JP2012194290A - Method for forming cured film, cured film, display element and radiation sensitive resin composition - Google Patents

Abstract

The present invention relates to curing capable of forming a cured film having excellent surface curability and deep curability even when an ultraviolet curing LED type ultraviolet curing device is used while suppressing sublimation of a photopolymerization initiator. It is to provide a film forming method.
(1) A step of applying a radiation-sensitive resin composition on a substrate to form a coating film; (2) a step of exposing the coating film through a photomask; and (3) the exposure. A cured film forming method comprising a step of developing a coating film, and (4) a step of heating the developed coating film, wherein the radiation-sensitive resin composition is [A] an alkali-soluble resin, [B] It contains a polymerizable compound having an ethylenically unsaturated bond, [C] a photopolymerization initiator, and [D] an acid generator, and in the step (2), exposure is performed using an ultraviolet LED as a light source. This is a cured film forming method.
[Selection figure] None

Description

  The present invention relates to a method for forming a cured film, a cured film, a display element, and a radiation-sensitive resin composition.

  As a method for producing a cured film having a fine pattern such as an interlayer insulating film, protective film, spacer, color filter, etc., a pigment-dispersed radiation-sensitive resin composition is applied on a substrate to form a coating film. A method obtained by irradiating (exposure) radiation to a film through a photomask and developing the film is known (see JP-A-2-144502 and JP-A-3-53201).

  However, in the above exposure process, when a conventional high-pressure mercury lamp or metal halide lamp is used as the ultraviolet light source, the photopolymerization initiator contained in the radiation-sensitive resin composition sublimates, and the sublimate adheres to the mask and is desired. There is a disadvantage that the pattern shape cannot be formed. In addition, when a sublimate adheres to the mask, it is necessary to temporarily stop the production line of the cured film and perform mask cleaning, leading to a reduction in production efficiency.

  As a cause of the sublimation of the photopolymerization initiator in the exposure process, when a conventional ultraviolet light source is used, such a light source emits infrared light simultaneously with ultraviolet light, and this infrared rays gives heat to the photopolymerization initiator, thereby photopolymerization. It is thought to induce the sublimation of the initiator.

  In order to avoid such inconvenience, attempts have been made to suppress the sublimation property of the photopolymerization initiator (see Japanese Patent Application Laid-Open No. 2008-224964), but the present situation is that the generation of sublimates cannot be sufficiently suppressed. . The high-pressure mercury lamp and the like are disadvantageous in terms of cost because they have a short life and a high frequency of lamp replacement.

  On the other hand, a UV curable resin composition using an ultraviolet LED that does not emit infrared light as a light source has been developed (see International Publication No. 2010/071711 and Japanese Unexamined Patent Publication No. 2010-126542). However, exposure using an ultraviolet LED as a light source is caused by lower energy of irradiation light than when a high-pressure mercury lamp or the like is used as a light source, or the surface curability of the formed cured film is at a satisfactory level. Although there is a disadvantage, it is inferior in curability in the deep part of the film.

  Under such circumstances, even in the case of using an ultraviolet curing device of an ultraviolet hard LED method, a cured film capable of forming a cured film having excellent surface curability and deep curability while suppressing sublimation of the photopolymerization initiator. A forming method is desired.

JP-A-2-144502 JP-A-3-53201 JP 2008-224964 A International Publication No. 2010/071711 JP 2010-126542 A

  The present invention has been made on the basis of the circumstances as described above, and its purpose is to suppress the sublimation of the photopolymerization initiator and to achieve excellent surface curing even when using an ultraviolet curing device of an ultraviolet curing LED method. It is providing the cured film formation method which can form the cured film which has the property and deep part sclerosis | hardenability.

The invention made to solve the above problems is
(1) A step of applying a radiation-sensitive resin composition on a substrate to form a coating film,
(2) a step of exposing the coating film through a photomask;
(3) A method for forming the exposed coating film, and (4) a cured film forming method comprising a step of heating the developed coating film,
The radiation sensitive resin composition is
[A] alkali-soluble resin,
[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as “[B] polymerizable compound”),
[C] A cured film forming method comprising: a photopolymerization initiator; and [D] an acid generator, and exposing in the step (2) using an ultraviolet LED as a light source.

  The radiation sensitive resin composition used in the forming method of the present invention contains [A] an alkali-soluble resin and [D] an acid generator, and can exhibit positive radiation sensitive characteristics. In response to the ultraviolet LED, the [C] photopolymerization initiator starts polymerization of the [B] polymerizable compound. According to the forming method of the present invention, by using the radiation-sensitive resin composition containing the specific component, even when an ultraviolet LED is used as an exposure light source, while suppressing sublimation of the photopolymerization initiator, Even when a hard LED UV curing device is used, a cured film having excellent surface curability and deep curability can be formed.

  [A] The alkali-soluble resin is preferably a copolymer containing at least one structural unit selected from the group consisting of a structural unit having a (meth) acryloyloxy group and a structural unit having an epoxy group. [A] When the alkali-soluble resin contains the specific structural unit, a cured film having excellent surface curability and deep part curability can be formed.

  [D] The acid generator is preferably an acid generator that generates an acid with light of 300 nm or more. [D] By using the acid generator as an acid generator that generates an acid with light of 300 nm or more, sufficient acid can be generated even in the case of using an ultraviolet curing LED type ultraviolet curing device.

  [D] The content ratio of the acid generator is preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A] alkali-soluble resin. [D] By making the content rate of an acid generator into the said specific range, the cured film which is more excellent in deep part sclerosis | hardenability can be formed.

  The radiation-sensitive resin composition may further contain a colorant [E]. Since the radiation sensitive resin composition further contains a colorant [E], the formation method can be suitably applied to the production of various color filters.

  The present invention suitably includes a cured film formed from the forming method and a display element including the cured film.

The radiation sensitive resin composition of the present invention is
[A] alkali-soluble resin,
[B] polymerizable compound,
[C] a photopolymerization initiator, and [D] an acid generator.

  The present invention suitably includes a radiation-sensitive resin composition for ultraviolet LEDs.

  According to the forming method of the present invention, a cured film having excellent surface curability and deep part curability is provided even when an ultraviolet curing LED type ultraviolet curing device is used while suppressing sublimation of a photopolymerization initiator. be able to. Therefore, the formation method can be suitably applied to the production of various color filters such as a color filter for color display elements, a color filter for color separation of a solid-state imaging element, a color filter for organic EL display elements, and a color filter for electronic paper.

  The cured film formation method of this invention has the said process (1)-(4), The radiation sensitive resin composition used for the said formation method is [A] alkali-soluble resin, [B] polymeric compound, [C] A photopolymerization initiator and [D] an acid generator are contained. Hereinafter, the radiation sensitive resin composition, each step, the cured film, and the display element will be described in detail.

<Radiation sensitive resin composition>
The radiation sensitive resin composition used for the forming method contains [A] an alkali-soluble resin, [B] a polymerizable compound, [C] a photopolymerization initiator, and [D] an acid generator. Moreover, you may contain a [E] colorant as a suitable component. Furthermore, you may contain another arbitrary component, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.

<[A] alkali-soluble resin>
[A] The alkali-soluble resin is not particularly limited as long as it is a resin that is hardly soluble or insoluble in alkali and has a property of being alkali-soluble by an acid generated by exposure, but a structural unit and epoxy having a (meth) acryloyloxy group A copolymer containing at least one structural unit selected from the group consisting of structural units having groups is preferred. [A] When the alkali-soluble resin contains the specific structural unit, a cured film having excellent surface curability and deep part curability can be formed.

  [A] The alkali-soluble resin includes (A1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter also referred to as “(A1) compound”), and (A2) an epoxy. It can be synthesized by copolymerizing a group-containing unsaturated compound (hereinafter also referred to as “(A2) compound”).

  [A] The alkali-soluble resin is obtained by, for example, copolymerizing a compound (A1) giving a carboxyl group-containing structural unit and a compound (A2) giving an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. Further, (A3) a hydroxyl group-containing unsaturated compound giving a hydroxyl group-containing structural unit (hereinafter also referred to as “(A3) compound”) may be further added to form a copolymer. Further, in the production of [A] the alkali-soluble resin, the compound (A4) (derived from the compounds (A1), (A2) and (A3)) together with the compound (A1), the compound (A2) and the compound (A3). An unsaturated compound that gives a structural unit other than the structural unit to be added) can be further added to form a copolymer. Hereinafter, each compound will be described in detail.

[(A1) Compound]
(A1) As the compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydride of unsaturated dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyvalent carboxylic acid, carboxyl group and hydroxyl group at both ends And mono (meth) acrylates of polymers having an unsaturated polycyclic compound having a carboxyl group and anhydrides thereof.

Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and the like;
Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
Examples of anhydrides of unsaturated dicarboxylic acids include, for example, anhydrides of the compounds exemplified as the above dicarboxylic acids;
Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like;
Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends include, for example, ω-carboxypolycaprolactone mono (meth) acrylate;
Examples of unsaturated polycyclic compounds having a carboxyl group and anhydrides thereof include 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] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2 .1] hept-2-ene anhydride and the like.

  Among these (A1) compounds, monocarboxylic acid, dicarboxylic acid anhydride, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are copolymerization reactivity, solubility in alkaline aqueous solution. And from the viewpoint of availability. These (A1) compounds may be used alone or in admixture of two or more.

  (A1) As a using ratio of a compound, 5-30 mass% is based on the sum total of (A1) compound and (A2) compound (arbitrary (A3) compound and (A4) compound as needed). Preferably, 10% by mass to 25% by mass is more preferable. (A1) The radiation sensitive resin composition which is excellent in the radiation sensitivity while optimizing the solubility with respect to the aqueous alkali solution of [A] alkali-soluble resin by making the usage-amount of a compound into 5 mass%-30 mass%. can get.

[(A2) Compound]
The compound (A2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

  Examples of unsaturated compounds having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and glycidyl α-n-butyl acrylate. 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethylacrylic-6,7-epoxyheptyl, o-Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl is preferable from the viewpoint of improvement in solvent resistance such as copolymerization reactivity and coloring pattern.

Examples of unsaturated compounds having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, and 3- (acryloyl). Oxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2 -Difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) ) Oxetane, 3- ( 2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyl) Oxyethyl) -2-pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxy) Ethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane and other acrylic acid esters;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) -2- Pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2,2 , 4-trifluorooxetane, methacrylic acid esters such as 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, and the like.

  Of these (A2) compounds, glycidyl (meth) acrylate is preferred. These (A2) compounds may be used alone or in combination of two or more.

  (A2) As a use ratio of a compound, 5 mass%-60 mass% are based on the sum total of (A1) compound and (A2) compound (arbitrary (A3) compound and (A4) compound as needed). Preferably, 10% by mass to 50% by mass is more preferable. (A2) By making the usage-amount of a compound into 5 mass%-60 mass%, the cured film which has the outstanding sclerosis | hardenability etc. can be formed.

[(A3) Compound]
(A3) As a compound, the (meth) acrylic acid ester which has a hydroxyl group, the phenolic hydroxyl group containing unsaturated compound represented by following formula (1), etc. are mentioned.

In the above formula (1), ^{R 1} is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^{2 to} R ⁶ are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. X is a single bond, —COO—, or —CONH—. a is an integer of 0-3. However, at least one of R ^{2 to} R ⁶ is a hydroxyl group.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol. (N = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methacryloxyethylglycoside and the like. .

  Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (1) include compounds represented by the following formula.

In the above formula, a is an integer of 1 to 3. R < ² > -R < ⁶ > is synonymous with the said Formula (1).

In said formula, R < ¹ > -R < ⁶ > is synonymous with the said Formula (1).

In the above formula, a is an integer of 1 to 3. R ^{1 to} R ⁶ have the same meaning as in the above formula (1).

In said formula, R < ¹ > -R < ⁶ > is synonymous with the said Formula (1).

In said formula, R < ¹ > -R < ⁶ > is synonymous with the said Formula (1).

  Of these (A3) compounds, 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in admixture of two or more.

  (A3) As a using ratio of a compound, 1 mass%-30 mass% are based on the sum total of (A1) compound, (A2) compound, and (A3) compound (any (A4) compound as needed). Preferably, 5% by mass to 25% by mass is more preferable.

[(A4) Compound]
The compound (A4) is not particularly limited as long as it is an unsaturated compound other than the compounds (A1), (A2) and (A3). As the (A4) compound, for example, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated compound having a skeleton represented by the following formula (2), and other unsaturated compounds Compounds and the like.

In the above formula (2), ^{R 7} is a hydrogen atom or a methyl group. b is an integer of 1 or more.

  Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-methacrylate. Examples include lauryl, tridecyl methacrylate, and n-stearyl methacrylate.

Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and tricyclomethacrylate [5.2.1]. .0 ^2,6] decan-8-yl oxy ethyl, and isobornyl methacrylate.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. Examples include lauryl, tridecyl acrylate, and n-stearyl acrylate.

Examples of acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2.1.0 ^2,6. ] Decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

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

  Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. Hept-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-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 -Cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2 2.1] Hept- -Ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-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.

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

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

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

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene- 2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2- Yl-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc. Is mentioned.

  Examples of unsaturated compounds containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one , 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like.

  Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran and 4- (1,5-dioxa-6-oxo. -7-octenyl) -6-methyl-2-pyran and the like.

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

Among these (A4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, represented by the above formula (4) An unsaturated compound having a skeleton, an unsaturated aromatic compound, and a cyclic alkyl ester of acrylic acid are preferred. Among these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, p-methoxy Styrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran 2-one is more preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These (A4) compounds may be used alone or in admixture of two or more.

  The proportion of the compound (A4) used is preferably 10% by mass to 80% by mass based on the total of the compound (A1), the compound (A2) and the compound (A4) (and any (A3) compound).

<[A] Synthesis method 1 of alkali-soluble resin>
[A] The alkali-soluble resin is produced, for example, by copolymerizing the compound (A1) and the compound (A2) (arbitrary (A3) compound and (A4) compound) in the presence of a polymerization initiator in a solvent. it can. According to such a synthesis method, a copolymer containing at least an epoxy group-containing structural unit can be synthesized.

  [A] Solvents used in the polymerization reaction for producing the alkali-soluble resin include, for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol mono Examples include alkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester and the like.

Examples of the alcohol include benzyl alcohol;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of the ethylene glycol alkyl ether acetate include ethylene glycol monobutyl ether acetate and diethylene glycol monoethyl ether acetate;
Examples of the diethylene glycol monoalkyl ether include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Examples of the diethylene glycol dialkyl ether include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;
Examples of the dipropylene glycol dialkyl ether include dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;
Examples of the propylene glycol monoalkyl ether include propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether;
Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate;
Examples of the propylene glycol monoalkyl ether propionate include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and the like;
Examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone;
Examples of the ester include ethyl acetate, butyl acetate, 3-methoxybutyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, butyl hydroxyacetate, Methyl lactate, ethyl lactate, propyl lactate, butyl lactate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Kishipuropion ethyl 3-ethoxy propionate propyl, 3-ethoxy propionate butyl, 3-propoxy-propionic acid methyl, and the like.

  Among these solvents, 3-methoxybutyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are more preferable.

  [A] As the polymerization initiator used in the polymerization reaction for producing the alkali-soluble resin, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane and peroxides Examples include hydrogen oxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

  [A] In the polymerization reaction for producing the alkali-soluble resin, a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

[A] As a weight average molecular weight (Mw) of alkali-soluble resin, 1,000-30,000 are preferable and 5,000-20,000 are more preferable. [A] By making Mw of alkali-soluble resin into the said range, the sensitivity and developability of a radiation sensitive resin composition can be improved. In addition, Mw and number average molecular weight (Mn) of the polymer in this specification were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined with mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[A] Synthesis method 2 of alkali-soluble resin>
[A] The alkali-soluble resin comprises, for example, a copolymer (hereinafter also referred to as “specific copolymer”) that can be synthesized using one or more of the above-described (A1) compounds, and the above-mentioned (A2) compound. It can be synthesized by reaction. According to this synthesis method, a copolymer containing at least a structural unit having a (meth) acryloyloxy group can be synthesized.

  [A] The structural unit having a (meth) acryloyloxy group contained in the alkali-soluble resin is represented by the following formula (3). This structural unit is obtained by reacting the carboxyl group in the specific copolymer derived from the compound (A1) with the epoxy group of the compound (A2) to form an ester bond.

In said formula (3), R < ⁸ > and R <^9> are respectively independently a hydrogen atom or a methyl group. c is an integer of 1-6. R ¹⁰ is a divalent group represented by the following formula (3-1) or (3-2).

In the formula ^{(3-1), R 11} is hydrogen atom or a methyl group. In the above formulas (3-1) and (3-2), * represents a site bonded to an oxygen atom.

For the structural unit represented by the above formula (3), for example, when a copolymer having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate as the compound (A2), the formula (3 R ¹⁰ in () is represented by formula (3-1). On the other hand, when a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted as the compound (A2), R ¹⁰ in the formula (3) becomes the formula (3-2).

In synthesizing the specific copolymer, a compound other than the compound (A1), for example, the above-described compound (A3) or compound (A4) may be used as a copolymerization component. These compounds include methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, tricyclomethacrylate [5.2.1.0 ^2,6 from the viewpoint of copolymerization reactivity. Decan-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, and 1,3-butadiene are preferred.

  Examples of the copolymerization method of the specific copolymer include a method of polymerizing the compound (A1) and, if necessary, the compound (A3) using a radical polymerization initiator in a solvent. As a radical polymerization initiator, the thing similar to what was illustrated by the term of the above-mentioned [A] alkali-soluble resin is mentioned. The usage-amount of a radical polymerization initiator is 0.1 mass%-50 mass% normally with respect to 100 mass% of polymerizable unsaturated compounds, Preferably it is 0.1 mass%-20 mass%. The specific copolymer may be used for the production of [A] alkali-soluble resin as it is in the polymerization reaction solution, or may be used for the production of [A] alkali-soluble resin after the copolymer is once separated from the solution.

  As Mw of a specific copolymer, 2,000-100,000 are preferable and 5,000-50,000 are more preferable. By setting Mw to 2,000 or more, a sufficient development margin of the radiation-sensitive resin composition is obtained, and a decrease in the remaining film ratio of the formed coating film (the ratio in which the patterned thin film remains properly) is prevented. In addition, the shape and heat resistance of the resulting pattern can be kept good. On the other hand, by setting Mw to 100,000 or less, high sensitivity can be maintained and a good pattern shape can be obtained. Moreover, as molecular weight distribution (Mw / Mn) of a specific copolymer, 5.0 or less are preferable and 3.0 or less are more preferable. By making Mw / Mn 5.0 or less, the shape of the obtained spacer pattern can be kept good. In addition, the radiation-sensitive resin composition containing the specific copolymer having Mw / Mn in the specific range has high developability, and easily forms a predetermined pattern shape without causing residual development in the development process. can do.

  [A] The content of the structural unit derived from the (A1) compound of the alkali-soluble resin is preferably 5% by mass to 60% by mass, more preferably 7% by mass to 50% by mass, and 8% by mass to 40% by mass. Is particularly preferred.

  [A] The content of structural units derived from compounds such as (A3) compound and (A4) compound other than (A1) compound of alkali-soluble resin is 10% by mass to 90% by mass, 20% by mass to 80% by mass. %.

  In the reaction of the specific copolymer with the compound (A2), an unsaturated compound having an epoxy group is preferably added to the copolymer solution containing a polymerization inhibitor in the presence of a suitable catalyst as necessary. And stirring for a predetermined time under heating. Examples of the catalyst include tetrabutylammonium bromide. Examples of the polymerization inhibitor include p-methoxyphenol. As reaction temperature, 70 to 100 degreeC is preferable. The reaction time is preferably 8 hours to 12 hours.

  (A2) As a use ratio of a compound, 10 mass%-99 mass% are preferable with respect to the carboxyl group derived from the (A2) compound in a copolymer, and 5 mass%-97 mass% are more preferable. (A2) By making the usage-amount of a compound into the said range, the reactivity with a copolymer, the sclerosis | hardenability of a cured film, etc. improve more. (A2) A compound can be used individually or in mixture of 2 or more types.

<[B] Polymerizable compound>
[B] The polymerizable compound is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond. For example, ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange ( (Meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl (meth) acrylate Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- ( In addition to (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, etc., it also has a linear alkylene group and an alicyclic structure, and two or more isocyanate groups And a urethane (meth) acrylate compound obtained by reacting a compound having 1 or more hydroxyl groups in the molecule with a compound having 3 to 5 (meth) acryloyloxy groups.

[B] Examples of commercially available polymerizable compounds include Aronix M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, and M. -7100, M-8030, M-8060, M-8100, M-8100, M-8530, M-8560, M-9050, Aronix TO-756, TO-1450, TO-1382 (above, Manufactured by Toagosei Co., Ltd.), KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPCA-120, MAX-3510 (manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.), New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.) as urethane acrylate compound , KAYARAD DPHA, KAYARAD DPHA-40H, UX-5000 (Nippon Kayaku), UN-9000H (Negami Kogyo), Aronix M-5300, M-5600, M-5700, M-210, M- 220, M-240, M-270, M-6200, M-305, M-309, M-309, M-310, M-315 (above, manufactured by Toagosei), KAYARAD HDDA, KAYARAD HX- 220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301, UX-3204, UX -3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Japan) Manufactured by Yakuhin), Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P (above, manufactured by Negami Industrial Co., Ltd.) ), SH-500B biscoat 260, 312 and 335HP (manufactured by Osaka Organic Chemical Industry).

  [B] The polymerizable compound may be used alone or in combination of two or more. As a content rate of [B] polymeric compound in the radiation sensitive resin composition used for the formation method of this invention, 10 mass parts-300 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, 20 Mass parts to 200 parts by mass are more preferable. [B] By making the content rate of a polymeric compound into the said specific range, a radiation sensitive resin composition can form the cured film which has curability also when using the ultraviolet curing device of an ultraviolet-hard LED system.

<[C] Photopolymerization initiator>
[C] The photopolymerization initiator contained in the radiation-sensitive resin composition used in the forming method of the present invention is a component that generates an active species that can initiate polymerization of the polymerizable compound [B] in response to light. is there. Examples of such a [C] photopolymerization initiator include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. These compounds may be used alone or in combination of two or more.

  Examples of the O-acyloxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl). ) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Among these, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4 -Morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  Of these, α-aminoketone compounds are preferred, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-Morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are more preferred.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 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′-bi Examples include imidazole. Among these, 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 or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is more preferred.

  [C] As a content rate of a photoinitiator, 0.1 mass part-40 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 1 mass part-30 mass parts are more preferable. [C] By making the content rate of a polymerization initiator into the said specific range, a radiation sensitive resin composition can form the cured film which has favorable sclerosis | hardenability, also when using the ultraviolet curing device of an ultraviolet curing LED system. .

<[D] Acid generator>
[D] The acid generator is a compound that generates an acid upon irradiation with an ultraviolet LED used as a light source of the present invention. When the radiation sensitive resin composition contains the [D] acid generator and the [A] polymer having an acid dissociable group, positive radiation sensitive characteristics can be exhibited. [D] The acid generator is not particularly limited as long as it is a compound that generates an acid by light of 300 nm or more. [D] The content of the acid generator in the radiation-sensitive resin composition is incorporated as part of [A] an alkali-soluble resin or other polymer even in the form of an acid generator that is a compound as described below. The acid generating group may be in the form or both of these forms. [D] As the acid generator, onium salts, sulfonimide compounds, tetrahydrothiophenium salts, oxime sulfonate compounds, and thianthrene compounds are preferable. These compounds may be used alone or in combination of two or more.

  Examples of the onium salt include a compound represented by the following formula (4).

In said formula (4), R < ¹² > -R < ¹⁶ > is respectively independently a C1-C12 alkyl group, a C1-C12 alkoxy group, a hydroxyl group, or a halogen atom. Y ⁻ is a non-nucleophilic anion. d, f, g, h, and i are each independently an integer of 0 to 5; e is 0 or 1. However, a + b satisfies the condition of 5 or less. However, Y ^- is a case of a plurality, the plurality of Y ^- is may be the same or different.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^{12 to} R ¹⁶ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group. , N-dodecyl group, n-tetradecyl group, n-octadecyl group and other linear alkyl groups, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group And a branched alkyl group. Of these, a methyl group is preferred.

Examples of the alkoxy group having 1 to 12 carbon atoms represented by R ^{12 to} R ¹⁶ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. It is done. Of these, a butoxy group is preferred.

Examples of the halogen atom represented by R ^{12 to} R ¹⁶ include a fluorine atom and a chlorine atom. Of these, a fluorine atom is preferred.

Examples of the non-nucleophilic anion represented by Y ⁻ include PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , B (C _j F _{2j + 1} ) ₄ ⁻ , C _j F _{2j + 1} SO ₃ ⁻ , and [PF _{6− k} (C _k F _{2j + 1} ) _k ] ⁻ is preferably an anion selected from the group consisting of j is an integer of 1-8. k is an integer of 1-5.

  Examples of the onium salt include compounds represented by the following formulas (4-1) to (4-27).

  Of these, compounds represented by the above formulas (4-1), (4-8), (4-12), (4-17), (4-24), and (4-26) are preferable.

  [D] The onium salt as the acid generator can be produced by a known method, but a commercially available product can also be used. As a commercial item, CPI-100P, CPI101A, CPI-200K etc. are mentioned, for example (above, the San Apro product).

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy). ) Succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N -(2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenyl monomer Imido, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (nonafluorobutane Sulfonyloxy) bicyclo [2.2.1] Pto-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-en-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenyl) Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyl) Ruoxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-di Ruboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2 , 3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (Phenylsulfonyloxy) naphthyl dicarboxylimide, N- 2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarbo Xylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, and the like.

  Examples of commercially available sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide (SI-105), N- (camphorsulfonyloxy) succinimide (SI-106), and N- (4-methylphenylsulfonyloxy). Succinimide (SI-101), N- (trifluoromethylsulfonyloxy) diphenylmaleimide (PI-105), N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide (NDI-100), N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NDI-101), N- (trifluoromethane Sulfonyloxy) bicyclo [2.2.1] hept-5-ene 2,3-dicarboxylimide (NDI-105), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (NDI-109), N -(Camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (NDI-106), N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (NAI-105) ), N- (camphorsulfonyloxy) naphthyl dicarboxylimide (NAI-106), N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (NAI-101), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (NAI-100), N- (Nonafluorobutyls Honiruokishi) naphthyl dicarboxylic imide (NAI-109), N-(butyl sulfonyloxy) naphthyl dicarboxylic imide (NAI-1004), etc. (manufactured by Midori Chemical) and the like.

  Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethane. And tetrahydrothiophenium salts such as sulfonate.

  As the oxime sulfonate compound, a compound having an oxime sulfonate group represented by the following formula (5) is preferable.

In the above formula (4), R ¹⁷ is a linear, branched or cyclic alkyl group which may be substituted, or an aryl group which may be substituted.

The alkyl group represented by R ¹⁷ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ¹⁷ may be substituted with an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (in addition, as the alicyclic group, 7,7-dimethyl-2-oxonor It includes a bridged alicyclic group such as a bornyl group, preferably a bicycloalkyl group, and the aryl group represented by R ¹² is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group represented by R ¹⁷ may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

  As the compound having an oxime sulfonate group represented by the above formula (5), a compound represented by the following formula (5-1) is more preferable.

In the formula ^{(5-1), R 18} is as defined in the above formula (5). R ¹⁹ is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. However, when R ¹⁹ is plural, plural R ¹⁹ may be different even in the same. The alkyl group represented by R ¹⁹ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group R ¹⁹ represents preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by R ¹⁹ is preferably a chlorine atom or a fluorine atom. As m, 0 or 1 is preferable. In the above formula (5-1), a compound in which m is 1, R ¹⁹ is a methyl group, and the substitution position of R ¹⁹ is ortho is more preferable.

  Examples of the compound represented by the formula (5-1) include compounds represented by the following formulas (5-1-1) to (5-1-5).

  Examples of the thianthrene compound include compounds represented by the following formulas (6-1) to (6-12).

  Among these [D] acid generators, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, The compounds represented by 5-1), (5-2), (6-3), and (6-9) are particularly preferable.

  [D] As a content rate of an acid generator, 0.05 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.1 mass part-5 mass parts are more preferable. [D] By making the content rate of an acid generator into the said specific range, the cured film which is more excellent in deep part sclerosis | hardenability can be formed.

<[E] Colorant>
The radiation-sensitive resin composition may further contain a colorant [E]. Since the radiation sensitive resin composition further contains a colorant [E], the formation method can be suitably applied to the production of various color filters.

  [E] The colorant is not particularly limited as long as it has colorability, and the color and material can be appropriately selected according to the use of the color pattern and the color filter. As the colorant, for example, any of pigments, dyes and natural pigments can be used. However, since color patterns and color filters require high color purity, brightness, contrast, etc., pigments and dyes are preferred, and dyes are more preferred. preferable.

  The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; The Society of Dyers and Colorists). Specifically, those having the following color index (CI) names are mentioned.

  C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211;

  C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

  C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

  C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;

  C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;

  C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;

  C. I. Pigment brown 23, C.I. I. Pigment brown 25;

  C. I. Pigment black 1, C.I. I. Pigment black 7 and the like.

  Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, Examples include cobalt green, amber, titanium black, synthetic iron black, and carbon black.

  As the dye, a known dye can be used as long as it is soluble in an organic solvent. Examples of the chemical structure of the dye include triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo. Of these, pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes, and anthrapyridone dyes are preferable.

  Examples of the dye include oil-soluble dyes, acid dyes or derivatives thereof, direct dyes, and modern dyes.

C. I. Examples of the oil-soluble dye include C.I. I. Solvent Yellow 4 (hereinafter, the description of “CI Solvent Yellow” is omitted and only the number is described. Other dyes are also described in the same manner), 14, 15, 23, 24, 38, 62, 63, 68, 82, 88, 94, 98, 99, 162, 179;
C. I. Solvent red 45, 49, 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 35, 37, 59, 67;
C. I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. are mentioned.

C. I. Examples of acid dyes include C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
Varifast yellow 1101, 1109, 1151, 3108, 3120, 3130, 3150, 3170, 4120;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 108, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 249, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324, 335, 340;
C. I. Acid Violet 6B, 7, 9, 17, 19, 49;
C. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109;
C. I. And dyes such as Acid Black 24.

C. I. Examples of the direct dye include C.I. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 etc. are mentioned.

C. I. Examples of modern dyes include C.I. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 etc. are mentioned.

  [E] As content of a coloring agent, 1 mass part-400 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 5 mass parts-350 mass parts are more preferable. [E] By adjusting the content of the colorant within the above range, the alkali developability of the radiation-sensitive resin composition, the heat resistance of the pixel, the solvent resistance, the coloring pattern, and the high brightness and high contrast as the color filter. Can be achieved with a high level of balance.

<Other optional components>
The radiation-sensitive resin composition used in the forming method of the present invention is [A] an alkali-soluble resin, [B] a polymerizable compound, [C] a photopolymerization initiator, [D] an acid generator, and a suitable component [ E] In addition to the colorant, other optional components such as a surfactant, a storage stabilizer, and an adhesion aid can be contained as necessary within a range not impairing the effects of the present invention. Each of these optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

[Surfactant]
The surfactant can be used for further improving the film-forming property of the radiation-sensitive resin composition. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and other surfactants.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable. For example, 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 di (1,1,2,2-tetrafluoro-n-butyl) ether, hexa Propylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecane Sodium sulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decuff Rho-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other fluoro Examples thereof include alkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and carboxylic acid fluoroalkyl ester.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471. F476 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-170C, -171, -430, -431 (above, manufactured by Sumitomo 3M), Surflon S-112, -113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above made by Asahi Glass), F-top EF301, 303, 352 (manufactured by Shin-Akita Kasei), FT FT-100, -110, -140A, -150, -250, and -25 , The -300, the -310, the -400S, Ftergent FTX-218, the -251 (or, Neos Co., Ltd.) and the like.

  Examples of commercially available silicone surfactants include Torresilicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, made by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  Examples of other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n- Polyoxyethylene aryl ethers such as nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth) acrylic acid copolymer polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  As the usage-amount of surfactant, 1.0 mass part or less is preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.7 mass part or less is more preferable. When the usage-amount of surfactant exceeds 1.0 mass part, it will become easy to produce a film | membrane nonuniformity.

[Storage stabilizer]
Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum, and the like. Is mentioned.

  As a usage-amount of a storage stabilizer, 3.0 mass parts or less are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 1.0 mass part or less is more preferable. When the amount of the storage stabilizer exceeds 3.0 parts by mass, the sensitivity may decrease and the pattern shape may deteriorate.

[Adhesion aid]
The adhesion assistant can be used to further improve the adhesion of the formed cured film. As the adhesion assistant, a functional silane coupling agent having a reactive functional group such as carboxyl group, methacryloyl group, vinyl group, isocyanate group, oxiranyl group is preferable, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxy. Examples include silane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  As the usage-amount of an adhesion assistant, 20 mass parts or less are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 15 mass parts or less are more preferable. When the usage-amount of an adhesion assistant exceeds 20 mass parts, there exists a tendency for it to become easy to produce the image development remainder.

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition used in the forming method of the present invention is [A] an alkali-soluble resin, [B] a polymerizable compound, [C] a photopolymerization initiator, [D] an acid generator, and a suitable component [ E] It is prepared by uniformly mixing the colorant and, if necessary, other optional components. This radiation-sensitive resin composition is preferably used in the form of a solution after being dissolved in an appropriate solvent.

  As a solvent used for the preparation of the radiation sensitive resin composition, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used. Examples of the 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, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, Diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene Glycol monomethyl ether, dipro (Poly) alkylene glycol monoalkyl ethers such as lenglycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; acetic acid Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate , Diethylene glycol acetate mono-n-butyl ether, propylene glycol acetate Acetic acid (poly) alkylene glycol monoalkyl ethers such as ethyl monomethyl ether, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl Other ethers such as ether and tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2 Ketones such as -one; diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate Alkyl lactates such as methyl lactate and ethyl lactate; ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, n-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate N-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, N-propyl pyruvate, methyl acetoacetate, acetoacetate , Other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone Amides such as N, N-dimethylformamide and N, N-dimethylacetamide.

  Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate Le acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate are preferred. The solvent can be used alone or in combination of two or more.

  Although it is not limited as content of a solvent, the total solid content concentration of each component except the solvent of the radiation sensitive resin composition from viewpoints of applicability | paintability of a radiation sensitive resin composition obtained, stability, etc. is 5 mass. % To 50% by mass is preferable, and 10% to 40% by mass is more preferable. The composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore diameter of about 0.5 μm.

<Curing film and cured film forming method>
The present invention suitably includes a cured film formed from the forming method. The cured film can be applied as a cured film for a display element as an interlayer insulating film, a protective film, a spacer, or a color pattern.

The cured film forming method of the present invention comprises:
(1) A step of applying a radiation-sensitive resin composition on a substrate to form a coating film,
(2) a step of exposing the coating film through a photomask;
(3) a step of developing the exposed coating film; and (4) a step of heating the developed coating film. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, the radiation sensitive resin composition is applied onto a substrate to form a coating film. Examples of the material for the substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, and alkali-free glass. In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  Examples of methods for applying the radiation-sensitive resin composition to the substrate include spraying, roll coating, spin coating (spin coating), slit die coating, and bar coating. Of these, spin coating and slit die coating are preferred.

  The prebaking conditions are usually about 70 to 110 ° C. and about 1 to 10 minutes. As a film thickness of a coating film, they are 0.6 micrometers-8.0 micrometers normally, Preferably they are 1.2 micrometers-5.0 micrometers.

[Step (2)]
In this step, the coating film formed in step (1) is exposed through a photomask. As an LED-type ultraviolet curing device (LED-UV) used as a light source, a device that emits single-peak ultraviolet light having a peak in the range of 340 nm to 380 nm is used. As the UV intensity that of 100mW ^/ cm ² ~3,000mW ^/ cm 2 about energy intensity is used.

[Step (3)]
In this step, the coating film exposed in step (2) is developed using an alkaline developer. Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [ 4.3.0] -5-Nonene is preferred.

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 seconds to 300 seconds at room temperature.

[Step (4)]
In this step, the coating film developed in step (3) is heated (post-baked). The heating condition for post-baking is usually about 200 ° C to 300 ° C. The post-baking heating time is about 10 to 60 minutes.

<Display element and manufacturing method thereof>
The display element provided with the said cured film is also suitably contained in this invention. The display element of the present invention can be produced, for example, by the following method.

  First, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the cured film is formed on the transparent conductive film of one of the substrates using a radiation-sensitive resin composition. A spacer or a protective film or both are formed according to the method. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the display element of the present invention is bonded to both outer surfaces of the liquid crystal cell such that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. can get.

  As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer or a color pattern or both, and an alignment film are formed are prepared in the same manner as the above method. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, the display element of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly to this Example.

<[A] Synthesis of alkali-soluble resin>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 12 parts by mass of methacrylic acid as the compound (A1), 40 parts by mass of glycidyl methacrylate as the compound (A2), 20 parts by mass of styrene as the compound (A4) and tricyclomethacrylate [5.2.1.0 ^2,6 ]. By charging 28 parts by mass of decan-8-yl, substituting with nitrogen, and gently stirring, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to polymerize, whereby a copolymer (A- A solution containing 1) was obtained. The solid content concentration of the obtained polymer solution was 31.3%, and Mw of the copolymer (A-1) was 12,000.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of AIBN and 300 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 23 parts by weight of methacrylic acid as the (A1) compound, 10 parts by weight of styrene as the (A4) compound, and benzyl methacrylate. 32 parts by mass and 35 parts by mass of methyl methacrylate were added, and 2.7 parts by mass of α-methylstyrene dimer was added. The temperature of the solution was raised to 80 ° C. while gently stirring, and this temperature was maintained for 4 hours. Thereafter, the temperature was raised to 100 ° C., and this temperature was maintained for 1 hour for polymerization to obtain a solution containing a copolymer. The resulting polymer solution had a solid content concentration of 24.9% and Mw of 12,500. Then, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere. (A2) A copolymer (A-2) was obtained by adding 16 parts by mass of glycidyl methacrylate as a compound and reacting at 90 ° C. for 10 hours. The obtained polymer solution had a solid content concentration of 29.0% and Mw of 14,200.

<Preparation of radiation-sensitive resin composition>
[Examples 1 to 11 and Comparative Examples 1 to 4]
After mixing the components of the types and amounts shown in Table 1 and adding propylene glycol monoethyl ether acetate as a solvent so that the solid content concentration is 30% by mass, the mixture is filtered through a Millipore filter with a pore size of 0.5 μm. Thus, a radiation sensitive resin composition was prepared. In addition, “-” in the column represents that the corresponding component was not used.

The detail of each component used for preparation of the radiation sensitive resin composition shown in Table 1 is shown below.
<[B] Polymerizable compound>
B-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku)
B-2: Succinic acid-modified pentaerythritol triacrylate (Aronix TO-756, manufactured by Toagosei Co., Ltd.)
B-3: Ethylene oxide modified dipentaerythritol hexaacrylate

<[C] Photopolymerization initiator>
C-1: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01, manufactured by Ciba Specialty Chemicals)
C-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02, manufactured by Ciba Specialty Chemicals) )
C-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals)
C-4: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure 379, manufactured by Ciba Specialty Chemicals)

<[D] Acid generator>
D-1: N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (manufactured by Midori Chemical, NAI-105)
D-2: 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate D-3 to D-6: compounds represented by the following formulae, respectively

<[E] Colorant>
E-1: C.I. I. Solvent Red 45
E-2: C.I. I. Solvent Yellow 98
E-3: C.I. I. Solvent Blue 59
E-4: Varifast yellow 1101
E-5: C.I. I. Acid Black 24

<Formation of cured film>
After applying each prepared radiation-sensitive resin composition on a 95 mm × 95 mm non-alkali glass substrate using a spin coating method, it was pre-baked on a hot plate at 90 ° C. for 3 minutes to obtain a film thickness of 3.5 μm. A coating film was formed. Next, the obtained coating film was exposed using an exposure apparatus having an ultraviolet LED emitting a single peak ultraviolet light at 365 nm as a light source through a photomask in which a circular pattern having a diameter of 12 μm was formed as an opening. . Thereafter, development with a 0.05% aqueous solution of potassium hydroxide at 25 ° C. for 60 seconds, followed by washing with pure water for 1 minute, followed by post-baking in an oven at 230 ° C. for 30 minutes, curing with a circular pattern A film was formed. In Examples 1 to 11 and Comparative Examples 4 and 5, as described above, an ultraviolet LED was used as the exposure light source, and in Comparative Examples 1 to 3, a high-pressure mercury lamp was used as the exposure light source.

<Evaluation>
The following evaluation was performed about the formed cured film. The results are shown in Table 1.

[Sensitivity (J / m ² )]
Sensitivity was defined as the minimum exposure when the remaining film ratio calculated from the following formula was 90% or more. When the minimum exposure amount was 2,000 J / m ² or less, the sensitivity was judged good.
Residual film ratio = (film thickness after post-baking / film thickness after exposure) × 100

[Curability (%)]
A circular pattern was formed on the substrate with the exposure amount at which the remaining film ratio was 90% or more by operating in the same manner as in the sensitivity evaluation. This pattern was subjected to a compression test with a load of 40 mN using a 50 μm square planar indenter with a micro compression tester (Fischerscope H100C, manufactured by Fisher Instruments), and the change in the amount of compressive displacement with respect to the load was measured. The recovery rate (%) was calculated from the amount of displacement at a load of 40 mN and the amount of displacement when the load of 40 mN was removed, and was regarded as curability. When the recovery rate was 90% or more, it was judged that the surface curability and deep part curability of the cured film were good, and when the recovery rate was less than 90%, it was judged that the deep part curability of the cured film was insufficient. .

[Sublimation]
In the same manner as in the above “pattern formation”, a coating film having a film thickness of 3.5 μm was formed on a 95 mm × 95 mm non-alkali glass substrate. Next, an adhesive tape having a width of 1 cm and a thickness of 100 μm was attached to both ends of another alkali-free glass substrate on which a coating film as a cover glass was not formed. This cover glass was stacked on a substrate on which a coating film having a thickness of 3.5 μm was formed. In this case, a gap of 100 μm exists between the substrate and the cover glass depending on the thickness of the adhesive tape. The superposed substrate was exposed by an exposure apparatus using an ultraviolet LED emitting a single peak ultraviolet light at 365 nm or a high-pressure mercury lamp. The surface of the cover glass after the exposure was washed with acetone, and the solution after the washing was analyzed by HPLC (high performance liquid chromatography) (elution solvent: acetonitrile, flow rate: 1.0 mL / min, sample concentration: 1.0 mass). %, Sample injection amount: 100 μL, detector: UV detector). As a result of HPLC analysis, a case where a sublimate derived from a photopolymerization initiator due to exposure could not be confirmed was designated as “A” (determined as good), and a case where a sublimate was confirmed as “B” (determined as poor).

  From the results of Table 1, the cured film formed from the forming method of the present invention has excellent surface curability and suppresses sublimation of the photopolymerization initiator even when an ultraviolet curing LED type ultraviolet curing apparatus is used. It was found to have deep part curability. In addition, when the mercury lamp generally used conventionally was used, although sufficient sclerosis | hardenability was acquired, the sublimate of the photoinitiator was confirmed. In addition, even when an ultraviolet curing device of an ultraviolet hard LED system was used, it was found that sufficient curability could not be obtained when the radiation sensitive resin composition did not contain the [D] acid generator. .

  According to the forming method of the present invention, a cured film having excellent surface curability and deep part curability is provided even when an ultraviolet curing LED type ultraviolet curing device is used while suppressing sublimation of a photopolymerization initiator. be able to. Therefore, the formation method can be suitably applied to the production of various color filters such as a color filter for color display elements, a color filter for color separation of a solid-state imaging element, a color filter for organic EL display elements, and a color filter for electronic paper.

Claims (8)

(1) A step of applying a radiation-sensitive resin composition on a substrate to form a coating film,
(2) a step of exposing the coating film through a photomask;
(3) A method for forming the exposed coating film, and (4) a cured film forming method comprising a step of heating the developed coating film,
The radiation sensitive resin composition is
[A] alkali-soluble resin,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] A photopolymerization initiator, and [D] An acid generator, and in the step (2), exposure is performed using an ultraviolet LED as a light source.   [A] The alkali-soluble resin is a copolymer containing at least one structural unit selected from the group consisting of a structural unit having a (meth) acryloyloxy group and a structural unit having an epoxy group. Cured film forming method.   [D] The method for forming a cured film according to claim 1 or 2, wherein the acid generator is an acid generator that generates an acid with light of 300 nm or more.   [D] The content ratio of the acid generator is 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A] alkali-soluble resin. Cured film forming method.   The cured film forming method according to any one of claims 1 to 4, wherein the radiation-sensitive resin composition further contains a colorant [E].   The cured film formed from the formation method of any one of Claims 1-5.   A display element provided with the cured film of Claim 6. [A] alkali-soluble resin,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] A photopolymerization initiator, and [D] a radiation-sensitive resin composition for ultraviolet LED containing an acid generator.