TW201543153A - Radiation-sensitive composition, cured film, display device and colorant dispersion liquid - Google Patents

Abstract

The present invention provides a radiation-sensitive composition having good storage stability and capable of forming a cured film having excellent solvent resistance. The solution of the present invention is a radiation-sensitive composition, which comprises a polymer (A), a polymeric compound (B), and a radiation-sensitive polymerization initiator (C). The polymer (A) is selected from a group comprising the following: a polymer (A1), a polymer (A2) and a polymer (A3), and is the polymer (A1) or a combination of the polymer (A2) and the polymer (A3). The polymer (A1) is a polymer having an oxiranyl group and an oxetanyl group. The polymer (A2) is a polymer having an oxiranyl group excluding the above polymer (A1). The polymer (A3) is a polymer having an oxetanyl group excluding the above polymer (A1). The proportion of the oxiranyl group (oxi) and the oxetanyl group (oxe) in the polymer (A) in a molar ratio (oxi / oxe) is 3/97~50/50.

Description

Radiation-sensitive composition, cured film, display element, and colorant dispersion

The present invention relates to a radiation sensitive composition, a cured film, and a display element, and more particularly to a color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, etc., which are formed in a transmissive or reflective type. The radiation-sensitive composition of the cured film used for the film is a cured film formed using the radiation-sensitive composition, and a display element including the cured film.

When a color filter is produced using a coloring sensitizing radiation composition, a method is known in which a pigment-dispersed color-sensing radiation-sensitive composition is applied onto a substrate and dried, and the dried coating film has a desired pattern. The shape is irradiated with radiation (hereinafter referred to as "exposure"), and development is performed to obtain pixels of respective colors (for example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is known (for example, see Patent Document 3). In addition, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed coloring resin composition is known (for example, refer to Patent Document 4).

Moreover, 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 viewpoint of solvent resistance, A composition having a polymer having an epoxy group or a propylene oxide group is a material capable of forming a cured film having good solvent resistance (for example, refer to Patent Documents 5 to 8).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188

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

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

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

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

[Patent Document 8] Japanese Patent Laid-Open Publication 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 also 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 which is excellent in storage stability and can form a cured film which is excellent in solvent resistance.

In view of the above facts, the present inventors conducted intensive studies and found that by using a radiation-sensitive composition containing a polymer having a specific ratio of ethylene oxide and propylene oxide groups, hard The solvent resistance of the film is surprisingly greatly improved, and the storage stability is also excellent, and the present invention has been completed.

That is, the present invention provides a radiation sensitive composition comprising (A) a polymer, (B) a polymerizable compound, and (C) a radiation-sensitive polymerization initiator, wherein the (A) polymer is selected from the group consisting of the polymerization described below In the group of the substance (A1), the polymer (A2) and the polymer (A3), it is a polymer (A1), or a combination of the polymer (A2) and the polymer (A3), and the polymer (A1): Polymer polymer (A2) having an epoxyethyl group and an oxypropylene group: a polymer having an epoxy group (excluding the above polymer (A1)) polymer (A3): having an oxypropylene group Polymer (wherein the above polymer (A1) is not included), the ratio of epoxy ethyl group (oxi) to oxypropylene (oxe) in the above (A) polymer is in molar ratio (oxi/oxe) Calculated as 3/97~50/50.

Further, the present invention provides a cured film formed using the above-described radiation sensitive composition and a display element including the cured film. Here, the "cured film" refers to each color pixel, a protective film, a black matrix, a spacer, an insulating film, or the like used in a display element or a solid-state imaging element.

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

Therefore, the radiation sensitive composition of the present invention is extremely suitable for producing a color filter for a color liquid crystal display element, a solid-state image sensor, a color filter for an organic EL display element, and a color filter for an electronic paper. The light sheet is represented by various color filters. Moreover, it is extremely useful as a protective film material, a spacer material, and an insulating film material.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

(sensing radioactivity 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 which undergoes 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 polymer (A1), the polymer (A2), and the polymer (A1) in the polymer (A3), or the polymer (A2) and the polymer (A3). The combination is as the component (A). As the component (A), as long as it contains the polymer (A1) or a combination of the polymer (A2) and the polymer (A3), it can be obtained from the polymer (A1), the polymer (A2), and the polymer (A3). The polymer is appropriately selected and contained. For example, when the polymer (A1) is used as the component (A), at least one selected from the group consisting of the polymer (A2) and the polymer (A3) may be contained in addition to the polymer (A1). The component (A) preferably contains at least the polymer (A1) from the viewpoint of solvent resistance.

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

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

Polymer (A3): a polymer having an oxypropylene group (wherein the polymer (A1) is not included).

Further, the present inventors have conducted intensive studies and found that the storage stability is surprisingly excellent by controlling the ratio of the epoxyethyl group to the oxypropylene group in the (A) polymer within a predetermined range. Further, it is possible to form a cured film which is extremely excellent in solvent resistance.

That is, the ratio of epoxy ethyl group (oxi) to oxypropylene group (oxe) in the (A) polymer is 3/97 to 50/50 in terms of molar ratio (oxi/oxe), from further improving solvent resistance. From the viewpoint of sexuality, it is preferably 4/96 to 30/70, more preferably 5/95 to 23/77, further preferably 6/94 to 20/80, and particularly preferably 7/93 to 16/84.

As the above polymer (A1), for example, may be a copolymer of a monomer comprising an ethylenically unsaturated monomer (a1) having an epoxy group and an ethylenically unsaturated monomer (a2) having an oxypropylene group. As the above polymer (A2), for example, a polymer containing a monomer having an ethylenically unsaturated monomer (a1) having an epoxy group (excluding the above polymer (A1)) may be mentioned as The polymer (A3), for example, may be a polymer of a monomer containing an ethylenically unsaturated monomer (a2) having an oxypropylene group (wherein the above polymer (A1) is not included).

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

Here, oxi/oxe is a ratio of the total number of moles of the epoxy group in the total polymer constituting the component (A) to the total number of moles of the propylene oxide group, and the mass ratio (w) _Oxi /w _oxe ) is an ethylenically unsaturated monomer having an epoxyethyl group (a1) in the total mass of the monomers constituting the (A) polymer, w _oxi and ethylene having an propylene oxide group The ratio of the total mass w _oxe of the saturated monomer (a2) in all the monomers constituting the (A) polymer. For example, as the component (A), when at least one polymer selected from the group consisting of the polymer (A2) and the polymer (A3) is contained in addition to the polymer (A1), the oxi/oxe is polymerization. And (A1) and at least one polymer selected from the group consisting of polymer (A2) and polymer (A3) having a total molar number of ethylene oxide (oxi) and a total mole of oxypropylene (oxe) The ratio of the number of ears, the mass ratio (w _oxi /w _oxe ) is occupied by all the monomers constituting the polymer (A1) and at least one polymer selected from the group consisting of the polymer (A2) and the 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 epoxy group include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and (meth)acrylic acid β. -ethylglycidyl ester, vinyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinyl vinyl shrinkage Glycerol 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-glycol (glycidyloxymethyl)styrene, 2,3,5-gin (glycidyloxymethyl)styrene, 2,3,6-gin ( Glycidyloxymethyl)styrene, 3,4,5-gin (glycidyloxymethyl)styrene, 2,4,6-gin (glycidyloxymethyl)styrene, etc. a glycidyl ether group-containing ethylenically unsaturated monomer; 1,2-epoxy-4-vinylcyclohexane; a compound represented by the following formula (1); a compound represented by the following formula (2); The compound represented by the following formula (3) or the like has an alicyclic group-containing ethylenically unsaturated monomer obtained by epoxidizing a carbon-carbon double bond.

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 the formulae (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 which 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, ethyl, 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-di 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 above 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 such a hetero atom-containing alkanediyl group include (*)-CH ₂ CH ₂ —O—, (*)-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 - and the like. Among them, (*) indicates a bonding bond with -COO-.

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

The compound represented by the formula (2) includes a compound represented by the formula (2-1) to (2-8).

The compound represented by the formula (3) may, for example, be a compound represented by the formula (3-1) to (3-8).

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

The ethylenically unsaturated monomer (a1) having an epoxy group may be used singly or in combination of two or more.

Examples of the propylene oxide group-containing ethylenically unsaturated monomer (a2) include a compound represented by the following formula (4), a compound represented by the following formula (5), and the following formula (6). The compound represented, etc.

[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 hetero atoms.

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

[In the formula (6), R ³¹ represents a hydrogen atom or a methyl group, and R ³² to R ³⁶ independently of each other represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted one. 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 hetero atoms.

The alkyl group having 1 to 6 carbon atoms may be linear or branched. Specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a n-pentyl group, a secondary pentyl group, and a new one. Amyl, n-hexyl and the like. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is further more preferable.

The aryl group means 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 thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, and a 9-fluorenyl group. Among them, a phenyl group 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. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or 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 from 1 to 6. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Further, the position and the number of the substituent are arbitrary, and for example, when a fluorine atom is used as a substituent, a perfluoroalkyl group may also be used. Further, when two or more substituents are present, the substituents may be the same or different.

The alkanediyl group having 1 to 6 carbon atoms may be linear or branched, and specific examples thereof include the same alkanediyl groups as described above. 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. Further, the alkanediyl group having 1 to 6 carbon atoms may contain one or more hetero atoms, and examples of the hetero atom include the same oxygen atom, sulfur atom, nitrogen atom and the like as described above. Specific examples of the alkanediyl group having one or more hetero atoms include, for example, the same alkanediyl group as described above, and -O-CH ₂ CH ₂ CH ₂ -O-CH ₂ -, -CH 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.

The compound represented by the formula (4) may, for example, be 3-(vinyloxymethyl)-2-methyl propylene oxide or 3-(vinyloxy). Methyl)-3-methyl propylene oxide, 3-(vinyloxymethyl)-2-ethyl propylene oxide, 3-(vinyloxymethyl)-3-ethyl propylene oxide, 3- (Vinyloxyethyl)-2-methyl propylene oxide, 3-(vinyloxyethyl)-3-methyl propylene oxide, 3-(vinyloxyethyl)-2-ethyl epoxy Propane, 3-(vinyloxyethyl)-3-ethyl propylene oxide, 2-(vinyloxymethyl)-2-methyl propylene 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-(vinyloxyethyl)-3-methyl propylene oxide, 2-(vinyloxyethyl)-2-ethyl propylene oxide, 2-(ethylene (Vinyloxyalkyl)alkyl propylene oxide such as oxyethyl)-3-ethyl propylene oxide.

The compound represented by the formula (5) includes, for example, 3-[(meth)acrylomethoxymethyl]epoxypropane, 3-[2-(methyl)acryloyloxyethyl]propylene oxide. , ([meth)acrylomethoxymethyl] propylene oxide, (meth) propylene oxyalkylene oxide such as 2-[2-(methyl) propylene oxyethyl] propylene oxide Propane; such as 3-[(meth)acrylomethoxymethyl]-2-methyl propylene oxide, 3-[(methyl) propylene oxymethyl] 3-methyl propylene oxide, 3-[( Methyl) propylene oxime methyl]-2-ethyl propylene oxide, 3-[(methyl) propylene 醯 oxymethyl]-3-ethyl propylene oxide, 3-[2-(methyl) propylene醯 ethoxyethyl]-2-methyl propylene oxide, 3-[2-(methyl) propylene oxiranyloxy] 3-methyl propylene oxide, 3-[2-(methyl) propylene oxime 2-ethyl propylene oxide, 3-[2-(methyl) propylene oxiranyl]-3-ethyl propylene oxide, 2-[(methyl) propylene oxymethyl]-2 -methyl propylene oxide, 2-[(meth)acrylomethoxymethyl]-3-methyl propylene oxide, 2-[(methyl) propylene oxymethyl] 4-methyl propylene oxide, 2-[(A Base) propylene oxime methyl]-2-ethyl propylene oxide, 2-[(methyl) propylene oxime methyl]-3-ethyl propylene oxide, 2-[(meth) propylene oxime 4-ethyl propylene oxide, 2-[2-(methyl) propylene oxyethyl]-2-methyl propylene oxide, 2-[2-(methyl) propylene oxirane] 3-methyl propylene oxide, 2-[2-(methyl) propylene oxiranyl] 4-methyl propylene oxide, 2-[2-(methyl) propylene oxirane ethyl]-2 -ethyl propylene oxide, 2-[2-(methyl)acryloyloxyethyl]-3-ethyl propylene oxide, 2-[2-(methyl) propylene oxyethyl]-4-B [(Methyl) propylene sulfoxyalkyl] alkyl propylene oxide such as propylene oxide; such as 3-[(methyl) propylene oxymethyl]-2-trifluoromethyl propylene oxide, 3 -[(Meth)acryloyloxymethyl]-2-pentafluoroethyl propylene oxide, 3-[(methyl) propylene oxymethyl]-2-fluoro propylene oxide, 3-[(methyl ) propylene oxime methyl]-2,2-difluoro propylene oxide, 3-[(methyl) propylene oxime methyl]-2,2,4-trifluoroepoxypropane, 3-[(methyl ) propylene oxime methyl]-2,2,4,4-tetrafluoro propylene oxide, 3-[2-(methyl) propylene oxyethyl]-2-trifluoromethyl propylene oxide, 3- [2-(methyl)acryloyloxyethyl]-2-pentafluoroethyl Propylene oxide, 3-[2-(methyl)acryloyloxyethyl]-2-fluoroepoxypropane, 3-[2-(methyl)acryloyloxyethyl]-2,2-difluoro Propylene oxide, 3-[2-(methyl)acryloyloxyethyl]-2,2,4-trifluoroepoxypropane, 3-[2-(methyl)propene oxiranyl]-2, 2,4,4-tetrafluoropropene oxide, 2-[(meth)acrylomethoxymethyl]-2-trifluoromethyl propylene oxide, 2-[(methyl) propylene oxime methyl]- 3-trifluoromethyl propylene oxide, 2-[(meth)acrylomethoxymethyl]-4-trifluoromethyl propylene oxide, 2-[(methyl) propylene oxymethyl]-2- Pentafluoroethyl propylene oxide, 2-[(meth)acrylomethoxymethyl]-3-pentafluoroethyl propylene oxide, 2-[(methyl) propylene oxymethyl]-4-pentafluoro Ethyl propylene oxide, 2-[(methyl) propylene oxime methyl]-2,3-difluoro propylene oxide 2-[(Meth)acryloyloxymethyl]-2,4-difluoroepoxypropane, 2-[(meth)acrylomethoxymethyl]-3,3-difluoroepoxypropane, 2 -[(Methyl)acryloxymethyl]-3,4-difluoroepoxypropane, 2-[(methyl)acryloxymethyl]-4,4-difluoropropene oxide, 2-[ (Meth)acryloyloxymethyl]-3,3,4-trifluoroepoxypropane, 2-[(meth)acrylomethoxymethyl]-3,4,4-trifluoroepoxypropane, 2 -[(Methyl)acryloxymethyl]-3,3,4,4-tetrafluoropropene oxide, 2-[2-(methyl)propenyloxyethyl]-2-trifluoromethyl ring Oxypropane, 2-[2-(methyl)acryloyloxyethyl]-3-trifluoromethylpropane, 2-[2-(methyl)propenyloxyethyl]-4-trifluoromethyl Propylene oxide, 2-[2-(methyl)acryloyloxyethyl]-2-pentafluoroethyl propylene oxide, 2-[2-(methyl) propylene oxiranyl]-3-five Fluoroethyl propylene oxide, 2-[2-(methyl) propylene oxyethyl]-4-pentafluoroethyl propylene oxide, 2-[2-(methyl) propylene oxirane ethyl]-2 , 3-difluoroepoxypropane, 2-[2-(methyl)acryloyloxyethyl]-2,4-difluoroepoxypropane, 2-[2-(methyl)propene oxiranyl] -3,3-difluoroepoxypropane, 2-[2-(methyl)acryloyloxyethyl]-3,4-difluoroepoxy Alkane, 2-[2-(methyl)acryloyloxyethyl]-4,4-difluoroepoxypropane, 2-[2-(methyl)acryloyloxyethyl]-3,3,4- Trifluoroepoxypropane, 2-[2-(methyl)acryloyloxyethyl]-3,4,4-trifluoroepoxypropane, 2-[2-(methyl)propene oxiranyl]- [(Meth)acryloyloxyalkyl]fluoroepoxypropane or [(meth)acryloyloxyalkyl]fluoroalkyl propylene oxide such as 3,3,4,4-tetrafluoropropylene oxide; Such as 2-[(meth)acrylomethoxymethyl]-2-phenyl propylene oxide, 2-[(methyl) propylene oxymethyl]-3-phenyl propylene oxide, 2-[(A Acetyl methoxymethyl]-4-phenyl propylene oxide, 2-[2-(methyl) propylene oxiranyloxy]-2-phenyl propylene oxide, 2-[2-(methyl) Propylene oxiranyl ethyl]-3-phenyl propylene oxide, 2-[2-(methyl) propylene oxyethyl]-4-phenyl propylene oxide [(Methyl) propylene oxyalkyl] phenyl propylene oxide and the like.

The compound represented by the formula (6) includes, for example, 4-[3-(3-ethyl propylene oxide-3-ylmethoxy)propoxy]styrene, 4-[4-(3). -ethyl propylene oxide-3-ylmethoxy)butoxy]styrene, 4-[5-(3-ethyl propylene oxide-3-ylmethoxy)pentyloxy]styrene, 4 -[6-(3-ethylepoxypropan-3-ylmethoxy)hexyloxy]styrene, 4-[7-(3-ethylepoxypropan-3-ylmethoxy)heptyloxy An aromatic vinyl compound having an oxypropylene group such as styrene.

Among these unsaturated monomers (a2), a compound represented by the formula (4) and a compound represented by the formula (5) are preferred. Among them, from the viewpoint of improving the solvent resistance of the obtained cured film, 3-(vinyloxymethyl)-3-ethyl propylene oxide and 3-[(meth) propylene oxime methyl group are preferable. Propylene oxide, 3-[(meth)acrylomethoxymethyl]-3-ethyl propylene oxide, 3-[(meth)acrylomethoxymethyl]-2-trifluoromethyl propylene oxide, 3-[(Methyl)acrylomethoxymethyl]-2-phenyl propylene oxide, 2-[(meth) propylene oxime oxymethyl] propylene oxide, 2-[(meth) propylene fluorene Base]-4-trifluoromethyl propylene oxide.

The polymers (A1) to (A3) may contain functional groups other than the epoxyethyl group and the propylene oxide group. For example, when the polymers (A1) to (A3) have a carboxyl group, it is preferable in terms of having alkali solubility, and the polymer can be imparted as a binder resin. Further, when the polymers (A1) to (A3) have a substituted or unsubstituted amino group, it is preferable in terms of excellent pigment dispersibility, and a function as a dispersing agent can be imparted to the polymer. 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 in the polymer (A3) A substituted or unsubstituted amino group may be used. Thereby, the component (A) can be more preferably used as a dispersing agent. Further, the substituted or unsubstituted amino 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 thereof include the same alkyl group and aromatic group as described above. base.

That is, the polymers (A1) to (A3) may contain an ethylenically unsaturated monomer (a1) having an epoxy group (hereinafter also referred to as "unsaturated monomer (a1)") and having an oxypropylene group. The ethylenically unsaturated monomer other than the ethylenically unsaturated monomer (a2) (hereinafter also referred to as "unsaturated monomer (a2)") is preferably a monomer unit, and from the viewpoint of storage stability, it is preferred to contain no A copolymer of a monomer unit other than the saturated monomer (a1) and the unsaturated monomer (a2). Examples of the unsaturated monomer other than the unsaturated monomer (a1) and the unsaturated monomer (a2) include an ethylenically unsaturated monomer (a3) having one or more carboxyl groups, and a substituted or non-substituted monomer. Substituted amine-based ethylenically unsaturated monomer (a4), other copolymerizable ethylenically unsaturated monomer (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 thereof include the same alkyl groups and aryl groups as 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. , succinic acid mono [2-(methyl) propylene oxiranyl] ester, ω-carboxy polycaprolactone mono (meth) acrylate, p-vinyl benzoic acid, and the like.

The unsaturated monomer (a3) may be used singly or in combination of two or more.

The ethylenically unsaturated monomer (a4) having a substituted or unsubstituted amino group (hereinafter also referred to as "unsaturated monomer (a4)") is exemplified by dimethylamino group (meth) acrylate. Ester, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like.

The unsaturated monomer (a4) may be used singly or in combination of two or more.

In addition, examples of the other copolymerizable ethylenically unsaturated monomer (a5) (hereinafter also referred to as "unsaturated monomer (a5)") include, for example, N-phenylmaleimide, N- N-position substituted maleimine such as cyclohexylmaleimide; such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, terpenes, and the like Aromatic vinyl compound; such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (a Allyl acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (methyl) Acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, (a) Isobornyl acrylate, tricyclo[5.1.02 ^2,6 ]non-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenylethyl methacrylate, pair a (meth) acrylate such as an ethylene oxide-modified (meth) acrylate of a phenol; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]癸a vinyl ether such as alkane-8-yl vinyl ether or pentacyclopentadecyl vinyl ether; such as polystyrene, poly(methyl) methacrylate, poly(methyl) acrylate, poly A macromonomer having a mono(meth)acrylinyl group at the end of the polymer molecular chain such as a siloxane or the like.

The unsaturated monomer (a5) may be used singly or in combination of two or more.

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

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

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

In the case where the polymer (A1) to (A3) is a copolymer 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, further preferably 3~30 % by mass, particularly preferably 5 to 20% by mass.

In the case where the polymer (A1) to (A3) is a copolymer 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, further preferably 10 to 45% by mass, particularly preferably 15 to 40% by mass.

In the case where the polymer (A1) to (A3) is a copolymer containing an unsaturated monomer (a5) as a monomer unit, the copolymerization ratio of the unsaturated monomer (a5) is preferably from 10 to 70% by mass, furthermore Good is 20~60% by mass, especially preferably 25~55% by mass. Thereby, the polymers (A1) to (A3) can be synthesized at a desired conversion rate without gelation, and the radiation-sensitive composition containing the obtained polymers (A1) to (A3) is resistant. Solvent and developability are more preferable, and therefore it is preferable.

When the polymer (A1) to (A3) has one or more carboxyl groups, the acid value of the polymer is preferably from 10 to 200 mgKOH/g, more preferably from 50 to 160 mgKOH/g, particularly preferably from 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, and specifically, it is described in the examples described later. Method to determine the value. Here, the "nonvolatile content" in the present specification is a component other than the solvent (F) described later.

Further, when the polymer (A1) to (A3) has a substituted or unsubstituted amine group, the amine value of the polymer is preferably from 1 to 200 mgKOH/g, further preferably from 10 to 150 mgKOH/g, particularly preferably from 20 ~100mgKOH/g. Here, the "amine value" in the present invention is the number of 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, and specifically, it is described later. Method described in the examples Measured value.

Further, the polymers (A1) to (A3) may have a polymerizable unsaturated bond such as a (meth)acryl fluorenyl group in the side chain. As such a polymer, for example, i) a monomer containing at least one selected from the group consisting of an unsaturated monomer (a1) and an unsaturated monomer (a2) and a polymerizable unsaturated compound having a hydroxyl group a polymer obtained by reacting a copolymer with an unsaturated isocyanate compound, ii) containing at least one selected from the group consisting of an unsaturated monomer (a1) and an unsaturated monomer (a2), and an ethylenic group having one or more carboxyl groups a polymer obtained by reacting a copolymer of a monomer of the unsaturated monomer (a3) with an ethylenically unsaturated monomer (a1) having an epoxy group, iii) having a polymer (A1) or (A2) and having A polymer obtained by reacting one or more carboxyl group-containing ethylenically unsaturated monomers (a3).

(A) The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the polymer is preferably 3,000 to 50,000, more preferably 5,000. 30000.

Further, the ratio (Mw/Mn) of the Mw of the (A) polymer to the polystyrene-converted number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) Good is 1~5, more preferably 1~4.

(A) The polymer can be synthesized by a known method, for example, JP-A-2012-255963, and JP-A-2009-116316.

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

In the present invention, the composition contains a (D) colorant described later. When the coloring composition is colored, the content of the (A) polymer is usually 5 to 200 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of the (D) colorant. By such an aspect, it is easy to achieve a desired color density when forming a film. Further, when the radiation sensitive composition containing no (D) coloring agent is formed, the content ratio of the (A) polymer is 5 to 70% by mass, preferably 10 to 50%, based on the solid content of the radiation sensitive composition. quality%. Here, the "solid content" in the present specification is a component other than the solvent (F) described later.

- (B) Polymeric 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)acrylinyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. An ester-modified polyfunctional (meth) acrylate, a polyfunctional (meth) acrylate modified with an alkylene oxide, a polyfunctional amine obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a carbamic acid ester (meth) acrylate, a (meth) acrylate having a hydroxyl group, and 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, or polypropylene glycol; for example, glycerin or trimethylolpropane Quarter A trivalent or higher aliphatic polyhydroxy compound such as tetraol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. Dipentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, such as pyromellitic acid. A tetrabasic acid dianhydride such as dianhydride, biphenyl tetracarboxylic dianhydride, or benzophenone tetracarboxylic dianhydride.

In addition, as the polyfunctional (meth) acrylate which is modified by the caprolactone, for example, the compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified. The polyfunctional (meth) acrylate modified with the alkylene oxide may, for example, be bisphenol A di(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. At least one modified iso-trisocyanate selected from at least one selected from the group consisting of ethylene oxide and propylene oxide, modified from at least one selected from the group consisting of ethylene oxide and propylene oxide a trimethylolpropane tri(meth) acrylate, at least one modified pentaerythritol tri(meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from ethylene oxide And at least one modified pentaerythritol tetra(meth)acrylate of propylene oxide, at least one modified dipentaerythritol penta (meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, At least one modified dipentaerythritol hexa(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the melamine structure and the benzoguanamine structure mean that there are one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton is also a concept including melamine, benzoguanamine or the like. 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)glycolil and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid or a polyfunctional (methyl group) modified with caprolactone is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. From the viewpoint of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in generation of scum, film residue, and the like on the unexposed portion of the substrate and the light-shielding layer, the aliphatic polyhydroxy compound having three or more members is used. Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Among the polyfunctional (meth) acrylates of a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferred.

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

In the coloring radiation-containing linear composition containing the coloring agent (D), the content of the (B) polymerizable compound in the present invention is usually 5 to 600 parts by mass, preferably 5 to 600 parts by mass, based on 100 parts by mass of the (A) polymer. It is 20 to 400 parts by mass. In such an aspect, sufficient curability can be obtained, and when alkali developability is imparted to the radiation sensitive composition of the present invention, alkali developability is good, and it is difficult to be on the substrate or the light shielding layer of the unexposed portion. Scum, film residue, etc. are generated. In addition, when the radiation sensitive composition containing no (D) coloring agent is formed, the content of the (B) polymerizable compound is usually 10 to 500 parts by mass, preferably 50%, based on 100 parts by mass of the (A) polymer. ~300 parts by mass.

-(C) Radiation-Based 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 which generates an active species capable of initiating polymerization of the above polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray, and the present invention can be used. The radiation sensitive composition acts as a negative radiation sensitive composition.

Examples of such a radiation-sensitive polymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. Compound, O-antimony compound, sulfonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polynuclear oxime compound, diazo compound, sulfhydrazine sulfonic acid An ester compound or the like.

In the present invention, the radiation-sensitive linear polymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a compound and an O-lanthanide compound.

In a preferred radiation-sensitive polymerization initiator of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-iso Propyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4 - Diisopropyl thioxanthone and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-phenylpropan-1-one and 2-benzyl-2. -dimethylamino-1-(4- Phenylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenylphenyl)butan-1-one and the like.

Further, specific examples of the biimidazole-based compound include 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.

Further, when a biimidazole-based compound is used as the radiation-sensitive polymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving the sensitivity. The "hydrogen donor" referred to herein means a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. A mercaptan such as a thiol-based hydrogen donor, an amine-based hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone . In the present invention, the hydrogen donor may be used singly or in combination of two or more. From the viewpoint of further improving the sensitivity, one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors are preferably used. Used in combination.

In addition, as the above three Specific examples of the compound include 2,4,6-paraxyl (trichloromethyl) symmetry III. 2-methyl-4,6-bis(trichloromethyl) symmetry three , 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetric three 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetric three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric three 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric three 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) symmetry three 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)symmetric three 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)symmetric three Three with a halomethyl group a compound.

Further, specific examples of the O-lanthanoid compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1 -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl- 6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl -6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidenyl}-9H-indazol-3-yl]- Ethyl ketone 1-(O-acetamidine) and the like. As a commercial item of the O-antimony-based compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), DFI-020, DFI-091 (manufactured by Daito Chemix Co., Ltd.), or the like can be used. .

In the present invention, when a radiation-sensitive polymerization initiator other than a biimidazole-based compound such as an acetophenone-based compound is used, it is also possible to use a sensitive one. Chemical agent. Examples of such a sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-di Ethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethyl Amino) ketone and the like.

In the present invention, the content of the (C) radiation-sensitive polymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100, per 100 parts by mass of the (B) polymerizable compound, with or without the coloring agent (D). Parts by mass. By such an aspect, the curability and film properties can be further improved.

The radiation sensitive composition of the present invention may contain 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 color sensitizing radiation composition for forming a coloring layer of a color filter can be obtained. Here, the "colored layer" refers to each color pixel, black matrix, or the like used in the color filter. The coloring agent can be used without particular limitation as long as it has coloring properties, and the color and material can be appropriately selected depending on the use of the radiation sensitive composition. When the radiation sensitive composition of the present invention is used to form pixels of the respective colors constituting the color filter, it is preferably selected from pigments and dyes because it requires high color purity, brightness, contrast, and the like for the color filter. At least one kind of coloring agent is particularly preferably an organic pigment or an organic dye.

Examples of the pigment include organic pigments and inorganic pigments. Preferred examples of the pigments include color index (C.I.). Name CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, Pigment 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. Preferable specific examples of the inorganic pigment include carbon black and titanium black.

As the pigment, a lake pigment is also preferable, and specific examples thereof include a triarylmethane dye using the same polyacid or heteropoly acid. A pigment obtained by performing a lake dyeing process. The triarylmethane-based lake pigment is disclosed, for example, in JP-A-2011-186043. The lake pigment is disclosed in, for example, Japanese Laid-Open Patent Publication No. 2010-191304.

Further, as the dye, it is preferably A dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye, an azo dye, or the like. More specifically, JP-A-2010-32999, JP-A-2010-254964, JP-A-2011-138094, International Publication No. 2010/123071, and JP-A-2011-116803 An organic dye described in, for example, Japanese Laid-Open Patent Publication No. 2011-174987, and Japanese Laid-Open Patent Publication No. 2011-174987. In general, it is known that a colored cured film formed using a dye-containing colored composition is insufficient in solvent resistance, but the colored composition of the present invention can form a color hardening excellent in solvent resistance even when a dye is contained as a coloring agent. membrane.

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

In the present invention, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or the like. Further, if necessary, the surface of the particles may be modified with a resin and used. Further, the organic pigment can be used by making the primary particles fine by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

When a pigment is used as the colorant in the present invention, it may be used together with a dispersing agent or a dispersing aid as needed. As the dispersing agent, for example, a suitable dispersing agent such as a cationic system, an anionic surfactant or a nonionic surfactant can be used, and a polymer dispersant is preferred. Specific examples thereof include an acrylic copolymer, a polyurethane, a polyester, a polyethyleneimine, and a polyallylamine.

Such a dispersing agent is commercially available, and examples of the acrylic dispersing agent include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, BYK-Chemie (BYK)), and the like. Examples of the polyurethane dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK-Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), etc., as a polyethyleneimine-based dispersing agent, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc., and as a polyester-based dispersing agent, Adisper PB821 and Adisper PB822, Adisper PB880, Adisper PB881 (above, Ajinomoto Fine-Techno Co., Ltd.), and BYK-LPN21324 (manufactured by BYK-Chemie (BYK) Co., Ltd.).

Further, a copolymer with an ethylenically unsaturated monomer (a4) having an amine group, that is, the (A) polymer of the present invention can be used as a dispersing agent. The preferred mode of using the (A) polymer as a dispersing agent is as described above.

In addition, specific examples of the pigment derivative include a sulfonium cyanine, a diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

The other coloring agents in the present invention may be used singly or in combination of two or more.

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

-(E) Adhesive Resin -

The radiation sensitive composition of the present invention may contain a binder resin (excluding the above polymer (A1) to polymer (A3)). Thereby, the alkali solubility of the radiation sensitive composition, the adhesion to the substrate, the storage stability, and the like can be improved. The binder resin is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, A polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as "unsaturated monomer". (e1)") a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (e2)").

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

In addition, examples of the unsaturated monomer (e2) include the same unsaturated monomers as the above-described unsaturated monomers (a4) to (a5), and these unsaturated monomers may be used singly 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 from 5 to 50% by mass, further preferably 10 ~40% by mass. By copolymerizing the unsaturated monomer (e1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2) include JP-A-7-140654, JP-A-8-259876, and JP-A-10-10 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Revealed copolymers.

In addition, in the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei 6-230212, and Japanese Polymerization such as (meth)acrylonyl group in a side chain disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having an unsaturated bond is used as a binder resin.

The polystyrene-equivalent weight average molecular weight (Mw) of the binder resin of the present invention measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually from 1,000 to 100,000, preferably 3000~50000. In such a manner, the residual film ratio, the pattern shape, the heat resistance, the electrical properties, and the resolution of the film can be further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.

Further, 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 from 1.0 to 5.0, more preferably from 1.0 to 3.0. Further, Mn mentioned herein means a polystyrene-converted number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, but the method disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871 can be used. Control its structure, Mw, Mw / Mn.

In the present invention, the binder resin may be used singly or in combination of two or more.

In the present invention, when the binder resin is used, the content thereof is from 1 to 300 parts by mass, preferably from 5 to 200 parts by mass, per 100 parts by mass of the (A) polymer, with or without the coloring agent (D). Such an aspect is preferred in that it is easy to obtain the desired effect of the present invention.

-(F) solvent -

The radiation sensitive composition of the present invention contains the above components (A) to (C) and any other components added arbitrarily, but is usually prepared into a liquid composition in combination with an organic solvent.

The organic solvent is appropriately selected and used as long as it disperses or dissolves the components (A) to (C) constituting the radiation sensitive composition and other components, and does not react with these components, and has appropriate volatility.

Examples of such an organic solvent 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. 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 single positive 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, tripropylene glycol monoethyl ether, etc. Alcohol monoalkyl ether; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexyl a (cyclo)alkyl alcohol such as an alcohol or a cyclohexanol; a ketone alcohol 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-methoxyacetic acid butyl ester Methyl-3-methoxybutyl acetate and butyl (poly) alkylene glycol monoalkyl ether acetate; Diol 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 Diacetate such as diacetate such as acid ester, 1,3-butanediol diacetate or 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, butyl 3-methyl-3-methoxypropionate Oxycarboxylic acid ester; 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 acetate, ethyl acetate, 2-side Fatty acid alkyl ester such as ethyl oxybutyrate; aromatic hydrocarbon such as toluene or xylene; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Indoleamine or indoleamine.

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

In the present invention, the organic solvent may be used singly or in combination of two or more. When a mixed organic solvent is used, it is preferred to mix at least (poly)alkylene glycol monoalkyl ether and (poly)alkylene glycol monoalkyl ether acetate, (poly)alkylene glycol monoalkyl ether acetate, and Alkoxycarboxylates are used.

The content of the organic solvent is not particularly limited, and when the coloring radiation-containing linear composition containing the coloring agent (D) is formed, 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 preferably 10 to 40% by mass. By adopting such a phenomenon, it is possible to obtain a color-sensing radiation composition having excellent dispersibility and stability. In addition, when the radiation sensitive composition containing no (D) coloring agent is formed, the total concentration of each component other than the solvent of the radiation sensitive composition is preferably from 10 to 75% by mass, more preferably 15 to 70% by mass. By adopting such an aspect, it is possible to obtain a radiation-sensitive composition having good coatability and stability.

-additive-

The colored composition of the present invention may further contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine-based surfactant or a lanthanoid surfactant; and ethylene. Trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxy Ethyloxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethyl An adhesion promoter such as oxydecane or 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4-methyl-6-tertiarybutylphenol), 2,6-di-tertiary butyl Phenol, pentaerythritol bismuth [3-(3,5-ditributyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-) Hydroxy-5-methylphenyl)-propenyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, thiodi An antioxidant such as ethyl bis[3-(3,5-ditributyl-4-hydroxyphenyl)propionate; 2-(3-tert-butyl-5-methyl-2-hydroxyl) Ultraviolet absorbers such as phenyl)-5-chlorobenzotriazole and alkoxybenzophenone; 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 group -1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and other residue improvers; succinic acid mono [2-(methyl) propylene oxime] A developer improving agent such as an ester, phthalic acid mono [2-(methyl) propylene oxime] or ω-carboxy polycaprolactone mono (meth) acrylate.

The radiation sensitive composition of the present invention can be prepared by mixing the components (A) to (C) and other components as needed in a predetermined ratio, preferably by dissolving in a suitable solvent. The prepared radiation sensitive composition is preferably filtered by, for example, a filter having a pore size of about 0.2 μm.

Further, when preparing a coloring radiation-sensitive composition, for example, it is preferred to use (D) a coloring agent and (A) a polymer, for example, by using a bead mill, a roll mill, or the like, as the case may be. A part of the (E) binder resin is mixed/dispersed in a (F) solvent in the presence of a dispersing agent while being pulverized to prepare a colorant dispersion, and then, to the colorant dispersion (B) a polymerizable compound and (C) a radiation-sensitive polymerization initiator are added, and (E) a binder resin is added as needed, and an additional solvent and other components are further added and mixed.

(hardened film and its formation method)

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 respective colors constituting the color filter, a black matrix, a protective film, a spacer, and an insulating film. Hereinafter, a case where the colored cured film of each color pixel constituting the color filter is formed will be described in detail as an example.

As a method of forming the coloring layer constituting the color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide the portion where the pixel is formed, as needed. Next, a liquid composition of the colored radiation-sensitive composition of the present invention containing, for example, a blue coloring agent is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkaline developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which a blue pixel pattern (colored cured film) is arranged in a predetermined array is formed.

Next, each coloring sensitizing radiation composition containing a green or red coloring agent is used, and each coloring feeling is performed in the same manner as described above. The coating, prebaking, exposure, development, and post-baking of the radioactive 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 disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above-described order.

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

Examples of the substrate used for forming the coloring layer include glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamidimide, and polyimine.

Further, as appropriate, these substrates may be subjected to an appropriate pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition.

When the radiation sensitive composition is applied onto the substrate, an appropriate coating method such as a spray coating method, a roll coating method, a spin coating method, a slit die coating method, or a bar coating method may be employed, and it is particularly preferable to use a spinning method. Coating method, slit type die coating method.

The conditions of heat drying in the prebaking are usually 70 to 110 ° C for about 1 to 10 minutes. Further, the pre-baking may be carried out by combining dry-pressure drying and heat-drying, and in this case, drying under reduced pressure is usually carried out up to 50 to 200 Pa.

The coating thickness is usually 0.6 to 8 μm in terms of the film thickness after drying. Preferably, it is 1.2 to 5 μm.

Examples of the light source that forms radiation used in at least one selected from the group consisting of a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a medium pressure mercury lamp. Light source such as low-pressure mercury lamp 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 can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is generally preferably from 10 to 10000 J/m ² .

Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4 is preferred. .0] an aqueous solution of 7-undecene, 1,5-diazabicyclo-[4.3.0]-5-decene.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer in an appropriate amount. Further, after alkaline development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be employed. The developing conditions are preferably normal temperature, 5 to 300 seconds.

The post-baking conditions are usually 180 to 280 ° C for about 10 to 60 minutes.

The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

In addition, as a second method of forming the coloring layer constituting the color filter, Japanese Patent Laid-Open No. Hei 7-318723, Japanese A method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. 2000-310706. In this method, first, a partition wall which also has a light blocking function is formed on the surface of the substrate. Next, a liquid composition of the thermally sensitive radiation composition of the present invention containing a blue colorant, for example, is ejected into the formed partition walls by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a blue pixel pattern.

Next, a green pixel pattern and a red pixel pattern were sequentially formed on the same substrate in the same manner as described above, using each of the thermal radiation-releasing compositions containing green or red coloring agents. 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 in which the pixels of the respective colors are formed is not limited to the above order.

Further, the partition wall not only functions as a light-shielding function, but also functions to prevent the color-sensing radiation-linear composition of each color discharged into the compartment from being mixed, so that the film thickness is thicker than the black matrix used in the first method. Therefore, the partition walls are usually formed using a radiation-sensitive linear composition in which a black colorant is dispersed.

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

After forming a protective film as needed on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, 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 spacer having a light-shielding property (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 to form the above protective film or spacer. The conditions for forming the protective film, the spacer, and the insulating film are the same as those of the above-described colored layer.

Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful in color liquid crystal display elements, color image sensor elements, color sensors, organic EL display elements, electronic paper, and the like.

(display element)

The display element of the present invention comprises 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 having the cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a color filter may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate for driving and a substrate on which the color filter is formed may be opposed to each other via a liquid crystal layer; Further, a substrate having a color filter formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed may be used, 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 an advantage that the aperture ratio can be remarkably increased, and a liquid crystal display element which is bright and high in definition can be obtained. Further, in the latter configuration, the black matrix and the spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed. Further, as the interlayer insulating film constituting the driving substrate on which the thin film transistor (TFT) is disposed, it is also possible to The cured film of the present invention is used.

The color liquid crystal display device 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. As the white LED, for example, a white LED in which a red LED, a green LED, and a blue LED are combined and white light is obtained by color mixing, a blue LED, a red LED, and a green phosphor are combined, and white light is obtained by color mixing. LED, a combination of a blue LED, a red illuminating phosphor and a green illuminating phosphor, and a white LED obtained by mixing colors, and a white LED of white light by a color mixture of a blue LED and a YAG-based phosphor, combined A blue LED, an orange illuminating phosphor, and a green illuminating phosphor are white LEDs obtained by mixing colors, and combined with an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor. A white LED or the like which obtains white light by color mixing.

The color liquid crystal display element having the cured film of the present invention may be a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, or an IPS (In-Planes Switching) type. A suitable liquid crystal mode such as a VA (Vertical Alignment) type or an OCB (Optically Compensated Birefringence) type.

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

Further, the electronic paper having the cured film of the present invention may have an appropriate structure, and for example, it is disclosed in Japanese Laid-Open Patent Publication No. 2007-41169. Structure.

(solid-state photographic element)

The solid-state imaging element of the present invention comprises the cured film of the present invention. Further, the solid-state imaging element of the present invention can adopt a suitable structure. For example, in one embodiment, a colored pixel (colored cured film) is formed on a semiconductor substrate such as a CMOS substrate by the same operation as described above by using the radiation sensitive composition of the present invention containing the (D) coloring agent. Thereby, a solid-state imaging element excellent in color separation property and color reproducibility can be obtained. In addition, as another embodiment, a solid-state imaging element including an insulating film (cured film) produced by using the radiation-sensitive linear composition of the present invention can be used, and specifically, it is disclosed in Japanese Laid-Open Patent Publication No. 2011-215597 Structure.

[Examples]

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the 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-(methacrylofluorenyloxy)-3-ethyl propylene 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.

0.5 g of the polymer solution was weighed to 1 mg unit and dispensed into a glass container. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, and titration was carried out with a 0.1 N aqueous solution of potassium hydroxide, and the end point colored to pink was used. The blank test was performed in the same manner. The acid value (unit: mgKOH/g) was calculated from the amount of the 0.1 N ethanolic potassium hydroxide aqueous solution of the polymer and the blank test.

<Measurement of amine value>

The amine value of the polymer obtained in each of the Synthesis Examples was measured in the following manner.

0.5 g of the polymer solution was weighed to 1 mg unit and dispensed into a glass container. 20 mL of acetic anhydride/acetic acid = 9/1 (volume ratio) was added and dissolved, and allowed to stand at room temperature for 3 hours. Thereafter, 30 mL of acetic acid was further added, and then titration was carried out using a potential difference measuring apparatus AT-510 (manufactured by Kyoto Electronics Co., Ltd.) using a 0.1 mol/L perchloric acid/acetic acid solution. The blank test was performed in the same manner. The amine value (unit: mgKOH/g) was calculated from the amount of the 0.1 mol/L perchloric acid/acetic acid solution dropped from the polymer and the blank test.

<Synthesis of a polymer having a carboxyl group in addition to an epoxyethyl group and/or an oxypropylene 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-epoxycyclohexylmethyl methacrylate) were dissolved in In 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 purge for 15 minutes. After the nitrogen purge, the reaction solution was stirred and heated to 80 ° C under nitrogen bubbling, and polymerization was carried out for 5 hours, whereby a solution containing 33% by mass of the polymer (A1-1-1) was obtained. The polystyrene-equivalent Mw of the polymer (A1-1-1) measured by GPC (elution solvent: THF) was 6000, and Mw/Mn was 2.5. 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, styrene 53.0 g, MA12.0 g, ARONIX M120 (manufactured by Toagosei Co., Ltd. 2-ethylhexyl EO-modified acrylate) 5.0 g, OXMA 25.0 g, and Cyclomer M100 were used: 5.0 g was dissolved in 200 g of PGMEA, and then 6.0 g of azobis-2,4-dimethylvaleronitrile and 5.0 g of α-methylstyrene dimer were charged, followed by nitrogen purge for 15 minutes. After the nitrogen purge, the reaction solution was stirred and heated to 80 ° C under nitrogen bubbling, and polymerization was carried out for 5 hours to obtain a solution containing 33% by mass of the polymer (A1-1-2). The polystyrene-equivalent Mw of the polymer (A1-1-2) measured by GPC (elution solvent: THF) was 5900, and Mw/Mn was 2.5. 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, styrene 55.0 g, MA 15.0 g, OXMA 20.0 g, GMA 2.0 g, and Cyclomer M100: 8.0 g The solution was dissolved in 200 g of methoxybutyl acetate, and then 4.0 g of azobis-2,4-dimethylvaleronitrile and 5.0 g of α-methylstyrene dimer were charged, followed by nitrogen purge for 15 minutes. After the nitrogen purge, the reaction solution was stirred and heated to 80 ° C under nitrogen bubbling, and polymerization was carried out for 5 hours, whereby a solution containing 33% by mass of the polymer (A1-1-3) was obtained. The polystyrene-equivalent Mw of the polymer (A1-1-3) measured by GPC (elution solvent: THF) was 12000, and Mw/Mn was 2.5. 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, styrene 54.0 g, MA14.0 g, MMA 2.0 g, and BLEMMER PME-200 (made by Nippon Oil Co., Ltd. methoxypolyethylene glycol monomethacrylate) 2.0 were used. g, OXMA14.0g and CyclomerM100: 14.0g dissolved in 200g of 3-methoxypropionate, and then added to azobis-2,4-dimethylvaleronitrile 5.0g and α-methylstyrene dimerization 5.0 g of the material was followed by a nitrogen purge for 15 minutes. After the nitrogen purge, the reaction solution was stirred and heated to 80 ° C under nitrogen bubbling, and polymerization was carried out for 5 hours, whereby a solution containing 33% by mass of the polymer (A1-1-4) was obtained. The polystyrene-equivalent Mw of the polymer (A1-1-4) measured by GPC (elution solvent: THF) was 10,000, and Mw/Mn was 2.5. 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 group was added. 5.0 g of valeronitrile and 5.0 g of α-methylstyrene dimer were thereafter subjected to nitrogen purge for 15 minutes. After flushing with nitrogen, the reaction solution was stirred and heated to 80 ° C with nitrogen bubbling for 5 hours. Polymerization, thereby obtaining a solution containing 33% by mass of the polymer (A3-1). The polystyrene-equivalent Mw of the polymer (A3-1) measured by GPC (elution solvent: THF) was 10,000, and Mw/Mn was 2.5. 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 α-methylstyrene dimer 5.0 g, followed by nitrogen purge for 15 minutes. After the nitrogen purge, the reaction solution was stirred and heated to 80 ° C under nitrogen bubbling, and polymerization was carried out for 5 hours, whereby a solution containing 33% by mass of the polymer (A2-1) was obtained. The polystyrene-equivalent Mw of the polymer (A2-1) measured by GPC (elution solvent: THF) was 12000, and Mw/Mn was 2.5. The polymer (A2-1) is equivalent to the polymer (A2).

Synthesis Example 7

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

Synthesis Example 8

In the synthesis example 1, a solution containing 33% by mass of the polymer (A1-1-6) was obtained in the same manner as in Synthesis Example 1 except that the type and amount of each component were changed as shown in Table 1. The polystyrene-equivalent Mw of the polymer (A1-1-6) measured by GPC (elution solvent: THF) was 6200, and Mw/Mn was 2.4. The polymer (A1-1-6) is equivalent to the polymer (A1).

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

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

"PME-200" means a repeating unit derived from methoxypolyethylene glycol monomethacrylate (BLEMMER PME-200, manufactured by Nippon Oil Co., Ltd.).

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

"oxi/oxe" represents the ratio of the total number of moles of the epoxy group in the total polymer constituting the (A) polymer to the total number of moles of the propylene oxide group, and "w _oxi /w _oxe " means The total mass w _oxi of the ethylenically unsaturated monomer (a1) of the epoxy group in the total monomers constituting the polymer of (A) and the ethylenically unsaturated monomer (a2) having an oxypropylene group are The ratio of the total mass w _oxe occupied by all the monomers constituting the (A) polymer.

<Synthesis of a polymer having an amine group other than an epoxyethyl group and/or an oxypropylene group>

Synthesis Example 9

In a flask equipped with a stirrer, MMA 6.2 g, nBMA 7.0 g, Cyclomer M100: 2.8 g, OXMA 2.8 g, ARONIX M120: 0.8 g, AIBN 235 mg, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl group) 605 mg of methyl ester was dissolved in 30 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the mixture was slowly stirred to raise the temperature of the reaction solution to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Next, a solution obtained by dissolving AIBN 437 mg and DAMA 8.4 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 40% by mass. The obtained polymer had a Mw of 8300 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 1.3.

Next, 5.4 g of benzyl chloride and 20.0 g of PGME were added to the obtained polymer solution, followed by slow stirring, the temperature of the polymer solution was raised to 90 ° C, and the temperature was maintained for 8 hours, which was obtained from DAMA. The methylamine group is partially quaternized. The reaction solution was measured by HPLC, and it was confirmed that the peak derived from benzyl chloride disappeared. This results in an A block having a repeating unit from DAMA and a portion thereof being quaternized and having repeats from MMA, nBMA, Cyclomer M100, OXMA and ARONIX M120 A block copolymer composed of B blocks of the unit. The obtained copolymer was designated as a polymer (A1-2-1). Finally, PGME was added, and the solid content concentration was adjusted to 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 stirrer, MMA 5.6 g, nBMA 5.6 g, Cyclomer M100: 0.8 g, OXMA 7.6 g, AIBN 235 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester 605 mg were dissolved in Nitrogen foaming was carried out for 30 minutes in 30 mL of toluene. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Next, a solution obtained by dissolving AIBN 481 mg and DAMA 8.4 g in toluene of 20 m and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 40% by mass. The obtained polymer had a Mw of 8400 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 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 to obtain two from DAMA. The methylamine group is partially 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 a repeating unit derived from DAMA and a part thereof being quaternized and a B block having repeating units derived from MMA, nBMA, Cyclomer M100 and OXMA was obtained. The obtained copolymer was designated as a polymer (A1-2-2). Finally, PGME was added, and the solid content concentration was adjusted to 35 mass%, and PGMEA/PGME=68/32 (mass ratio). The polymer (A1-2-2) is equivalent to the polymer (A1).

Synthesis Example 11

Add 6.6 mL of toluene, 2.7 mL of 1,2-dimethoxyethane, and 0.38 M of toluene solution of isobutylbis(2,6-ditributyl-4-methylphenoxy)aluminum in 13.7 mL. , cooled to 10 ° C. To this was added 0.7 mL of a 1.3 M solution of a secondary butyllithium in hexane, followed by stirring for 20 minutes. Thereafter, a solution obtained by dissolving 0.81 g of nBMA, 0.87 g of MMA, 0.84 g of OXMA, and 0.21 g of Cyclomer M100 in 2.8 mL of toluene at 10 ° C was added dropwise thereto over 5 minutes.

After 30 minutes from the completion 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 the mixture was 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 to give a nonvolatile content of 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 repeating units derived from MMA, nBMA, Cyclomer M100 and OXMA was obtained. The obtained polymer had a Mw of 6300 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 1.3.

The obtained copolymer was designated as 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 stirrer, MMA 6.4 g, nBMA 6.4 g, Cyclomer M100: 2.5 g, OXMA 5.9 g, MA 0.6 g, AIBN 290 mg, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) A were added. Ester 714mg dissolved in A Nitrogen foaming was carried out for 30 minutes in 30 mL of benzene. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Next, a solution obtained by dissolving ABBN 352 mg and DAMA 6.2 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 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 repeating units derived from MMA, nBMA, Cyclomer M100, OXMA and MA was obtained. The obtained polymer had a Mw of 8200 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 1.3. The obtained copolymer was designated as a polymer (A1-2-4). The polymer (A1-2-4) is equivalent to the polymer (A1). Further, the polymer (A1-2-4) also has a carboxyl group, but is formally classified into a polymer having an amine group.

Synthesis Example 13

In a flask equipped with a stirrer, MMA 3.6 g, nBMA 5.0 g, Cyclomer M100: 0.6 g, OXMA 5.6 g, DAMA 13.1 g, AIBN 340 mg, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) A were added. 837 mg of the ester was dissolved in 50 mL of toluene, and nitrogen gas was bubbled for 30 minutes. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 40% by mass. Thereby obtaining 40% by mass of repeating sheets having MMA, nBMA, Cyclomer M100, OXMA and DAMA A solution of a random copolymer of the element. The obtained polymer had a Mw of 8100 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 1.3. The obtained copolymer was designated as 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 stirrer, MMA 1.4 g, nBMA 2.0 g, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (compound represented by the following formula (8) and the following formula ( 9) The compound shown was mixed with 1.7 g of a molar ratio of 50:50, OXMA 15.1 g, 190 mg of AIBN, and 467 mg of cyano (dimethyl)methyl ester of pyrazole-1-dithiocarboxylate in 30 mL of toluene. Nitrogen foaming for 30 minutes. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Next, a solution obtained by dissolving AIBN 753 mg and DAMA 7.8 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 40% by mass. Thus, 40 parts by mass of an A block having a repeating unit derived from DAMA and a repeating unit having a repeating unit derived from MMA, nBMA, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate and OXMA were obtained. A solution of a block copolymer composed of B blocks. The obtained polymer had a Mw of 7200 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 1.3. The obtained copolymer was designated as 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 stirrer, MMA 7.0 g, nBMA 7.0 g, Cyclomer M100: 1.4 g, AIBN 227 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester 559 mg were dissolved in 30 mL of toluene. Nitrogen foaming was carried out for 30 minutes. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Next, a solution obtained by dissolving AIBN 721 mg and DAMA 12.6 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 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 Cyclomer M100 was obtained. The obtained polymer had a Mw of 8,000 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 1.3. The obtained copolymer was designated as 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 stirrer, MMA 7.0 g, nBMA 7.0 g, OXMA 5.6 g, AIBN 270 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester (664 mg) were dissolved in 30 mL of toluene. Nitrogen foaming for 30 minutes. Thereafter, the mixture was slowly stirred to raise the temperature of the reaction solution to 57 ° C. The temperature was maintained for 34 hours, and living radical polymerization was carried out.

Next, a solution obtained by dissolving AIBN 481 mg and DAMA 8.4 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 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 OXMA was obtained. The obtained polymer had a Mw of 7900 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 1.3. The obtained copolymer was designated as a polymer (A3-2). The polymer (A3-2) is equivalent to the polymer (A3).

Synthesis Example 17

In a flask equipped with a stirrer, MMA 7.0 g, nBMA 6.4 g, Cyclomer M100: 0.4 g, OXMA 8.0 g, AIBN 290 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester 714 mg were dissolved in Nitrogen foaming was carried out for 30 minutes in 30 mL of toluene. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Next, a solution obtained by dissolving ABBN 352 mg and DAMA 6.2 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 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 repeating units derived from MMA, nBMA, Cyclomer M100 and OXMA was obtained. . The obtained polymer had Mw of 8100 and Mw/Mn of 1.3. The obtained copolymer was designated as 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 stirrer, MMA 5.6 g, nBMA 5.6 g, OXMA 8.2 g, Cyclomer M100: 0.2 g, AIBN 254 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester 626 mg were dissolved in Nitrogen foaming was carried out for 30 minutes in 30 mL of toluene. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Next, a solution obtained by dissolving AIBN 481 mg and DAMA 8.4 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 40% by mass. The obtained polymer had a Mw of 8200 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 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 to obtain A portion of the dimethylamine 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 a repeating unit derived from DAMA and a part thereof being quaternized and a B block having repeating units derived from MMA, nBMA, Cyclomer M100 and OXMA was obtained. The obtained copolymer was designated as a polymer (A1-2-8). Finally add PGME, the solid concentration is 35 mass %, PGMEA/PGME = 68/32 (mass ratio) mode adjustment. The polymer (A1-2-8) is equivalent to the polymer (A1).

Synthesis Example 19

In a flask equipped with a stirrer, MMA 5.6 g, nBMA 5.6 g, OXMA 2.9 g, Cyclomer M100: 5.5 g, AIBN 251 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester 617 mg were dissolved in Nitrogen foaming was carried out for 30 minutes in 30 mL of toluene. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 57 ° C, and the temperature was maintained for 34 hours to carry out living radical polymerization.

Next, a solution obtained by dissolving AIBN 481 mg and DAMA 8.4 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 40% by mass. The obtained polymer had a Mw of 8300 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 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, which was obtained from A portion of the dimethylamine 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 a repeating unit derived from DAMA and a part thereof being quaternized and a B block having repeating units derived from MMA, nBMA, Cyclomer M100 and OXMA was obtained. The obtained copolymer was designated as a polymer (A1-2-9). Finally, PGME was added, and the solid content concentration was adjusted to 35 mass%, and PGMEA/PGME=68/32 (mass ratio). polymer (A1-2-9) is equivalent to the polymer (A1).

<Polymer having a carboxyl group in addition to an epoxyethyl group and/or an oxypropylene group and having a (meth)acryl fluorenyl group in a side chain>

Synthesis Example 20

In a flask equipped with a cooling tube and a stirrer, OXMA 22.0 g, MA 18.0 g, succinic acid mono-2-propenyloxyethyl ester 9.0 g, N-phenylmaleimide 10.0 g, BzMA 24.0 g, methyl group 14.0 g of 2-hydroxyethyl acrylate and 3.0 g of Cyclomer M-100 were dissolved in 300 g of propylene glycol monomethyl ether acetate, and then 6.0 g of AIBN and 6.0 g of α-methylstyrene dimer were added, followed by 15 minutes. Flush with nitrogen. After the nitrogen purge, the reaction solution was stirred and heated to 80 ° C while bubbling with nitrogen, and polymerization was carried out for 5 hours, whereby a precursor copolymer solution was obtained.

To 200 g of the obtained precursor copolymer solution, 13.4 g of 2-methylpropenyloxyethyl isocyanate and 0.2 g of 4-methoxyphenol as a polymerization inhibitor were added, and the mixture was reacted at 90 ° C for 2 hours. After cooling to room temperature, it was washed with 75 g of ion-exchanged water once, washed twice with water, and concentrated under reduced pressure to obtain a solution containing 33% by mass of the polymer (A1-1-7). The polystyrene-equivalent Mw of the polymer (A1-1-7) measured by GPC (elution solvent: THF) was 11,000, and Mw/Mn was 1.9. 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 stirrer, MMA 5.6 g, nBMA 5.6 g, CHMA 8.4 g, AIBN 235 mg, and pyrazole-1-dithiocarbamic acid cyano (dimethyl) methyl ester 605 mg were dissolved in 30 mL of toluene. Nitrogen foaming for 30 minutes. Thereafter, the mixture was slowly stirred to raise the temperature of the reaction solution to 57 ° C. The temperature was maintained for 34 hours, and living radical polymerization was carried out.

Next, a solution obtained by dissolving AIBN 481 mg and DAMA 8.4 g in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 57 ° C for 34 hours. Thereafter, the solvent was removed by concentration under reduced pressure, and PGMEA was added to give a nonvolatile content of 40% by mass. The obtained polymer had a Mw of 8300 in terms of polystyrene measured by GPC (elution solvent: THF), and Mw/Mn was 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, which was obtained from A portion of the dimethylamine 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 a repeating unit derived from DAMA and a part thereof being quaternized and a B block having repeating units derived from MMA, nBMA and CHMA was obtained. The obtained copolymer was designated as a polymer (A4). Finally, PGME was added, and the solid content concentration was adjusted to 35 mass%, and PGMEA/PGME=68/32 (mass ratio) was adjusted. 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 Toagosei Co., Ltd.).

"PME-200" means a repeating unit derived from methoxypolyethylene glycol monomethacrylate (BLEMMER PME-200, manufactured by Nippon Oil Co., Ltd.).

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

"Formula (8) / Formula (9)") represents a decyl acrylate derived from 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] (the compound represented by the formula (8) and the compound represented by the formula (9) are Repeating unit of the substance obtained by mixing the ear with 50:50.

"DAMA" means a repeating unit derived from DAMA without quaternary ammonium.

"DAMA-BzCl" means a four-stage ammonium repeating unit derived from DAMA.

"oxi/oxe" represents the ratio of the total number of moles of the epoxy group in the total polymer constituting the (A) polymer to the total number of moles of the propylene oxide group, and "w _oxi /w _oxe " means The total mass w _oxi of the ethylenically unsaturated monomer (a1) of the epoxy group in the total monomers constituting the polymer of (A) and the ethylenically unsaturated monomer (a2) having an oxypropylene group The ratio of total mass w _oxe .

[Evaluation of cured film as insulating film]

Example 1

100 parts by mass of the polymer (A1-1-1) solution as the (A) polymer (solid content concentration: 33% by mass), dipentaerythritol hexaacrylate as the (B) polymerizable compound, and dipentaerythritol pentaacrylate 50 parts by mass of a mixture (trade name: ARONIXM-402, manufactured by Toagosei Co., Ltd.) and a succinic anhydride modified product of dipentaerythritol pentaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: ARONIXM-520) , manufactured by Toagosei Co., Ltd., 20 parts by mass of 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 as (C) sensitizing radiation polymerization initiator -yl]-ethanone-1-(O-acetamidine) (IRGACURE OXE02, manufactured by Ciba Specialty Chemicals) 1 part by mass and 2-dimethylamino-2-(4-methylbenzyl)-1- (4- Phenyl-4-yl-phenyl)-butan-1-one (IRGACURE 379, manufactured by Ciba Specialty Chemicals) 5 parts by mass, and pentaerythritol quinone [3-(3,5-di-tertiary butyl-) as an antioxidant 1 part by mass of 4-hydroxyphenyl)propionate was added, and diethylene glycol methyl ethyl 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 linear composition. (S-1).

(Evaluation of solvent resistance)

The radiation sensitive composition was applied onto the tantalum substrate using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film 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 ruthenium 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 tantalum substrate on which the cured film was formed was immersed in dimethyl sulfoxide having a temperature controlled at 70 ° C for 20 minutes, and then the film thickness (T2) of the cured film after immersion was measured, and the film thickness change was calculated by the following formula. Rate, which is used as an indicator of solvent resistance.

Film thickness change rate = {(T2-T1) / T1} × 100 (%)

The case where the absolute value of the value is less than 3% is evaluated as "A" When the absolute value of the value is 3% or more and less than 4%, it is evaluated as "B", and when the absolute value of the value is 4% or more and less than 5%, the value is evaluated as "C", and the value is evaluated. The case where the absolute value is 5% or more and 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)

The radiation sensitive composition was applied onto the SUS substrate using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. The coating film was exposed to an exposure amount of 1000 J/m ² using an exposure machine (MPA-600FA, manufactured by Cannon), and the exposed substrate was heated in a clean oven at 200 ° C for 30 minutes, thereby being on a SUS substrate. A cured film is formed. Next, a Pt/Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for dielectric constant measurement. For the substrate having the electrode pattern, an electrode (HP16451B, manufactured by Yokogawa Co., Ltd.) and a precision LCR tester (HP4284A, manufactured by Yokogawa Co., Hewlett-Packard) were used to measure the relative dielectric constant by a CV method at a frequency of 10 kHz. In this case, the case where the relative dielectric constant was 3.9 or less was evaluated as “○”, and the case where the relative dielectric constant exceeded 3.9 was evaluated as “×”. The results are shown in Table 3.

(Evaluation of storage stability)

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

Examples 2 to 8 and Comparative Examples 1 to 3

In the same manner as in Example 1, except that the type and amount of each component used were changed as shown in Table 3, the radiation sensitive composition (S-2) to (S-11) was prepared. . Next, evaluation was performed in the same manner as in Example 1 except that the radiation sensitive composition (S-2) to (S-11) was used instead of the radiation sensitive composition (S-1). The results are shown in Table 3.

The components in Table 3 are as follows.

B-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toagosei Co., Ltd.)

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

C-1:1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone-1-(O-acetamidine) (trade name) IRGACURE OX02, manufactured by Ciba Specialty Chemicals)

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

G-1: pentaerythritol 肆 [3-(3,5-ditributyl-4-hydroxyphenyl)propionate], (ADK STAB AO-60, manufactured by ADEKA)

"oxi/oxe" represents the ratio of the total number of moles of the epoxy group in the total polymer constituting the (A) polymer to the total number of moles of the propylene oxide group, and "w _oxi /w _oxe " means The total mass w _oxi of the ethylenically unsaturated monomer (a1) of the epoxy group in the total monomers constituting the polymer of (A) and the ethylenically unsaturated monomer (a2) having an oxypropylene group are The ratio of the total mass w _oxe occupied by all the monomers constituting the (A) polymer.

[Evaluation of colorant dispersion 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, and 15.0 parts by mass of the polymer (A1-2-1) solution were used as a colorant. (nonvolatile content = 35 mass%), 64.0 parts by mass of PGMEA as a solvent, and 6.0 parts by mass of PGME, and treated with a bead mill to prepare a colorant dispersion (D-1).

(Evaluation of storage stability)

The viscosity of the obtained colorant dispersion was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) as an initial viscosity. Further, the obtained colorant dispersion was filled in a light-shielding glass container, and after standing at 23 ° C for 14 days in a sealed state, the viscosity was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Then, the increase rate of the viscosity after 14 days of storage with respect to the initial viscosity is calculated, and the case where the increase rate is less than 5% is "A", and the case where the increase rate is 5% or more and less than 10% is set to "B". In the case where the increase rate is 10% or more, it is set to "C", and the storage stability of the colorant dispersion liquid is 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 the same manner as in Preparation Example 1, the colorant dispersions (D-2) to (D-6) and (D) were prepared in the same manner as in Preparation Example 1 except that the types and amounts of the respective components were changed as shown in Table 4. -8)~(D-15). Next, using the colorant dispersions (D-2) to (D-6) and (D-8) to (D-15) instead of the colorant dispersion (D-1), in addition to the preparation examples 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), a nonvolatile content of 60% by mass, 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) as a coloring agent, 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 solution of the polymer (A1-2-2) (nonvolatile content = 35 mass) %), a polymer (A1-2-8) solution, 13.0 parts by mass (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, evaluation was performed in the same manner as in Production Example 1. The evaluation results are shown in Table 4.

The components in Table 4 are 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): a 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), having a nonvolatile content of 60% by mass and an amine value of 72 mgKOH/g)

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

"oxi/oxe" represents the ratio of the total number of moles of the epoxy group in the total polymer constituting the (A) polymer to the total number of moles of the propylene oxide group, and "w _oxi /w _oxe " means The total mass w _oxi of the ethylenically unsaturated monomer (a1) of the epoxy group in the total monomers constituting the polymer of (A) and the ethylenically unsaturated monomer (a2) having an oxypropylene group are The ratio of the total mass w _oxe occupied by all the monomers constituting the (A) polymer.

Further, 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- were added. Methylstyrene dimer 8.0 g, followed by a nitrogen purge for 15 minutes. After the nitrogen purge, the reaction solution was stirred and heated to 80 ° C while bubbling with nitrogen, and polymerization was carried out for 5 hours.

Next, MA17.0 g, p-methoxyphenol 0.5 g, and tetrabutylammonium bromide (4.4 g) were added to the reaction solution, and the mixture was reacted at 120 ° C 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. After cooling to room temperature and washing twice, the solution was concentrated under reduced pressure to obtain a solution containing 33% by mass of a binder resin (E-1). The binder resin (E-1) had a polystyrene-equivalent Mw of 7800 and Mw/Mn = 2.8 as measured by GPC (elution solvent: THF). Further, the epoxy ethyl 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 mono-2-methylpropenyloxyethyl succinate 12.5 were used. 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 added to azobis-2,4-dimethylvaleronitrile 4.0 g and α-methyl group. The styrene dimer was 5.0 g, followed by a nitrogen purge for 15 minutes. After the nitrogen purge, the reaction solution was stirred and heated to 80 ° C under nitrogen bubbling, and polymerization was carried out for 5 hours to obtain a solution containing 33% by mass of the binder resin (E-2). The binder resin (E-2) was determined by GPC (elution solvent: THF) The polystyrene-converted Mw = 10000, Mw / Mn = 2.5.

<Preparation of Colored Radioactive Composition and Evaluation of Colored Curing Film>

Example 101

(Preparation of coloring radiation composition)

100 parts by mass of the colorant dispersion (D-1) as a colorant, 34.1 parts by mass of a resin (E-1) solution as a binder resin, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a polymerizable compound 11.3 parts by mass of a mixture (trade name M-402, manufactured by Toagosei Co., Ltd.) as a photopolymerization initiator 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole -3-yl]-ethanone 1-(O-acetamidine) (trade name: IRGACURE OX02, manufactured by Ciba Specialty Chemicals Co., Ltd.) 4.2 parts by mass, MEGAFAC F-554 as an additive (fluorine-based surfactant, DIC shares limited) 0.1 parts by mass and 162 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed to obtain a colored radiation linear composition (CR-1).

(Evaluation of solvent resistance)

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

Next, after the substrate was cooled to room temperature, the radiation containing the wavelengths of 365 nm, 405 nm, and 436 nm was exposed to the coating film on the substrate at an exposure amount of 1000 J/m ² without using a high-pressure mercury lamp. Thereafter, it was baked at 220 ° C for 20 minutes, and a red cured film was formed on the substrate.

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

(Evaluation of voltage retention rate)

The colored composition (CR-1) was applied onto a glass substrate having a predetermined shape by vapor deposition on an ITO (indium-tin oxide alloy) electrode using a slit die coater, and then prebaked in a clean oven at 90 ° C for 10 minutes. A coating film having a film thickness of 1,8 μm was formed.

Next, the film containing the respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to the coating film at an exposure amount of 500 J/m ² without using a high-pressure mercury lamp. Thereafter, the substrate was immersed in a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C for 1 minute, and after development, it was washed with ultrapure water, air-dried, and further baked at 180 ° C for 30 minutes, and then baked. The coating film is hardened 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 ratio (VHR) of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement 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 msec/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 a period of 16.7 milliseconds, and can sufficiently make the liquid The crystal alignment is preferable because it is less likely to cause "image sticking" such as afterimage.

Examples 102 to 111 and Comparative Examples 101 to 105

In the same manner as in Example 101 except that the type and amount of each component were changed as shown in Table 4, a coloring-sensing radioactive composition (CR-2) to (CR-15) was prepared. Next, evaluation was performed in the same manner as in Example 101 except that the coloring sensitizing radiation composition (CR-2) to (CR-15) was used instead of the coloring sensitizing radiation 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-sensing radiation linear composition (CR-2). 3.5 parts by mass of a copolymer of ammonium hydroxide and MMA in a ratio of 3:1 (mass ratio), and in Example 107, 3-[dimethyl group] was further added to the obtained color-sensing radiation linear composition (CR-7). 1.3 parts by mass of (3-decylguanidinium propyl)ammonium]-2-hydroxypropane-1-sulfonate, in Example 111, further to the obtained color-sensing radiation linear composition (CR-11) 0.5 parts by mass of 3-(dimethyldodecylammonium)-2-hydroxypropane-1-sulfonate was added.

The components in Table 5 are as follows.

B-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toagosei Co., Ltd.)

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

C-1:1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine) (trade name IRGACURE OX02, manufactured by Ciba Specialty Chemicals)

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

C-4: NCI-831 (made by ADEKA Co., Ltd.)

F-1: ethyl 3-ethoxypropionate

F-2: propylene glycol monomethyl ether

F-3: 3-methoxyacetic acid butyl ester

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

"oxi/oxe" represents the ratio of the total number of moles of the epoxy group in the total polymer constituting the (A) polymer to the total number of moles of the propylene oxide group, and "w _oxi /w _oxe " indicates The total mass w _oxi of the ethylenically unsaturated monomer (a1) having an epoxy group in all the monomers constituting the polymer of (A) and the ethylenically unsaturated monomer having a propylene oxide group (a2) The ratio of the total mass w _oxe in the total monomers constituting the (A) polymer.

Claims (13)

A radiation sensitive composition comprising (A) a polymer, (B) a polymerizable compound, and (C) a radiation-sensitive polymerization initiator, the (A) polymer being selected from the group consisting of the following polymer (A1), polymerized a group of the substance (A2) and the polymer (A3), and is a polymer (A1), or a combination of the polymer (A2) and the polymer (A3), the polymer (A1): having an epoxy group and a propylene oxide-based polymer, polymer (A2): a polymer having an epoxy group, wherein the polymer (A1) is not included, and the polymer (A3): a polymer having an oxypropylene group, wherein Excluding the polymer (A1), the ratio of epoxy ethyl group (oxi) to oxypropylene (oxe) in the (A) polymer is 3/97 in terms of oxi/oxe 50/50. The radiation-sensitive linear composition of claim 1, wherein the polymer (A1) is an ethylenically unsaturated monomer (a1) having an epoxy group and an ethylenically unsaturated monomer having an epoxidized group ( a copolymer of a monomer of a2) which is a polymer of a monomer comprising an ethylenically unsaturated monomer (a1) having an epoxy group, wherein the polymer (A1) is not included, The polymer (A3) is a polymer of a monomer comprising an ethylenically unsaturated monomer (a2) having an oxypropylene group, wherein the polymer (A1) is not included. The radiation-sensitive linear composition of claim 2, wherein the unsaturated monomer (a1) comprises an ethylenically unsaturated monomer having a glycidyl ether group or An ethylenically unsaturated monomer having an alicyclic group obtained by epoxidizing a carbon-carbon double bond. The radiation-sensitive linear composition of claim 2 or 3, wherein the unsaturated monomer (a1) comprises at least 1 selected from the group consisting of compounds represented by any one of the following formulas (1) to (3) Kind, 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 the formulae (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 which may contain a hetero atom. The radiation-sensitive linear composition of claim 2 or 3, wherein the unsaturated monomer (a2) comprises at least 1 selected from the group consisting of compounds represented by any one of the following formulas (4) to (6) Kind, In the formulae (4), (5) and (6), R ²¹ and R ³¹ each 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 independently represented by each other. 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 , Y ² and Y ³ each independently represent a single bond or may contain one or more kinds of impurities. An alkanediyl group having 1 to 6 carbon atoms in an atom. The radiation-sensitive linear composition of claim 1, wherein at least one of the polymers (A1) to (A3) further has a substituted or unsubstituted amino group. The radiation sensitive composition of claim 1, which further comprises (D) a colorant. The radiation-sensitive linear composition of claim 7, wherein the (D) colorant contains a dye. A cured film formed using the radiation-sensitive composition of any one of claims 1 to 8. A display element comprising the cured film of claim 9. A dispersant comprising (A) a polymer selected from the group consisting of the following polymer (A1), polymer (A2), and polymer (A3), and is a polymer (A1) ), or a combination of polymer (A2) and polymer (A3), polymer (A1): polymer having epoxy ethyl group and propylene oxide group, polymer (A2): having epoxy ethyl group a polymer in which the polymer (A1) is not included, Polymer (A3): a polymer having an oxypropylene group, wherein the polymer (A1) is not included, and the epoxy group (oxi) and propylene oxide group (oxe) in the (A) polymer The ratio is 3/97 to 50/50 in terms of oxi/oxe. The dispersing agent according to claim 11, wherein at least one of the polymers (A1) to (A3) further has a substituted or unsubstituted amino group. A colorant dispersion containing (A) a polymer, (D) a colorant, and (F) a solvent selected from the group consisting of the following polymers (A1), polymers (A2), and polymers Group of (A3), and is a polymer (A1), or a combination of a polymer (A2) and a polymer (A3), a polymer (A1): a polymer having an epoxyethyl group and an oxypropylene group , polymer (A2): a polymer having an epoxy group, wherein the polymer (A1) is not included, and the polymer (A3): a polymer having an oxypropylene group, wherein the polymer is not included ( A1), the ratio of epoxy ethyl group (oxi) to oxypropylene group (oxe) in the (A) polymer is 3/97 to 50/50 in terms of oxi/oxe.