TWI509352B - Radiation-sensitive resin composition, cured film, method for forming the cured film, color filter, and method for forming the color filter - Google Patents

Description

Radiation-sensitive linear resin composition, cured film, method for forming cured film, color filter, and color filter forming method

The present invention relates to a radiation sensitive resin composition, a cured film, a method of forming a cured film, a color filter, and a method of forming a color filter.

In recent years, liquid crystal display elements have been widely used in liquid crystal televisions, mobile phones, and the like, and liquid crystal display elements are required to have a larger screen, higher brightness, and thinner thickness. Therefore, from the viewpoint of shortening the process time and cost reduction, it is required that the radiation-sensitive resin composition which is a material of a cured film such as an interlayer insulating film, a protective film or a gasket used in a display element can be highly sensitive and highly resolved. Rate. Further, the obtained cured film is required to have higher flatness, adhesion, high transmittance, and the like (JP-A-2009-36858).

On the other hand, flexible displays such as e-books are spreading. As a substrate of the flexible display, a flexible substrate such as polyethylene terephthalate is being studied. Since the substrate elongates/contracts upon heating, resulting in a poor condition that hinders the function of the display, it is necessary to lower the temperature in the baking process of the cured film.

In view of the above-described facts, a technique of a coating liquid for a gate insulating film for a flexible display comprising a polyimine precursor which can be cured even at a low temperature is developed (see Japanese Patent Laid-Open Publication No. 2009-4394). However, this coating liquid has no ability to form a pattern by exposure and development, and thus a fine pattern cannot be formed. Further, the curing reaction may not be sufficiently performed, and the compression properties, heat resistance, relative dielectric constant, solvent resistance, hardness, voltage holding ratio, and the like of the obtained cured film may not be satisfactory.

Therefore, a method in which a crosslinking reaction can be carried out even at a low temperature by adding an amine compound used as a hardener of an epoxy-based material is also considered, and a conventional amine compound is added to exist in the composition. The epoxy group undergoes a reaction which changes with time, and the storage stability is lowered (see WO2008/099732A1).

In view of such conditions, it is desired to develop a radiation-sensitive resin composition capable of both storage stability and short-time low-temperature calcination, and having sufficient sensitivity and developability, as well as compression characteristics, heat resistance, relative dielectric constant, and resistance. A cured film excellent in solvent, hardness and voltage retention.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-36858

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-4394

[Patent Document 3] WO2008/099732A1

The present invention has been made in view of the above circumstances, and an object thereof is to provide a radiation-sensitive resin composition having both storage stability and short-time low-temperature calcinability, and having sufficient sensitivity and developability, compression characteristics, heat resistance, A cured film excellent in dielectric constant, solvent resistance, hardness, and voltage holding ratio, a method of forming the cured film, and a color filter excellent in heat resistance, solvent resistance, voltage holding ratio, and the like.

The invention capable of solving the above problems is a radiation sensitive resin composition containing

[A] an alkali-soluble resin (hereinafter also referred to as "[A] alkali-soluble resin") which is at least one compound selected from the group consisting of (A1) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides ( Hereinafter, it is also referred to as "(A1) compound") and (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as "(A2) compound").

[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as "[B] polymerizable compound");

[C] a radiation sensitive linear polymerization initiator;

[D] a compound represented by the following formula (1) (hereinafter, also referred to as "[D] compound");

[E] a compound which is an organic acid or an inorganic acid (hereinafter, also referred to as "[E] compound"),

Its viscosity at 25 ° C is 1.0 mPa‧s~50 mPa‧s,

In the formula (1), m is an integer of 2 to 6, wherein some or all of the hydrogen atoms of the alkylene group in the formula (1) may be substituted with an organic group.

The radiation sensitive resin composition contains [A] an alkali-soluble resin, [B] a polymerizable compound, [C] a radiation-sensitive polymerization initiator, a [D] compound, and a [E] compound. The radiation-sensitive resin composition as a radiation-sensitive material can be easily formed into a fine and delicate pattern by utilizing radiation-sensitive exposure and development, and further has sufficient sensitivity and developability. In addition, when the radiation sensitive linear resin composition contains a [C] radiation-sensitive polymerization initiator, it is possible to further improve the heat resistance and the like as a desired property of the cured film even in the case of a low exposure amount. Further, the radiation-sensitive resin composition can function as an effective hardening catalyst by containing the [D] compound and the [E] compound, and can control the viscosity of the radiation-sensitive resin composition at 25 ° C to 1.0. mPa‧s~50mPa‧s. As a result, the radiation-sensitive resin composition can simultaneously have a storage stability at a high level and a hardening promoting action of the cured film under low-temperature baking. In addition, the above-mentioned so-called alkylene group means tetrahydropyridyl Both an alkylene group in the ring and an alkylene group represented by (CH ₂ )m in the above (1).

The [C] radiation-sensitive polymerization initiator is preferably an O-indenyl ruthenium compound. As the [C] radiation-sensitive polymerization initiator, by using the specific compound described above, heat resistance and the like can be further improved even in the case of a low exposure amount.

The radiation sensitive resin composition preferably mixes the onium salt formed of the [D] compound and the [E] compound in the [A] alkali-soluble resin, the [B] polymerizable compound, and the [C] radiation-sensitive polymerization initiator. preparation. Through the above steps, the radiation sensitive resin composition containing a cerium salt can be efficiently produced.

The onium salt is preferably a sulfonate. By making the onium salt a sulfonate, the action as a curing catalyst can be further enhanced.

Further, in the present invention, there is further provided a method for producing a radiation sensitive resin composition in which [A] an alkali-soluble resin, a [B] polymerizable compound, and a [C] radiation-sensitive polymerization initiator are mixed by [D The compound and the bismuth salt formed by the compound [E] were prepared, and the viscosity at 25 ° C was 1.0 mPa ‧ s to 50 mPa ‧ s.

The radiation sensitive resin composition is preferably used as a cured film for an interlayer insulating film, a protective film or a gasket. Further, in the present invention, it is preferable to include a cured film as an interlayer insulating film, a protective film or a gasket. . The cured film which is an interlayer insulating film, a protective film or a gasket formed of the radiation sensitive resin composition is excellent in compression characteristics, heat resistance, relative dielectric constant, solvent resistance, hardness, and voltage holding ratio.

The color filter of the present invention has the cured film, and an alignment film formed of a liquid crystal aligning agent laminated on the cured film. The color filter of the present invention is excellent in heat resistance, solvent resistance, voltage holding ratio, and the like.

The liquid crystal aligning agent is preferably a liquid crystal aligning agent containing a radiation-sensitive polymer having a photo-alignment group, or a liquid crystal aligning agent containing a polyimide having no photo-alignment group.

The method for forming a cured film of the present invention has:

(1) a step of applying the radiation sensitive resin composition on a substrate to form a coating film,

(2) a step of irradiating radiation on at least a part of the coating film,

(3) a step of developing the above-mentioned radiation-coated coating film, and

(4) A step of baking the above-developed coating film.

According to the formation method of the present invention, a cured film excellent in compression characteristics, heat resistance, relative dielectric constant, solvent resistance, hardness, and voltage holding ratio can be formed.

The calcination temperature in the above step (4) is preferably 200 ° C or lower. Since the radiation-sensitive resin composition contains the [D] compound and the [E] compound as the curing accelerator as described above, it is possible to achieve low-temperature baking, and is preferably a cured film used in a flexible display or the like which is desired to be baked at a low temperature. Forming material.

In the method for forming a color filter of the present invention, the steps (1) to (4) and (5) of the method for forming a cured film are applied to a baked coating film, and the liquid crystal aligning agent is applied by heating at 200 ° C or lower. The step of orienting the film.

By the method of forming the color filter, a color filter having an alignment film for liquid crystal alignment can be formed.

In addition, the term "baking" as used herein means heating to obtain a surface hardness required for a cured film such as an interlayer insulating film, a protective film, and a gasket. In addition, the "radiation" of the "radiation-sensitive linear resin composition" includes concepts such as visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle rays. Further, the viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., VISCONIC ELD. R) to measure the viscosity (mPa‧s) of the composition at 25 °C.

As described above, the radiation sensitive resin composition of the present invention is capable of easily forming a fine and delicate pattern, has both storage stability and short-time low-temperature baking, and has sufficient sensitivity and developability. Further, the cured film formed of the radiation sensitive resin composition is excellent in compression characteristics, heat resistance, relative dielectric constant, solvent resistance, hardness, and voltage holding ratio. Therefore, the radiation sensitive composition is preferably used as a material for forming a cured film such as an interlayer insulating film, a protective film, or a gasket which is used in a flexible display or the like which is desired to be baked at a low temperature. Further, the color filter having the cured film forming the alignment film is excellent in heat resistance, solvent resistance, voltage holding ratio, and the like.

[Formation for implementing the invention] <Inductive Radiation Resin Composition>

The radiation sensitive resin composition of the present invention contains [A] alkali-soluble resin, [B] polymerizable compound, [C] radiation sensitive polymerization initiator, [D] compound, [E] compound, viscosity at 25 ° C It is 1.0mPa‧s or more and 50mPa‧s or less. Further, the radiation sensitive resin composition may further contain an optional component as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.

<[A] alkali soluble resin>

[A] The alkali-soluble resin can be synthesized by copolymerizing a compound of (A1) and a compound of (A2) in a solvent in the presence of a polymerization initiator. Further, in the synthesis of the [A] alkali-soluble resin, the (A1) compound and the (A2) compound may be freely reacted with the unsaturated compound other than the above (A1) compound and (A2) compound as the (A3) compound. Copolymerization. Hereinafter, each component will be described in detail. Further, each compound may be used in combination of two or more.

[(A1) compound]

The compound (A1) is at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. The (A1) compound may, for example, be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride or a monocarboxylic acid mono[(meth)acryloxyalkylalkyl] ester, in two A mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group at the terminal, an unsaturated polycyclic compound having a carboxyl group, and an acid anhydride thereof.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, methyl fumaric acid, itaconic acid, and the like. The unsaturated dicarboxylic acid anhydride is, for example, an acid anhydride which is a compound exemplified as the above dicarboxylic acid. As the mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid, for example, succinic acid mono [2-(methyl) propylene methoxyethyl ester], phthalic acid mono [2- ( Methyl) propylene methoxyethyl ester] and the like. Examples of the mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals include ω-carboxypolycaprolactone mono(meth)acrylate. Examples of the unsaturated polycyclic compound having a carboxyl group and an acid anhydride thereof include, for example, 5-carboxybicyclo[2.2.1]hept-2-ene and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene. 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[ 2.2.1] Anhydride of hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, etc. .

Among them, an acid anhydride of a monocarboxylic acid or a dicarboxylic acid is preferred, and (meth)acrylic acid and maleic anhydride are more preferable from the viewpoints of copolymerization reactivity, solubility in an aqueous alkali solution, and ease of availability.

The content ratio of the structural unit derived from the (A1) compound in the [A] alkali-soluble resin is preferably from 5 mol% to 35 mol%, more preferably from 10 mol% to 30 mol%, based on the entire structural unit. %. By making the content ratio of the structural unit derived from the (A1) compound 5 mol% to 35 mol%, the solubility of the [A] alkali-soluble resin in an aqueous alkali solution can be optimized, and radiation can be obtained. A radiation sensitive resin composition excellent in sensitivity and developability.

[(A2) compound]

The compound (A2) is an epoxy group-containing unsaturated compound. Examples of the epoxy group include an oxyheteropropyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

Examples of the unsaturated compound having an oxopropyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl acrylate, and 2-methyl glycidyl acrylate α-- Glycidyl ethacrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-cyclomethacrylate Oxybutyl acrylate, acrylate-6,7-epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidol Ethyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like.

Examples of the unsaturated compound having an oxetanyl group include 3-(acryloxymethyl)oxetane and 3-(acryloxymethyl)-2-methyloxacyclohexane. Butane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-( Propylene methoxymethyl)-2-pentafluoroethyl oxetane, 3-(acryloxymethyl)-2-phenyl oxetane, 3-(acryloxymethyl) )-2,2-difluorooxetane, 3-(acryloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl)- 2,2,4,4-tetrafluorooxetane, 3-(2-propenyloxyethyl)oxetane, 3-(2-propenyloxyethyl)-2-ethyl Oxycyclobutane, 3-(2-propenyloxyethyl)-3-ethyloxetane, 3-(2-propenyloxyethyl)-2-trifluoromethyloxy Heterocyclic butane, 3-(2-propenyloxyethyl)-2-pentafluoroethyl oxetane, 3-(2-propenyloxyethyl)-2-phenyl oxacyclohexane Butane, 3-(2-propenyloxyethyl)-2,2-difluorooxetane, 3-(2-propenyloxyethyl)-2,2,4-trifluoroox Heterocyclic butane, 3-(2 -Acetyloxyethyl)-2,2,4,4-tetrafluorooxetane and the like; 3-(methacryloxymethyl)oxetane, 3-(A Acryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxyl) Methyl)-2-trifluoromethyl oxetane, 3-(methacryloxymethyl)-2-pentafluoroethyl oxetane, 3-(methacryl oxime) Methyl)-2-phenyloxetane, 3-(methacryloxymethyl)-2,2-difluorooxetane, 3-(methacryloxyl group -2,2,4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2 -Methacryloxymethoxyethyl)oxetane, 3-(2-methylpropenyloxyethyl)-2-ethyloxetane, 3-(2-methylpropene oxime Oxyethyl)-3-ethyloxetane, 3-(2-methylpropenyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methyl Propylene methoxyethyl)-2-pentafluoroethyl oxetane, 3-(2-methylpropenyloxyethyl)-2-phenyl oxetane, 3-(2- Methyl propylene oxide -2,2-difluorooxetane, 3-(2-methylpropenyloxyethyl)-2,2,4-trifluorooxetane, 3-(2-methyl A methacrylate such as a propylene methoxyethyl)-2,2,4,4-tetrafluorooxetane or the like.

Among them, from the viewpoint of copolymerization reactivity and improvement of the curability of the resin composition, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether is preferred. , m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate.

The content ratio of the structural unit derived from the (A2) compound in the [A] alkali-soluble resin is preferably from 5 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%, based on the entire structural unit. %. By setting the content ratio of the structural unit derived from the (A2) compound to 5 mol% to 70 mol%, a cured film having excellent solvent resistance can be formed.

[(A3) compound]

The compound (A3) is a compound other than the compound (A1) and the compound (A2), and is not particularly limited as long as it is a radical polymerizable unsaturated compound. Examples of the (A3) compound include a chain alkyl methacrylate, a cyclic alkyl methacrylate, a methacrylate having a hydroxyl group, a cyclic alkyl acrylate, an aryl methacrylate, and acrylic acid. Aryl ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyridyl An oxane skeleton, an unsaturated compound of a skeleton represented by the following formula (2), an unsaturated compound having a phenolic hydroxyl group represented by the following formula (3), and other unsaturated compounds.

In the above formula (2), R ¹ is a hydrogen atom or a methyl group. s is an integer of 1 or more.

In the above formula (3), R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ to R ⁷ each independently represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO- or -CONH-. p is an integer from 0 to 3. Among them, at least one of R ³ to R ⁷ is a hydroxyl group.

Examples of the above-mentioned chain alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, and butyl methacrylate. 2-ethylhexyl acrylate, isodecyl methacrylate, n-dodecyl methacrylate, tridecyl methacrylate, n-octadecyl methacrylate, and the like.

Examples of the cyclic alkyl methacrylate include cyclohexyl methacrylate, 2-ethylcyclohexyl methacrylate, and tricyclo [5.2.1.0 ^2.6 ] 癸-8-yl methacrylate. Tricyclo[meth] methacrylate [5.2.1.0 ^2.6 ] 癸-8-yloxyethyl, isobornyl methacrylate, and the like.

Examples of the methacrylate having the above hydroxyl group include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and methacrylic acid. Diethylene glycol ester, 2,3-dihydroxypropyl methacrylate, 2-methylpropenyloxyethyl saccharide, 4-hydroxyphenyl methacrylate, and the like.

Examples of the above-mentioned cyclic alkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2.6 ] 癸-8-yl acrylate, and tricyclopropyl acrylate [5.2.1.0 ^2.6癸-8-yloxyethyl ester, isobornyl acrylate, and the like.

Examples of the aryl methacrylate include phenyl methacrylate and benzyl methacrylate.

Examples of the aryl acrylate include phenyl acrylate and benzyl acrylate.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate.

The bicyclic unsaturated compound may, for example, be bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] g- 2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2. 1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-tris-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5- Cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tertiarybutoxycarbonyl)bicyclo[ 2.2.1] hept-2-ene, 5,6-di(cyclohexylcarbonyl)bicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]heptane- 2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di ( 2'-Hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2 .1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, and the like.

The above-mentioned maleimide compound may, for example, be N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide or N-(4-hydroxyphenyl). ) maleimide, N-(4-hydroxybenzyl)maleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4- Maleic acid imide butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9- Acridinyl) maleic imine and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

Examples of the conjugated diene include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrakis(meth)acrylate, 2-methylpropenyloxy-propionic acid tetrahydrofuran ester, and 3-(methyl)propenyltetrahydrofuran-2-one. .

Examples of the unsaturated compound containing a furan skeleton include 2-methyl-5-(3-furyl)-1-indol-3-one, furyl (meth)acrylate, and 1-furan-2-butane. 3--3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)-2-methyl-1-hexyl En-3-one, 6-furan-2-yl-hex-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furanyl) -6-methyl-1-hept-3-ene and the like.

Examples of the unsaturated compound containing a tetrahydropyran skeleton include, for example, (tetrahydropyran-2-yl)methyl methacrylate and 2,6-dimethyl-8-(tetrahydropyran-2- Benzyl)-oct-1-en-3-one, 2-hydropyran-2-yl methacrylate, 1-(tetrahydropyran-2-yloxy)-butyl-3-ene- 2-ketone and the like.

The unsaturated compound containing a pyran skeleton may, for example, be 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyran, 4- (1,5-Dioxa-6-o-oxy-octenyl)-6-methyl-2-pyran and the like.

Examples of the unsaturated compound having a skeleton represented by the above formula (2) include polyethylene glycol (n=2 to 10) mono(meth)acrylate and polypropylene glycol (n=2 to 10) mono(methyl). Acrylate and the like.

Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (3) include compounds represented by the following formulas (4) to (8).

In the above formula (4), q is an integer of 1 to 3. R ² to R ⁷ are the same as defined in the above formula (3).

In the above formula (5), R ² to R ⁷ are the same as defined in the above formula (3).

In the above formula (6), r is an integer of 1 to 3. R ² to R ⁷ are the same as defined in the above formula (3).

In the above formula (7), R ² to R ⁷ are the same as defined in the above formula (3).

In the above formula (8), R ² to R ⁷ are the same as defined in the above formula (3).

Examples of the other unsaturated compound include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (A3) compounds, preferred are methacrylic chain alkyl esters, methacrylic cyclic alkyl esters, maleimide compounds, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, and pyridyl groups. An unsaturation of a skeleton represented by the above formula (2), an unsaturated compound having a phenolic hydroxyl group represented by the above formula (3), an unsaturated aromatic compound, and a cyclic alkyl acrylate, from copolymerization reactivity and From the viewpoint of solubility of the aqueous alkali solution, more preferred are styrene, tertiary butyl methacrylate, n-dodecyl methacrylate, and tricyclo [5.2.1.0 ^2.6 ]癸-8-yl group. Acrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofuran (meth) acrylate, polyethyl b Glycol (n=2~10) mono(meth)acrylate, 3-(meth)acryloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (Meth) acrylate, m-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene.

The content ratio of the structural unit derived from the compound (A3) in the [A] alkali-soluble resin is preferably from 10 mol% to 80 mol% based on the total structural unit. By setting the content ratio of the structural unit derived from (A3) to 10 mol% to 80 mol%, it is possible to obtain a radiation-sensitive resin composition excellent in developability and solvent resistance of the formed cured product.

The weight average molecular weight (Mw) of the [A] alkali-soluble resin is more preferably 2 × 10 ³ to 1 × 10 ⁵ , still more preferably 5 × 10 ³ to 5 × 10 ⁴ . By making the Mw of the [A] alkali-soluble resin 2 × 10 ³ to 1 × 10 ⁵ , the sensitivity and developability of the radiation-sensitive resin composition can be improved. Further, the Mw and the number average molecular weight (Mn) in the present specification are measured by gel permeation chromatography (GPC) under the following conditions.

Device: GPC-101 (Showa Denko Co., Ltd.)

Column: combined with GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 ° C

Flow rate: 1.0 mL / min

Sample concentration: 1.0% by mass

Sample injection amount: 100 μL

Detector: Differential Refractometer

Reference material: monodisperse polystyrene

The solvent used in the polymerization reaction for producing the [A] alkali-soluble resin may, for example, be an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol monoalkyl ether, or a diethylene glycol. Alcohol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketones, esters and the like.

Examples of the alcohol include benzyl alcohol and the like. Examples of the glycol ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Examples of the ethylene glycol alkyl ether acetate include ethylene glycol single. Butane ether acetate, diethylene glycol monoethyl ether acetate, etc.; as the diethylene glycol monoalkyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.; The alcohol dialkyl ether may, for example, be diethylene glycol dimethyl ether, diethylene glycol diethyl ether or diethylene glycol ethyl methyl ether.

Examples of the dipropylene glycol dialkyl ether include dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether; and examples of the propylene glycol monoalkyl ether include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol. Examples of the propylene glycol alkyl ether acetate include propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; and propylene glycol monoalkyl ether propionate, for example, propylene glycol methyl ether An acid ester, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate or the like; examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like. The ester may, for example, be ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate or a hydroxyl group. Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, Methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2- Butyl butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, and the like.

Among these solvents, preferred are ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, More preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

As the polymerization initiator to be used in the polymerization for producing the [A] alkali-soluble resin, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2,2'-azo. An azo compound such as bis-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, laurel peroxide, tertiary butyl peroxy valerate, 1,1'- An organic peroxide such as di-(tri-butyl peroxide) cyclohexane and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a peroxide is also used as a reducing agent to form a redox type initiator.

In the polymerization reaction for producing the [A] alkali-soluble resin, a molecular weight modifier may be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl mercaptan, and thio a thiol such as a glycolic acid; a xanthogen such as dimethyl xanthogen thioether or diisopropylxanthogen disulfide; a terpinolene olefin and an α-methyl styrene dimer.

<[B] polymerizable compound>

The polymerizable compound [B] contained in the radiation-sensitive resin composition is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond, and examples thereof include ω-carboxypolycaprolactam. (Meth) acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, tetraethylene Alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, diphenoxyethanol thin di(meth)acrylate, dimethylol three Cyclodecane di(meth) acrylate, 2-hydroxy-3-(methyl) propylene methoxy propyl methacrylate, 2-(2'-vinyloxyethoxy)ethyl (methyl Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, tris(2-(meth)acryloxyethyl)phosphate, ethylene oxide modified pentaerythritol hexaacrylate, succinic acid modified pentaerythritol Further, an enoate or the like may be a compound having a linear alkyl group and an alicyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule, and having 3 to 5 ( A urethane (meth) acrylate compound obtained by reacting a compound of a methyl propylene oxy group.

Commercial products of the [B] polymerizable compound include, for example, ARONIX M-400, ARONIX M-402, ARONIX M-405, ARONIX M-450, ARONIX M-1310, ARONIX M-1600, ARONIX M-1960 , ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, ARONIX M-8100, ARONIX M-8530, ARONIX M-8560, ARONIX M-9050, ARONIX TO-1450, ARONIX TO-1382 (above for East Asia Synthesis) Company); KAYARAD DPHA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60, KAYARADDPCA-120, KAYARADMAX-3510 (above is Nippon Chemical Co., Ltd.); VISCOAT 295, VISCOAT 300, VISCOAT 360, VISCOAT GPT, VISCOAT 3PA, VISCOAT 400 (above is Osaka Organic Chemical Industry Co., Ltd.); as a urethane acrylate compound, NEW FRONTIER R-1150 (First Industrial Pharmaceutical Company); KAYARAD DPHA-40H, UX-5000 (above is Japanese) Pharmaceutical company); UN-9000H (Guanshang Industrial Co., Ltd.); ARONIX M-5300, ARONIX M-5600, ARONIX M-5700, M-210, ARONIX M-220, ARONIX M-240, ARONIX M-270, ARONIX M- 6200, ARONIX M-305, ARONIX M-309, ARONIX M-310, ARONIX M-315 (above is East Asia Synthetic ); KAYARAD HDDA, KAYARAD HX-220, KAYARADHX-620, KAYARADR-526, KAYARADR-167, KAYARADR-604, KAYARADR-684, KAYARADR-551, KAYARADR-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above is Nippon Chemical Co., Ltd.); ART-RESIN UN-9000PEP, ART-RESIN UN-9200A, ART-RESIN UN-7600, ART-RESIN UN-333, ART-RESIN UN-1003, ART-RESIN UN-1255, ART-RESIN UN-6060PTM, ART-RESIN UN-6060P (above the root industry Company); SH-500B VISCOAT 260, VISCOAT 312, VISCOAT 335HP (above is Osaka Organic Chemical Industry Co., Ltd.).

[B] The polymerizable compound may be used singly or in combination of two or more. The content of the [B] polymerizable compound in the radiation sensitive resin composition is preferably 20 parts by mass to 200 parts by mass, more preferably 40 parts by mass to 160 parts by mass per 100 parts by mass of the [A] alkali-soluble resin. Share. When the content ratio of the [B] polymerizable compound is within the above specific range, it is possible to obtain a cured film having excellent adhesion to the substrate and having a sufficient hardness at a low exposure amount.

<[C] sensitizing radiation polymerization initiator>

The [C] radiation-sensitive polymerization initiator contained in the radiation-sensitive resin composition is a component capable of inducing radiation and generating an active species that initiate polymerization of the [B] polymerizable compound. Examples of the [C] radiation-sensitive polymerization initiator include an O-indenyl hydrazine compound, an acetophenone compound, and a biimidazole compound. Further, the [C] radiation-sensitive polymerization initiator may be used in combination of two or more.

As the O-indenyl ruthenium compound, ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-B醯肟), 1-[9-ethyl-6-benzylidene-9H-carbazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl -6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-n-butyl-6-( 2-ethylbenzhydryl)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone-1-[9-ethyl-6-(2 -methyl-4-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2- Methyl-4-tetrahydropyranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-( 2-methyl-5-tetrahydrofuranylbenzylidene)-9H-carbazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-{2 -Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-1-(O-B醯肟) and so on. Among them, preferred is ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetyl), B. Keto-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine) or ethyl ketone 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indole Zyridin-3-yl]-1-(O-acetamidine).

The acetophenone compound may, for example, be an α-amino ketone compound or an α-hydroxy ketone compound.

As the α-amino ketone compound, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Physo-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Phenanpropan-1-one and the like.

As the α-hydroxyketone compound, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropene- 1-ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.

Among these acetophenone compounds, an α-amino ketone compound is preferred, and 2-benzyl-2-dimethylamino-1-(4-) is more preferred. Phenylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Polin-4-yl-phenyl)-butan-1-one.

As the bisimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-double can be mentioned. Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-di(2,4-di Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4' , 5,5'-tetraphenyl-1,2'-bisimidazole, and the like. Among them, preferred is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-di(2, 4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4 , 4',5,5'-tetraphenyl-1,2'-bisimidazole, more preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5' -Tetraphenyl-1,2'-bisimidazole.

A commercially available product of the [C] radiation-sensitive polymerization initiator may, for example, be 2-methyl-1-(4-methylthiophenyl)-2- Isogacure 907, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenylphenyl)-butan-1-one (Irgacure 379), ethane-1-[9-ethyl-6-(2-methylbenzhydrazide)-9H-indazol-3-yl]-1- (O-Acetyl) (Irgacure OXE02) (above is Ciba Speciality Chemicals) and the like.

The content of the [C] radiation-sensitive polymerization initiator in the radiation-sensitive resin composition is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. ~30 parts by mass. By making the content ratio of the [C] radiation-sensitive polymerization initiator to 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition can form a high hardness and adhesion even at a low exposure amount. Hardened film.

<[D] compound>

The compound represented by the above formula (1) is not particularly limited as long as it is a compound represented by the above formula (1), and it is preferred to form a phosphonium salt with the [E] compound. Compound. By containing the [D] compound and the [E] compound, the radiation sensitive resin composition can simultaneously maintain the storage stability of the radiation sensitive composition and the hardening acceleration of the cured film at low temperature baking at a high level.

The compound [D] is a compound represented by the above formula (1). In the above formula (1), m is an integer of 2-6. Here, a part or all of the hydrogen atoms of the alkyl group in the formula (1) may be optionally substituted with an organic group.

The compound represented by the above formula (1) may, for example, be 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN) or 1,5-diazabicyclo[4,4, 0]-pinene-5,1,8-diazabicyclo[5,4,0]-undecene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo[5, 4,0]-undecene-7,5-dibutylamino-1,8-diazabicyclo[5,4,0]-undecene-7 and the like. Among them, DBN and DBU are preferred.

Examples of the organic group include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a n-butyl group, a tertiary butyl group, and a n-hexyl group; a hydroxymethyl group and a 2-hydroxy group B; a hydroxyalkane having 1 to 6 carbon atoms such as a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxyisopropyl group, a 3-hydroxytributyl group, and a 6-hydroxyhexyl group. Carbon atom number such as dimethylamino group, methyl ethylamino group, diethylamino group, diisopropylamino group, dibutylamino group, tertiary butylmethylamino group or di-n-hexylamino group It is a 2 to 12 dialkylamino group or the like.

<[E] compound>

The [E] compound is a compound which is an organic acid or an inorganic acid. The compound [E] is not particularly limited as long as it is an organic acid or an inorganic acid, and a compound capable of forming a phosphonium salt with the [D] compound is preferred.

Examples of the organic acid include a carboxylic acid, a monoalkyl carbonate, an aromatic hydroxy compound, and a sulfonic acid.

Examples of the carboxylic acid include saturated fatty acids such as formic acid, acetic acid, 2-ethylhexanoic acid, and isovaleric acid; acrylic acid, crotonic acid, methacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, and rich Horse acid, maleic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, octadecadienoic acid, stearidonic acid, arachidonic acid, cinnamic acid, naphthoic acid, benzoic acid , unsaturated carboxylic acid such as toluic acid; chloroacetic acid, amino acetic acid, dichloroacetic acid, trichloroacetic acid, trimethylacetic acid, fluoroacetic acid, bromoacetic acid, methoxyacetic acid, thioglycolic acid, iodoacetic acid, ethylene Alpha-substituted acetic acid such as acetic acid, pendant oxyacetic acid, phenylacetic acid or phenoxyacetic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, azelaic acid, etc. Dicarboxylic acid; hydroxy acid such as glycolic acid, lactic acid, citric acid, d-tartaric acid, meso-tartaric acid, ascorbic acid, mandelic acid; ketocarboxylic acid such as pyruvic acid or acetyl propionate; 2-chloropropionic acid, A halogenated carboxylic acid such as 3-chloropropionic acid.

Examples of the monoalkyl carbonate include methyl carbonate, ethyl carbonate, and the like.

Examples of the aromatic hydroxy compound include phenol, cresol, naphthol and the like.

Examples of the sulfonic acid include octylbenzenesulfonic acid, butylbenzenesulfonic acid, toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and the like.

The inorganic acid may, for example, be a halogenated acid such as hydrochloric acid, hydrofluoric acid or hydrobromic acid; or a perhalogenic acid such as carbonic acid, perchloric acid or perbromic acid.

The compound [E] is preferably an organic acid, more preferably a carboxylic acid, an aromatic hydroxy compound or a sulfonic acid, still more preferably a saturated fatty acid, an aromatic hydroxy compound or a sulfonic acid, particularly preferably a sulfonic acid as a strong acid. Most preferred are toluenesulfonic acid, methanesulfonic acid, and octylbenzenesulfonic acid.

<脒盐>

In the radiation sensitive resin composition, at least a part of the [D] compound forms a phosphonium salt with the [E] compound. If a usual amine compound and an epoxy compound coexist, in the preservation of the composition solution, a hardening reaction occurs due to nucleophilic attack of the amine to the epoxy group, which may impair the quality of the product. However, in the present invention, by containing a phosphonium salt of a cyclic ammonium salt, even in the case of coexistence with an epoxy compound, the storage stability is good, and a coating film is formed from the composition, and it is sufficient when heated. Acts as a catalyst.

The onium salt is preferably a sulfonate, and by making the onium salt a sulfonate, it is possible to further enhance the function as a hardening catalyst. As the onium salt, a salt of DBU and toluenesulfonic acid, a salt of DBU and octylbenzenesulfonic acid, a salt of DBN and toluenesulfonic acid, and a salt of DBN and octylbenzenesulfonic acid are more preferable.

The phosphonium salt may be used singly or in combination of two or more. When the onium salt is formed in advance and is contained in the radiation sensitive resin composition, the content of the onium salt in the radiation sensitive resin composition is preferably 0.01 based on 100 parts by mass of the [A] alkali-soluble resin. The mass fraction is preferably 3 parts by mass, more preferably 0.01 parts by mass to 1 part by mass. By setting the content of the onium salt within the above specific range, it is possible to simultaneously have the storage stability of the radiation sensitive resin composition and the hardening acceleration effect of the cured film at a high level.

<optional ingredients>

The radiation sensitive resin composition is in a range that does not impair the desired effect, in addition to the above [A] alkali-soluble resin, [B] polymerizable compound, [C] radiation-sensitive polymerization initiator, [D] compound, and [E] compound. Further, if necessary, an optional component such as an adhesion aid, a surfactant, a storage stabilizer, and a heat resistance improving agent may be contained. These optional components may be used singly or in combination of two or more. Each optional component is described in detail below.

[Adhesive Aid]

The adhesion aid can be used to further improve the adhesion of the resulting cured film to the substrate. The adhesive auxiliary agent is preferably a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an oxirane group, and examples thereof include a trimethoxymethyl decyl group. Benzoic acid, γ-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, γ-isocyanatepropyltriethoxydecane, γ-glycidol Propyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

The amount of the binder to be used is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. When the amount of the binder to be used exceeds 20 parts by mass, there is a tendency that development residue tends to occur.

[Surfactant]

Surfactants can be used to further improve the film formability of the radiation sensitive composition. As the surfactant, for example, a fluorine-based surfactant, a polyoxyalkylene-based surfactant, and other surfactants can be mentioned. The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluoroalkylene group at at least any one of a terminal group, a main chain and a side chain, and examples thereof include 1,1,2,2- Tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl)ether, hexaethylene glycol di( 1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octaethylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, hexapropylene glycol di(1, 1,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, sodium perfluoro-n-dodecylsulfonate 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, fluorinated Sodium alkylbenzene sulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkylcarboxylate, diglycerol tetra(fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine Other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylenes, perfluoroalkyl alcoholates, fluoroalkyl carboxylates, and the like.

Examples of the commercially available product of the fluorine-based surfactant include BM-1000, BM-1100 (above, BM CHEMIE), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183, MEGAFAC F178, MEGAFAC F191, and MEGAFAC F471. MEGAFAC F476 (above is Dainippon Ink Chemical Industry Co., Ltd.), FLUORAD FC-170C, FLUORAD FC-171, FLUORAD FC-430, FLUORAD FC-431 (above Sumitomo 3M), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 ( The above are Asahi Glass Co., Ltd., EFTOP EF301, EFTOP EF303, EFTOP EF352 (above is New Akita Chemical Co., Ltd.), FTERGENT FT-100, FTERGENT FT-110, FTERGENT FT-140A, FTERGENT FT-150, FTERGENT FT-250, FTERGENT FT -251, FTERGENT FT-300, FTERGENT FT-310, FTERGENT FT-400S, FTERGENT FTX-218, FTERGENT FTX-251 (above is Rios).

As a commercial product of a polyoxyalkylene surfactant, for example, Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190 Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone SF-8428, Toray Silicone DC-57, Toray Silicone DC-190 (above Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF- 4445, TSF-4446, TSF-4460, TSF-4452 (above is GE Toshiba Silicone Corporation), organic alkane polymer KP341 (Shin-Etsu Chemical Industry Co., Ltd.) and the like.

Examples of the other surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl sulfonyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether; a polyoxyethylene aryl ether such as oxyethylene n-nonylphenyl ether; a nonionic surfactant such as polyoxyethylene dialkyl ester such as polyoxyethylene dilauryl ester or polyoxyethylene distearyl phthalate; Methyl)acrylic copolymer POLYFLOW No. 57, POLYFLOW No. 95 (above is Kyoeisha Chemical Co., Ltd.) and the like.

The amount of the surfactant to be used is preferably 1.0 part by mass or less, and more preferably 0.8 part by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. If the amount of the surfactant used exceeds 1.0 part by mass, film unevenness is likely to occur.

[storage stabilizer]

Examples of the storage stabilizer include sulfur, anthracene, hydroquinone, a polyoxy compound, an amine, a nitronitroso compound, and the like, and more specifically, 4-methoxyphenol and N-nitroso -N-phenylhydroxylamine aluminum or the like.

The amount of the storage stabilizer to be used is preferably 3.0 parts by mass or less, more preferably 1.0 part by mass or less, per 100 parts by mass of the [A] alkali-soluble resin. If the amount of the storage stabilizer used exceeds 3.0 parts by mass, the sensitivity of the radiation-sensitive resin composition is lowered, and the pattern shape may be deteriorated.

[heat resistance improver]

The heat resistance improving agent may, for example, be an N-(alkoxymethyl)glycol urea compound or an N-(alkoxymethyl)melamine compound.

As the N-(alkoxymethyl) glycol urea compound, for example, N,N',N",N'''-tetrakis(methoxymethyl)glycol urea, N,N',N" may be mentioned. , N'''-tetrakis (ethoxymethyl) glycol urea, N, N', N", N'''-tetrakis (n-propoxymethyl) glycol urea, N, N', N ", N'''-tetrakis(isopropoxymethyl) glycol urea, N, N', N", N'''-tetrakis (n-butoxymethyl) glycol urea, N, N' , N", N'''-tetrakis (tertiary butoxymethyl) glycol urea, and the like. Among them, preferred are N,N',N",N'''-tetrakis(methoxymethyl)glycol urea.

As the N-(alkoxymethyl)melamine compound, for example, N,N,N',N',N",N"-hexa(methoxymethyl)melamine, N,N,N' may be mentioned. ,N',N",N"-hexa(ethoxymethyl)melamine, N,N,N',N',N",N"-hexa(n-propoxymethyl)melamine, N ,N,N',N',N",N"-hexa(isopropoxymethyl)melamine, N,N,N',N',N",N"-hexa(n-butoxymethyl) Base) melamine, N, N, N', N', N", N"-hexa(tris-butoxymethyl) melamine, and the like. Among them, N, N, N', N', N", N"-hexa(methoxymethyl) melamine is preferable, and as a commercial item, for example, NIKALAC N-2702, NIKALAC MW-30M (for example, Sanwa Chemicals) and so on.

The amount of use of the heat resistance improving agent is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. When the amount of the heat resistance improving agent used exceeds 50 parts by mass, the sensitivity of the radiation sensitive resin composition is lowered, and the pattern shape may be deteriorated.

<Preparation method of radiation sensitive resin composition>

The radiation sensitive resin composition of the present invention may be mixed with [A] alkali-soluble resin, [B] polymerizable compound, [C] radiation-sensitive polymerization initiator, [D] compound, and [E] compound, as needed. The optional components are mixed in a prescribed ratio to prepare. The radiation sensitive linear resin composition can be prepared by mixing an onium salt formed of a [D] compound and an [E] compound in [A] an alkali-soluble resin, a [B] polymerizable compound, and a [C] radiation-sensitive polymerization initiator. . Through the above steps, the radiation sensitive resin composition containing a cerium salt can be efficiently produced.

As the solvent to be used in the preparation of the radiation sensitive resin composition, those which can uniformly dissolve or disperse the respective components but do not react with the respective components can be used. The solvent is the same as those exemplified as the solvent which can be used for the synthesis of the above [A] alkali-soluble resin. The solvent may be used singly or in combination of two or more.

From the viewpoints of solubility of each component, non-reactivity with each component, easiness of formation of a coating film, etc., it is particularly preferable to use, for example, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, and diethyl Glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3- Methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol.

Further, in order to improve the surface uniformity of the above solvent and film thickness, a high boiling point solvent may be used in combination. Examples of the high boiling point solvent include N-methylpyrrolidone, N,N-dimethylacetamide, benzylethyl ether, dihexyl ether, acetamylmethylacetone, 1-octanol, and 1-nonanol. , benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, dipropyl carbonate, and the like. Among them, preferred is N-methylpyrrolidone, γ-butyrolactone or N,N-dimethylacetamide.

When the solvent of the radiation-sensitive linear resin composition is used in combination with a high-boiling solvent, the amount of the solvent is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30%. Below mass%. When the amount of the high-boiling solvent used is 50% by mass or less, the film thickness uniformity, sensitivity, and residual film ratio of the coating film are good.

When the radiation sensitive resin composition is prepared in a solvent state, the solid content concentration (component other than the solvent in the composition solution) can be set to an arbitrary value depending on the purpose of use or the desired film thickness. Concentration (for example, 5 to 50% by mass). The solid content concentration which is more preferable varies depending on the method of forming the coating film on the substrate, which will be described later. The composition solution thus prepared is filtered using a micropore filter or the like having a pore diameter of about 0.5 μm.

<Method of Forming Cured Film>

The radiation sensitive resin composition is preferably used for forming a cured film as an interlayer insulating film, a protective film or a gasket, and a cured film as an interlayer insulating film, a protective film or a gasket is preferably contained in the present invention. The cured film of the interlayer insulating film, the protective film or the spacer formed of the radiation-sensitive resin composition is excellent in compression characteristics, heat resistance, relative dielectric constant, solvent resistance, hardness, and voltage holding ratio.

The method for forming a cured film of the present invention has:

(1) a step of applying the radiation sensitive resin composition on a substrate to form a coating film,

(2) a step of irradiating at least a part of the coating film with radiation,

(3) a step of developing a coating film irradiated with the above radiation, and

(4) a step of baking the above-described developed coating film.

According to the formation method of the present invention, a cured film excellent in compression characteristics, heat resistance, relative dielectric constant, solvent resistance, hardness, and voltage holding ratio can be formed. Hereinafter, each step will be described in detail.

[step 1)]

In this step, a transparent conductive film is formed on one surface of the transparent substrate, and a coating film of a radiation-sensitive resin composition is formed on the transparent conductive film. Examples of the transparent substrate include glass substrates such as soda lime glass and alkali-free glass; and plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and polyimide. A resin substrate or the like.

Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film composed of tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and indium oxide-tin oxide (In ₂ O ₃ -SnO _{2 ).} Constituting an ITO film or the like.

When a coating film is formed by a coating method, after applying a solution of the radiation sensitive resin composition onto the transparent conductive film, it is preferred to heat (prebaking) the coated surface to form a coating film. The solid content concentration of the composition solution used in the coating method is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, particularly preferably 15% by mass to 35% by mass. As a coating method of the radiation sensitive resin composition, for example, a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slot die coating method), a bar coating method, and an inkjet coating method can be employed. Wait for the appropriate method. Among these coating methods, a spin coating method or a slit coating method is particularly preferred.

The conditions for the prebaking are different depending on the type of each component, the mixing ratio, and the like, and it is preferably about 1 to 15 minutes at 70 to 120 °C. The film thickness of the coating film after prebaking is preferably from 0.5 to 10 μm, more preferably from about 1.0 to 7.0 μm.

[Step (2)]

In this step, at least a part of the coating film is irradiated with radiation. At this time, when only a part of the coating is irradiated, for example, a method of irradiating with a mask having a predetermined pattern may be employed.

Examples of the radiation used for the irradiation include visible light rays, ultraviolet rays, and far ultraviolet rays. Among them, radiation having a wavelength in the range of 250 to 550 nm is preferable, and radiation containing ultraviolet rays of 365 nm is more preferable.

The amount of radiation (exposure amount) is measured by an illuminometer (OAI model 356, manufactured by Optical Associates Inc.) to measure the illuminance at a wavelength of 365 nm of the irradiated radiation, preferably 100 J/m ² to 5000 J/m ^{2 .} More preferably, it is 200 J/m ² ~3000 J/m ² .

The radiation sensitive resin composition is highly sensitive to known compositions, and even when the radiation exposure amount is 850 J/m ² or less, a desired film thickness, a good shape, and an excellent density can be obtained. Sticky and high hardness hardened film.

[Step (3)]

In this step, the coating film after the radiation irradiation is developed to remove unnecessary portions, thereby forming a predetermined pattern. As the developer to be used for development, for example, an inorganic compound such as sodium hydroxide, potassium hydroxide or sodium carbonate, or a basic compound such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. Aqueous solution. A water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be appropriately added to the aqueous solution of the basic compound.

The development method may be any one of a liquid-filling method (spinning immersion method), a dipping method, a shower method, and the like, and the development time is preferably about 10 to 180 seconds at normal temperature. After the development treatment, for example, washing with running water for 30 seconds to 90 seconds, and then air-drying with compressed air or compressed nitrogen, a desired pattern is obtained.

[Step (4)]

In this step, the obtained patterned coating film is baked (post-baking) by a suitable heating means such as a hot plate or an oven to obtain a cured film. The baking temperature is preferably 200 ° C or lower, more preferably 150 ° C to 180 ° C. The baking time is preferably, for example, 5 to 30 minutes on a hot plate and 30 to 180 minutes in an oven. Since the radiation-sensitive resin composition contains the [D] compound and the [E] compound as the hardening accelerator as described above, low-temperature baking can be achieved, and it is preferably used in a flexible display or the like which is desired to be used for low-temperature baking. A material for forming a cured film.

<Method of Forming Color Filter>

The color filter of the present invention has the cured film and an alignment film formed by laminating the cured film and passing through a liquid crystal aligning agent.

The color filter of the present invention is excellent in heat resistance, solvent resistance, voltage holding ratio, and the like.

[Step (5)]

In the method for forming a color filter of the present invention, the steps (1) to (4) and (5) of the method for forming the cured film are applied to a baked coating film, and the liquid crystal aligning agent is applied and heated at 200 ° C or lower. The step of forming an oriented film. According to the method of forming the color filter, a color filter having an alignment film for liquid crystal alignment can be formed.

The liquid crystal aligning agent is preferably a liquid crystal aligning agent containing a radiation-sensitive polymer having a photo-alignment group (hereinafter also referred to as "[F] radiation-sensitive polymer)", or contains no photo-alignment group. A liquid crystal aligning agent of polyimine (hereinafter also referred to as "[G] polyimine).

The coating method of the liquid crystal aligning agent is preferably a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slot die coating method), a bar coating method, an inkjet coating method, or the like. method. Among them, a spin coating method or a slit coating method is preferred. Further, after the liquid crystal aligning agent is applied, the coated film can be formed by heating the coated surface. Each of the liquid crystal aligning agents can form an alignment film at a heating temperature of a low temperature (for example, 200 ° C or lower). In addition, the liquid crystal aligning agent may contain, for example, a curing agent, a curing catalyst, an epoxy compound, a functional decane compound, a surfactant, a photosensitizer, and the like as long as the optional component does not impair the effects of the present invention. Hereinafter, the [F] radiation sensitive polymer and [G] polyimine are described in detail.

<[F] Radiation-sensitive polymer>

[F] The photo-alignment group of the radiation-sensitive polymer is a functional group capable of imparting anisotropy to the film by light irradiation, and imparts anisotropy to the film by a photoisomerization reaction or a photodimerization reaction. Examples of the photo-alignment group include those selected from the group consisting of azobenzene, stilbene, α-imino-β-ketoester, spiropyran, and spiro a group of structures of at least one compound of the group consisting of cinnamic acid, styrene benzene, styrene pyridine, benzylidene phthalimide, coumarin, diphenylacetylene and hydrazine . The photo-alignment group preferably has a structure derived from cinnamic acid.

As the [F] radiation-sensitive polymer, a polymer in which a photo-alignment group is bonded directly or through a linking group is preferred. Examples of the [F] radiation-sensitive polymer include a polymer in which a photo-alignment group is bonded to a polymer such as polyacrylamide or polyimine. Further, examples of the [F] radiation-sensitive polymer include polyglycine, polyimine, and other polymers, and the other polymer is a photo-alignment group. Examples of the basic skeleton of the other polymer include poly(meth)acrylate, poly(meth)acrylamide, polyvinyl ether, polyfluorene, polyorganosiloxane, and the like.

As the [F] radiation sensitive polymer, a polymer having a polyamine, a polyamidene or a polyorganosiloxane as a basic skeleton is preferable. More preferably, it is a polyorganosiloxane. The [F] radiation sensitive polymer can be synthesized by, for example, the method described in WO2009/025386.

<[G]polyimine]

The [G] polyimine which has no photo-alignment group can be synthesized by dehydrating a poly-proline which has no photo-alignment group, and performing hydrazine imidation. The polyamic acid can be synthesized by reacting tetracarboxylic dianhydride with a diamine according to, for example, the method described in JP-A-2010-97188.

[G] Polyimine may be a complete quinone imide of a lysine structure in which all of the proline acids of the polyglycolic acid as a precursor are dehydrated, or a part of the proline structure may be dehydrated and closed only to form a guanamine. A partial quinone imide that has an acid structure and a quinone ring structure. The ruthenium amination ratio of [G] polyimine is preferably 30% or more, more preferably 50% to 99%, and particularly preferably 65% to 99%. The ratio of the ruthenium imidization ratio is expressed as a percentage of the number of the quinone imine ring structure in the sum of the number of the guanidine structure of the polyimine and the sum of the number of the quinone ring structures.

A color filter having a cured film in which an alignment film for liquid crystal alignment is formed is also preferably included in the present invention. This color filter is excellent in heat resistance, solvent resistance, voltage holding ratio, and the like. The liquid crystal aligning agent for forming the alignment film for a color filter preferably contains a [F] radiation sensitive polymer.

[Examples]

Hereinafter, the present invention will be described in detail based on the examples, but the present invention is not to be construed as limiting.

<[A] Synthesis of alkali-soluble resin> [Synthesis Example 1]

In a flask having a condenser and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Followed by addition of 16 parts by mass of methyl methacrylate (A1) compound, 20 parts by mass of methacrylic acid (A2) and the glycidyl compound 16 parts by mass of (A3) the compounds of tricyclo [5.2.1.0 ^2.6] dec - 8-based methacrylate, 38 parts by mass of methyl methacrylate and 10 parts by mass of styrene, after being replaced with nitrogen, slowly stirring, and raising the temperature to 70 ° C, maintaining the temperature for 4 hours to carry out polymerization, thereby obtaining a content A solution of the copolymer (A-1) (solid content concentration = 34.4% by mass, Mw = 8000, Mw / Mn = 2.3). Further, the solid content concentration means the ratio of the mass of the copolymer to the total mass of the copolymer solution.

[Synthesis Example 2]

In a flask having a condenser and a stirrer, 8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 20 parts by mass of methacrylic acid as the compound (A1), 20 parts by mass of glycidyl methacrylate as the compound (A2), 30 parts by mass of n-lauryl methacrylate as the compound (A3), and 30 mass are added. After the styrene was replaced with nitrogen, the mixture was slowly stirred, and the solution was heated to 70 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution containing the copolymer (A-2) (solid content concentration = 31.9 mass%, Mw) =8000, Mw/Mn = 2.3).

[Synthesis Example 3]

In a flask having a condenser and a stirrer, 8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 20 parts by mass of methacrylic acid as the compound (A1), 50 parts by mass of glycidyl methacrylate as the compound (A2), and 25 parts by mass of a tricyclic ring of the compound (A3) [5.2.1.0 ^2.6 ]癸- 8-based methacrylate and 5 parts by mass of styrene, after being replaced with nitrogen, stirring slowly, and raising the temperature to 70 ° C, maintaining the temperature for 5 hours to carry out polymerization, thereby obtaining a solution containing the copolymer (A-3) (solid content concentration = 32.3 mass%, Mw = 8000, Mw / Mn = 2.3).

[Synthesis Example 4]

In a flask having a condenser and a stirrer, 8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether were added. Next, 20 parts by mass of methacrylic acid as the compound (A1), 50 parts by mass of 2-methylglycidyl methacrylate as the compound (A2), and 25 parts by mass of a tricyclic ring as a compound of (A3) [5.2.1.0] ^2.6 ] 癸-8-yl methacrylate and 5 parts by mass of styrene, after replacing with nitrogen, stirring slowly, and raising the temperature to 70 ° C, maintaining the temperature for 5 hours to carry out polymerization, thereby obtaining a copolymer (A- 4) solution (solid content concentration = 32.3 mass%, Mw = 8500, Mw / Mn = 2.2).

<Preparation of a radiation sensitive resin composition>

Each detailed component used in the preparation of each of the radiation sensitive resin compositions is shown below.

<[B] polymerizable compound>

B-1: KAYARAD DPHA (Nippon Chemical Pharmaceutical Co., Ltd.)

B-2: KAYARAD DPHA-40H (Nippon Chemical Co., Ltd.)

B-3: KAYARAD DPEA-12 (Nippon Chemical Pharmaceutical Co., Ltd.)

<[C] sensitizing radiation polymerization initiator>

C-1: 2-benzyl-2-dimethylamino-1-(4- Porphyrin phenyl)-butan-1-one (Irgacure 369, Ciba Speciality Chemicals)

C-2: 2-methyl-1-(4-methylthiophenyl)-2- Porphyrin-1-one (Irgacure 907, Ciba Speciality Chemicals)

C-3: Ethyl-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetyl) (Ciba Speciality) Chemicals, Irgacure OX02)

<[D] compound>

D-1:1,5-diazabicyclo[4.3.0]-nonene-5

D-2: 1,8-diazabicyclo[5.4.0]-undecene-7

<[E] compound>

E-1: toluenesulfonic acid

E-2: Carboxylic acid

<脒盐>

H-1 to H-3 which are the onium salts shown below are salts of the above-mentioned [D] compound and [E] compound, respectively.

H-1: D-1 tosylate

H-2: D-2 tosylate

H-3: D-2 carboxylate

H-1: triethylamine

[Examples 1 to 14 and Synthesis Examples 5 to 7]

Each component of the type and content shown in Table 1 was mixed, dissolved in propylene glycol monomethyl ether acetate, and the solid content concentration was 30% by mass, and each of the radiation was prepared by filtration through a microporous membrane having a pore diameter of 0.5 μm. Resin composition. Further, "-" in Table 1 indicates that the component is not used. Further, the measurement results of the viscosity (mPa‧s) of each of the radiation sensitive resin compositions at 25 ° C are also shown.

<evaluation>

Using the prepared radiation sensitive resin composition, a cured film was formed as follows, and the following evaluation was performed. The results are shown in Table 2.

<Formation of hardened film>

Each of the radiation-sensitive resin compositions described in Table 2 was used to form a cured film according to the baking temperature and the baking time described in Table 2, respectively, as the cured films of Examples 1 to 14 and Comparative Examples 1 to 9. Hereinafter, the formation of the cured film will be described in detail.

On each of the alkali-free glass substrates, each of the radiation-sensitive resin composition solutions described in Table 2 was applied by a spin coater, and then prebaked at 85 ° C for 2 minutes with a hot plate to form a coating film having a film thickness of 3.50 μm. Next, on the obtained coating film, exposure was carried out by an exposure gap of 250 μm through a photomask having a circular residual pattern having a diameter of 13 μm. Then, it was developed with a 0.05% by mass (1.5 wt% CD150CR) aqueous potassium hydroxide solution at 25 ° C, followed by rinsing with pure water for 1 minute. Further, in the oven, baking was carried out by the baking temperature and the baking time described in Table 2 to form a gasket. Exposure was carried out without using a mask, and then, similarly to the formation of the spacer, another cured film was formed by development and baking. This cured film can be evaluated as a protective film or an interlayer insulating film.

[Sensitivity (J/m ² )]

The residual film rate expressed by the following formula was evaluated for sensitivity (J/m ² ).

Residual film rate (%) = (film thickness after baking / film thickness after exposure) × 100

The exposure amount of the residual film ratio of 90% or more was taken as the sensitivity. In the case where the exposure amount is 850 J/m ² or less, the sensitivity is judged to be good.

[developability (seconds)]

After the development, the residue having no residue (residual development) in the unexposed portion was measured, and the shortest development time (second) in which the pattern was formed was measured as developability. The shorter the development time is judged, the better the developability is.

[Compression characteristics]

The same operation as the above-described sensitivity evaluation was carried out, and a pattern having a pellet shape was formed on the substrate at an exposure amount of a residual film ratio of 90% or more. In a Fisher Scope H100C (Fisher Instruments), a 50 μm square flat pressure was used, and a compression test was performed under a load of 50 mN to measure the amount of compressive deformation. When the value of the compression deformation amount is 0.5 μm or less, the pattern-like film can be said to have high hardness, and therefore the compression characteristics are considered to be "A" (determined to be good). When the value of the amount of compressive deformation exceeds 0.5 μm, the compression characteristic is considered to be "B" (it is judged to be poor).

<Formation of hardened film>

A spin coater was used on the polyoxyalkylene plate to coat the radiation sensitive resin compositions (S-1) to (S-14) and (CS-1) to (CS-3), respectively, and then at 90 ° C. The film was prebaked for 2 minutes with a hot plate to form a coating film having a film thickness of 3.0 μm. Exposure was carried out using an exposure machine (Canon, MPA-600FA) at a cumulative irradiation amount of 9000 J/m ² , and the substrate was baked in a cleaning oven by the baking temperature and baking time shown in Table 2 to form a cured film. .

[heat resistance (%)]

The cured film was further heated in an oven at 180 ° C for 30 minutes, and the change in film thickness before and after heating was measured. The rate of change (%) represented by the following formula is taken as heat resistance.

Rate of change (%) = (additional heating film thickness / film thickness after baking) × 100

When the rate of change was 96% or more, it was judged that the heat resistance was good.

[Relative permittivity(%)]

On the SUS substrate, a coating film was formed in the same manner as in the formation of the cured film described above, and then a Pt/Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for dielectric constant measurement. On the substrate having the electrode pattern, the relative dielectric constant (%) was measured by a CV method at a frequency of 10 kHz using an HP16451B electrode and an HP4284A Precision LCR meter (the above is Yokogawa ‧ Hewlett-Packard Co., Ltd.).

[Solvent resistance (%)]

In the formation of the cured film described above, the same operation was carried out except that the ultraviolet light was irradiated with a cumulative irradiation amount of 3000 J/m ² by a mercury lamp, and a cured film was obtained. The film thickness (T1) of the obtained cured film was measured. Then, the sulfoxyalkylene plate forming the cured film was immersed in dimethyl sulfoxide having a temperature of 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film was measured, and the film caused by the immersion was calculated from the following formula. Thickness change rate (%) as solvent resistance. When the film thickness change rate is 5% or less, it is judged that the solvent resistance is good.

Film thickness change rate (%) = {(t1-T1) / T1} × 100

[hardness]

The hardness of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990 on the substrate having the cured film formed in the evaluation of the solvent resistance described above. In the case of 3H or more, the hardness was judged to be good.

[Voltage retention rate (%)]

An SiO ₂ film capable of preventing sodium ions from eluting is formed on the surface, and a ITO (indium oxide-tin oxide alloy) electrode is deposited on a soda glass substrate in a predetermined shape, and the radiation sensitive resin composition is spin-coated, and then at 90 ° C. The baking oven was prebaked for 2 minutes to form a coating film having a film thickness of 2.0 μm. Then, without using a photomask, radiation of each wavelength of 365 nm, 405 nm, and 436 nm was applied to the coating film, and exposure was performed at an exposure amount of a cumulative irradiation amount of 3000 J/m ² . Then, development was carried out according to the dipping method using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 80 seconds. The baking was carried out in accordance with the baking temperature and the baking time described in Table 2 to form a cured film. Then, after the glass bead spacer having a diameter of 5.5 μm is spread on the substrate having the cured film, the soda-lime glass substrate on which the ITO electrode is vapor-deposited only in a predetermined shape on the surface is left in a relative state, and the liquid crystal injection port is vacated. The four sides were bonded with a sealant mixed with 0.8 mm glass beads, poured into a liquid crystal made of Merck (MLC6608), and then the liquid crystal injection port was closed, thereby preparing a liquid crystal cell. Next, a liquid crystal cell was placed in a constant temperature layer of 60 ° C, and the voltage holding ratio (%) of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system (VHR-1A type, Dongyang Technica Co., Ltd.). The applied voltage at this time was a square wave of 5.5 V, and the number of measurement frequencies was 60 Hz. The voltage holding ratio is a value calculated by the following formula. The lower the value of the voltage holding ratio of the liquid crystal cell, the higher the possibility that a so-called "burning screen" is formed during the formation of the liquid crystal panel. On the other hand, the lower the value of the voltage holding ratio, the liquid crystal cell cannot maintain the applied voltage at a predetermined level for 16.7 microseconds, which means that the liquid crystal cannot be sufficiently oriented, and the risk of "burning" such as afterimages is high. .

Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 milliseconds from the reference) / (voltage after applying 0 milliseconds) × 100

[Save stability (%)]

The same operation as the above-described evaluation of the solvent resistance was carried out to form a cured film of the radiation-sensitive resin composition solution after the preparation, and the film thickness was measured (in the following formula, the film thickness after preparation). Further, the solution of the radiation sensitive resin composition was stored at 25 ° C for 5 days, and the film thickness of the cured film formed in the same manner was measured after 5 days (in the following formula, it is referred to as "film thickness after 5 days"). The film thickness increase rate (%) was calculated from the following formula.

Film thickness increase rate (%) = (film thickness after 5 days - film thickness after preparation) / (film thickness after preparation) × 100

When the film thickness increase rate was 2% or less, it was judged that the storage stability was A (good). When the film thickness increase rate is 3% or more, it is judged that the storage stability is B (poor).

From the results of Table 2, it was found that the radiation sensitive resin composition had good sensitivity, developability, and storage stability. Further, the cured film formed of the radiation-sensitive resin composition can be formed not only by low-temperature baking at 200 ° C or lower, but also excellent in compression characteristics, heat resistance, relative dielectric constant, solvent resistance, hardness, and voltage holding ratio.

[Industry use possibility]

The radiation sensitive resin composition of the present invention can easily form a fine and delicate pattern, has both storage stability and short-time low-temperature baking, and has sufficient sensitivity and developability. Further, the cured film formed of the radiation sensitive resin composition is excellent in compression characteristics, heat resistance, relative dielectric constant, solvent resistance, hardness, and voltage holding ratio. Therefore, the radiation sensitive resin composition is preferably used as a material for forming a cured film such as an interlayer insulating film, a protective film, or a gasket in a flexible display or the like which is desired to be baked at a low temperature. Further, the color filter having the cured film forming the alignment film is excellent in heat resistance, solvent resistance, voltage holding ratio, and the like.

Claims (12)

A radiation sensitive linear resin composition comprising: [A] an alkali-soluble resin, wherein (A1) is at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (A2) Obtained by copolymerization of an epoxy group-containing unsaturated compound; [B] a polymerizable compound having an ethylenically unsaturated bond; [C] a radiation-sensitive polymerization initiator; [D] a compound represented by the following formula (1); E] as a compound of organic or inorganic acid, its viscosity at 25 ° C is 1.0 mPa. s~50mPa. s, In the formula (1), m is an integer of 2 to 6, wherein some or all of the hydrogen atoms of the alkylene group in the formula (1) may be substituted with an organic group. The radiation sensitive linear resin composition of claim 1, wherein the [C] radiation sensitive linear polymerization initiator is an O-indenyl hydrazine compound. The radiation-sensitive resin composition of claim 1, wherein [D] compound and [E] are mixed in [A] alkali-soluble resin, [B] polymerizable compound, and [C] radiation-sensitive polymerization initiator The sulfonium salt formed by the compound is prepared. A radiation sensitive resin composition according to claim 3, wherein the above sulfonium salt is a sulfonate. The radiation sensitive resin composition according to any one of claims 1 to 4, which is used for forming a cured film as an interlayer insulating film, a protective film or a gasket. A method for producing a radiation-sensitive resin composition, wherein a mixture of [D] compound and [E] compound is formed in [A] alkali-soluble resin, [B] polymerizable compound, and [C] radiation-sensitive polymerization initiator The cerium salt is prepared, and the viscosity of the composition at 25 ° C is 1.0 mPa. s~50mPa. s. A cured film as an interlayer insulating film, a protective film or a gasket formed of a radiation-sensitive resin composition of the fifth application of the patent application. A color filter comprising a cured film according to item 7 of the patent application, and an oriented film formed of a liquid crystal aligning agent laminated on the cured film. The color filter of the eighth aspect of the invention, wherein the liquid crystal aligning agent is a liquid crystal aligning agent containing a radiation sensitive polymer having a photo-alignment group, or a polyfluorene containing no photo-alignment group. A liquid crystal aligning agent of an imine. A method for forming a cured film, comprising: (1) a step of coating a substrate with a radiation-sensitive resin composition as disclosed in claim 5, forming a coating film; and (2) irradiating at least a portion of the coating film. a step of emitting radiation; (3) a step of developing the above-mentioned radiation-coated coating film; and (4) a step of baking the developed coating film. The method for forming a cured film according to claim 10, wherein the baking temperature in the step (4) is 200 ° C or lower. A method for forming a color filter, comprising the steps (1) to (4) of claim 10, and (5) applying a liquid crystal aligning agent on a coating film after baking, and heating at 200 ° C or lower The step of forming an oriented film.