JP5821282B2 - NOVEL COMPOUND, METHOD FOR PRODUCING NOVEL COMPOUND, RADIATION-SENSITIVE COMPOSITION CONTAINING NOVEL COMPOUND, AND CURED FILM - Google Patents

Description

  The present invention relates to a novel compound, a method for producing the novel compound, a radiation-sensitive composition containing the novel compound, and a cured film.

  A cured film formed from the radiation-sensitive composition is widely used in liquid crystal devices, semiconductor devices, photocurable inks, photosensitive printing plates and the like. The radiation sensitive composition contains, for example, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, etc., and the cured film is coated by applying the radiation sensitive composition on a glass substrate or the like. It can be formed by forming a film and then exposing with an exposure apparatus equipped with a mercury lamp.

  The mercury lamp has an emission line spectrum peculiar to mercury in the ultraviolet to visible wavelength region, and has a strong emission line at 254 nm, 365 nm, 405 nm, and the like. For example, Japanese Patent Application Laid-Open No. 2001-233842 discloses a technique of a photoinitiator with high radiation sensitivity that effectively uses the 365 nm and 405 nm emission lines. Many photopolymerization initiators with high radiation sensitivity have a maximum absorption in the visible region, and the photopolymerization initiator itself is often slightly reddish. Thus, the cured film formed from the conventional photopolymerization initiator that is slightly reddish is slightly cured in red and has a reduced transparency. This is inconvenient when high permeability is required.

  On the other hand, an acetophenone-based initiator as disclosed in, for example, Japanese Patent Application Laid-Open No. 58-157805 has a maximum absorption around 300 nm, and the photopolymerization initiator itself is almost white, so it is formed. The cured film exhibits high transparency in the visible region. However, this acetophenone-based initiator has low radiation sensitivity, and requires a high exposure to form a cured film having sufficient surface hardness. In addition, many of these acetophenone-based initiators have high sublimation properties (see Japanese Patent Application Laid-Open No. 2007-86565), and there are disadvantages of contamination of the baking furnace due to sublimation and contamination of the photomask during exposure.

  In view of such circumstances, a compound having a low sublimation property and a high radiation sensitivity when used as a photopolymerization initiator, and a radiation-sensitive composition capable of forming a cured film having high transparency and surface hardness. Development is desired.

JP 2001-233842 A JP 58-157805 A JP 2007-86565 A

  The present invention has been made based on the above circumstances, and its object is to provide a novel compound having low sublimation property and high radiation sensitivity when used as a photopolymerization initiator, and a method for producing the same. It is to be. Moreover, it is providing the radiation sensitive composition which contains the said compound as a photoinitiator and can form the cured film which has high transparency and surface hardness.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して炭素数１〜６のアルキル基である。ｎは、１〜６の整数である。Ｒ^３は、炭素数１〜１２のアルキル基、炭素数５〜２０のシクロアルキル−アルキル基、炭素数４〜２０の脂環式基、フェニル基、ナフチル基又はアントリル基である。但し、上記炭素数１〜１２のアルキル基が有する水素原子の一部又は全部は、ハロゲン原子で置換されていてもよい。また、上記フェニル基、ナフチル基及びアントリル基が有する水素原子の一部又は全部は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、ハロゲン原子、ビニル基、１−プロペニル基、アリル基又はイソプロペニル基で置換されていてもよい。） The invention made to solve the above problems is
It is a compound represented by the following formula (1).

(In the formula (1), ^{R 1} and ^{R 2,} a is .n is independently an alkyl group having 1 to 6 carbon atoms, .R ³ is an integer from 1 to 6, 1 to 12 carbon atoms An alkyl group, a cycloalkyl-alkyl group having 5 to 20 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, a phenyl group, a naphthyl group, or an anthryl group, provided that the alkyl group having 1 to 12 carbon atoms has. Part or all of the hydrogen atoms may be substituted with a halogen atom, and part or all of the hydrogen atoms of the phenyl group, naphthyl group, and anthryl group are alkyl groups having 1 to 6 carbon atoms, (It may be substituted with an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a vinyl group, a 1-propenyl group, an allyl group or an isopropenyl group.)

  The compound of the present invention is a compound having a specific structure represented by the above formula (1), and exhibits high radiation sensitivity when used as a photopolymerization initiator. As a result, an accurate pattern can be obtained with a small exposure amount. In addition, a cured film having a sufficient surface hardness can be obtained. In addition, the compound has low sublimation properties, and when a radiation-sensitive composition containing the compound is used as a resist material, contamination of equipment and a photomask due to sublimation can be effectively suppressed.

R ¹ and R ² in the above formula (1) are an alkyl group having 1 to 3 carbon atoms, and R ³ is a cycloalkyl-alkyl group having 5 to 10 carbon atoms and an alicyclic group having 6 to 8 carbon atoms. The group or a part or all of the hydrogen atoms is preferably a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or a vinyl group. By making the said compound into the said specific structure, when using as a photoinitiator, it has higher radiation sensitivity and lower sublimation property.

  The present compound suitably includes the compound as a photopolymerization initiator.

The radiation sensitive composition of the present invention comprises:
[A] the compound as a photopolymerization initiator (hereinafter also referred to as “[A] photopolymerization initiator”), and [B] a polymerizable compound having an ethylenically unsaturated double bond (hereinafter referred to as “[B] Also referred to as “polymerizable compound”)
Containing.

  Since the radiation sensitive composition uses the compound of the present invention as the photopolymerization initiator [A] and further contains the polymerizable compound [B], it has high radiation sensitivity and low sublimation. Moreover, the said radiation sensitive composition can form the cured film which has high transparency and surface hardness.

  The radiation-sensitive composition preferably further contains [C] an alkali-soluble resin. [C] Since the alkali-soluble resin is soluble in an alkali developer used in the development step, it exhibits high developability and can form a cured film having an accurate pattern.

  The present invention suitably includes a cured film formed from the radiation-sensitive composition. As described above, the cured film formed from the radiation-sensitive composition has high transparency and surface hardness.

（式（２）中、Ｒ^１、Ｒ^２及びｎは、上記式（１）と同義である。） The method for producing the compound is as follows:
In the presence of a base, there is a step of reacting a precursor compound represented by the following formula (2) with an organic acid chloride.

(In the formula (2), R ¹ , R ² and n have the same meaning as in the above formula (1).)

  The said manufacturing method is a novel manufacturing method of the said compound, and can manufacture the said compound cheaply and efficiently.

  The present invention provides a compound having low sublimation and high radiation sensitivity when used as a photopolymerization initiator, and a radiation-sensitive composition capable of forming a cured film having high transparency and surface hardness. Can do.

<New compound>
The compound of the present invention is a compound represented by the above formula (1), and when used as a photopolymerization initiator, exhibits high radiation sensitivity, and as a result, an accurate pattern and sufficient surface can be obtained with a small exposure amount. A cured film having hardness can be obtained. In addition, the compound has low sublimation properties, and when a radiation-sensitive composition containing the compound is used as a resist material, contamination of equipment and a photomask due to sublimation can be effectively suppressed.

The formula (1), ^{R 1} and ^{R 2} are each independently an alkyl group having 1 to 6 carbon atoms. n is an integer of 1-6. R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl-alkyl group having 5 to 20 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, a phenyl group, a naphthyl group, or an anthryl group. However, one part or all part of the hydrogen atom which the said C1-C12 alkyl group has may be substituted by the halogen atom. In addition, part or all of the hydrogen atoms of the phenyl group, naphthyl group, and anthryl group are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, halogen atoms, vinyl groups, and 1-propenyl groups. , May be substituted with an allyl group or an isopropenyl group.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ and R ² include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t- A butyl group, n-pentyl group, n-hexyl group, etc. are mentioned.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, An n-pentyl group, an n-hexyl group, etc. are mentioned.

Examples of the cycloalkyl-alkyl group having 5 to 20 carbon atoms represented by R ³ include a cyclohexyl-methyl group, a cycloheptyl-methyl group, a norbornyl-methyl group, and a norbornyl-ethyl group.

Examples of the alicyclic group having 4 to 20 carbon atoms represented by R ³ include a monocyclic or polycyclic alicyclic group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A bornyl group, a norbornyl group, an adamantyl group, etc. are mentioned.

  Examples of the halogen atom in which part or all of the hydrogen atoms of the alkyl group having 1 to 12 carbon atoms may be substituted include a chlorine atom and a fluorine atom. Examples of the alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms of the phenyl group, naphthyl group and anthryl group may be substituted include a methyl group and an ethyl group. Examples of the alkoxy group having 1 to 6 carbon atoms in which part or all of the hydrogen atoms of the phenyl group, naphthyl group and anthryl group may be substituted include, for example, a methoxy group, an ethoxy group, an n-propoxy group, i- A propoxy group, a butoxy group, a pentyloxy group, etc. are mentioned.

R ¹ and R ² in the above formula (1) are an alkyl group having 1 to 3 carbon atoms, and R ³ is a cycloalkyl-alkyl group having 5 to 10 carbon atoms and an alicyclic group having 6 to 8 carbon atoms. The group or a part or all of the hydrogen atoms is preferably a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or a vinyl group. By making the said compound into the said specific structure, when using as a photoinitiator, it has higher radiation sensitivity and lower sublimation property.

  As the compound represented by the above formula (1), a compound represented by the following formula is more preferable.

<Method of synthesizing new compound>
Although it does not specifically limit as a synthesis method of the compound represented by the said Formula (1), It has a process with which the precursor compound represented by the said Formula (2) and organic acid chloride are made to react in the presence of a base. Is preferred. The said manufacturing method is a novel manufacturing method of the said compound, and can manufacture the said compound cheaply and efficiently.

  As a method for synthesizing the precursor compound represented by the formula (2), for example, 2-bromo-2-methylpropionyl bromide is reacted with fluorobenzene to give 2-bromo-4′-fluoro-2-methylpropiophenone. Synthesize. Next, morpholine is added to 2-bromo-4'-fluoro-2-methylpropiophenone and stirred to react, and the salt precipitated from this reaction solution is filtered off. The aqueous phase is separated from the filtrate by adding an acid aqueous solution to make it acidic, and an aqueous alkali solution is added to the aqueous phase to make it basic, and then the aqueous phase is extracted. The extract is collected in a separatory funnel and the extract is washed with distilled water, and then the organic solvent is distilled off under reduced pressure to obtain a crude product. The crude product is recrystallized and purified with ethanol to synthesize 1- (4-fluorophenyl) -2-methyl-2-morpholino-1-propane. Next, this 1- (4-fluorophenyl) -2-methyl-2-morpholino-1-propane was reacted with 2-mercaptoethal, distilled water was added, and then the product was extracted. Washing and distillation under reduced pressure give a crude product. By recrystallizing and purifying the crude product with the following specific solvent, 1- [4- (hydroxyethylthio) -phenyl-2-methyl], which is one of the precursor compounds represented by the above formula (2), is obtained. 2-Morpholino-1-propane is obtained.

  The specific solvent used for recrystallization purification includes n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, 2-methylbutane, 2-methylpentane, 3-methylpentane, 3 -Ethylpentane, 2-methylhexane, 3-methylhexane, 3-ethylhexane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, cyclo Pentane, cyclohexane, cycloheptane, cyclooctane, methylcyclopentane, methylcyclohexane, methylcycloheptane, methylcyclooctane, dimethylcyclopentane, dimethylcyclohexane, dimethylcycloheptane, dimethylcyclooctane, cyclopentanone, cyclohexanone, cyclone Heptanone, cyclooctanone, toluene preferable. These solvents may be used alone or in combination of two or more. In the recrystallization, a solvent other than the above solvent can be mixed, but it is preferable to use 50% by mass or more of the above solvent.

  To the precursor compound, a base and a solvent are added and dissolved, and an organic acid chloride is added dropwise to react. After adding distilled water to the reaction solution, the product is extracted, and the extract is washed and distilled under reduced pressure to obtain a crude product. The compound of the present invention can be obtained by recrystallizing and purifying the crude product with methanol.

  Examples of the base include pyridine, triethylamine, trimethylamine, diisopropylethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, N, N-dimethylcyclohexylamine, picoline, lutidine, collidine, quinoline, isoquinoline, acridine, phenidine. Nanthridine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, N , N-dimethylaminopyridine, N, N-dimethyl-9-acridinamine, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like. Of these, pyridine and triethylamine are preferred.

Examples of the organic acid chloride include a compound represented by R ⁴ COCl. In the above formula, R ⁴ includes a saturated or unsaturated alkyl group having 1 to 24 carbon atoms, an alicyclic group having 3 to 24 carbon atoms, or an optionally substituted phenyl group.

Examples of the compound represented by R ⁴ COCl include acetic acid chloride, propionic acid chloride, butanoic acid chloride, pentanoic acid chloride, hexanoic acid chloride, octanoic acid chloride, pelargonic acid chloride, caprylic acid chloride, undecanoic acid chloride, lauric acid chloride. Linear aliphatic acid chlorides such as tridecyl chloride, myristic acid chloride, palmitic acid chloride, stearic acid chloride, behenic acid chloride, lignoceric acid chloride;
Unsaturated aliphatic acid chlorides such as acrylic acid chloride, crotonic acid chloride, methacrylic acid chloride, 3-pentenoic acid chloride, caproleic acid chloride, oleic acid chloride;
Branched aliphatic acids such as isobutanoic acid chloride, isopentanoic acid chloride, neopentanoic acid chloride, isooctanoic acid chloride, 2-ethylhexanoic acid chloride, neohexanoic acid chloride, isononanoic acid chloride, neodecanoic acid chloride, isopalmitic acid chloride, isostearic acid chloride Chloride;
Cycloalkanecarboxylic acid chlorides such as cyclopentanecarboxylic acid chloride and cyclohexanecarboxylic acid chloride;
Cycloalkyl-substituted carboxylic acid chlorides such as cyclohexyl acetic acid chloride, norbornyl acetic acid chloride, cyclohexylpropionic acid chloride, norbornylpropionic acid chloride;
Examples thereof include aromatic acid chlorides such as o-benzoic acid chloride, m-benzoic acid chloride, p-benzoic acid chloride, p-vinylacetic acid chloride, p-nitrobenzoic acid chloride, and p-bromobenzoic acid chloride. Of these, cyclohexanecarboxylic acid chloride, norbornyl acetic acid chloride, o-benzoic acid chloride, m-benzoic acid chloride, p-benzoic acid chloride, and p-vinylacetic acid chloride (benzoyl chloride) are preferable.

  Examples of the solvent used in the reaction include N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol Ethoxyethane, dimethoxyethane, benzene, toluene, xylene, ethylbenzene, tetrahydrofuran, dioxane, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, 1,4-dichloro Examples include butane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, and octane. Of these, dichloromethane, chloroform, toluene, tetrahydrofuran and dioxane are preferred.

  As another synthesis method of the compound represented by the above formula (1), dicyclohexylcarbodiimide is used as a dehydrating condensing agent, N, N-dimethylaminopyridine is used as a catalyst, and esterification of a carboxyl group and a hydroxyl group is performed. Can also be done.

<Radiation sensitive composition>
The radiation-sensitive composition of the present invention contains [A] the compound as a photopolymerization initiator and [B] an epolymerizable compound. Moreover, the said radiation sensitive composition can contain [C] alkali-soluble resin as a suitable component. Furthermore, as long as the effects of the present invention are not impaired, [D] other photopolymerization initiators, [E] polyfunctional epoxy compounds, [F] adhesion assistants, and [G] surfactants can be contained as other optional components. . Hereinafter, each component will be described in detail. In addition, since the compound used as [A] a photoinitiator is as above-mentioned, description is abbreviate | omitted here.

<[B] Polymerizable compound>
[B] The polymerizable compound is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated double bond, but it is monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth). Acrylate is preferred. By containing the [B] polymerizable compound having these specific structures, the radiation-sensitive composition can form a cured film in which transparency and surface hardness are more highly balanced.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl- Examples include 2-hydroxypropyl phthalate. Examples of commercially available products include Aronix M-101, M-111, M-114 (manufactured by Toagosei), KAYARAD TC-110S, TC-120S (manufactured by Nippon Kayaku), Biscote 158, 2311 (Osaka Organic) Chemical industry).

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate and bisphenoxyethanol full orange (meth) acrylate. As these commercially available products, for example, Aronix M-210, M-240, M-6200 (manufactured by Toagosei), KAYARAD HDDA, HX-220, R-604 (manufactured by Nippon Kayaku), Biscote 260, 312 and 335HP (manufactured by Osaka Organic Chemical Industry) and the like.

  Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, mono- [3- (3- (meth) acryloyloxy-2,2-bis- (meth) acryloyloxymethyl-propoxy) -2 , 2-bis- (meth) acryloyloxymethyl-propyl] ester, succinic acid-modified pentaerythritol tri (meth) acrylate, and the like. As a commercial item, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, M-8060, TO-756 (manufactured by Toagosei) KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku), Biscoat 295, 300, 360, GPT, 3PA, 400 (Osaka organic chemical industry) etc. are mentioned.

  Among these [B] polymerizable compounds, from the viewpoint of curability of the radiation-sensitive composition, trifunctional or higher (meth) acrylates are preferable, and trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, succinic acid mono- [3- (3- (meth) acryloyloxy-2,2-bis- (meth) acryloyloxymethyl-propoxy) -2,2-bis- (meth ) Acryloyloxymethyl-propyl] ester, succinic acid-modified pentaerythritol tri (meth) acrylate is particularly preferred. [B] A polymeric compound can be used individually or in mixture of 2 or more types.

  As content of the [B] polymeric compound in the said radiation sensitive composition, Preferably it is 3 mass parts-50 mass parts with respect to 1 mass part of [A] photoinitiator, More preferably, it is 5 mass parts -30 mass parts. [B] By making content of a polymeric compound into the said specific range, the radiation sensitivity of a radiation sensitive composition and transparency of the cured film obtained can be improved more.

<[C] Alkali-soluble resin>
The [C] alkali-soluble resin contained in the radiation-sensitive composition is not particularly limited as long as it is soluble in an alkali developer used in the development processing step of the radiation-sensitive composition containing the component. It is not limited. As such [C] alkali-soluble resin, an alkali-soluble resin having a carboxyl group is preferable, and (a1) at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “a”). And a compound of an unsaturated compound other than (a2) and (a1) (hereinafter also referred to as “compound (a2)”).

Examples of the compound (a1) include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydro. Monocarboxylic acids such as phthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid;
The acid anhydride of the said dicarboxylic acid etc. are mentioned.

  Among these compounds (a1), acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl succinic acid from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in an alkaline developer. Acid and maleic anhydride are preferred.

  A compound (a1) can be used individually or in mixture of 2 or more types. The content of the structural unit derived from the compound (a1) is preferably 5% by mass to 60% by mass, more preferably 7% by mass to 50% by mass, and particularly preferably 8% by mass to 40% by mass. By setting the content of the structural unit derived from the compound (a1) within the specific range, a radiation-sensitive composition in which various properties such as radiation sensitivity and developability are balanced at a higher level can be obtained.

Examples of the compound (a2) include alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, and t-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] acrylate Acrylic alicyclic esters such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate) Decane-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;
Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;
Methacrylic acid hydroxyalkyl esters such as methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester;
Aryl esters or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;
Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate and diethyl fumarate;
Acrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylate esters having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, p-methoxystyrene;
Conjugated diene compounds such as 1,3-butadiene and isoprene;
Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, 4-acryloyloxybutyl glycidyl ether, (3-ethyl-3-oxetanyl) methyl acrylate, (3-ethyl- 3-oxetanyl) methyl methacrylate and the like.

Among these compounds (a2), from the viewpoint of copolymerization reactivity, n-butyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, styrene, P-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, and 2-hydroxyethyl methacrylate are preferred.

  A compound (a2) can be used individually or in mixture of 2 or more types. The content of the structural unit derived from the compound (a2) is preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 85% by mass. By controlling the content of the structural unit of the compound (a2) within the above specific range, the molecular weight of the [C] alkali-soluble resin can be easily controlled, and the radiation sensitivity is balanced at a higher level of developability, radiation sensitivity, and the like. A composition is obtained.

<[C] Method for synthesizing alkali-soluble resin>
[C] The alkali-soluble resin can be produced by polymerizing constituent monomers in a suitable solvent in the presence of a radical polymerization initiator. As the solvent used for such polymerization, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, and acetate are preferred. These solvents can be used alone or in admixture of two or more.

  Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2). , 4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (4-methoxy-2) , 4-dimethylvaleronitrile) and the like. These radical polymerization initiators can be used alone or in admixture of two or more.

  [C] The polystyrene-reduced weight average molecular weight (Mw) of the alkali-soluble resin by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. [C] By setting the Mw of the alkali-soluble resin in the specific range, a radiation-sensitive composition in which developability, radiation sensitivity, and the like are balanced at a higher level, and a cured film having high heat resistance can be obtained.

In addition, Mw and Mn of this specification were measured by 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 are combined Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

  As content of [C] alkali-soluble resin in the said radiation sensitive composition, Preferably it is 5 mass parts-60 mass parts with respect to 1 mass part of [A] photoinitiator, More preferably, it is 8 mass parts- 40 parts by mass. [C] By making content of alkali-soluble resin into the said specific range, the radiation sensitive composition excellent in developability can be formed.

<[D] Other photopolymerization initiator>
The said radiation sensitive composition can add [D] other photoinitiators. [D] The other photopolymerization initiator is not particularly limited as long as it is a component that generates an active species capable of initiating polymerization of the polymerizable compound [B] in response to radiation. [D] Other photopolymerization initiators include, for example, O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. These [D] other photopolymerization initiators can be used alone or in admixture of two or more.

  Examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9- Ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- Ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1 -[9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl -6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4 -(2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2- And methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime).

  Among these O-acyloxime compounds, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- { 2-Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound (excluding those having the same structure as the [A] photopolymerization initiator).

  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, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4 -(2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like.

  Of these acetophenone compounds, α-aminoketone compounds are preferred, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is 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 biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole Is more preferable.

  As content of [D] other photoinitiators in the said radiation sensitive composition, Preferably it is 0.01 mass part-5 mass parts with respect to 1 mass part of [A] photoinitiator, More preferably. Is 0.05 part by mass to 1 part by mass. [D] By setting the content of the other photopolymerization initiator in the specific range, the radiation-sensitive composition exhibits a high radiation sensitivity even when the exposure amount is low, and has a sufficient surface hardness. Can be formed.

<[E] polyfunctional epoxy compound>
[E] A polyfunctional epoxy compound can be added to the radiation sensitive composition in order to increase the polymerization reactivity and further improve the surface hardness of a cured film formed from the radiation sensitive composition. [E] Examples of the polyfunctional epoxy compound include cationically polymerizable compounds having two or more epoxy groups in one molecule.

  Examples of the cationically polymerizable compound having two or more epoxy groups in one molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F di. Polyglycidyl ethers of bisphenols such as glycidyl ether and hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether Polyglycidyl ethers of polyhydric alcohols such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; Compound having 3,4-epoxycyclohexyl group; phenol novolac type epoxy resin such as bisphenol A novolak type epoxy resin; cresol novolac type epoxy resin; polyphenol type epoxy resin; cyclic aliphatic epoxy resin; Examples include glycidyl esters; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxidized linseed oil, and the like. Of these, phenol novolac epoxy resins are preferred.

  Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl- 5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4- Epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexyl) of ethylene glycol Methyl) ether, Chirenbisu (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate and the like.

  Examples of commercially available compounds having two or more epoxy groups in one molecule include, for example, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 as bisphenol A type epoxy resins ( Epicoat 807 as a bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin); Epicoat 152, 154 and 157S65 as a phenol novolac type epoxy resin (bisphenol A novolak type epoxy resin, etc.) , Japan Epoxy Resin), EPPN201, 202 (above, Nippon Kayaku); EOCN102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku) as a cresol novolak type epoxy resin Epicoat 180S75 (made by Japan Epoxy Resin); Epicoat 1032H60 as polyphenol type epoxy resin, XY-4000 (above, made by Japan Epoxy Resin); CY-175, 177, 179, and Araldite CY as cyclic aliphatic epoxy resins -182, 192, 184 (made by Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (UCC), Shodyne 509 (Showa Denko), Epicron 200 400 (above, manufactured by Dainippon Ink), Epicoat 871, 872 (above, made by Japan Epoxy Resin), ED-5661, 5862 (above, made by Celanese Coating); Epolite 100MF as aliphatic polyglycidyl ether (Kyoeisha conversion Ltd.), and a Epiol TMP (manufactured by NOF), and the like.

  [E] Polyfunctional epoxy compounds can be used alone or in admixture of two or more. As content of [E] polyfunctional epoxy compound in the said radiation sensitive composition, Preferably it is 0.01 mass part-5 mass parts with respect to 1 mass part of [A] photoinitiator, More preferably, it is 0. .05 parts by mass to 1 part by mass. [E] By making content of a polyfunctional epoxy compound into the said specific range, while improving polymerization reactivity, the surface hardness of the formed cured film can be maintained at a high level.

<[F] Adhesion aid>
[F] The adhesion assistant can be used to further improve the adhesion between the obtained cured film and the substrate. As such [F] adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferable. [F] Examples of the adhesion assistant include γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri And methoxysilane. These adhesion assistants can be used alone or in admixture of two or more.

  The content of [F] adhesion assistant in the radiation-sensitive composition is preferably 0.001 to 1 part by mass, more preferably 1 part by mass of [A] photopolymerization initiator. 0.005 to 0.5 parts by mass. [F] By making content of adhesion assistant into the above-mentioned specific range, pattern formation ability can be maintained at a high level while improving adhesion of a cured film to a substrate.

<[G] Surfactant>
[G] Surfactant can be used in order to further improve the film-forming property of the radiation-sensitive composition. [G] 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. Examples of the fluorosurfactant include 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetra. Fluoro-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, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetra) Fluoro-n-butyl) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1, , 2,3,3,9,9,10,10-decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether) ), Fluoroalkyl ammonium iodides, fluoroalkyl betaines, other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylates, carboxylic acid fluoroalkyl esters, and the like.

  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 Co., Ltd.), FT-100, -110, -140A, -150, -250, 251, 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.

  [G] Surfactants can be used alone or in admixture of two or more. As content of [G] surfactant in the said radiation sensitive composition, Preferably it is 0.001 mass part-1 mass part with respect to 1 mass part of [A] photoinitiator, More preferably 0.005 parts by mass to 0.5 parts by mass. By setting the content of the surfactant within the specific range, it is possible to reduce coating unevenness when forming a coating film on the substrate.

<Method for preparing radiation-sensitive composition>
The radiation sensitive composition of the present invention is prepared by uniformly mixing [A] a photopolymerization initiator, [B] a polymerizable compound, and optional components. This radiation-sensitive composition is preferably used in a solution state after being dissolved in an appropriate solvent. For example, a radiation sensitive composition in a solution state can be prepared by mixing [A] a photopolymerization initiator, [B] a polymerizable compound, and optional components in a solvent at a predetermined ratio.

  As the solvent used for the preparation of the radiation-sensitive composition, those that can dissolve each component uniformly and do not react with each component are used. As such a solvent, the thing similar to what was illustrated above as a solvent which can be used in order to manufacture a [C] alkali-soluble resin is mentioned.

  Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, and aromatic hydrocarbons. , Ketones, other esters and the like.

  Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

  Examples of ethers include cyclic ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate and the like.

  Examples of the cyclic ether include tetrahydrofuran 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 methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

  Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

  Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

  Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like. .

  Examples of aromatic hydrocarbons include toluene and xylene.

  Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl acetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl ropoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl xylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  These solvents may be used alone or in combination of two or more. When the radiation-sensitive composition is prepared in a solution state, the solid content concentration (ratio of components other than the solvent in the composition solution) can be set to any concentration (depending on the purpose of use, desired film thickness, etc.) For example, it can set to 5 mass%-50 mass%. The solution of the radiation-sensitive composition thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

<Method for forming cured film>
The present invention suitably includes a cured film formed from the radiation-sensitive composition. As described above, the cured film formed from the radiation-sensitive composition has high transparency and surface hardness. The method for forming a cured film using the radiation-sensitive composition includes at least the following steps (1) to (4) in the order described below. Step (3) can be performed when pattern formation is required.

The method of forming the cured film is as follows:
(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, a transparent conductive film is formed on one side of the transparent substrate, and a coating film of the radiation-sensitive 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 resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

As the transparent conductive film provided on one surface of the transparent substrate, a NESA film (registered trademark) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Is mentioned.

  When forming a coating film by the apply | coating method, after apply | coating the solution of the said radiation sensitive composition on the said transparent conductive film, a coating film can be formed preferably by prebaking an application surface. As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. Examples of the coating method include spraying, roll coating, spin coating (spin coating), slit coating (slit die coating), bar coating, and ink jet coating. Of these, spin coating and slit coating are preferred.

  As prebaking conditions, although it changes with the kind of each component, a mixture ratio, etc., 70 to 120 degreeC is preferable and it is about 1 to 15 minutes. The film thickness after pre-baking of the coating film is preferably 0.5 μm to 10 μm, more preferably 1.0 μm to 7.0 μm.

[Step (2)]
In this step, at least a part of the formed coating film is irradiated with radiation. At this time, when irradiating only a part of the coating film, for example, a method of irradiating through a photomask having a predetermined pattern can be used. Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable.

Radiation dose (exposure dose), as a value measured by a luminometer intensity at a wavelength 365nm of the radiation emitted (OAI model 356, Optical Associates Inc., ^{Inc.), 100J / m 2 ~5,000J /} m 2 is Preferably, 200 J / m ^{2 to} 3,000 J / m ² is more preferable.

[Step (3)]
In this step, the coating film irradiated with the radiation is developed, unnecessary portions are removed, and a predetermined pattern is formed.

  Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and aqueous solutions of alkaline compounds such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound. The concentration of the alkali in the alkaline aqueous solution is preferably 0.01% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability.

  Examples of the developing method include a liquid piling method, a dipping method, and a shower method. The development time is preferably about 10 seconds to 180 seconds at room temperature. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.

[Step (4)]
In this step, the obtained patterned coating film is baked (post-baked) by a suitable heating device such as a hot plate or an oven. As a baking temperature, 100 to 250 degreeC is preferable. The radiation-sensitive composition achieves low-temperature firing as described above, has both storage stability, and has sufficient radiation sensitivity. Therefore, the radiation-sensitive composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, or a spacer used for a flexible display or the like where low-temperature firing is desired. The firing time is preferably, for example, 5 minutes to 30 minutes on a hot plate and 30 minutes to 180 minutes in an oven.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<[A] Synthesis of photopolymerization initiator>
[Example 1]
[A] The compound (A-1) of the present invention as a photopolymerization initiator was synthesized according to the following reaction scheme. Hereinafter, the synthesis method will be described in detail.

  In a 200 mL three-necked flask equipped with a thermometer and a dropping funnel, 28.8 g (300 mmol) of fluorobenzene was weighed into a container and the inside of the container was put into a nitrogen atmosphere, and then 29.3 g (220 mmol) of anhydrous aluminum chloride was added and stirred. When the inside of the container is cooled with ice and water and the temperature in the container becomes 10 ° C. or less, 46.0 g (220 mmol) of 2-bromo-2-methylpropionyl bromide is applied for 40 minutes through the dropping funnel. The solution was added dropwise while maintaining the temperature at 10 to 15 ° C. After completion of the dropwise addition, the temperature in the reaction vessel was further set to 23 ° C. and stirred for 2 hours. Next, the reaction contents were put into 100 g of ice to stop the reaction, and the reaction product was extracted three times with 100 mL of toluene. The extract was collected in a separatory funnel and washed three times with 100 g of distilled water, and then the organic solvent was distilled off under reduced pressure to give 49 g of 2-bromo-4′-fluoro-2-methylpropiophenone as intermediate 1 (yield). 100%).

  49 g of Intermediate 1 was weighed out in a 500 mL three-necked flask, 69.7 g (800 mmol) of morpholine was added, and the mixture was stirred at 23 ° C. for 12 hours under a nitrogen atmosphere. Methylene chloride 50mL was added here, and also it stirred at 23 degreeC for 48 hours. Next, 200 mL of toluene was added to the reaction solution and stirred, and the precipitated salt (toluene insoluble matter) was filtered off by suction filtration. The filtrate was acidified with 5% by weight dilute hydrochloric acid, and the aqueous phase was separated with water. Next, an aqueous sodium carbonate solution was added to the aqueous phase to make it basic, and then extracted three times with 100 mL of chloroform. The extract was collected in a separatory funnel and washed once with 100 g of distilled water, and then the organic solvent was distilled off under reduced pressure to obtain a crude product. By recrystallizing and purifying the crude product with ethanol, 40.2 g (yield 80%) of 1- (4-fluorophenyl) -2-methyl-2-morpholino-1-propane as Intermediate 2 was obtained. It was.

  In a 200 mL three-necked flask, 20 g (80 mmol) of Intermediate 2 was weighed and dissolved in 30 mL of N, N-dimethylformamide. To this were added 22.0 g (160 mmol) of potassium carbonate and 6.83 g (88 mmol) of 2-mercaptoether, and the mixture was heated and stirred at 60 ° C. for 4 hours in a nitrogen atmosphere. The reaction solution is cooled to room temperature, and distilled water is added thereto to dissolve the generated salt. The reaction solution is transferred to a separatory funnel and extracted three times with 100 mL of toluene. This extract is separated. After collecting in a funnel and washing once with 100 g of distilled water, the organic solvent was distilled off under reduced pressure to obtain a crude product. This crude product was recrystallized and purified with n-hexane, and 1- [4- (hydroxyethylthio) -phenyl-2-methyl] -2-morpholino as a precursor compound represented by the above formula (2). 13.4 g of propane (yield 95%) was obtained.

In a 200 mL three-necked flask equipped with a thermometer and a dropping funnel, 10 g (32 mmol) of the precursor compound (1- [4- (hydroxyethylthio) -phenyl-2-methyl] -2-morpholino-1-propane) was weighed, 100 mL of toluene was added and dissolved. Next, 4.80 g (48 mmol) of triethylamine was added to the reaction solution, and the mixture was stirred at 22 ° C. Under a nitrogen atmosphere, 4.79 g of benzoyl chloride was added dropwise over 10 minutes through a dropping funnel. After completion of dropping, the mixture was stirred at 22 ° C. for 3 hours. Distilled water was added to the reaction solution and extracted three times with 100 mL of toluene. The extract was collected in a separatory funnel and washed once with 100 g of distilled water, and then the organic solvent was distilled off under reduced pressure to obtain a crude product. . This crude product was recrystallized and purified with methanol to obtain 12.8 g (yield 96%) of compound (A-1). ¹ H-NMR measurement (manufactured by Bruker, AVANCE 500 type) of the compound (A-1) was carried out to confirm that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) chemical shift σ: 8.50 ppm (hydrogen on benzene ring, 2H), 8.00 ppm (hydrogen on benzene ring, 2H), 7.56 ppm (hydrogen on benzene ring, 1H), 7.43 ppm (benzene ring on hydrogen, 2H), 7.36ppm (benzene ring on _{hydrogen, 2H), 4.55ppm (-C (} = O) O-C H 2 -CH 2 -S-, 2H), 3 .68 ppm (hydrogen on morpholine ring, 4H), 3.38 ppm (—C (═O) O—CH ₂ —CH ₂ —S—, 2H), 2.56 ppm (hydrogen on morpholine ring, 4H), 1.30 ppm (—CO—C (C H ₃ ) ₂ , 6H)

  Compound (A-1) was also synthesized by another method not shown in the above reaction scheme. Specifically, 8 g of the precursor compound was weighed into a 200 mL three-necked flask, and 80 mL of methylene chloride was added and dissolved. Next, 4.80 g of benzoic acid was added to the reaction solution, and the reaction vessel was ice-cooled. Under a nitrogen atmosphere, 6.40 g of dicyclohexylcarbodiimide and 0.31 g of N, N-dimethylaminopyridine were added and stirred for 30 minutes. Subsequently, reaction container temperature was 23 degreeC and it stirred for further 3 hours. Here, 80 mL of n-hexane was added, and the produced precipitate was suction filtered. The filtrate was extracted 3 times with 100 mL of toluene. The extract was collected in a separatory funnel and washed with 100 mL of 5% by mass hydrochloric acid. The organic layer was washed once with 100 g of distilled water, and then the organic solvent was distilled off under reduced pressure to obtain a crude product. This crude product was recrystallized and purified with methanol to obtain 10.2 g (yield 95%) of compound (A-1).

[Example 2]
Precursor compound 1- [4- (hydroxyethylthio) -phenyl-2-methyl] -2-morpholino-1-propane (7.99 g, 25.8 mmol) and o-toluic acid in a 200 mL three-necked flask equipped with a thermometer 4.40 g (32.3 mmol) was weighed, and the inside of the flask was placed in a nitrogen atmosphere, and 75 mL of dichloromethane was added and dissolved. This solution was stirred, and then N, N-dicyclohexylcarbodiimide (7.99 g, 38.8 mmol) and N, N-dimethylaminopyridine (0.95 g, 7.7 mmol) were added in an ice bath (about 0 ° C.). After stirring for 30 minutes in an ice bath, the temperature was raised to about 22 ° C. and stirring was continued for 2 hours. After confirming the disappearance of the raw materials, the insoluble matter produced in the reaction solution was filtered with suction. The filtrate was then washed twice with 100 mL of dilute hydrochloric acid, twice with 100 mL of saturated sodium bicarbonate solution and then three times with 100 mL of distilled water, and then the reaction solution was evaporated under reduced pressure to remove the crude product. Obtained. The obtained crude product was recrystallized and purified with methanol to obtain 10.4 g of Compound (A-2) (yield 94%). ¹ H-NMR measurement of the compound (A-2) was performed, and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) chemical shift σ: 8.50 ppm (hydrogen on benzene ring, 2H), 7.87 ppm (hydrogen on benzene ring, 1H), 7.39 ppm (hydrogen on benzene ring, 3H), 7.23Ppm (benzene ring on _{hydrogen, 2H), 4.53ppm (-S- -C} (= O) O-C H 2 -CH 2, 2H), 3.68ppm ( morpholine ring on hydrogen, 4H), 3 .38 ppm (—C (═O) O—CH ₂ —CH ₂ —S—, 2H), 2.60 ppm (hydrogen on morpholine ring, 4H), 2.57 ppm (methyl benzene ring, 3H), 1.31 ppm ( _{-CO-C (CH 3) 2} , 6H)

[Example 3]
Precursor compound 1- [4- (hydroxyethylthio) -phenyl-2-methyl] -2-morpholino-1-propane (7.99 g, 25.8 mmol) and m-toluic acid in a 200 mL three-necked flask equipped with a thermometer 4.40 g (32.3 mmol) was weighed, and the inside of the flask was placed in a nitrogen atmosphere, and 75 mL of dichloromethane was added and dissolved. This solution was stirred, and then N, N-dicyclohexylcarbodiimide (7.99 g, 38.8 mmol) and N, N-dimethylaminopyridine (0.95 g, 7.7 mmol) were added in an ice bath (about 0 ° C.). After stirring for 30 minutes in an ice bath, the temperature was raised to about 22 ° C. and stirring was continued for 2 hours. After confirming the disappearance of the raw materials, the insoluble matter produced in the reaction solution was filtered with suction. The filtrate was then washed twice with 100 mL of dilute hydrochloric acid, twice with 100 mL of saturated sodium bicarbonate solution and then three times with 100 mL of distilled water, and then the reaction solution was evaporated under reduced pressure to remove the crude product. Obtained. The obtained crude product was purified by silica gel column chromatography to obtain 8.5 g of compound (A-3) (yield 77%). ¹ H-NMR measurement of the compound (A-3) was performed, and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) chemical shift σ: 8.50 ppm (hydrogen on benzene ring, 2H), 7.80 ppm (hydrogen on benzene ring, 2H), 7.37 ppm (hydrogen on benzene ring, 3H), 7.26 ppm (benzene ring on _{hydrogen, 1H), 4.54ppm (-S- -C} (= O) O-C H 2 -CH 2, 2H), 3.68ppm ( morpholine ring on hydrogen, 4H), 3 .38 ppm (—C (═O) O—CH ₂ —CH ₂ —S—, 2H), 2.56 ppm (hydrogen on morpholine ring, 4H), 2.39 ppm (benzene ring methyl, 3H), 1.30 ppm ( _{-CO-C (CH 3) 2} , 6H)

[Example 4]
Precursor compound 1- [4- (hydroxyethylthio) -phenyl-2-methyl] -2-morpholino-1-propane (7.99 g, 25.8 mmol) and p-toluic acid in a 200 mL three-necked flask equipped with a thermometer 4.40 g (32.3 mmol) was weighed, and the inside of the flask was placed in a nitrogen atmosphere, and 75 mL of dichloromethane was added and dissolved. This solution was stirred, and then N, N-dicyclohexylcarbodiimide (7.99 g, 38.8 mmol) and N, N-dimethylaminopyridine (0.95 g, 7.7 mmol) were added in an ice bath (about 0 ° C.). After stirring for 30 minutes in an ice bath, the temperature was raised to about 22 ° C. and stirring was continued for 2 hours. After confirming the disappearance of the raw materials, the insoluble matter produced in the reaction solution was filtered with suction. The filtrate was then washed twice with 100 mL of dilute hydrochloric acid, twice with 100 mL of saturated sodium bicarbonate solution and then three times with 100 mL of distilled water, and then the reaction solution was evaporated under reduced pressure to remove the crude product. Obtained. The obtained crude product was recrystallized and purified with methanol to obtain 8.6 g (yield 78%) of compound (A-4). ¹ H-NMR measurement of the compound (A-4) was performed, and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) chemical shift σ: 8.50 ppm (hydrogen on benzene ring, 2H), 7.88 ppm (hydrogen on benzene ring, 2H), 7.37 ppm (hydrogen on benzene ring, 2H), 7.22 ppm (benzene ring on _{hydrogen, 2H), 4.53ppm (-S- -C} (= O) O-C H 2 -CH 2, 2H), 3.68ppm ( morpholine ring on hydrogen, 4H), 3 .37 ppm (—C (═O) O—CH ₂ —CH ₂ —S—, 2H), 2.56 ppm (hydrogen on the morpholine ring, 4H), 2.40 ppm (methyl benzene ring, 3H), 1.30 ppm ( _{-CO-C (CH 3) 2} , 6H)

[Example 5]
Precursor compound 1- [4- (hydroxyethylthio) -phenyl-2-methyl] -2-morpholino-1-propane (7.50 g, 24.2 mmol) and cyclohexanecarboxylic acid 3 were added to a 200 mL three-necked flask equipped with a thermometer. .88 g (30.3 mmol) was weighed, the inside of the flask was placed in a nitrogen atmosphere, and 75 mL of dichloromethane was added and dissolved. The solution was stirred, and then 7.50 g (36.3 mmol) of N, N-dicyclohexylcarbodiimide and 0.89 g (7.3 mmol) of N, N-dimethylaminopyridine were added in an ice bath (about 0 ° C.). After stirring for 30 minutes in an ice bath, the temperature was raised to about 22 ° C. and stirring was continued for 2 hours. After confirming the disappearance of the raw materials, the insoluble matter produced in the reaction solution was filtered with suction. The filtrate was then washed twice with 100 mL of dilute hydrochloric acid, twice with 100 mL of saturated sodium bicarbonate solution and then three times with 100 mL of distilled water, and then the reaction solution was evaporated under reduced pressure to remove the crude product. Obtained. The obtained crude product was recrystallized and purified with methanol to obtain 10.0 g (yield 99%) of compound (A-5). ¹ H-NMR measurement of the compound (A-5) was performed, and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) Chemical shift σ: 8.50 ppm (hydrogen on benzene ring, 2H), 7.33 ppm (hydrogen on benzene ring, 2H), 4.30 ppm (—C (═O) O— C ₂ H ₂ —CH ₂ —S—, 2H), 3.68 ppm (hydrogen on morpholine ring, 4H), 3.22 ppm (—C (═O) O—CH ₂ —CH ₂ —S—, 2H), 2 .57 ppm (hydrogen on morpholine ring, 4H), 2.27 ppm (tertiary hydrogen on cyclohexane ring, 1H), 1.90 ppm to 1.24 ppm (hydrogen on cyclohexane ring, 10H), 1.30 ppm (-CO-C ( CH _{3) 2,} 6H)

[Example 6]
In a 200 mL three-necked flask equipped with a thermometer, the precursor compound 1- [4- (hydroxyethylthio) -phenyl-2-methyl] -2-morpholino-1-propane (7.00 g, 22.6 mmol) and 2-norbornaneic acid were added. 3.49 g (30.3 mmol) was weighed and the flask was placed under a nitrogen atmosphere, and 75 mL of dichloromethane was added and dissolved. The solution was stirred, and then 7.00 g (33.9 mmol) of N, N-dicyclohexylcarbodiimide and 0.83 g (6.7 mmol) of N, N-dimethylaminopyridine were added in an ice bath (about 0 ° C.). After stirring for 30 minutes in an ice bath, the temperature was raised to about 22 ° C. and stirring was continued for 2 hours. After confirming the disappearance of the raw materials, the insoluble matter produced in the reaction solution was filtered with suction. The filtrate was then washed twice with 100 mL of dilute hydrochloric acid, twice with 100 mL of saturated sodium bicarbonate solution and then three times with 100 mL of distilled water, and then the reaction solution was evaporated under reduced pressure to remove the crude product. Obtained. The obtained crude product was purified by silica gel column chromatography to obtain 10.5 g (yield 97%) of compound (A-6). ¹ H-NMR measurement of the compound (A-6) was performed, and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) Chemical shift σ: 8.50 ppm (hydrogen on benzene ring, 2H), 7.33 ppm (hydrogen on benzene ring, 2H), 4.29 ppm (—C (═O) O— C ₂ H ₂ —CH ₂ —S—, 2H), 3.68 ppm (hydrogen on morpholine ring, 4H), 3.22 ppm (—C (═O) O—CH ₂ —CH ₂ —S—, 2H), 2 .57Ppm (morpholine ring on _{hydrogen, 4H), 2.28ppm (-C (} = O) - CH 2 -, 1H), 2.23ppm ( norbornane ring on hydrogen, 1H), 2.13ppm (-C ( = O _{) - CH 2 -, 1H)} , 1.98ppm ( norbornane ring on hydrogen, 2H), 1.88ppm (norbornane ring on hydrogen, 1H), 1.53ppm (norbornane ring on hydrogen, 2H), 1.30ppm (- CO-C (C _{3) 2, 6H), 1.28ppm~1.03ppm} ( cyclohexane ring on hydrogen, 5H)

[Example 7]
In a 200 mL three-necked flask equipped with a thermometer, precursor compound 1- [4- (hydroxyethylthio) -phenyl-2-methyl] -2-morpholino-1-propane (7.99 g, 25.8 mmol) and p-vinylbenzoic acid 4.40 g (29.7 mmol) of acid was weighed and the flask was placed under a nitrogen atmosphere, and 140 mL of dichloromethane was added and dissolved. This solution was stirred, and then N, N-dicyclohexylcarbodiimide (7.99 g, 38.9 mmol) and N, N-dimethylaminopyridine (0.95 g, 7.75 mmol) were added in an ice bath (about 0 ° C.). After stirring for 30 minutes in an ice bath, the temperature was raised to about 22 ° C. and stirring was continued for 2 hours. After confirming the disappearance of the raw materials, the insoluble matter produced in the reaction solution was filtered with suction. The filtrate was then washed twice with 100 mL of dilute hydrochloric acid, twice with 100 mL of saturated sodium bicarbonate solution and then three times with 100 mL of distilled water, and then the reaction solution was evaporated under reduced pressure to remove the crude product. Obtained. The obtained crude product was recrystallized and purified with methanol to obtain 9.75 g (yield 86%) of compound (A-7). ¹ H-NMR measurement of the compound (A-7) was performed, and it was confirmed that the target compound was obtained. The analysis results were as follows.

¹ H-NMR (solvent: CDCl ₃ ) chemical shift σ: 8.50 ppm (hydrogen on benzene ring, 2H), 7.93 ppm (hydrogen on benzene ring, 2H), 7.44 ppm (hydrogen on benzene ring, 2H), 7.37 ppm (hydrogen on benzene ring, 2H), 6.74 ppm (terminal olefin hydrogen, 1H), 5.86 ppm (olefin hydrogen, 1H), 5.39 ppm (terminal olefin hydrogen, 1H), 4.56 ppm (-C _{(= O) O-C H} 2 -CH 2 -S-, 2H), 3.68ppm ( morpholine ring on hydrogen, 4H), 3.38ppm (-C ( = O) O-CH 2 - CH 2 -S -, 2H), 2.56ppm (morpholine ring on _{hydrogen, 4H), 1.30ppm (-CO-} C (CH 3) 2, 6H)

<[C] 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′-azobisisobutyronitrile and 250 parts by mass of propylene glycol monomethyl ether acetate, followed by 18 parts by mass of methacrylic acid and tricyclomethacrylate [5 .2.1.0 ^2,6 ] Decan-8-yl 25 parts by mass, styrene 5 parts by mass, methacrylic acid 2-hydroxyethyl ester 30 parts by mass, and benzyl methacrylate 22 parts by mass were charged with nitrogen. Subsequently, while gently stirring, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to perform polymerization, whereby a copolymer (C-1) solution having a solid content concentration of 28.8% was obtained. Obtained. It was 13,000 when Mw was measured about the obtained copolymer (C-1) using the following apparatuses and conditions.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 250 parts by mass of propylene glycol monomethyl ether acetate, followed by 18 parts by mass of methacrylic acid, Tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate 25 parts by mass, styrene 5 parts by mass, glycidyl methacrylate 30 parts by mass, and benzyl methacrylate 22 parts by mass were charged and purged with nitrogen. Subsequently, while gently stirring, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to perform polymerization, whereby a copolymer (C-2) solution having a solid content concentration of 28.8% was obtained. Obtained. It was 8,000 when Mw was measured about the obtained copolymer (C-2) using the following apparatuses and conditions.

<Preparation of radiation-sensitive composition>
The detail of each component used for preparation of each radiation sensitive composition is shown below.

[B] Polymerizable compound B-1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku, KAYARAD DPHA)
B-2: Succinic acid-modified pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd., Aronix TO-756)

[D] Other photopolymerization initiator D-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Ciba・ Irgacure OXE02, manufactured by Specialty Chemicals)
D-2: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (manufactured by Ciba Specialty Chemicals, Irgacure 379)
D-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, Irgacure 907)

[E] Polyfunctional epoxy compound E-1: Phenol novolac type epoxy resin (Japan Epoxy Resin, Epicoat 152)
E-2: Bisphenol A novolak epoxy resin (Japan Epoxy Resin, Epicoat 157S65)

[F] Adhesion aid F-1: γ-glycidoxypropyltrimethoxysilane

[Example 8]
[A] A solution containing the compound (A-1) as a photopolymerization initiator in an amount corresponding to 1 part by mass (solid content), [B] 3 parts by mass of (B-1) as a polymerizable compound, and (B-2) 12 parts by mass and [F] 0.01 part by mass of (F-1) adhesion assistant are mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content is 30% by mass. Thereafter, the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution of the radiation sensitive composition.

[Examples 9 to 17, Comparative Examples 1 to 3]
Each radiation-sensitive composition was prepared in the same manner as in Example 8 except that the types and amounts of each component were as described in Table 1. In Table 1, “-” indicates that the corresponding component was not used.

<Evaluation>
The following evaluation was performed about each prepared radiation sensitive composition. The results are shown in Table 1.

[Radiation sensitivity (J / m ² )]
A solution of each radiation-sensitive composition was applied onto an alkali-free glass substrate with a spinner, and then pre-baked on an 80 ° C. hot plate for 3 minutes, whereby a coating film (film thickness 4. 0 μm) was formed. On the obtained coating film, it exposed using the photomask which has a plurality of 15-micrometer-diameter round residue patterns. At this time, a predetermined gap (exposure gap) was provided between the coating film surface and the photomask. Next, using a high pressure mercury lamp, the coating film was exposed through the photomask while changing the exposure amount. Subsequently, using a potassium hydroxide aqueous solution with a concentration of 0.05 mass%, development was performed by a shower method at 25 ° C. for 20 seconds, followed by washing with pure water for 1 minute, and further in an oven at 230 ° C. A round pattern was formed by post-baking for 20 minutes. The height of this circular pattern after post-baking was measured using a laser microscope (manufactured by Keyence, VK-8500). The residual film ratio (%) was determined from this value and the following formula.
Residual film ratio (%) = (pattern height after post-baking / initial film thickness) × 100
The minimum exposure amount at which the remaining film ratio was 90% or more was defined as the radiation sensitivity (J / m ² ) of the radiation-sensitive composition. When the exposure amount was 1,000 J / m ² or less, it was judged that the radiation sensitivity was good.

[transparency(%)]
A cured film was formed on a glass substrate (NA35, manufactured by NH Techno Glass) in the same manner as in the evaluation of radiation sensitivity, except that a photomask was not used and the exposure amount was 1,500 J / m ² . . Using a spectrophotometer (150-20 type double beam, manufactured by Hitachi, Ltd.), the light transmittance (%) of the glass substrate having this cured film is 400 nm to 800 nm with the glass substrate having no protective film as a reference side. Measured at a range of wavelengths. The value of the minimum light transmittance at that time was defined as the transparency (%) of the cured film. When this value was 95% or more, it was judged that the cured film had good transparency.

[surface hardness]
The pencil hardness (surface hardness) of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990 for the substrate having the formed cured film by operating in the same manner as the evaluation of the transparency. And surface hardness. When this value was 3H or more, the surface hardness of the cured film was judged to be good.

[Sublimation volatilization amount (μg)]
The solution of each radiation sensitive composition was apply | coated with the spinner on the silicon substrate, respectively, and the coating film with a coating film thickness of 6.0 micrometers was formed. About this coating film, by head space gas chromatography / mass spectrometry (head space sampler; manufactured by Nihon Analytical Industries, JHS-100A, gas chromatography / mass spectrometer; manufactured by JEOL Ltd., JEOL JMS-AX505W type mass spectrometer) Analysis was carried out. The purge area was set to 100 ° C./10 min, and the peak area A related to generation of volatile components derived from the photopolymerization initiator was determined. Using n-octane (specific gravity: 0.701, injection amount: 0.02 μL) as a standard substance, and using the peak area as a reference, the sublimate volatilization amount derived from the photopolymerization initiator in terms of n-octane from the following formula ( μg) was calculated.
Sublimate volatilization amount (μg) = A × (n-octane amount) / (n-octane peak area)
When this value was 1.5 or less, it was judged that there was little sublimate from the cured film, and the sublimation property of the photopolymerization initiator was sufficiently low.

  As is apparent from Table 1, in Examples using the radiation-sensitive composition containing the photopolymerization initiator [A] which is a novel compound of the present invention, the radiation sensitivity, the transparency of the resulting cured film, and the surface hardness are high. It was found that the balance was excellent and the volatilization amount of the sublimate was reduced.

  The present invention provides a compound having low sublimation and high radiation sensitivity when used as a photopolymerization initiator, and a radiation-sensitive composition capable of forming a cured film having high transparency and surface hardness. Can do.

Claims (7)

A compound represented by the following formula (1).

(In the formula (1), ^{R 1} and ^{R 2,} a is .n each independently represents an alkyl group having 1 to 3 carbon atoms, is an integer from 1 to 6 .R ^3, the number 5 to 10 carbon cycloalkyl - alkyl group, or a phenyl group that is substituted in some or all Gabi sulfonyl group hydrogen atoms).   The compound according to claim 1, which is used as a photopolymerization initiator. [A] A radiation-sensitive composition containing the compound according to claim 2 and [B] a polymerizable compound having an ethylenically unsaturated double bond.   [C] The radiation-sensitive composition according to claim 3, further comprising an alkali-soluble resin.   [F] The radiation-sensitive composition according to claim 3 or 4, further comprising an adhesion assistant.   A cured film formed from the radiation-sensitive composition according to claim 3, 4 or 5. The manufacturing method of the compound of Claim 1 or Claim 2 which has a process with which the precursor compound represented by following formula (2) and an organic acid chloride are made to react in base presence.

(In the formula (2), R ¹ , R ² and n have the same meaning as in the above formula (1).)