WO2011024557A1 - Novel compound, process for preparation thereof, radiation -sensitive compositions containing the novel compound, and cured films - Google Patents

Abstract

A compound having multiple groups represented by general formula (1') which are the same or different. In general formula (1'), R¹ and R² are each independently a C_1-6 alkyl group, and n is an integer of 1 to 6.

Description

NOVEL COMPOUND, PROCESS FOR PRODUCING THE SAME, RADIATION-SENSITIVE COMPOSITION CONTAINING THE NOVEL COMPOUND, AND CURED FILM

The present invention relates to a novel compound useful as a photopolymerization initiator, a production method thereof, a radiation-sensitive composition containing the novel compound, and a cured film.

Cured films formed from radiation-sensitive compositions are widely used for liquid crystal devices, semiconductor devices, photocurable inks, photosensitive printing plates, and the like. This radiation-sensitive composition contains, for example, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and the like. The cured film can be formed by applying the radiation-sensitive composition on a glass substrate or the like to form a film, and then exposing the film 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 red like the photopolymerization initiator and has reduced transparency, so that it is applied to liquid crystal devices and the like in the visible region. It may not be applicable to a cured film that requires high permeability.

On the other hand, for example, an acetophenone initiator as disclosed in JP-A-58-157805 has a maximum absorption around 300 nm, and the photopolymerization initiator itself is almost white. The cured film formed from the system initiator 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. Furthermore, this acetophenone-based initiator has high sublimation properties (see, for example, Japanese Patent Application Laid-Open No. 2007-86565), and there is a disadvantage that contamination of the baking furnace due to sublimation and contamination of the photomask during exposure.

In view of such a situation, a compound having low sublimation properties and high radiation sensitivity when used as a photopolymerization initiator, a radiation-sensitive composition containing this compound, and a cured film having high transparency and surface hardness Development is desired.

JP 2001-233842 A JP 58-157805 A JP 2007-86565 A US Publication No. 2003-225179

The present invention has been made based on the above circumstances, and its main purpose is to provide a compound having a low sublimation property and a high radiation sensitivity when used as a photopolymerization initiator, and a method for producing the compound. Is to provide. Furthermore, another object of the present invention is to provide a radiation-sensitive composition capable of forming a cured film having high transparency and surface hardness when the compound is used as a photopolymerization initiator.

The invention made to solve the above problems is
It is a compound having a plurality of groups represented by the following formula (1 ′) which is the same or different.

(In 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 to 6)

Since the compound of the present invention has two or more groups represented by the above formula (1 ′) and two or more sites that generate radicals, it has high radiation sensitivity when used as a photopolymerization initiator. The cured film which expresses and has an accurate pattern and sufficient surface hardness by the small exposure amount as a result can be obtained. In addition, since the compound has low sublimability, contamination of equipment and a photomask due to sublimation can be effectively suppressed. Furthermore, when using the said compound as a photoinitiator, the cured film which has high transparency can be obtained.

As a compound of this invention, the compound shown by following formula (1) is preferable.

(In the formula (1), R ¹ , R ² and n are as defined in the above formula (1 ′). X is any one of the divalent groups represented by the formulas (2) (i) to (iv). is there.
In the formulas (2) and (i), m is an integer of 1 to 6. In formula (2) (iii), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. )

When the compound has the specific structure represented by the above formula (1), it exhibits higher radiation sensitivity when used as a photopolymerization initiator. The compound also has lower sublimability. Furthermore, when using the said compound as a photoinitiator, the cured film which has higher transparency can be obtained.

The radiation-sensitive composition can be constituted by using a photopolymerization initiator as the above compound as the [A] component and further including a polymerizable compound having an ethylenically unsaturated double bond as the [B] component. Since such a radiation sensitive composition contains the said compound, it has a high radiation sensitivity and shows low sublimation property. Moreover, the cured film which has high surface hardness and transparency can be obtained from such a radiation sensitive composition.

The radiation-sensitive composition preferably further contains an alkali-soluble resin as the [C] component. As described above, the radiation-sensitive composition contains an alkali-soluble resin, so that the alkali-soluble resin is soluble in the alkali used in the development process, thereby exhibiting high developability and having an accurate pattern. A cured film can be formed.

Moreover, the manufacturing method of the compound shown by said Formula (1) consists of an organic acid dichloride shown by the precursor compound shown by following formula (3), phosgene, triphosgene, and following formula (4) in presence of a base. A step of reacting with at least one selected from the group.

(In the formula (3), R ¹ , R ² and n are as defined in the above formula (1). In the formula (4), R ⁵ is a divalent group represented by the formulas (5) (i) to (iii). In formula (5) (i), m is an integer of 1 to 6. In formula (5) (ii), R ³ and R ⁴ are each independently a hydrogen atom, carbon An alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.)

These methods are novel methods for producing the compound represented by the above formula (1). By such a method, the compound represented by the above formula (1) can be produced inexpensively and efficiently.

The novel compound of the present invention exhibits high radiation sensitivity when used as a photopolymerization initiator, and the radiation-sensitive composition containing this compound has an accurate pattern, high surface hardness, and high with a small exposure dose. A cured film having transparency can be formed. Moreover, since the said compound has low sublimation property, it becomes possible to suppress effectively the contamination of the facilities etc. by sublimation.

<New compound>
The compound of the present invention is a compound having a plurality of groups represented by the same or different formula (1 ′). In the above 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. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n- A hexyl group etc. are mentioned.

Examples of the compound represented by the above formula (1 ') include compounds represented by the following formulas (6) to (12).

As the compound of the present invention, a compound represented by the above formula (1) is preferable. The formula ^(1), R 1, ^{R 2} and n are as defined in the above formula (1 '). X is any one of divalent groups represented by formulas (2) (i) to (iv).

In the above formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n- A hexyl group etc. are mentioned. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, butoxy group, pentyloxy group and the like.

Examples of the compound represented by the above formula (1) include compounds represented by the following formulas (13) to (21).

The compound exhibits high radiation sensitivity as a photopolymerization initiator, and a cured film having high surface hardness can be obtained without requiring a large exposure amount. In addition, since the compound has low sublimation properties, contamination of a baking furnace, a photomask, or the like can be effectively prevented. Such low sublimation is considered to be caused by the molecular structure of the compound. Furthermore, since the compound itself is excellent in transparency, a cured film having high transparency can be obtained.

The method for producing the compound represented by the formula (1) is not particularly limited. For example, in the presence of a base, the precursor compound represented by the formula (3), phosgene, triphosgene, and the organic compound represented by the formula (4). A step of reacting at least one selected from the group consisting of acid dichlorides. That is, first, a precursor compound represented by formula (3) (for example, R ¹ and R ² are methyl groups and n is 2) by the method described in US Publication No. 2003-225179 (Patent Document 4). The precursor compound 1- [4- (2-hydroxyethylthio) -phenyl] -2-methyl-2-morpholino-propan-1-one) is synthesized. Next, in the presence of a base, phosgene, triphosgene, or an organic acid dichloride (a compound represented by the formula (4)) is added dropwise thereto, and a predetermined temperature (for example, −50 ° C. to 100 ° C., preferably −20 ° C. to 50 ° C.). In the following, the reaction is carried out for a predetermined time (for example, 30 minutes or more and 300 minutes or less), followed by separation and purification to obtain a desired compound. Preferred examples of the base used in this reaction include pyridine, triethylamine, trimethylamine, diisopropylethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, N, N-dimethylcyclohexylamine, picoline, lutidine, collidine, Quinoline, isoquinoline, acridine, phenanthridine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] Nona-5-ene, N, N-dimethylaminopyridine, N, N-dimethyl-9-acridinamine, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like. Among these bases, pyridine And triethylamine , Especially preferable. Preferred examples of the solvent used in this reaction include N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl Sulfoxide, diethylene glycol dimethyl ether, diethoxyethane, dimethoxyethane, benzene, toluene, xylene, ethylbenzene, tetrahydrofuran, dioxane, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, dichloromethane (methylene chloride), 1,2-dichloroethane, chloroform, Examples include carbon tetrachloride, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, and the like. , Dichloromethane, chloroform, toluene, tetrahydrofuran, carbon tetrachloride and dioxane chloride are particularly preferred. Among the compounds represented by the above formulas (13) to (21), the compounds of formulas (15) and (16) can be obtained by using phosgene or triphosgene, and organic acid dichloride is used. Can yield compounds of formulas (13), (14), and (17)-(21). In addition, it can manufacture according to said method also about the compound shown by said formula (1 ').

<Radiation sensitive composition>
The radiation sensitive composition of the present invention contains [A] the above compound as a photopolymerization initiator and [B] a polymerizable compound having an ethylenically unsaturated double bond. Moreover, the said radiation sensitive composition can contain [C] alkali-soluble resin as a suitable arbitrary 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 having an ethylenically unsaturated double bond>
Preferred examples of the polymerizable compound having an ethylenically unsaturated double bond used in the radiation-sensitive composition include monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or higher (meth) acrylate. Is mentioned. By using these compounds in the radiation-sensitive composition, a cured film in which transparency and surface hardness are highly balanced can be formed.

Examples of monofunctional (meth) acrylates 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 monofunctional (meth) acrylates include Aronix M-101, M-111, M-114 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S (Japan) Kayaku Co., Ltd.), Biscoat 158, 2311 (Osaka Organic Chemical Co., Ltd.) and the like.

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. Commercially available products of these bifunctional (meth) acrylates include, for example, Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604. (Nippon Kayaku Co., Ltd.), Viscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.) 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, 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, and the like. Commercially available products of these tri- or higher functional (meth) acrylates include, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, and M- 8060, TO-756 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 295, 300, 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Among these polymerizable compounds having an ethylenically unsaturated double bond, a trifunctional or higher functional (meth) acrylate is preferably used from the viewpoint of curability of the radiation-sensitive composition. Among them, trimethylolpropane tri (meth) acrylate, 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. These polymerizable compounds having an ethylenically unsaturated double bond can be used alone or in admixture of two or more.

The addition amount of the polymerizable compound having [B] ethylenically unsaturated bond in the radiation-sensitive composition is not particularly limited, but is preferably relative to 1 part by mass of [A] photopolymerization initiator. The amount is 3 to 50 parts by mass, more preferably 5 to 30 parts by mass. By using the polymerizable compound in an amount of 3 to 50 parts by mass, it is possible to form a radiation sensitive composition in which the radiation sensitivity and the transparency of the resulting cured film are highly balanced.

<[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 an alkali-soluble resin, an alkali-soluble resin having a carboxyl group is preferable, and (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “compound (a1)”. ) ”And an unsaturated compound other than (a2) and (a1) (hereinafter referred to as“ compound (a2) ”) (hereinafter referred to as copolymer [α]). .

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

Of these compounds (a1), acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 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.

In the copolymer [α], the compound (a1) can be used alone or in admixture of two or more. In the copolymer [α], the content of the repeating unit derived from the compound (a1) is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and particularly preferably 8 to 40% by mass. By setting the content of the repeating unit derived from the compound (a1) to 5 to 60% by mass, a radiation-sensitive composition in which various characteristics such as radiation sensitivity and developability are balanced at a higher level can be obtained.

Specific examples of the compound (a2) include
Alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, 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 ] decane-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;

Hydroxyalkyl esters of methacrylic acid 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;
Methacrylic acid ester 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;
Other examples include acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

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, methacrylic acid 2-hydroxyethyl ester and the like are preferable.

In the copolymer [α], the compound (a2) can be used alone or in admixture of two or more. In the copolymer [α], the content of the repeating unit derived from the compound (a2) is preferably 10 to 70% by mass, more preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass. When the content of the repeating unit of the compound (a2) is 10 to 70% by mass, the molecular weight of the copolymer can be easily controlled, and the radiation-sensitive composition balanced at a higher level of developability and radiation sensitivity. Things are obtained.

The copolymer [α] can be produced by polymerizing the constituent monomers in an appropriate solvent in the presence of a radical polymerization initiator. As a solvent used for such polymerization, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate ester and the like are preferable. These solvents can be used alone or in admixture of two or more.

The radical polymerization initiator is not particularly limited, and examples thereof 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), Examples thereof include azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used alone or in admixture of two or more.

The polystyrene-converted weight average molecular weight (Mw) of the copolymer [α] by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. By setting the Mw of the copolymer [α] to 2,000 to 100,000, 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 are obtained. be able to.

The amount of the [C] alkali-soluble resin used in the radiation-sensitive composition is preferably 5 to 60 parts by mass, more preferably 8 to 40 parts by mass with respect to 1 part by mass of the [A] photopolymerization initiator. . By using the alkali-soluble resin in an amount of 5 to 60 parts by mass, a radiation-sensitive composition having excellent developability can be formed.

<[D] Other photopolymerization initiator>
In addition to the [A] component, other photopolymerization initiators can be added to the radiation-sensitive composition as the [D] component. The radiation-sensitive polymerization initiator is not particularly limited as long as it is a component that generates an active species capable of initiating polymerization of a polymerizable compound having an ethylenically unsaturated double bond in response to radiation. Examples of such other radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like.

Specific 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-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. -Carbazol-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), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

Of these, preferable O-acyloxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-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). These O-acyloxime compounds can be used alone or in admixture of two or more.

Examples of the acetophenone compound include α-aminoketone compounds and α-hydroxyketone compounds (except for [A] photopolymerization initiator).

Specific examples of α-aminoketone compounds 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.

Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1- ON, 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 particularly preferred. These acetophenone compounds can be used alone or in admixture of two or more.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, , 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 Examples include '-biimidazole.

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 particularly preferred. These biimidazole compounds can be used alone or in admixture of two or more.

In the radiation-sensitive composition of the present invention, when a biimidazole compound is used as the [D] radiation-sensitive polymerization initiator, an aliphatic or aromatic compound having a dialkylamino group (hereinafter, referred to as “sensitivity”) is used. "Amino sensitizer") can be added.

Examples of such amino sensitizers include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferred. The amino sensitizers can be used alone or in admixture of two or more.

Furthermore, when a biimidazole compound and an amino sensitizer are used in combination in the radiation-sensitive composition, a thiol compound can be added as a hydrogen radical donor. A biimidazole compound is sensitized by an amino sensitizer and cleaved to generate an imidazole radical, but may not exhibit high polymerization initiation ability as it is. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from the thiol compound to the imidazole radical. As a result, the imidazole radical is converted into neutral imidazole, and a component having a sulfur radical having a high polymerization initiating ability is generated, whereby a cured film having a high surface hardness can be formed.

Specific examples of such thiol compounds include
Aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole;
Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionate;
Bifunctional or higher functional aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be mentioned. Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

When a biimidazole compound and an amino sensitizer are used in combination, the addition amount of the amino sensitizer is preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the biimidazole compound. 1 to 20 parts by mass. By setting the addition amount of the amino sensitizer to 0.1 to 50 parts by mass, the curing reactivity during exposure of the radiation-sensitive composition can be improved, and the surface hardness of the resulting cured film can be increased.

Further, when the biimidazole compound, the amino sensitizer and the thiol compound are used in combination, the addition amount of the thiol compound is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the biimidazole compound. More preferably, it is 1 to 20 parts by mass. By setting the addition amount of the thiol compound to 0.1 to 50 parts by mass, the surface hardness of the obtained cured film can be improved.

[D] The radiation-sensitive polymerization initiator preferably contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound. [D] The radiation-sensitive polymerization initiator may contain at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound, and a biimidazole compound.

The amount of the [D] radiation-sensitive polymerization initiator used in the radiation-sensitive composition is preferably 0.05 to 10 parts by mass, more preferably 0.8 parts per 1 part by mass of the [A] photopolymerization initiator. 1 to 5 parts by mass. [D] By using the other photopolymerization initiator in an amount of 0.05 to 10 parts by mass, the radiation-sensitive composition exhibits high radiation sensitivity even when the exposure amount is low, and has sufficient surface hardness. A cured film having can be formed.

<[E] polyfunctional epoxy compound>
[E] The 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 the cured film formed from the radiation-sensitive composition. As the polyfunctional epoxy compound, a cationic polymerizable compound having two or more epoxy groups in one molecule is used.

Specific examples of such cationically polymerizable compounds having two or more epoxy groups in one molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether. Bisphenol polyglycidyl ethers such as hydrogenated bisphenol F diglycidyl ether and hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, Polyglycidyl of polyhydric alcohol such as trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Ethers; 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; Compounds having one or more 3,4-epoxycyclohexyl groups; phenol novolac epoxy resins such as bisphenol A novolac epoxy resins; cresol novolac epoxy resins; polyphenol epoxy resins; cyclic aliphatic epoxy resins; Examples include diglycidyl esters of acids; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxidized linseed oil, and the like. Of these cationically polymerizable compounds having two or more epoxy groups in one molecule, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

Specific 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, ethylene glycol di (3,4 -Epoxycyclohexylmethyl) Le, ethylenebis (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 the like as bisphenol A type epoxy resins. 828 (manufactured by Japan Epoxy Resin Co., Ltd.); Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.) as bisphenol F type epoxy resin; Epicote 152, as the phenol novolac type epoxy resin (bisphenol A novolac type epoxy resin, etc.) 154, 157S65 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN201, 202 (manufactured by Nippon Kayaku Co., Ltd.); cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (Japan) Conversion Manufactured by Co., Ltd.), Epicoat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.); as a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (manufactured by Japan Epoxy Resin Co., Ltd.); as a cyclic aliphatic epoxy resin, CY- 175, 177, 179, Araldite CY-182, 192, 184 (Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (UCC), Shodyne 509 (manufactured by Showa Denko KK), Epicron 200, 400 (manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (manufactured by Japan Epoxy Resin), ED-5661, 5662 (Celanese coating) Epolite 10 as aliphatic polyglycidyl ether MF (produced by Kyoeisha Chemical Co.), Epiol TMP (manufactured by NOF Corporation) and the like.

[E] Polyfunctional epoxy compounds can be used alone or in admixture of two or more. The amount of the [E] polyfunctional epoxy compound used in the radiation-sensitive composition is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 0.1 parts by weight with respect to 1 part by weight of the [A] photopolymerization initiator. 5 parts by mass. [E] By using the polyfunctional epoxy compound in an amount of 0.05 to 10 parts by mass, the polymerization reactivity can be improved and 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 an 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. Specific examples of adhesion assistants include γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane etc. are mentioned. These adhesion assistants can be used alone or in admixture of two or more.

The amount of the [F] adhesion assistant used in the radiation-sensitive composition is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 1 part by mass of the [A] photopolymerization initiator. ~ 3 parts by mass. By using 0.005 to 5 parts by mass of the adhesion aid, the pattern forming ability can be maintained at a high level while improving the adhesion of the cured film to the substrate.

<[G] Surfactant>
[G] A surfactant can be used to further improve the film-forming property of the radiation-sensitive composition. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and other surfactants.

As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group at least at any one of the terminal, main chain and side chain is preferable. Examples of fluorosurfactants include 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2- Tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2) 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- Tetrafluoro-n-butyl) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2 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, F471, F476 (above, manufactured by Dainippon Ink & Chemicals, Inc.), 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, manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, 352 (above, Shin-Akita Kasei Co., Ltd.), FT-100, -110, -140A,- 50, the same -250, the -251, the -300, the -310, the -400S, Ftergent FTX-218, the -251 (or, Co. NEOS), and the like.

Specific examples of the silicone-based surfactant are commercially available product names such as Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-190, SH- 193, SZ-6032, SF-8428, DC-57, DC-190 (made by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF- 4446, TSF-4460, TSF-4442 (manufactured by GE Toshiba Silicone Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

These [G] surfactants can be used alone or in admixture of two or more. The amount of the [G] surfactant used in the radiation-sensitive composition is preferably 0.001 to 1 part by mass, more preferably 0.005, per 1 part by mass of the [A] photopolymerization initiator. Is 0.5 parts by mass. By setting the amount of the surfactant used to be 0.001 to 1 part by mass, it is possible to reduce coating unevenness when forming a film on the substrate.

<Preparation of radiation-sensitive composition>
The radiation-sensitive composition of the present invention includes the above-mentioned [A] photopolymerization initiator, [B] a polymerizable compound having an ethylenically unsaturated double bond, and other optional additions as described above. Prepared by mixing the ingredients uniformly. This radiation-sensitive composition is preferably used in a solution state after being dissolved in an appropriate solvent. For example, by mixing [A] a photopolymerization initiator, [B] a polymerizable compound having an ethylenically unsaturated double bond, and other components optionally added, in a solvent at a predetermined ratio. A radiation-sensitive composition in a solution state can be prepared.

As the solvent used for the preparation of the radiation-sensitive composition, [A] a photopolymerization initiator, [B] a polymerizable compound having an ethylenically unsaturated double bond, and other optional components are homogeneous. Those that can be dissolved in the aqueous solution 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 [C] alkali-soluble resin is mentioned.

Among such solvents, from the viewpoint of solubility of each component, non-reactivity with each component, ease of film formation, etc., for example, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, Propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, and 3-methoxybutanol can be particularly preferably used. These solvents may be used alone or in combination of two or more.

When preparing the radiation-sensitive composition in a solution state, the solid content concentration (components other than the solvent in the composition solution, that is, the above-mentioned [A] photopolymerization initiator and [B] ethylenically unsaturated double bond) The ratio of the total amount of the polymerizable compound and other optional components) can be set to an arbitrary concentration (for example, 5 to 50% by mass) depending on the purpose of use, a desired film thickness value, and the like. 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 to 0.5 μm.

<Method for forming cured film>
Next, a method for forming a cured film using the radiation-sensitive composition of the present invention will be described. 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.
That is, the method of forming the cured film is as follows:
(1) A step of forming a film of the radiation-sensitive composition of the present invention on a substrate,
(2) A step of irradiating at least a part of the coating with radiation,
(3) a step of developing the coating after irradiation, and (4) a step of heating the coating after development.

Hereinafter, each of these steps will be described sequentially.

(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate Forming a transparent conductive film on the single side | surface of a transparent substrate, and forming the coating film of a radiation sensitive composition on this transparent conductive film. Can do. Examples of the transparent substrate used here include a glass substrate and a resin substrate. Specific examples of these transparent substrates include glass substrates such as soda lime glass and alkali-free glass; resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

As a transparent conductive film provided on one surface of a transparent substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Etc.

When forming a film by the apply | coating method, after apply | coating the solution of a radiation sensitive composition on a transparent conductive film, a film can be formed preferably by heating (prebaking) an application surface. The solid concentration of the composition solution used in the coating method is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 35% by mass. The coating method of the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet coating method or the like is adopted. can do. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable.

The pre-baking conditions vary depending on the type of each component, the blending ratio, etc., but preferably at 70 to 120 ° C. for about 1 to 15 minutes. The film thickness of the film after pre-baking is preferably 0.5 to 10 μm, more preferably about 1.0 to 7.0 μm.

(2) A step of irradiating at least a part of the film Next, at least a part of the formed film is irradiated with radiation. At this time, when irradiating only a part of the film, for example, the irradiation can be performed through a photomask having a predetermined pattern.

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 to 550 nm is preferable.

The radiation irradiation amount (exposure amount) is preferably 100 to 5,000 J / m ² , as a value obtained by measuring the intensity of irradiated radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.). 200 to 3,000 J / m ² is preferable.

(3) Step of developing the film after radiation irradiation Next, by developing the film after radiation irradiation, unnecessary portions are removed to form a predetermined pattern.

Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and alkalis (basic compounds) such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to these aqueous alkali solutions. The concentration of the alkali in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. The developing method may be any of a liquid filling method, a dipping method, a shower method, and the like, and the developing time is preferably about 10 seconds to 180 seconds at room temperature.

(4) Step of heating the film after development After the above development treatment, the patterned film is preferably washed with running water for 30 to 90 seconds and then air-dried with compressed air or compressed nitrogen. Next, the obtained pattern-shaped film is subjected to a predetermined temperature, for example, 100 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, and 30 in the oven by a suitable heating device such as a hot plate or an oven. A cured film having a high surface hardness can be obtained by heating (post-baking) for ˜180 minutes.

The cured film thus formed from the radiation-sensitive composition of the present invention has high surface hardness and excellent transparency, as will be apparent from the examples described later.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<[A] Synthesis of photopolymerization initiator>
[Example 1]
A 1 L three-necked flask was equipped with a thermometer and a dropping funnel, and 1- [4- (2-hydroxyethylthio) -phenyl] -2-methyl-2-morpholino-propan-1-one (patented) under nitrogen atmosphere 110 g of Document 4 (see US Publication No. 2003-225179) and 60 g of pyridine were dissolved in 360 g of methylene chloride and cooled in an ice bath to 5 ° C. or lower. Subsequently, a solution obtained by dissolving 33.2 g of adipoyl chloride in 100 g of methylene chloride was dropped over 2 hours through a dropping funnel. It stirred for 2 hours after completion | finish of dripping. After completion of the reaction, 500 mL of water was added to dissolve the produced salt in the aqueous layer, and then the organic layer was extracted using a separatory funnel. This organic layer was washed twice with 200 mL of 10% by mass aqueous HCl and then twice with 200 mL of distilled water. Anhydrous sodium sulfate was added to the separated organic layer to remove water, and the anhydrous sodium sulfate was separated, and then the organic layer was concentrated with an evaporator. To the obtained crude crystals, 400 g of di-i-propyl ether was added and once dissolved by heating, the temperature was lowered to 10 ° C. and recrystallization was performed. After the precipitated crystals were filtered and dried, 98.5 g of a white solid was obtained. Furthermore, recrystallization was performed once again using 400 g of di-i-propyl ether, and this was filtered and dried to obtain 85.3 g of compound (A-1) as a white powder.

This compound was subjected to ¹ H-NMR measurement, FT-IR measurement, and UV measurement to confirm that the target compound was obtained. The analysis results were as follows.

¹ H-NMR measurement (solvent: CDCl ₃ ) Chemical shift σ: 8.50 ppm (aromatic ring hydrogen, 4H), 7.32 ppm (aromatic ring hydrogen, 4H), 4.35 ppm (ester group —O—CH ₂ , 4H ), 3.68 ppm (morpholine ring hydrogen —O—CH ₂ , 8H), 3.27 ppm (—S—CH ₂ , 4H), 2.56 ppm (morpholine ring hydrogen —N—CH ₂ , 8H), 2 .21 ppm (methylene-CO—CH ₂ , 2H), 1.50 ppm (methylene-CH ₂ —CH ₂ 4H), 1.31 ppm (dimethyl, 12H)
IR measurement (KBr) 3005 cm ⁻¹ , 2993 cm ⁻¹ , 2935 cm ⁻¹ , 2850 cm ⁻¹ , 2821 cm ⁻¹ , 1754 cm ⁻¹ , 1666 cm ⁻¹ , 1585 cm ⁻¹
UV measurement (solvent: methylene chloride) Maximum absorption wavelength: 295 nm

[Example 2]
A 1 L three-necked flask was equipped with a thermometer and a dropping funnel, and 1- [4- (2-hydroxyethylthio) -phenyl] -2-methyl-2-morpholino-propan-1-one (patented) under nitrogen atmosphere 110 g of Document 4 (see US Publication No. 2003-225179) and 60 g of pyridine were dissolved in 360 g of methylene chloride and cooled in an ice bath to 5 ° C. or lower. Next, a solution obtained by dissolving 53.8 g of triphosgene in 100 g of methylene chloride was dropped over 2 hours through a dropping funnel. After completion of the dropwise addition, the mixture was stirred for 2 hours. After completion of the reaction, 500 mL of water was added to dissolve the generated salt in the aqueous layer, and then the organic layer was extracted using a separatory funnel. This organic layer was washed twice with 200 mL of 10% by mass aqueous HCl and then twice with 200 mL of distilled water. Anhydrous sodium sulfate was added to the separated organic layer to remove water, and the anhydrous sodium sulfate was separated, and then the organic layer was concentrated with an evaporator. To the obtained crude crystals, 400 g of di-i-propyl ether was added, and once dissolved by heating, the temperature was lowered to 10 ° C. and recrystallization was performed. After the precipitated crystals were filtered and dried, 100.4 g of a yellow solid was obtained. Further, recrystallization was performed once again using 400 g of di-i-propyl ether, and this was filtered and dried to obtain 90.2 g of yellow powder compound (A-2).

This compound was subjected to ¹ H-NMR measurement, FT-IR measurement, and UV measurement 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 (aromatic ring hydrogen, 4H), 7.32 ppm (aromatic ring hydrogen, 4H), 4.35 ppm (ester group —O—CH ₂ , 4H) 3.68 ppm (morpholine ring hydrogen —O—CH ₂ , 8H), 3.27 ppm (—S—CH ₂ , 4H), 2.56 ppm (morpholine ring hydrogen —N—CH ₂ , 8H), 31ppm (dimethyl, 12H)
IR measurement (KBr) 2973 cm ⁻¹ , 2935 cm ⁻¹ , 2850 cm ⁻¹ , 2821 cm ⁻¹ , 1754 cm ⁻¹ , 1666 cm ⁻¹ , 1585 cm ⁻¹
UV measurement (solvent: methylene chloride) Maximum absorption wavelength: 299 nm

[Example 3]
A 1 L three-necked flask was equipped with a thermometer and a dropping funnel, and 1- [4- (2-hydroxyethylthio) -phenyl] -2-methyl-2-morpholino-propan-1-one (patented) under nitrogen atmosphere 110 g of Document 4 (see US Publication No. 2003-225179) and 60 g of pyridine were dissolved in 360 g of methylene chloride and cooled in an ice bath to 5 ° C. or lower. Next, a solution obtained by dissolving 42.3 g of 4-methoxyphthalic acid dichloride in 100 g of methylene chloride was dropped over 2 hours through a dropping funnel. It stirred for 2 hours after completion | finish of dripping. After completion of the reaction, 500 mL of water was added to dissolve the generated salt in the aqueous layer, and then the organic layer was extracted using a separatory funnel. This organic layer was washed twice with 200 mL of 10% by mass aqueous HCl and then twice with 200 mL of distilled water. Anhydrous sodium sulfate was added to the separated organic layer to remove moisture, and the anhydrous sodium sulfate was separated, and then the organic layer was concentrated with an evaporator. To the obtained crude crystals, 400 g of di-i-propyl ether was added, and once dissolved by heating, the temperature was lowered to 10 ° C. and recrystallization was performed. After the precipitated crystals were filtered and dried, 98.4 g of a yellow solid was obtained. Furthermore, recrystallization was performed once again using 400 g of di-i-propyl ether, and this was filtered and dried to obtain 88.2 g of a yellow powdered compound (A-3).

This compound was subjected to ¹ H-NMR measurement, FT-IR measurement, and UV measurement 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 (aromatic ring hydrogen, 4H), 7.62 ppm (aromatic ring hydrogen, 1H), 7.45 ppm (aromatic ring hydrogen, 1H), 7.37 ppm (Aromatic ring hydrogen, 1H), 7.32 ppm (aromatic ring hydrogen, 4H), 4.35 ppm (ester group —O—CH ₂ , 4H), 3.74 ppm (aromatic ring —O—CH ₃ , 3H), 3 .68 ppm (morpholine ring hydrogen —O—CH ₂ , 8H), 3.27 ppm (—S—CH ₂ , 4H), 2.56 ppm (morpholine ring hydrogen —N—CH ₂ , 8H), 1.31 ppm ( Dimethyl, 12H)
IR measurement (KBr) 2973 cm ⁻¹ , 2935 cm ⁻¹ , 2850 cm ⁻¹ , 2821 cm ⁻¹ , 1754 cm ⁻¹ , 1666 cm ⁻¹ , 1585 cm ⁻¹
UV measurement (solvent: methylene chloride) Maximum absorption wavelength: 305 nm

[Example 4]
A 1 L three-necked flask was equipped with a thermometer and a dropping funnel, and 1- [4- (2-hydroxyethylthio) -phenyl] -2-methyl-2-morpholino-propan-1-one (patented) under nitrogen atmosphere 110 g of Document 4 (see US Publication No. 2003-225179) and 60 g of pyridine were dissolved in 360 g of methylene chloride and cooled in an ice bath to 5 ° C. or lower. Next, a solution in which 37.9 g of 1,4-cyclohexanedicarboxylic acid dichloride was dissolved in 100 g of methylene chloride was dropped through a dropping funnel over 2 hours. It stirred for 2 hours after completion | finish of dripping. After completion of the reaction, 500 mL of water was added to dissolve the generated salt in the aqueous layer, and then the organic layer was extracted using a separatory funnel. This organic layer was washed twice with 200 mL of 10% by mass aqueous HCl and then twice with 200 mL of distilled water. Anhydrous sodium sulfate was added to the separated organic layer to remove water, and the anhydrous sodium sulfate was separated, and then the organic layer was concentrated with an evaporator. To the obtained crude crystals, 400 g of di-i-propyl ether was added, and once dissolved by heating, the temperature was lowered to 10 ° C. and recrystallization was performed. After the precipitated crystals were filtered and dried, 88.3 g of a white solid was obtained. Furthermore, recrystallization was performed once again using 400 g of di-i-propyl ether, and this was filtered and dried to obtain 82.3 g of compound (A-4) as a white powder.

This compound was subjected to ¹ H-NMR measurement, FT-IR measurement, and UV measurement 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 (aromatic ring hydrogen, 4H), 7.32 ppm (aromatic ring hydrogen, 4H), 4.35 ppm (ester group —O—CH ₂ , 4H) 3.68 ppm (morpholine ring hydrogen —O—CH ₂ , 8H), 3.27 ppm (—S—CH ₂ , 4H), 2.72 ppm (cyclohexane-CH ₂ , 8H), 2.56 ppm (morpholine ring) Hydrogen-N—CH ₂ , 8H), 1.31 ppm (dimethyl, 12H)
IR measurement (KBr) 3005 cm ⁻¹ , 2993 cm ⁻¹ , 2935 cm ⁻¹ , 2850 cm ⁻¹ , 2821 cm ⁻¹ , 1754 cm ⁻¹ , 1666 cm ⁻¹ , 1585 cm ⁻¹
UV measurement (solvent: methylene chloride) Maximum absorption wavelength: 295 nm

<[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, 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. With respect to the obtained copolymer (C-1), Mw was measured using the following apparatus and conditions, and it was 13,000.
Device: GPC-101 (manufactured by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran

<Preparation of radiation-sensitive composition>
[Example 5]
[A] A solution containing the compound (A-1) as a component in an amount corresponding to 1 part by mass (solid content), [B] dipentaerythritol hexaacrylate as a polymerizable compound having an ethylenically unsaturated double bond (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.) 15 parts by mass, 0.01 parts by mass of γ-glycidoxypropyltrimethoxysilane as [F] adhesion aid, and fluorine-based as [G] surfactant Surfactant (“FTX-218” manufactured by Neos Co., Ltd.) 0.01 parts by mass was mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 30% by mass, and then the pore size was 0.2 μm. The solution of the radiation sensitive composition was prepared by filtering with a membrane filter.

[Examples 6 to 14, Comparative Examples 1 to 6]
A solution of the radiation sensitive resin composition was prepared in the same manner as in Example 5 except that the types and amounts shown in Table 1 were used as the components [A] to [G].

In Table 1, the abbreviations for the components [B], [D], [E], [F] and [G] mean the following compounds, respectively.
B-1: Dipentaerythritol hexaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
B-2: Succinic acid-modified pentaerythritol triacrylate (“Aronix TO-756” manufactured by Toagosei Co., Ltd.)
D-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (manufactured by Ciba Specialty Chemicals Irgacure OXE02 ")
D-2: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (“Irgacure” manufactured by Ciba Specialty Chemicals) 379 ")
D-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name “Irgacure 907”, manufactured by Ciba Specialty Chemicals)
E-1: Phenol novolac type epoxy resin (“Epicoat 152” manufactured by Japan Epoxy Resin Co., Ltd.)
E-2: Bisphenol A novolac type epoxy resin (“Epicoat 157S65” manufactured by Japan Epoxy Resin Co., Ltd.)
F-1: γ-Glycidoxypropyltrimethoxysilane G-1: Fluorosurfactant (“FTX-218” manufactured by Neos Co., Ltd.)

<Characteristic evaluation of radiation-sensitive composition and cured film>
The radiation-sensitive composition prepared as described above and the cured film formed therefrom were evaluated as follows. The evaluation results are shown in Table 1.

[(1) Evaluation of radiation sensitivity of radiation-sensitive composition]
After coating the solution of the radiation sensitive composition on a non-alkali glass substrate with a spinner, the coating of the radiation sensitive composition (film thickness: 4.0 μm) is performed by pre-baking on a hot plate at 80 ° C. for 3 minutes. Formed. On the obtained film, it exposed using the photomask which has two or more round residual patterns with a diameter of 15 micrometers. At this time, a predetermined gap (exposure gap) was provided between the coating 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 the round pattern after post-baking was measured using a laser microscope (VK-8500 manufactured by Keyence). The residual film ratio (%) was obtained by applying this value to the following equation.
Residual film ratio (%) = (pattern height after post-baking / initial film thickness 4.0 μm) × 100
The minimum exposure amount at which the residual film ratio is 90% or more is shown in Table 1 as the radiation sensitivity of the radiation-sensitive composition. If the exposure amount is 1,000 J / m ² or less, it can be said that the radiation sensitivity is good.

[(2) Evaluation of transparency of cured film]
A glass substrate (“NA35 (NH Technotech) was used in the same manner as in“ (1) Evaluation of radiation sensitivity of radiation-sensitive composition ”except that a photomask was not used and the exposure amount was 1,500 J / m ^2. A cured film was formed on “Glass Co., Ltd.)”). 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 to 800 nm with the glass substrate having no protective film as the reference side. Measured at a wavelength in the range of. The value of the minimum light transmittance at that time is shown in Table 1 as the evaluation of the transparency of the cured film. When this value is 95% or more, it can be said that the transparency of the cured film is good.

[(3) Measurement of pencil hardness (surface hardness) of cured film]
For a substrate having a cured film formed in the same manner as in “(2) Evaluation of transparency of cured film”, the pencil hardness (surface hardness) of the cured film was determined by the 8.4.1 pencil scratch test of JIS K-5400-1990. ) And the results are shown in Table 1. When this value is 3H or larger, it can be said that the surface hardness of the cured film is good.

[(4) Evaluation of sublimate volatilization amount during formation of cured film]
Each solution of the radiation sensitive composition was applied onto a silicon substrate by a spinner to form a coating film having a coating thickness of 6.0 μm. About this coating, head space gas chromatography / mass spectrometry (head space sampler: manufactured by Nihon Analytical Industries, model name “JHS-100A”; gas chromatography / mass spectrometer: manufactured by JEOL Ltd., “ JEOL JMS-AX505W type mass spectrometer "). 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 is calculated from the following formula. The results are shown in Table 1.
Sublimate volatilization amount (μg) = A × (n-octane amount (μg)) / (n-octane peak area)
When the sublimate volatilization amount is 1.5 μg or less, it can be said that the sublimate from the cured film is small and the sublimation property of the photopolymerization initiator is sufficiently low.

From the results shown in Table 1, in Examples 5 to 14 using the radiation-sensitive composition containing the photopolymerization initiator, which is a novel compound according to the present invention, the radiation sensitivity, the transparency of the resulting cured film, and the surface It was found that the hardness was excellent in a well-balanced manner, and that the sublimate volatilization amount was significantly reduced as compared with Comparative Examples 1-6.

When used as a photopolymerization initiator, the novel compound of the present invention exhibits high radiation sensitivity, has low sublimation properties, and can form a cured film having high transparency and sufficient surface hardness. Therefore, it is extremely useful as a component of the radiation sensitive composition.

Claims (6)

1. A compound having a plurality of groups represented by the following formula (1 ′) which is the same or different.
   

   

   (In 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 to 6)
2. The compound of Claim 1 shown by following formula (1).
   

   

   

   (In the formula (1), R ¹ , R ² and n are as defined in the above formula (1 ′). X is any one of the divalent groups represented by the formulas (2) (i) to (iv). is there.
   In the formulas (2) and (i), m is an integer of 1 to 6. In formula (2) (iii), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. )
3. [A] A radiation-sensitive composition containing the compound according to claim 1 or 2 as a photopolymerization initiator and [B] a polymerizable compound having an ethylenically unsaturated double bond.
4. The radiation sensitive composition according to claim 3, further comprising [C] an alkali-soluble resin.
5. A cured film formed from the radiation-sensitive composition according to claim 3 or 4.
6. A process comprising reacting a precursor compound represented by the following formula (3) with at least one selected from the group consisting of phosgene, triphosgene and an organic acid dichloride represented by the following formula (4) in the presence of a base. 2. A method for producing the compound according to 2.
   

   

   

   

   (In the formula (3), R ¹ , R ² and n are as defined in the above formula (1). In the formula (4), R ⁵ is a divalent group represented by the formulas (5) (i) to (iii). In formula (5) (i), m is an integer of 1 to 6. In formula (5) (ii), R ³ and R ⁴ are each independently a hydrogen atom, carbon An alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.)