented by formula (4) and a compound represented by formula (5) are preferred. Among these, from the viewpoint of improving the solvent resistance of the obtained cured film, 3- (vinyloxymethyl) -3-ethylpropylene oxide and 3-[(meth) acrylic acid oxymethyl] are preferred. Propylene oxide, 3-[(meth) acrylic oxomethyl] -3-ethyl propylene oxide, 3-[(meth) propylene oxomethyl] -2-trifluoromethyl propylene oxide, 3-[(meth) acryloxymethyl] -2-phenylpropylene oxide, 2-[(meth) acryloxymethyl] propylene oxide, 2-[(meth) acryloxymethyl Group] -4-trifluoromethylpropylene oxide.

The polymers (A1) to (A3) may contain functional groups other than ethylene oxide and propylene oxide. For example, if the polymers (A1) to (A3) have a carboxyl group, it is preferable to have alkali solubility, and the polymer can be provided with a function as a binder resin. In addition, if the polymers (A1) to (A3) have a substituted or unsubstituted amine group, it is preferable in terms of excellent pigment dispersibility, and the polymer can be provided with a function as a dispersant. That is, at least one of the polymers (A1) to (A3) may further have a substituted or unsubstituted amine group, as long as at least the polymer (A1) has a substituted or unsubstituted amine group, or is selected from the polymer (A2) And at least 1 of polymer (A3) The species may have a substituted or unsubstituted amine group. This makes it possible to better use the component (A) as a dispersant. In addition, the substituted or unsubstituted amine group may be in the form of a salt. Here, examples of the substituent of the amine group include an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms. Specific examples include the same alkyl group and aromatic group as those described above. base.

That is, the polymers (A1) to (A3) may contain an ethylenically unsaturated monomer (a1) (hereinafter also referred to as "unsaturated monomer (a1)") having an epoxy ethyl group and As the monomer unit, an ethylenically unsaturated monomer other than the ethylenically unsaturated monomer (a2) (hereinafter also referred to as "unsaturated monomer (a2)") preferably contains an unsaturated monomer from the viewpoint of storage stability. A copolymer of monomer units other than the saturated monomer (a1) and the unsaturated monomer (a2). Examples of such unsaturated monomers other than the unsaturated monomer (a1) and the unsaturated monomer (a2) include ethylenically unsaturated monomers (a3) having one or more carboxyl groups, and substituted or non-substituted monomers. Substituted amine-based ethylenically unsaturated monomers (a4) and other copolymerizable ethylenically unsaturated monomers (a5). Examples of the substituent of the amine group include an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms. Specific examples include the same alkyl groups and aryl groups as those described above.

Examples of the ethylenically unsaturated monomer (a3) having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (a3)") include (meth) acrylic acid, maleic acid, and maleic anhydride. , Mono [2- (meth) acryloyloxyethyl] succinate, ω-carboxy polycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, and the like.

The unsaturated monomer (a3) can be used alone or in combination of two or more.

Examples of the ethylenically unsaturated monomer (a4) having a substituted or unsubstituted amine group (hereinafter also referred to as "unsaturated monomer (a4)") include, for example, dimethylaminoethyl (meth) acrylate Esters, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like.

The unsaturated monomer (a4) can be used alone or in combination of two or more.

Examples of other copolymerizable ethylenically unsaturated monomers (a5) (hereinafter also referred to as "unsaturated monomers (a5)") include, for example, N-phenylmaleimide, N- N-position substituted maleimide such as cyclohexylmaleimide; such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, pinene and the like Aromatic vinyl compounds; such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (formaldehyde) Base) allyl acrylate, benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (methyl) Acrylate, polyethylene glycol (polymerization degree 2 ~ 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 ~ 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, (formaldehyde) ) Isobornyl acrylate, tricyclo [5.2.1.0 ^2,6 ] dec-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, ( 4-hydroxyphenyl meth) acrylate, (Meth) acrylates such as ethylene oxide-modified (meth) acrylates based on phenol; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0 ^2,6 ] decane Alkyl-8-yl vinyl ethers, vinyl ethers such as pentacyclopentadecyl vinyl ethers; such as polystyrene, poly (meth) acrylate, poly (meth) acrylate, polybutyl A macromonomer such as a siloxane having a mono (meth) acrylfluorene group at the end of a polymer molecular chain.

The unsaturated monomer (a5) can be used alone or in combination of two or more.

When the polymer (A1) is a copolymer containing a monomer having an ethylenically unsaturated monomer (a1) having an epoxy ethylene group and an ethylenically unsaturated monomer (a2) having a propylene oxide group, the polymer (A1) The copolymerization ratio of the unsaturated monomer (a1) and the unsaturated monomer (a2) in) is preferably 3/97 to 50/50 in terms of mass ratio (a1 / a2). From the viewpoint of further improving the solvent resistance, the mass ratio (a1 / a2) is preferably 3/97 to 30/70, more preferably 4/96 to 25/75, and still more preferably 5/95 to 20/80. , Even more preferably 7/93 ~ 15/85.

When the polymer (A2) is a polymer including a monomer having an ethylenically unsaturated monomer (a1) having an epoxyethyl group, the copolymerization ratio of the unsaturated monomer (a1) in the polymer (A2) is preferably 3 to 40 mass%, more preferably 5 to 30 mass%.

When the polymer (A3) is a polymer containing a monomer having an ethylenically unsaturated monomer (a2) having a propylene oxide group, the copolymerization ratio of the unsaturated monomer (a2) in the polymer (A3) is preferably 5 to 65 mass%, more preferably 10 to 55 mass%.

When the polymers (A1) to (A3) are copolymers containing an unsaturated monomer (a3) as a monomer unit, the copolymerization ratio of the unsaturated monomer (a3) is preferably 1 from the viewpoint of developability. ~ 40% by mass, more preferably 3 ~ 30 Mass%, particularly good 5 to 20 mass%.

When the polymers (A1) to (A3) are copolymers containing an unsaturated monomer (a4) as a monomer unit, the copolymerization ratio of the unsaturated monomer (a4) is preferably 5 from the viewpoint of dispersibility. ~ 50% by mass, more preferably 10 ~ 45% by mass, and particularly preferably 15 ~ 40% by mass.

When the polymers (A1) to (A3) are copolymers containing an unsaturated monomer (a5) as a monomer unit, the copolymerization ratio of the unsaturated monomer (a5) is preferably 10 to 70% by mass, and more preferably It is preferably 20 to 60% by mass, and particularly preferably 25 to 55% by mass. Thereby, the polymers (A1) to (A3) can be synthesized at a desired conversion rate without gelation, and the resistance of the radiation-sensitive composition containing the obtained polymers (A1) to (A3) is improved. Solvent properties and developability are further improved, and thus are preferred.

When the polymers (A1) to (A3) have more than one carboxyl group, the acid value of the polymer is preferably 10 to 200 mgKOH / g, more preferably 50 to 160 mgKOH / g, and particularly preferably 70 to 120 mgKOH / g. . Here, the "acid value" in the present invention is the number of mg of KOH required to neutralize 1 g of the non-volatile component obtained by removing the solvent of the polymer solution. Specifically, it is described in the examples described later. The value determined by the method. Here, the "non-volatile component" in this specification is a component other than the (F) solvent mentioned later.

In addition, when the polymers (A1) to (A3) have a substituted or non-substituted amine group, the amine value of the polymer is preferably 1 to 200 mgKOH / g, more preferably 10 to 150 mgKOH / g, and particularly preferably 20 ~ 100mgKOH / g. Herein, the "amine value" in the present invention is the mg of KOH equivalent to the acid required for neutralizing 1 g of the non-volatile component obtained by removing the solvent of the polymer solution. Specifically, it is described later. Methods described in the examples Measured value.

The polymers (A1) to (A3) may have a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain. Examples of such a polymer include: i) a monomer containing at least one selected from unsaturated monomers (a1) and unsaturated monomers (a2) and a polymerizable unsaturated compound having a hydroxyl group; A polymer obtained by reacting a copolymer with an unsaturated isocyanate compound, and ii) an ethylenic composition containing at least one selected from the unsaturated monomers (a1) and the unsaturated monomers (a2) and having one or more carboxyl groups A polymer obtained by reacting a copolymer of a monomer of an unsaturated monomer (a3) with an ethylenically unsaturated monomer (a1) having an epoxy ethyl group, and iii) a polymer (A1) or (A2) with A polymer obtained by reacting one or more carboxyl groups of an ethylenically unsaturated monomer (a3).

(A) The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the polymer measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

In addition, the ratio (Mw / Mn) of the Mw of the polymer (A) to the polystyrene-equivalent quantity average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is smaller than It is preferably 1 to 5, more preferably 1 to 4.

(A) The polymer can be synthesized by referring to a known method, for example, Japanese Patent Application Laid-Open No. 2012-255963 and Japanese Patent Application Laid-Open No. 2009-116316.

The radiation-sensitive composition of the present invention can be used alone or in combination of the polymers (A1) to (A3).

In the present invention, the composition contains a (D) colorant described later In the case of a color-sensitive radioactive composition, the content of the (A) polymer is usually 5 to 200 parts by mass, and preferably 10 to 100 parts by mass, relative to 100 parts by mass of the (D) colorant. By adopting such a state, it is easy to achieve a desired color density when forming a thin film. In addition, when the radiation-sensitive composition containing no (D) colorant is included, the content ratio of the (A) polymer is 5 to 70% by mass, preferably 10 to 50% of the solid content of the radiation-sensitive composition. quality%. Here, the "solid content" in this specification is a component other than the (F) solvent mentioned later.

-(B) polymerizable compound-

The polymerizable compound in the present invention means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acrylfluorenyl groups, or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylfluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and caprolactone. Ester-modified polyfunctional (meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional amine obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate A urethane (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group, and the like obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include a two-membered aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and glycerol and trimethylolpropane. Ji Wu A trivalent or higher aliphatic polyhydroxy compound such as tetraol and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, Dipentaerythritol penta (meth) acrylate, glycerol dimethacrylate and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, such as pyromellitic acid. Tetracarboxylic dianhydride such as dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride.

Examples of the polyfunctional (meth) acrylate modified with caprolactone include compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. Examples of the polyfunctional (meth) acrylate modified with the alkylene oxide include bisphenol A di (meth) acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. , Modified by at least one kind selected from the group consisting of ethylene oxide and propylene oxide, tris (meth) acrylate isocyanurate, and modified by at least one kind selected from the group consisting of ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, and selected from ethylene oxide And at least one modified pentaerythritol tetra (meth) acrylate in propylene oxide, at least one modified dipentaerythritol penta (meth) acrylate selected from ethylene oxide and propylene oxide, Dipentaerythritol hexa (meth) acrylate and the like modified with at least one selected from ethylene oxide and propylene oxide.

Examples of the compound having two or more N-alkoxymethylamine groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the melamine structure and the benzoguanamine structure mean that one or more Ring or phenyl substituted tri The chemical structure of a ring as a basic skeleton is a concept that also includes melamine, benzoguanamine, or these condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine, N, N, N', N'-tetrakis (alkoxymethyl) glycolurea and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting a ternary or higher aliphatic polyhydroxy compound with (meth) acrylic acid, and polyfunctional (methyl) modified with caprolactone are preferred. ) Acrylic esters, polyfunctional urethane (meth) acrylates, polyfunctional (meth) acrylates with carboxyl groups, N, N, N ', N', N ", N" -hexa (alkoxy) Methyl) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine. From the viewpoints of high strength of the colored layer, excellent surface smoothness of the colored layer, and less occurrence of scale and film residues on the substrate of the unexposed portion and the light-shielding layer, the ternary or higher aliphatic polyhydroxy compound and Among the polyfunctional (meth) acrylates obtained by the (meth) acrylic acid reaction, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among the carboxyl polyfunctional (meth) acrylates, compounds obtained by reacting pentaerythritol triacrylate and succinic anhydride, and compounds obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride are particularly preferred.

In the present invention, the (B) polymerizable compound may be used alone or in combination of two or more.

When the colored radiation-sensitive composition containing the (D) colorant is constituted, the content of the (B) polymerizable compound in the present invention is usually 5 to 600 parts by mass relative to 100 parts by mass of the (A) polymer, and it is preferably It is 20 to 400 parts by mass. By being in such a state, sufficient hardenability can be obtained. In addition, when alkali developability is imparted to the radiation-sensitive composition of the present invention, alkali developability is good, and it is not easy on a substrate or a light-shielding layer in an unexposed portion. Fouling, film residue, etc. are generated. When the radiation-sensitive composition containing no (D) colorant is included, the content of the polymerizable compound (B) is usually 10 to 500 parts by mass, and preferably 50 to 100 parts by mass of the polymer (A). ~ 300 parts by mass.

-(C) Radiation-sensitive polymerization initiator-

The radiation-sensitive composition of the present invention contains a radiation-sensitive polymerization initiator. The radiation-sensitive polymerization initiator used in the present invention is a compound that generates active species that can initiate the polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays. The present invention can be used The radiation sensitive composition is used as a negative radiation sensitive composition.

Examples of such a radiation-sensitive polymerization initiator include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, Based compounds, O-hydrazine based compounds, onium salt based compounds, benzoin based compounds, benzophenone based compounds, α-diketone based compounds, polynuclear quinone based compounds, diazonium based compounds, amidine sulfonic acid Ester-based compounds.

In this invention, a radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, At least one of a system compound and an O-hydrazine system compound.

Among the preferred radiation-sensitive polymerization initiators in the present invention, as specific examples of the thioxanthone-based compound, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-iso Propylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4 -Diisopropylthioxanthone and the like.

Specific examples of the acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2-linepropane-1-one and 2-benzyl-2 -Dimethylamino-1- (4- Phenylphenyl) butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4- Phenylphenyl) butane-1-one and the like.

Moreover, as a specific example of the said biimidazole-based compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole , 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4 , 6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

When a biimidazole-based compound is used as the radiation-sensitive polymerization initiator, it is preferable to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The "hydrogen donor" mentioned here refers to a compound capable of supplying a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzo Thiol-based hydrogen donors such as azole, amine-based hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone . In the present invention, the hydrogen donor may be used alone or in combination of two or more. From the viewpoint of further improving the sensitivity, it is preferable to use one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors. Use in combination.

In addition, as the above three Specific examples of the compounds are 2,4,6-ginsyl (trichloromethyl) symmetric tris , 2-methyl-4,6-bis (trichloromethyl) symmetrical three , 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) symmetric tri , 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) symmetric tris , 2- [2- (4-diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) symmetric tri , 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) symmetric tri , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) symmetrical tris , 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) symmetrical tris , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) symmetrical three Halomethyl Department of compounds.

Specific examples of the O-fluorenoxime-based compound include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzidineoxime), 1 -[9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime), 1- [9-ethyl- 6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime), 1- [9-ethyl -6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzyl} -9H-carbazol-3-yl]- Ethyl ketone 1- (O-acetamoxime) and the like. As commercially available products of O-hydrazine-based compounds, NCI-831, NCI-930 (the above are manufactured by ADEKA Co., Ltd.), DFI-020, DFI-091 (the above are manufactured by Daito Chemix Co., Ltd.), etc. .

In the present invention, when a radiation-sensitive polymerization initiator other than a biimidazole-based compound such as an acetophenone-based compound is used, a sensitive 化 剂。 Chemical agent. Examples of such a sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and 4-bis Ethylaminoacetophenone, 4-dimethylaminophenylacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl) coumarin, 4- (diethyl Amine) chalcone and the like.

In the present invention, whether or not (D) a colorant is present, the content of the (C) radiation-sensitive polymerization initiator is preferably 0.01 to 120 parts by mass with respect to 100 parts by mass of the polymerizable compound, and particularly preferably 1 to 100. Parts by mass. By setting it as such an aspect, hardenability and film characteristics can be further improved.

The radiation-sensitive composition of the present invention may include at least the components (A) to (C), but may further contain other components.

-(D) Colorant-

The radiation-sensitive composition of the present invention may further contain (D) a colorant. Thereby, for example, a colored radiation-sensitive composition for forming a colored layer of a color filter can be obtained. Here, the "colored layer" refers to each color pixel, black matrix, and the like used in a color filter. The colorant can be used without particular limitation as long as it has colorability, and the color and material can be appropriately selected according to the use of the radiation-sensitive composition. When the radiation-sensitive composition of the present invention is used to form each color pixel constituting a color filter, the color filter is required to have high color purity, brightness, contrast, etc., so it is preferably selected from pigments and dyes. At least one kind is used as a colorant, and particularly preferred are organic pigments and organic dyes.

Examples of the pigment include organic pigments and inorganic pigments. As specific examples of the organic pigment, color index (C.I.) is mentioned. CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, Pigments represented by the following formula (7), CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Blue 15: 6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Orange 38, CI Pigment Violet 23, and the like. Preferred specific examples of the inorganic pigment include carbon black and titanium black.

As a pigment, a lake pigment is also preferable, and specifically, a triarylmethane-based dye using an isopoly acid or a heteropoly acid, A pigment obtained by lake-based dyes. Triarylmethane-based lake pigments are disclosed in, for example, Japanese Patent Application Laid-Open No. 2011-186043. The lake pigment is disclosed in, for example, Japanese Patent Application Laid-Open No. 2010-191304.

Moreover, as said dye, it is preferable that Based dyes, triarylmethane based dyes, cyanine based dyes, anthraquinone based dyes, azo based dyes, and the like. More specifically, Japanese Patent Laid-Open No. 2010-32999, Japanese Patent Laid-Open No. 2010-254964, Japanese Patent Laid-Open No. 2011-138094, International Publication No. 2010/123071, and Japanese Patent Laid-Open No. 2011-116803 are mentioned. Organic dyes described in Japanese Patent Application Laid-Open No. 2011-117995, Japanese Patent Application Laid-Open No. 2011-133844, Japanese Patent Application Laid-Open No. 2011-174987, and the like. Generally, it is known that a colored hardened film formed using a colored composition containing a dye is insufficient in solvent resistance, but the colored composition of the present invention can form colored hardened resin having excellent solvent resistance even when a dye is contained as a colorant. membrane.

In the present invention, the pigment and the dye may be used alone or in combination of two or more kinds.

In the present invention, the pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. In addition, if necessary, the surface of the particles may be modified with a resin and then used. The organic pigment can be used by miniaturizing the primary particles by a so-called salt mill. As a method of salt milling, for example, the method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be adopted.

When a pigment is used as the colorant in the present invention, it may be used together with a dispersant and a dispersing aid as needed. As the dispersant, for example, a suitable dispersant such as a cationic, anionic, or nonionic type can be used, and a polymer dispersant is preferred. Specific examples include acrylic copolymers, polyurethanes, polyesters, polyethyleneimines, and polyallylamines.

Such dispersants can be obtained from commercial sources. For example, as the acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (the above are manufactured by BYK-Chemie (BYK)), etc., Examples of the polyurethane-based dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (the above are manufactured by BYK-Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.) and the like. Examples of the polyethylene imine dispersant include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) and the like. Examples of the polyester dispersant include Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (the above are manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc., and BYK-LPN21324 (manufactured by BYK-Chemie (BYK)) and the like.

In addition, a copolymer with the ethylenically unsaturated monomer (a4) having an amine group, that is, the polymer (A) of the present invention can be used as a dispersant. The preferable aspect when using the (A) polymer as a dispersant is as described above.

Examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone.

Other colorants in the present invention may be used alone or in combination of two or more.

From the viewpoint of forming a pixel having high heat resistance and brightness and excellent color purity, or a black matrix and black spacer having excellent light shielding properties, the content ratio of the (D) colorant is usually 5 in the solid content of the coloring radiation-sensitive composition. ~ 70 mass%, preferably 5 to 60 mass%. The solid content means a component other than the solvent mentioned later.

-(E) Binder resin-

The radiation-sensitive composition of the present invention may contain a binder resin (wherein the polymer (A1) to polymer (A3) are not included). This makes it possible to improve the alkali solubility of the radiation-sensitive composition, adhesion to the substrate, storage stability, and the like. Although it does not specifically limit as a binder resin, The resin which has an acidic functional group, such as a carboxyl group and a phenolic hydroxyl group, is preferable. Of which A polymer having a carboxyl group (hereinafter also referred to as a "carboxyl-containing polymer") is preferred, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as an "unsaturated monomer" (e1) ") is a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as" unsaturated monomer (e2) ").

Examples of the unsaturated monomer (e1) include the same unsaturated monomers as the unsaturated monomer (a3) described above, and these unsaturated monomers may be used alone or in combination of two or more.

Examples of the unsaturated monomer (e2) include the same unsaturated monomers as the unsaturated monomers (a4) to (a5) described above. These unsaturated monomers can be used alone or in combination of two or more. .

In the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2), the copolymerization ratio of the unsaturated monomer (e1) in the copolymer is preferably 5 to 50% by mass, and more preferably 10 ~ 40% by mass. By copolymerizing the unsaturated monomer (e1) within such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2) include, for example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Application Laid-Open No. 8-259876, and Japanese Patent Laid-Open No. 10- Japanese Patent Publication No. 31308, Japanese Patent Application Publication No. 10-300922, Japanese Patent Application Publication No. 11-174224, Japanese Patent Application Publication No. 11-258415, Japanese Patent Application Publication No. 2000-56118, Japanese Patent Application Publication No. 2004-101728, etc. Revealed copolymers.

In the present invention, for example, Japanese Patent Application Laid-Open No. 5-19467, Japanese Patent Application Laid-Open No. 6-230212, and Japanese Patent No. 6-230212 can also be used. Polymerizations having a (meth) acryl fluorenyl group in a side chain, etc. disclosed in Japanese Patent Application Laid-Open No. 7-207211, Japanese Patent Application Laid-Open No. 9-325494, Japanese Patent Application Laid-Open No. 11-140144, Japanese Patent Application Laid-Open No. 2008-181095, and the like Polymers containing carboxyl groups of unsaturated bonds serve as binder resins.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC) (eluting solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 100,000, preferably 3000 ~ 50000. By adopting such an aspect, it is possible to further improve the residual film rate, pattern shape, heat resistance, electrical characteristics, and resolution of the film, and to suppress the occurrence of dry foreign matter during coating at a high level.

In addition, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. In addition, Mn mentioned here means the number average molecular weight of polystyrene conversion measured by GPC (eluting solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a well-known method, but may also be a method disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, and International Publication No. 07/029871. Control its structure, Mw, Mw / Mn.

In this invention, a binder resin can be used individually or in mixture of 2 or more types.

In the present invention, when a binder resin is used, the content is 1 to 300 parts by mass, preferably 5 to 200 parts by mass, with respect to 100 parts by mass of the polymer (A), with or without (D). Such an aspect is preferable in that a desired effect of the present invention is easily obtained.

-(F) Solvent-

The radiation-sensitive composition of the present invention contains the above-mentioned components (A) to (C) and other components added arbitrarily, but is usually prepared as a liquid composition by blending an organic solvent.

As the organic solvent, as long as the components (A) to (C) and other components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components, and have appropriate volatility, they can be appropriately selected and used.

Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethyl ether. Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether (Poly) alkyl ethers such as propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. Alcohol monoalkyl ethers; alkyl lactates such as methyl lactate and ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexyl (Cyclo) alkyl alcohols such as alcohols and cyclohexanol; keto alcohols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate Methyl-3-methoxybutyl acetate and butyl (poly) alkylene glycol monoalkyl ether acetate; Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diethyl Diacetates such as diacetates, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, and other diacetates; methyl 3-methoxypropionate, 3-methyl Ethyloxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, butyl 3-methyl-3-methoxypropionate, etc. Oxycarboxylic acid esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate , N-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, 2-side Fatty acid alkyl esters such as ethyl oxybutyrate; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Amidoamine, or lactamamine.

Among these organic solvents, (poly) alkylene glycol monoalkyl ether, alkyl lactate, and (poly) alkylene glycol monoalkyl ether acetic acid are preferred from the viewpoints of solubility, pigment dispersibility, and coatability. Esters, glycol ethers, ketones, diacetates, alkoxycarboxylic acid esters, fatty acid alkyl esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monoester Methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone , 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, 3-methyl 3-methoxypropionate butyl, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate , Ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In this invention, an organic solvent can be used individually or in mixture of 2 or more types. When mixed with an organic solvent, it is preferable to mix at least (poly) alkanediol monoalkyl ether and (poly) alkanediol monoalkyl ether acetate, (poly) alkanediol monoalkyl ether acetate, and Alkoxycarboxylic acid esters are used.

The content of the organic solvent is not particularly limited. When constituting the colored radiation-sensitive composition containing the (D) colorant, the total concentration of each component other than the organic solvent of the radiation-sensitive composition is preferably 5 to 50% by mass. The amount is more preferably 10 to 40% by mass. By setting it as such an aspect, a coloring radiation composition with good dispersibility and stability can be obtained. When the radiation-sensitive composition containing no (D) colorant is formed, the total concentration of each component other than the solvent of the radiation-sensitive composition is preferably an amount of 10 to 75% by mass, and more preferably 15 to 70% by mass. By setting it as such a form, a radiation sensitive composition with favorable coating property and stability can be obtained.

-additive-

The coloring composition of the present invention may further contain various additives as necessary.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicon-based surfactants; ethylene Trimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxy Ethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethyl Oxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethyl Adhesion promoters such as oxysilane and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tertiarybutylphenol), 2,6-ditertiarybutyl Phenol, pentaerythritol [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) -propanyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodioxane Ethyl bis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate] and other antioxidants; 2- (3-tertiary-butyl-5-methyl-2-hydroxy Phenyl) -5-chlorobenzotriazole, alkoxybenzophenones and other ultraviolet absorbers; anti-agglomerating agents such as sodium polyacrylate; malonic acid Adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino -1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and other residue improving agents; succinic acid mono [2- (meth) acrylic acid oxyethyl] Esters, developing agents such as mono- [2- (meth) acryloxyethyl] phthalate, ω-carboxy polycaprolactone mono (meth) acrylate, and the like.

The radiation-sensitive composition of the present invention can be prepared by mixing the components (A) to (C) and other components as required in a predetermined ratio, and it is preferably dissolved in an appropriate solvent for preparation. The prepared radiation-sensitive composition is preferably filtered with a filter having a pore size of about 0.2 μm, for example.

In addition, when the colored radiation-sensitive composition is prepared, for example, it is preferable to use, for example, a bead mill, a roll mill, or the like, and (D) the colorant and the (A) polymer, as appropriate, Part of the predetermined (E) binder resin is mixed and dispersed in the (F) solvent in the presence of a dispersant while being pulverized to prepare a colorant dispersion liquid, and then, into the colorant dispersion liquid. (B) a polymerizable compound and (C) a radiation-sensitive polymerization initiator are added, (E) a binder resin is added as needed, and an additional solvent and other components are added and mixed.

(Hardened film and method of forming)

The cured film of the present invention is formed using the radiation-sensitive composition of the present invention. The cured film of the present invention is not particularly limited, and examples thereof include pixels of each color constituting a color filter, a black matrix, a protective film, a spacer, an insulating film, and the like. Hereinafter, the case where the colored hardened film which is a pixel of each color which comprises a color filter is formed is described in detail as an example.

As a method of forming the coloring layer which comprises a color filter, the following method is mentioned first. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so that a portion where a pixel is formed is divided as necessary. Next, the substrate is coated with a liquid composition of the color-sensitive radiation composition of the present invention containing a blue coloring agent, for example, and then pre-baked to evaporate the solvent to form a coating film. Next, after exposing this coating film through a photomask, it develops using an alkaline developing solution, and melt | dissolves and removes the unexposed part of a coating film. Thereafter, a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement is formed by post-baking.

Next, each coloring sensation is performed in the same manner as described above using each coloring radiating composition containing a green or red coloring agent. The coating, pre-baking, exposure, development, and post-baking of the radiation composition sequentially form a green pixel array and a red pixel array on the same substrate. Thereby, a color filter in which a pixel array of three primary colors of blue, green, and red is arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the order described above.

In addition, the black matrix can be formed using a photolithography method to form a thin metal film such as chromium formed by sputtering or vapor deposition into a desired pattern, or a radiation-sensitive composition in which a black colorant is dispersed can be used to form the black matrix. The above-mentioned pixels are formed in the same manner. The radiation-sensitive composition of the present invention can also be suitably used to form the black matrix.

Examples of the substrate used when forming the coloring layer include glass, silicon, polycarbonate, polyester, aromatic polyamine, polyimide, polyimide, and the like.

In addition, these substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, and vacuum evaporation, as necessary.

When applying a radiation-sensitive composition to a substrate, a suitable coating method such as a spray method, a roll coating method, a spin coat method, a slit die coating method, or a bar coating method may be used, and a spin coating method is particularly preferred. Coating method, slit die coating method.

The conditions for heating and drying during pre-baking are usually 70 to 110 ° C and about 1 to 10 minutes. In addition, pre-baking can be performed by combining reduced-pressure drying and heat-drying. In this case, the reduced-pressure drying is usually performed until it reaches 50 to 200 Pa.

The coating thickness is based on the film thickness after drying, usually 0.6 ~ 8μm , Preferably 1.2 to 5 μm.

Examples of the light source for forming radiation used when at least one selected from a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a medium-pressure mercury lamp , Low-pressure mercury lamp and other lamp light sources or argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the light source for exposure, an ultraviolet LED may be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The radiation exposure is generally preferably 10 to 10,000 J / m ² .

In addition, as the alkaline developer, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4 .0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and other aqueous solutions.

An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, and a surfactant may be added to the alkaline developer. In addition, after alkaline development, water washing is usually performed.

As the development processing method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be adopted. The developing conditions are preferably room temperature and 5 to 300 seconds.

Post-baking conditions are usually 180 ~ 280 ° C, about 10 ~ 60 minutes.

The film thickness of the pixel formed in this manner is usually 0.5 to 5 μm, and preferably 1.0 to 3 μm.

In addition, as a second method of forming a coloring layer constituting a color filter, Japanese Patent Application Laid-Open No. 7-318723, Japanese A method for obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Application Laid-Open No. 2000-310706 and the like. In this method, first, a partition wall having a light shielding function is formed on the surface of the substrate. Next, a liquid composition such as the thermal radiation composition of the present invention containing a blue colorant is ejected into the formed partition wall by an inkjet device, and then pre-baking is performed to evaporate the solvent. Next, after exposing the coating film as necessary, it is cured by post-baking to form a blue pixel pattern.

Next, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above using each thermal radiation composition containing a green or red coloring agent. Thereby, a color filter in which pixel patterns of three primary colors of blue, green, and red are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the order described above.

In addition, the partition wall not only exhibits a light shielding function, but also functions to prevent the thermal radiation composition of each color ejected into the partition area from mixing colors. Therefore, the film thickness is thicker than the black matrix used in the first method. Therefore, the partition wall is usually formed using a radiation-sensitive composition in which a black colorant is dispersed.

The substrate, the light source for radiation, and the pre-baking and post-baking methods and conditions used when forming the colored layer are the same as the first method described above. Thereby, the film thickness of the pixel formed by the inkjet method is equal to the height of the partition wall.

After forming a protective film on the pixel pattern thus obtained as needed, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. Protective films and spacers are usually formed using a radiation-sensitive composition, but they can also be made A light-shielding spacer (black spacer). In this case, a color-sensitive radiation composition in which a black colorant is dispersed is used. The radiation-sensitive composition of the present invention can also be suitably used for forming the protective film and the spacer. The conditions for forming the protective film, the spacer, and the insulating film are the same as those in the case of the above-mentioned colored layer.

The color filter of the present invention thus obtained has extremely high brightness and color purity, and is therefore extremely useful in color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

(Display element)

The display element of the present invention includes the cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element including the cured film of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be adopted. For example, a structure in which a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween; Alternatively, a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is arranged, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed may be opposed to each other via a liquid crystal layer. Structure. The latter structure has the advantage that the aperture ratio can be significantly increased, and a bright and high-definition liquid crystal display element can be obtained. In the latter configuration, the black matrix and the spacer may be formed on either of the substrate side on which the color filter is formed and the substrate side on which the ITO electrode is formed. In addition, as an interlayer insulating film constituting a driving substrate on which a thin film transistor (TFT) is disposed, it is also possible to use Use the cured film of the present invention.

The color liquid crystal display element including the cured film of the present invention includes a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. Examples of the white LED include a white LED that combines red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors, and a white LED that combines blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors. LED, a combination of blue LED, red light-emitting phosphor and green light-emitting phosphor to obtain white light by mixing colors, and a white LED of white light by mixing color of blue LED and YAG-based phosphor, combination Blue LED, orange luminescent phosphor, and green luminescent phosphor, and white LED obtained by mixing colors to obtain white light, combined with ultraviolet LED, red luminescent phosphor, green luminescent phosphor, and blue luminescent phosphor White LEDs and the like that obtain white light by color mixing.

The color liquid crystal display element provided with the cured film of the present invention may be a TN (Twisted Nematic: twisted nematic) type, a STN (Super Twisted Nematic: super twisted nematic) type, an IPS (In-Planes Switching: in-plane switching) type, Suitable liquid crystal modes such as a VA (Vertical Alignment) type and an OCB (Optically Compensated Birefringence) type.

In addition, the organic EL display element provided with the cured film of the present invention may have a suitable structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.

In addition, the electronic paper provided with the cured film of the present invention may have a suitable structure. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2007-41169. Structure.

(Solid State Photographic Element)

The solid-state imaging element of the present invention includes the cured film of the present invention. In addition, the solid-state imaging element of the present invention can adopt an appropriate structure. For example, as one embodiment, by using the radiation-sensitive composition of the present invention containing a (D) colorant, a colored pixel (colored cured film) is formed on a semiconductor substrate such as a CMOS substrate by the same operation as described above. Accordingly, a solid-state imaging element having excellent color separation properties and color reproducibility can be obtained. In addition, as another embodiment, a solid-state imaging device including an insulating film (cured film) made using the radiation-sensitive composition of the present invention may be produced, and specifically disclosed in Japanese Patent Application Laid-Open No. 2011-215597 Structure.

[Example]

Hereinafter, examples will be given to further specifically describe embodiments of the present invention. However, the present invention is not limited to the following examples.

The abbreviations of the raw materials used in the following synthesis examples are as follows.

THF: tetrahydrofuran

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

AIBN: 2,2’-azobisisobutyronitrile

ST: styrene

MA: methacrylic acid

MMA: methyl methacrylate

nBMA: n-butyl methacrylate

BzMA: benzyl methacrylate

CHMA: cyclohexyl methacrylate

OXMA: 3- (methacryloxymethyl) -3-ethylpropylene oxide

GMA: glycidyl methacrylate

DAMA: dimethylaminoethyl methacrylate

<Measurement of acid value>

The acid value of the polymer obtained in each Synthesis Example was measured in the following manner.

Weigh 0.5 g of the polymer solution to the nearest 1 mg unit and dispense into a glass container. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, and titration was performed with a 0.1N ethanolic potassium hydroxide aqueous solution, and the end point was a coloring point to pink. A blank test was performed similarly. The acid value (unit: mgKOH / g) was calculated from the dropwise addition amount of the 0.1N ethanolic potassium hydroxide aqueous solution of the polymer and the blank test.

<Determination of Amine Value>

The amine value of the polymer obtained in each synthesis example was measured in the following manner.

Weigh 0.5 g of the polymer solution to the nearest 1 mg unit and dispense into a glass container. 20 mL of acetic anhydride / acetic acid = 9/1 (volume ratio) was added and dissolved, and left at room temperature for 3 hours. Thereafter, 30 mL of acetic acid was further added, and titration was performed with a 0.1 mol / L perchloric acid / acetic acid solution using a potential difference measuring device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.). A blank test was performed similarly. The amine value (unit: mgKOH / g) was calculated from the dropwise addition amount of the 0.1 mol / L perchloric acid / acetic acid solution of the polymer and the blank test.

<Synthesis of polymer having carboxyl group in addition to ethylene oxide and / or propylene oxide group>

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 58.0 g of styrene, 15.0 g of MA, 22.0 g of OXMA, and 5.0 g of Cyclomer M100 (manufactured by DAICEL Co., Ltd .. 3,4-epoxycyclohexyl methyl methacrylate) were dissolved in To 200 g of methyl 3-methoxypropionate, 6.0 g of azobis-2,4-dimethylvaleronitrile and 5.0 g of α-methylstyrene dimer were further added, followed by nitrogen flushing for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. while stirring with nitrogen foaming, and polymerized for 5 hours to obtain a solution containing 33% by mass of the polymer (A1-1-1). The polymer (A1-1-1) had Mw = 6000 and Mw / Mn = 2.5 in terms of polystyrene, measured by GPC (eluting solvent: THF). The polymer (A1-1-1) is equivalent to the polymer (A1).

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 53.0 g of styrene, MA 12.0 g, ARONIX M120 (manufactured by Toa Synthesis Co., Ltd .. 2-ethylhexyl EO modified acrylate) 5.0 g, 25.0 g of OXMA, and Cyclomer M100: 5.0 g was dissolved in 200 g of PGMEA, and 6.0 g of azobis-2,4-dimethylvaleronitrile and 5.0 g of α-methylstyrene dimer were added, followed by nitrogen flushing for 15 minutes. After purging with nitrogen, the reaction liquid was heated to 80 ° C. while being stirred and bubbled with nitrogen, and polymerized for 5 hours to obtain a solution containing 33% by mass of a polymer (A1-1-2). The polymer (A1-1-2) had a polystyrene equivalent Mw = 5900 and Mw / Mn = 2.5 measured by GPC (eluting solvent: THF). The polymer (A1-1-2) is equivalent to the polymer (A1).

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 55.0 g of styrene, MA 15.0 g, OXMA 20.0 g, GMA 2.0 g, and Cyclomer M100: 8.0 g It was dissolved in 200 g of methoxybutyl acetate, 4.0 g of azobis-2,4-dimethylvaleronitrile, and 5.0 g of α-methylstyrene dimer were added, followed by 15 minutes of nitrogen flushing. After the nitrogen gas was purged, the reaction solution was heated to 80 ° C. while being stirred with nitrogen bubbles, and polymerized for 5 hours to obtain a solution containing 33% by mass of a polymer (A1-1-3). The polymer (A1-1-3) had a polystyrene equivalent Mw = 12000 and a Mw / Mn = 2.5 measured by GPC (eluting solvent: THF). The polymer (A1-1-3) is equivalent to the polymer (A1).

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 54.0 g of styrene, MA 14.0 g, MMA 2.0 g, and BLEMMER PME-200 (manufactured by Nippon Oil Co., Ltd .. Methoxy polyethylene glycol monomethacrylate) 2.0 were used. g, OXMA14.0g and CyclomerM100: 14.0g is dissolved in 200g of methyl 3-methoxypropionate, then 5.0g of azobis-2,4-dimethylvaleronitrile and α-methylstyrene dimerization 5.0 g of the product was added, followed by nitrogen purge for 15 minutes. After purging with nitrogen, the reaction liquid was heated to 80 ° C. while being stirred and bubbled with nitrogen, and polymerized for 5 hours to obtain a solution containing 33% by mass of a polymer (A1-1-4). The polymer (A1-1-4) had Mw = 10000 and Mw / Mn = 2.5 measured in terms of polystyrene by GPC (eluting solvent: THF). The polymer (A1-1-4) is equivalent to the polymer (A1).

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 58.0 g of styrene, 15.0 g of MA, and 27.0 g of OXMA were dissolved in 200 g of methyl 3-methoxypropionate, and then azobis-2,4-dimethyl was added. 5.0 g of valeronitrile and 5.0 g of α-methylstyrene dimer were then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was stirred and heated to 80 ° C with nitrogen foaming for 5 hours. Polymerization was performed to obtain a solution containing 33% by mass of the polymer (A3-1). The polymer (A3-1) had Mw = 10000 and Mw / Mn = 2.5 measured in terms of polystyrene by GPC (eluting solvent: THF). The polymer (A3-1) is equivalent to the polymer (A3).

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 58.0 g of styrene, 15.0 g of MA, and 27.0 g of GMA were dissolved in 200 g of methoxybutyl acetate, and then azobis-2,4-dimethylvaleronitrile 4.0 was added. g and 5.0 g of α-methylstyrene dimer, followed by 15 minutes of nitrogen flushing. After purging with nitrogen, the reaction solution was heated to 80 ° C. while stirring with nitrogen foaming, and polymerized for 5 hours to obtain a solution containing 33% by mass of a polymer (A2-1). The polymer (A2-1) had a polystyrene equivalent Mw of 12,000 and a Mw / Mn of 2.5 measured by GPC (eluting solvent: THF). The polymer (A2-1) is equivalent to the polymer (A2).

Synthesis Example 7

In Synthesis Example 1, except that the amount of each component was changed as shown in Table 1, a solution containing 33% by mass of a polymer (A1-1-5) was obtained in the same manner as in Synthesis Example 1. The polymer (A1-1-5) had Mw = 6000 and Mw / Mn = 2.5 measured in terms of polystyrene by GPC (eluting solvent: THF). The polymer (A1-1-5) is equivalent to the polymer (A1).

Synthesis Example 8

In Synthesis Example 1, except that the types and amounts of the components were changed as shown in Table 1, a solution containing 33% by mass of a polymer (A1-1-6) was obtained in the same manner as in Synthesis Example 1. The polymer (A1-1-6) had Mw = 6200 and Mw / Mn = 2.4 measured in terms of polystyrene by GPC (eluting solvent: THF). The polymer (A1-1-6) is equivalent to the polymer (A1).

In Table 1, the amount of each unsaturated compound represents the mass% with respect to the entire unsaturated compound.

"M120" represents a repeating unit derived from 2-ethylhexyl EO modified acrylate (ARONIX M120, manufactured by Toa Synthesis Co., Ltd.).

"PME-200" represents a repeating unit derived from methoxy polyethylene glycol monomethacrylate (BLEMMER PME-200, manufactured by Nippon Oil Corporation).

"M100" represents a repeating unit derived from 3,4-epoxycyclohexyl methacrylate (Cyclomer M100, manufactured by DAICEL Co., Ltd.).

"Oxi / oxe" represents the ratio of the total moles of ethylene oxide groups to the total moles of propylene oxide groups in all polymers constituting the polymer (A), and "w _oxi / w _oxe " represents that The total mass of the ethylene ethylenically unsaturated monomer (a1) in all the monomers constituting the polymer (A), w _{oxi is equal} to that of the ethylenically unsaturated monomer (a2) having a propylene oxide group. The proportion of the total mass _woxe of all the monomers constituting the (A) polymer.

<Synthesis of polymers having amine groups in addition to ethylene oxide and / or propylene oxide groups>

Synthesis Example 9

In a flask equipped with a stir bar, MMA6.2g, nBMA7.0g, CyclomerM100: 2.8g, OXMA2.8g, ARONIX M120: 0.8g, AIBN235mg, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl 605 mg of methyl ester was dissolved in 30 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution obtained by dissolving 437 mg of AIBN and 8.4 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. The obtained polymer had a Mw in polystyrene conversion measured by GPC (eluting solvent: THF) of 8,300 and a Mw / Mn of 1.3.

Next, 5.4 g of benzyl chloride and 20.0 g of PGME were added to the obtained polymer solution, and then slowly stirred to raise the temperature of the polymer solution to 90 ° C, and the temperature was maintained for 8 hours. A part of the methylamino group is quaternized. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. Thereby, a repeat consisting of an A block having a repeating unit from DAMA and a part of which is quaternized and a repeat having MMA, nBMA, CyclomerM100, OXMA, and ARONIX M120 are obtained. A block copolymer composed of B blocks of units. Let the obtained copolymer be a polymer (A1-2-1). Finally, PGME was added, and it adjusted so that solid content concentration might become 35 mass%, and PGMEA / PGME = 68/32 (mass ratio). The polymer (A1-2-1) is equivalent to the polymer (A1).

Synthesis Example 10

In a flask equipped with a stir bar, 5.6 g of MMA, 5.6 g of nBMA, 0.8 g of Cyclomer M100, 7.6 g of OXMA, 235 mg of AIBN, and 605 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in In 30 mL of toluene, nitrogen was bubbled for 30 minutes. After that, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution obtained by dissolving 481 mg of AIBN and 8.4 g of DAMA in 20 m of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C. for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. The obtained polymer had a Mw in polystyrene conversion measured by GPC (eluting solvent: THF) of 8400 and a Mw / Mn of 1.3.

Next, 5.4 g of benzyl chloride and 20.0 g of PGME were added to the obtained polymer solution, and then slowly stirred to raise the temperature of the polymer solution to 90 ° C., and the temperature was maintained for 8 hours, so that DAMA's A part of the methylamino group is quaternized. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. Thereby, a block copolymer composed of an A block having repeating units from DAMA and a part of which is quaternized and a B block having repeating units from MMA, nBMA, CyclomerM100, and OXMA was obtained. Let the obtained copolymer be a polymer (A1-2-2). Finally, PGME was added, and it adjusted so that solid content concentration might become 35 mass%, and PGMEA / PGME = 68/32 (mass ratio). The polymer (A1-2-2) is equivalent to the polymer (A1).

Synthesis Example 11

6.6 mL of toluene, 2.7 mL of 1,2-dimethoxyethane, and 0.38 M of isobutyl bis (2,6-di-tert-butyl-4-methylphenoxy) aluminum in toluene were added. 13.7 mL , Cool to 10 ° C. 0.7 mL of a 1.3 M solution of secondary butyllithium in hexane was added thereto, and the mixture was stirred for 20 minutes. Thereafter, a solution prepared by dissolving nBMA 0.81 g, MMA 0.87 g, OXMA 0.84 g, and Cyclomer M100: 0.21 g in toluene 2.8 mL at 10 ° C. over 5 minutes was added dropwise.

30 minutes after the end of the dropwise addition, a solution obtained by diluting 0.77 g of DAMA with 0.4 mL of toluene was added over 10 seconds, and stirred for 120 minutes. Methanol was added to stop the reaction. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. Thereby, a solution containing 40% by mass of a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from MMA, nBMA, CyclomerM100, and OXMA was obtained. The obtained polymer had a Mw in terms of polystyrene of 6300 and a Mw / Mn of 1.3 measured by GPC (eluting solvent: THF).

Let the obtained copolymer be a polymer (A1-2-3). The polymer (A1-2-3) is equivalent to the polymer (A1).

Synthesis Example 12

In a flask equipped with a stir bar, MMA6.4g, nBMA6.4g, CyclomerM100: 2.5g, OXMA5.9g, MA0.6g, AIBN290mg, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) formaldehyde 714mg of ester dissolved in formazan In 30 mL of benzene, nitrogen was bubbled for 30 minutes. After that, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution obtained by dissolving 352 mg of AIBN and 6.2 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. Thus, a solution containing 40% by mass of a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from MMA, nBMA, Cyclomer M100, OXMA, and MA was obtained. The obtained polymer had a Mw in polystyrene conversion measured by GPC (eluting solvent: THF) of 8200 and a Mw / Mn of 1.3. Let the obtained copolymer be a polymer (A1-2-4). The polymer (A1-2-4) is equivalent to the polymer (A1). In addition, the polymer (A1-2-4) has a carboxyl group, but is formally classified as a polymer having an amine group.

Synthesis Example 13

In a flask equipped with a stir bar, 3.6 g of MMA, 5.0 g of nBMA, 0.6 g of Cyclomer M100, 5.6 g of OXMA, 13.1 g of DAMA, 340 mg of AIBN, and cyano (dimethyl) methyl of pyrazole-1-dithiocarboxylic acid 837 mg of the ester was dissolved in 50 mL of toluene, and nitrogen gas was bubbled for 30 minutes. After that, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. Thereby, a repeating list containing 40% by mass of MMA, nBMA, CyclomerM100, OXMA, and DAMA was obtained. Solution of a random random copolymer. The obtained polymer had a polystyrene equivalent Mw of 8100 and a Mw / Mn of 1.3 measured by GPC (eluting solvent: THF). Let the obtained copolymer be a polymer (A1-2-5). The polymer (A1-2-5) is equivalent to the polymer (A1).

Synthesis Example 14

In a flask equipped with a stir bar, 1.4 g of MMA, 2.0 g of nBMA, and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the following formula (8) and the following formula ( 9) The compound shown is mixed at a molar ratio of 50:50) 1.7 g, OXMA 15.1 g, AIBN 190 mg, and 467 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester are dissolved in 30 mL of toluene 30 minutes of nitrogen bubbling. After that, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution obtained by dissolving 753 mg of AIBN and 7.8 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C. for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. Thereby, 40% by mass of an A block having a repeating unit derived from DAMA and a repeating unit derived from MMA, nBMA, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate and OXMA were obtained A solution of a block copolymer consisting of B blocks. The obtained polymer had a Mw in terms of polystyrene of 7200 and a Mw / Mn of 1.3 measured by GPC (eluting solvent: THF). Let the obtained copolymer be a polymer (A1-2-6). The polymer (A1-2-6) is equivalent to the polymer (A1).

Synthesis Example 15

In a flask equipped with a stir bar, dissolve MMA7.0g, nBMA7.0g, CyclomerM100: 1.4g, AIBN227mg, and 559mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester in 30mL of toluene. Nitrogen bubbling was performed for 30 minutes. After that, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution obtained by dissolving 721 mg of AIBN and 12.6 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. Thus, a solution containing 40% by mass of a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from MMA, nBMA, and CyclomerM100 was obtained. The obtained polymer had a Mw of polystyrene equivalent measured by GPC (eluting solvent: THF) of 8000 and a Mw / Mn of 1.3. Let the obtained copolymer be a polymer (A2-2-1). The polymer (A2-2-1) is equivalent to the polymer (A2).

Synthesis Example 16

In a flask equipped with a stir bar, dissolve MMA7.0g, nBMA7.0g, OXMA5.6g, AIBN270mg, and 664mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester in 30mL of toluene. 30 minutes of nitrogen bubbling. After that, the temperature of the reaction solution was raised to 57 ° C. by stirring slowly. This temperature was maintained for 34 hours, and living radical polymerization was performed.

Next, a solution obtained by dissolving 481 mg of AIBN and 8.4 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. Thereby, a solution containing 40% by mass of a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from MMA, nBMA, and OXMA was obtained. The obtained polymer had a Mw in terms of polystyrene of 7900 and a Mw / Mn of 1.3 measured by GPC (eluting solvent: THF). Let the obtained copolymer be a polymer (A3-2). The polymer (A3-2) is equivalent to the polymer (A3).

Synthesis Example 17

In a flask equipped with a stir bar, 7.0 g of MMA, nBMA 6.4 g, Cyclomer M100: 0.4 g, OXMA 8.0 g, AIBN 290 mg, and 714 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in In 30 mL of toluene, nitrogen was bubbled for 30 minutes. After that, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution obtained by dissolving 352 mg of AIBN and 6.2 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. Thus, a solution containing 40% by mass of a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from MMA, nBMA, CyclomerM100, and OXMA was obtained. . Mw of the obtained polymer was 8100, and Mw / Mn was 1.3. Let the obtained copolymer be a polymer (A1-2-7). The polymer (A1-2-7) is equivalent to the polymer (A1).

Synthesis Example 18

In a flask equipped with a stir bar, 5.6 mg of MMA, 5.6 g of nBMA, 8.2 g of OXMA, Cygomer M100: 0.2 g, 254 mg of AIBN, and 626 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in In 30 mL of toluene, nitrogen was bubbled for 30 minutes. After that, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution obtained by dissolving 481 mg of AIBN and 8.4 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. The obtained polymer had a Mw in polystyrene conversion measured by GPC (eluting solvent: THF) of 8200 and a Mw / Mn of 1.3.

Next, 5.4 g of benzyl chloride and 20.0 g of propylene glycol monomethyl ether were added to the obtained polymer solution, and then slowly stirred to raise the temperature of the polymer solution to 90 ° C., and the temperature was maintained for 8 hours so that Part of the dimethylamino group of DAMA is quaternized. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. Thus, a block copolymer composed of an A block having a repeating unit derived from DAMA and a part of which is quaternized and a B block having a repeating unit derived from MMA, nBMA, CyclomerM100, and OXMA was obtained. Let the obtained copolymer be a polymer (A1-2-8). Finally, PGME is added so that the solid content concentration becomes 35 mass %, PGMEA / PGME = 68/32 (mass ratio). The polymer (A1-2-8) is equivalent to the polymer (A1).

Synthesis Example 19

In a flask equipped with a stir bar, 5.6 g of MMA, 5.6 g of nBMA, 2.9 g of OXMA, 5.5 g of Cyclomer M100: 5.5 g of AIBN, and 617 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in In 30 mL of toluene, nitrogen was bubbled for 30 minutes. After that, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution obtained by dissolving 481 mg of AIBN and 8.4 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. The obtained polymer had a Mw in polystyrene conversion measured by GPC (eluting solvent: THF) of 8,300 and a Mw / Mn of 1.3.

Next, 5.4 g of benzyl chloride and 20.0 g of propylene glycol monomethyl ether were added to the obtained polymer solution, and then slowly stirred to raise the temperature of the polymer solution to 90 ° C, and the temperature was maintained for 8 hours. Part of the dimethylamino group of DAMA is quaternized. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. Thereby, a block copolymer composed of an A block having repeating units from DAMA and a part of which is quaternized and a B block having repeating units from MMA, nBMA, CyclomerM100, and OXMA was obtained. Let the obtained copolymer be a polymer (A1-2-9). Finally, PGME was added, and it adjusted so that solid content concentration might become 35 mass%, and PGMEA / PGME = 68/32 (mass ratio). polymer (A1-2-9) is equivalent to polymer (A1).

<Polymer having a carboxyl group in addition to ethylene oxide and / or propylene oxide and having a (meth) acrylfluorenyl group in a side chain>

Synthesis Example 20

In a flask equipped with a cooling tube and a stirrer, 22.0 g of OXMA, 18.0 g of MA, 9.0 g of 2-propenyloxyethyl succinate, 10.0 g of N-phenylmaleimide, 24.0 g of BzMA, 14.0 g of 2-hydroxyethyl acrylate and CyclomerM-100: 3.0 g were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 4.0 g of AIBN and 6.0 g of α-methylstyrene dimer were added, followed by 15 minutes. Purge with nitrogen. After flushing with nitrogen, the reaction solution was heated to 80 ° C. while being stirred and bubbled with nitrogen, and polymerized for 5 hours to obtain a precursor copolymer solution.

To 200 g of the obtained precursor copolymer solution were added 13.4 g of 2-methacryloxyethyl isocyanate and 0.2 g of 4-methoxyphenol as a polymerization inhibitor, and the mixture was reacted at 90 ° C. for 2 hours. After cooling to room temperature, it was washed once with 75 g of ion-exchanged water, and washed twice with water, and then concentrated under reduced pressure to obtain a solution containing 33% by mass of the polymer (A1-1-7). The polymer (A1-1-7) had a polystyrene equivalent Mw = 11000 and a Mw / Mn = 1.9 measured by GPC (eluting solvent: THF). The polymer (A1-1-7) is equivalent to the polymer (A1).

Synthesis Example 21

(Polymers other than polymers (A1) to (A3))

In a flask equipped with a stir bar, 5.6 mg of MMA, 5.6 g of nBMA, 8.4 g of CHMA, 235 mg of AIBN, and 605 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene, and 30 minutes of nitrogen bubbling. After that, the temperature of the reaction solution was raised to 57 ° C. by stirring slowly. This temperature was maintained for 34 hours, and living radical polymerization was performed.

Next, a solution obtained by dissolving 481 mg of AIBN and 8.4 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added so that the non-volatile content was 40% by mass. The obtained polymer had a Mw in polystyrene conversion measured by GPC (eluting solvent: THF) of 8,300 and a Mw / Mn of 1.3.

Next, 5.4 g of benzyl chloride and 20.0 g of propylene glycol monomethyl ether were added to the obtained polymer solution, and then slowly stirred to raise the temperature of the polymer solution to 90 ° C, and the temperature was maintained for 8 hours. Part of the dimethylamino group of DAMA is quaternized. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. Thus, a block copolymer composed of an A block having repeating units from DAMA and a part of which is quaternized and a B block having repeating units from MMA, nBMA, and CHMA was obtained. Let the obtained copolymer be a polymer (A4). Finally, PGME was added and adjusted so that the solid content concentration became 35% by mass and PGMEA / PGME = 68/32 (mass ratio). The polymer (A4) does not correspond to any of the polymers (A1) to (A3).

In Table 2, the amount of each unsaturated compound represents the mass% with respect to the entire unsaturated compound.

"ST" represents a repeating unit derived from styrene.

"M120" represents a repeating unit derived from 2-ethylhexyl EO modified acrylate (ARONIX M120, manufactured by Toa Synthesis Co., Ltd.).

"PME-200" represents a repeating unit derived from methoxy polyethylene glycol monomethacrylate (BLEMMER PME-200, manufactured by Nippon Oil Corporation).

"M100" represents a repeating unit derived from 3,4-epoxycyclohexyl methyl methacrylate (Cyclomer M100, manufactured by DAICEL Co., Ltd.).

"Formula (8) / Formula (9)" represents a 3,4-epoxy tricyclic [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by formula (8) and the compound represented by formula (9) are Ear ratio 50:50 mixed substance).

"DAMA" indicates that there are no repeating units from DAMA that are quaternized.

"DAMA-BzCl" means a quaternized ammonium repeat unit from DAMA.

"Oxi / oxe" represents the ratio of the total moles of ethylene oxide groups to the total moles of propylene oxide groups in all polymers constituting the polymer (A), and "w _oxi / w _oxe " represents that The total mass of the ethylene ethylenically unsaturated monomer (a1) in all the monomers constituting the polymer (A), w _oxi and the ethylenically unsaturated monomer (a2) having a propylene oxide group. The proportion of total mass _woxe .

[Evaluation of a cured film as an insulating film]

Example 1

100 parts by mass of a polymer (A1-1-1) solution as a polymer (A) (solid content concentration 33% by mass), and (B) a polymerizable compound of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 50 parts by mass of a mixture (trade name ARONIXM-402, manufactured by Toa Synthesis Co., Ltd.) and a succinic anhydride modified product of dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name ARONIXM-520 , Manufactured by Toa Synthesis Co., Ltd.) 20 parts by mass of 1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazole-3 as (C) radiation-sensitive polymerization initiator -Methyl] -ethanone-1- (O-acetamoxime) (IRGACURE OXE02, manufactured by Ciba Specialty Chemicals) 1 part by mass and 2-dimethylamino-2- (4-methylbenzyl) -1- (4- 5 parts by mass of quinolin-4-yl-phenyl) -butane-1-one (IRGACURE 379, manufactured by Ciba Specialty Chemicals) and pentaerythritol [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] 1 part by mass was mixed, and then diethylene glycol methyl ether was added so that the solid content concentration became 30% by mass, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition物 (S-1).

(Evaluation of solvent resistance)

After applying a radiation-sensitive composition on a silicon substrate using a spinner, pre-baking was performed on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount became 1000 J / m ² . Next, the silicon substrate was heated on a hot plate at 200 ° C. for 30 minutes, and the film thickness (T1) of the obtained cured film was measured. Then, the silicon substrate on which the cured film was formed was immersed in dimethylsulfine at a temperature controlled at 70 ° C for 20 minutes, and the film thickness (T2) of the cured film after the immersion was measured, and the film thickness change was calculated from the following formula. Rate as an index of solvent resistance.

Change rate of film thickness = ((T2-T1) / T1) × 100 (%)

A case where the absolute value of this value is less than 3% is evaluated as "A" , The case where the absolute value of the value is 3% or more and less than 4% is evaluated as "B", the case where the absolute value of the value is 4% or more and less than 5% is evaluated as "C", and the value is The case where the absolute value of 5% or more is less than 6% is evaluated as "D", and the case where the absolute value of the value is 6% or more is evaluated as "E". The results are shown in Table 3.

(Evaluation of Relative Dielectric Constant)

After using a spinner to apply a radiation-sensitive composition on a SUS substrate, pre-baking was performed on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. Using an exposure machine (MPA-600FA, manufactured by Cannon), the above coating film was exposed so that the cumulative irradiation amount became 1000 J / m ² , and the exposed substrate was heated at 200 ° C. for 30 minutes in a clean oven to thereby place it on the SUS substrate. A hardened film is formed. Next, a Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a dielectric constant measurement sample. About the board | substrate which has this electrode pattern, the relative dielectric constant was measured by the CV method using the electrode (HP16451B, Yokogawa. Hewlett-Packard) and the precision LCR tester (HP4284A, Yokogawa. Hewlett-Packard) at a frequency of 10 kHz. At this time, a case where the relative dielectric constant was 3.9 or less was evaluated as “○”, and a case where the relative dielectric constant was more than 3.9 was evaluated as “×”. The results are shown in Table 3.

(Evaluation of storage stability)

Radiation sensitivity measured with an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) The viscosity of the sexual composition is used as the initial viscosity. In addition, the obtained radiation-sensitive composition was filled in a light-shielding glass container, and left to stand at 5 ° C. for 14 days in a sealed state, and then the viscosity was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Then, the increase rate of the viscosity with respect to the initial viscosity after 14 days of storage is calculated. The case where the increase rate is less than 5% is set to "A", and the case where the increase rate is 5% or more and less than 10% is set to "B". ", The case where the increase rate was 10% or more was" C ", and the storage stability of the radiation-sensitive composition was evaluated. The evaluation results are shown in Table 3.

Examples 2 to 8 and Comparative Examples 1 to 3

In Example 1, except that the types and amounts of the components used were changed as shown in Table 3, the same operations as in Example 1 were performed to prepare radiation-sensitive compositions (S-2) to (S-11). . Next, evaluation was performed in the same manner as in Example 1 except that the radiation-sensitive composition (S-2) to (S-11) were used instead of the radiation-sensitive composition (S-1). The results are shown in Table 3.

Each component in Table 3 is as follows.

B-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toa Synthesis Co., Ltd.)

B-2: A mixture of dipentaerythritol pentaacrylate with succinic acid, a mixture of dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toa Synthesis Co., Ltd.)

C-1: 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -ethanone-1- (O-acetamoxime) (trade name (IRGACURE OX02, manufactured by Ciba Specialty Chemicals)

C-2: 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Porphyrin-4-yl-phenyl) -butane-1-one (IRGACURE 379, manufactured by Ciba Specialty Chemicals)

G-1: Pentaerythritol [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], (ADK STAB AO-60, manufactured by ADEKA)

"Oxi / oxe" represents the ratio of the total moles of ethylene oxide groups to the total moles of propylene oxide groups in all polymers constituting the polymer (A), and "w _oxi / w _oxe " represents that The total mass of the ethylene ethylenically unsaturated monomer (a1) in all the monomers constituting the polymer (A), w _{oxi is equal} to that of the ethylenically unsaturated monomer (a2) having a propylene oxide group. The proportion of the total mass _woxe of all the monomers constituting the (A) polymer.

[Evaluation of colorant dispersion liquid or colorant solution]

(Preparation of colorant dispersion)

Preparation Example 1

7.5 parts by mass of C.I. Pigment Red 177 and 7.5 parts by mass of C.I. Pigment Red 254 as a colorant and 15.0 parts by mass of a polymer (A1-2-1) solution were used (Non-volatile content = 35% by mass), 64.0 parts by mass of PGMEA and 6.0 parts by mass of PGME as solvents, and processed with a bead mill to prepare a colorant dispersion liquid (D-1).

(Evaluation of storage stability)

The viscosity of the obtained toner dispersion liquid was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), and this was used as the initial viscosity. In addition, the obtained toner dispersion liquid was filled in a light-shielding glass container, and left to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Then, the increase rate of the viscosity with respect to the initial viscosity after 14 days of storage is calculated. The case where the increase rate is less than 5% is set to "A", and the case where the increase rate is 5% or more and less than 10% is set to "B". "", The case where the increase rate was 10% or more was "C", and the storage stability of the colorant dispersion liquid was evaluated. The evaluation results are shown in Table 4.

Preparation Examples 2 to 6, Preparation Examples 8 to 11 and Comparative Preparation Examples 1 to 4

In Preparation Example 1, except that the types and amounts of the components were changed as shown in Table 4, the same operations as in Preparation Example 1 were performed to prepare colorant dispersions (D-2) to (D-6), (D -8) ~ (D-15). Next, the colorant dispersion liquids (D-2) to (D-6) and (D-8) to (D-15) were used instead of the colorant dispersion liquid (D-1). 1 Evaluation was performed in the same manner. The evaluation results are shown in Table 4.

Further, in Comparative Preparation Example 1, a dispersant BYK-LPN6919 (manufactured by BYK-Chemie (BYK) Co., Ltd., a nonvolatile content of 60% by mass, and an amine value of 72 mgKOH / g) was used instead of the polymer (A1-2-1) .

(Preparation of colorant solution)

Preparation Example 7

2.5 parts by mass of the compound (D2), 1.2 parts by mass of the compound (D3), 11.3 parts by mass of the compound (D4), and 2.0 parts by mass of the polymer (A1-2-2) solution (nonvolatile matter = 35 parts by mass) %), 13.0 parts by mass of the polymer (A1-2-8) solution (nonvolatile content = 35% by mass), and 70.0 parts by mass of PGME as a solvent were mixed to prepare a colorant solution (D-7). Then, it evaluated similarly to preparation example 1. The evaluation results are shown in Table 4.

Each component in Table 4 is as follows.

G58: C.I. Pigment Green 58

G7: C.I. Pigment Green 7

Y138: C.I. Pigment Yellow 138

Y215: C.I. Pigment Yellow 215

Y185: C.I. Pigment Yellow 185

R177: C.I. Pigment Red 177

R254: C.I. Pigment Red 254

R264: C.I. Pigment Red 264

Compound (D1): Pigment represented by the above formula (7)

B15: 6: C.I. Pigment Blue 15: 6

Compound (D2): A compound represented by the following formula (D2)

Compound (D3): A compound represented by the following formula (D3)

Compound (D4): A compound represented by the following formula (D4)

Compound (D5): A compound represented by the following formula (D5)

Compound (D6): A compound represented by the following formula (D6)

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

LPN6919: BYK-LPN6919 (manufactured by BYK-Chemie (BYK), non-volatile content is 60% by mass, and amine value is 72mgKOH / g)

S41000: Solsperse 41000 (manufactured by Lubrizol Co., Ltd., non-volatile content is 100% by mass)

"Oxi / oxe" represents the ratio of the total moles of ethylene oxide groups to the total moles of propylene oxide groups in all polymers constituting the polymer (A), and "w _oxi / w _oxe " represents that The total mass of the ethylene ethylenically unsaturated monomer (a1) in all the monomers constituting the polymer (A), w _{oxi is equal} to that of the ethylenically unsaturated monomer (a2) having a propylene oxide group. The proportion of the total mass _woxe of all the monomers constituting the (A) polymer.

The C.I. Pigment Yellow 215 uses a pigment having an average primary particle diameter of 70 nm.

<Synthesis of Binder Resin>

Synthesis Example 22

In a flask equipped with a cooling tube and a stirrer, 44.0 g of p-vinylbenzyl glycidyl ether, 40.0 g of N-phenylmaleimide, and 16.0 g of BzMA were dissolved in 300 g of PGMEA, and then AIBN 8.0 g and α- 8.0 g of methylstyrene dimer, followed by 15 minutes of nitrogen flushing. After purging with nitrogen, the reaction solution was heated to 80 ° C. while being stirred and bubbled with nitrogen, and polymerized for 5 hours.

Next, 17.0 g of MA, 0.5 g of p-methoxyphenol, and 4.4 g of tetrabutylammonium bromide were added to this reaction solution, and it was made to react at 120 degreeC for 9 hours. Further, 18.5 g of succinic anhydride was added, and after reacting at 100 ° C for 6 hours, the liquid temperature was maintained at 85 ° C for 1 hour for reaction. After cooling to room temperature, washing with water twice, and concentrating under reduced pressure, a solution containing 33% by mass of the binder resin (E-1) was obtained. This binder resin (E-1) had Mw = 7800 and Mw / Mn = 2.8 in terms of polystyrene measured by GPC (eluting solvent: THF). In addition, the epoxyethyl group did not remain in the binder resin (E-1).

Synthesis Example 23

In a flask equipped with a cooling tube and a stirrer, 12.0 g of N-phenylmaleimide, 10.0 g of styrene, 13.0 g of MMA, 30.0 g of CHMA, and 12.5 g of 2-methacryloxyethyl succinate g, 12.5 g of 2-hydroxyethyl methacrylate and 15.0 g of MA were dissolved in 200 g of propylene glycol monomethyl ether acetate, and then 4.0 g of azobis-2,4-dimethylvaleronitrile and α-methyl 5.0 g of styrene dimer, followed by 15 minutes of nitrogen purge. After the nitrogen gas was purged, the reaction solution was heated to 80 ° C. while being stirred and bubbled with nitrogen, and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (E-2). The binder resin (E-2) was measured by GPC (eluting solvent: THF). Mw = 10000 and Mw / Mn = 2.5.

<Preparation of colored radiation-sensitive composition and evaluation of colored cured film>

Example 101

(Preparation of colored radiation-sensitive composition)

100 parts by mass of a coloring agent dispersion liquid (D-1), 34.1 parts by mass of a resin (E-1) solution as a binder resin, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as polymerizable compounds 11.3 parts by mass of a mixture (trade name M-402, manufactured by Toa Synthesis Co., Ltd.) as a photopolymerization initiator 1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazole -3-yl] -Ethyl ketone 1- (O-acetamoxime) (trade name IRGACURE OX02, manufactured by Ciba Specialty Chemicals) 4.2 parts by mass of MEGAFAC F-554 (fluorine-based surfactant, DIC Corporation Limited) as an additive 0.1 part by mass of the company) and 162 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed to obtain a colored radiation-sensitive composition (CR-1).

(Evaluation of solvent resistance)

The obtained colored radiation-sensitive composition (CR-1) was applied on a glass substrate using a slit die coater, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.5 μm.

Next, after the substrate was cooled to room temperature, the high-pressure mercury lamp was used to expose the coating film on the substrate to an exposure amount of 1000 J / m ² with a radiation amount including 365 nm, 405 nm, and 436 nm through a photomask. Thereafter, post-baking was performed at 220 ° C. for 20 minutes to form a red cured film on the substrate.

This substrate was immersed in N-methylpyrrolidone at 60 ° C for 30 minutes. Then, the color change ΔEab ^* before and after the immersion was determined. A case where ΔEab ^{* is} less than 2 is evaluated as "A", a case where ΔEab ^* is 2 or more and less than 3 is evaluated as "B", and a case where ΔEab ^* is 3 or more and less than 4 is evaluated as "A""C" and "D" were evaluated when ΔEab ^* was 4 or more and less than 5, and "E" was evaluated when ΔEab ^* was 5 or more. It can be said that the smaller the ΔEab ^* , the better the solvent resistance. The results are shown in Table 5.

(Evaluation of voltage holding ratio)

After applying a colored composition (CR-1) on a glass substrate having a predetermined shape deposited on a ITO (indium-tin oxide) electrode by using a slot die coater, pre-baking in a clean oven at 90 ° C for 10 minutes. A coating film having a film thickness of 1,8 μm was formed.

Next, using a high-pressure mercury lamp, the coating film was exposed to radiation having a wavelength of 365 nm, 405 nm, and 436 nm at an exposure amount of 500 J / m ^{2 without} a mask. Thereafter, the substrate was immersed in a developing solution composed of a 0.04% by mass potassium hydroxide aqueous solution at 23 ° C for 1 minute, and after development, the substrate was washed with ultrapure water and air-dried, and further post-baked at 180 ° C for 30 minutes. The coating film is cured to form a red cured film on the substrate.

Next, the liquid crystal cell was placed in a constant-temperature layer at 60 ° C, and the voltage holding rate (VHR) of the liquid crystal cell was measured using a liquid crystal voltage holding rate measuring system VHR-1A (trade name) manufactured by TOYO Technica. The applied voltage at this time was a square wave of 5.0 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value of (the liquid crystal cell potential difference after 16.7 milliseconds / the applied voltage). The evaluation results are shown in Table 5. The larger the value of the voltage holding ratio, the better. In particular, if the voltage holding ratio is 90% or more, the liquid crystal cell can hold the applied voltage at a predetermined level for 16.7 milliseconds, which can fully make the liquid Crystal orientation and the possibility of "image sticking" such as afterimages are small, so it is preferable.

Examples 102 to 111, Comparative Examples 101 to 105

In Example 101, except that the kinds and amounts of the components were changed as shown in Table 4, the same operations as in Example 101 were performed to prepare colored radiation-sensitive compositions (CR-2) to (CR-15). Next, evaluation was performed in the same manner as in Example 101 except that the colored radiation-sensitive composition (CR-2) to (CR-15) were used instead of the colored radiation-sensitive composition (CR-1). The results are shown in Table 5.

However, in Example 102, [2- (methacryloxy) ethyl] dimethyl- (3-sulfopropyl) was further added to the obtained color-sensitive radiation composition (CR-2). 3.5 parts by mass of a 3: 1 (mass ratio) copolymer of ammonium hydroxide and MMA. In Example 107, 3- [dimethyl group was further added to the obtained color-sensitive radiation composition (CR-7). 1.3 parts by mass of (3-dodecanoylaminopropyl) ammonium] -2-hydroxypropane-1-sulfonate was further added to the obtained color-sensitive radiation composition (CR-11) in Example 111. 0.5 parts by mass of 3- (dimethyldodecylammonium) -2-hydroxypropane-1-sulfonate was added.

Each component in Table 5 is as follows.

B-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toa Synthesis Co., Ltd.)

B-3: A mixture of dipentaerythritol pentaacrylate and succinic acid, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toa Synthesis Co., Ltd.)

C-1: 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime) (trade name IRGACURE OX02, manufactured by Ciba Specialty Chemicals)

C-3: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4- Porphyrin) butane-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals)

C-4: NCI-831 (made by ADEKA Corporation)

F-1: ethyl 3-ethoxypropionate

F-2: Propylene glycol monomethyl ether

F-3: 3-methoxybutyl acetate

G-2: MEGAFAC F-554 (fluorine-based surfactant, manufactured by DIC Corporation)

"Oxi / oxe" represents the ratio of the total moles of ethylene oxide groups to the total moles of propylene oxide groups in all polymers constituting the polymer (A), and "w _oxi / w _oxe " represents The total mass of the ethylenically unsaturated monomer (a1) having an epoxy ethyl group in all the monomers constituting the polymer (A) w _oxi and the ethylenically unsaturated monomer (a2) having a propylene oxide group The ratio of the total mass _{woxe to} all the monomers constituting the (A) polymer.

Claims (16)

A radiation-sensitive composition comprising (A) a polymer, (B) a polymerizable compound, and (C) a radiation-sensitive polymerization initiator, and the (A) polymer is selected from the group consisting of the following polymer (A1), polymerization Polymer (A2) and polymer (A3), and is a polymer (A1), or a combination of polymer (A2) and polymer (A3), polymer (A1): having an epoxy ethyl group and Polymer of glycidyl group, polymer (A2): polymer having ethylene oxide group, excluding the polymer (A1), polymer (A3): polymer having propylene oxide group, where , Excluding the polymer (A1), the ratio of ethoxylate (oxi) to propylene oxide (oxe) in the (A) polymer is 3/97 ~ in terms of mole ratio (oxi / oxe) 50/50. The radiation-sensitive composition according to claim 1, wherein the polymer (A1) comprises an ethylenically unsaturated monomer (a1) having an epoxy ethyl group and an ethylenically unsaturated monomer (a1) having a propylene oxide group ( a2) is a copolymer of monomers, and the polymer (A2) is a polymer containing a monomer having an ethylenically unsaturated monomer (a1) having an epoxyethyl group, and the polymer (A1) is not included, The polymer (A3) is a polymer including a monomer having an propylene oxide-containing ethylenically unsaturated monomer (a2), and the polymer (A1) is not included. The radiation-sensitive composition according to claim 2, wherein the unsaturated monomer (a1) includes an ethylenically unsaturated monomer having a glycidyl ether group or an alicyclic ring obtained by epoxidizing a carbon-carbon double bond An ethylenically unsaturated monomer of the formula group. The radiation-sensitive composition according to claim 2 or 3, wherein the unsaturated monomer (a1) contains at least 1 selected from the group consisting of a compound represented by any one of the following formulae (1) to (3) Species, In formula (1), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, which may contain a hetero atom, In formulas (2) and (3), R ² independently represents a hydrogen atom or a methyl group, and X ² independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms that may contain a hetero atom. The radiation-sensitive composition according to claim 2 or 3, wherein the unsaturated monomer (a2) contains at least 1 selected from the group consisting of a compound represented by any one of the following formulae (4) to (6) Species, In the formulae (4), (5), and (6), R ²¹ and R ³¹ independently represent a hydrogen atom or a methyl group, and R ¹¹ to R ¹⁵ , R ²² to R ^26, and R ³² to R ³⁶ are independent of each other. A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group, Y ¹ , Y ^2, and Y ³ each independently represent a single bond or may contain one or more hetero atoms An alkanediyl group having 1 to 6 carbon atoms. The radiation-sensitive composition according to claim 1, wherein at least one of the polymers (A1) to (A3) further has a substituted or unsubstituted amine group. The radiation-sensitive composition according to claim 1, further comprising (D) a colorant. The radiation-sensitive composition according to claim 7, wherein the (D) colorant contains a dye. The radiation-sensitive composition according to claim 1, wherein the ratio of the oxiethylene group (oxi) to the propylene oxide group (oxe) in the (A) polymer is 3 in terms of mole ratio (oxi / oxe) / 97 ~ 30/70. A cured film formed using the radiation-sensitive composition according to any one of claims 1 to 9. A display element having a cured film as claimed in claim 10. A dispersant containing (A) a polymer selected from the group consisting of a polymer (A1), a polymer (A2), and a polymer (A3), and a polymer (A1) ), Or a combination of polymer (A2) and polymer (A3), polymer (A1): a polymer having ethylene oxide and propylene oxide groups, polymer (A2): a polymer having ethylene oxide Polymer (excluding the polymer (A1), polymer (A3): a polymer having a propylene oxide group, wherein the polymer (A1) is not included, and the epoxy in the (A) polymer is not included) The ratio of ethyl (oxi) to propylene oxide (oxe) is 3/97 ~ 50/50 in terms of molar ratio (oxi / oxe). The dispersant according to claim 12, wherein at least one of the polymers (A1) to (A3) further has a substituted or unsubstituted amine group. For example, the dispersant according to claim 12, wherein the ratio of oxiethylene (oxi) to propylene oxide (oxe) in the (A) polymer is 3/97 ~ in terms of molar ratio (oxi / oxe). 30/70. A colorant dispersion containing (A) a polymer, (D) a colorant, and (F) a solvent, the (A) polymer being selected from the group consisting of the following polymer (A1), polymer (A2), and polymer (A3), and is a polymer (A1), or a combination of a polymer (A2) and a polymer (A3), and the polymer (A1): a polymer having an ethylene oxide group and a propylene oxide group , Polymer (A2): a polymer having an epoxy ethyl group, wherein the polymer (A1) is not included, and a polymer (A3): a polymer having an propylene oxide group, which does not include the polymer ( A1). The ratio of oxirane (oxi) to propylene oxide (oxe) in the (A) polymer is 3/97 to 50/50 in terms of molar ratio (oxi / oxe). For example, the colorant dispersion liquid of claim 15, wherein the ratio of oxirane (oxi) to propylene oxide (oxe) in the (A) polymer is 3 / in terms of molar ratio (oxi / oxe) 97 ~ 30/70.