JP6935287B2 - Hydrogen barrier agent, composition for forming hydrogen barrier membrane, hydrogen barrier membrane, method for producing hydrogen barrier membrane, and electronic device - Google Patents

Description

The present invention relates to a hydrogen barrier agent, a composition for forming a hydrogen barrier membrane, a hydrogen barrier membrane, a method for producing a hydrogen barrier membrane, and an electronic device.

Conventionally, various functional films have been formed in various electronic devices. Among electronic devices, the development of organic electronic devices is progressing with the progress of the development of conductive organic materials and organic semiconductors. A typical example of such an organic electronic device is an organic EL device.
When the electronic element is an organic EL element, examples of the functional film include a passivation film, a transparent electrode film, a transparent insulating layer, a flattening film, an organic light emitting film, and a protective film.

The electronic element is often provided with a TFT in order to drive the element like an organic EL element. Further, the electronic element is often provided with wiring made of a metal such as copper. Here, the function of the TFT may be impaired by the reduction reaction due to the contact with the hydrogen gas, and the electrical characteristics of the metal wiring may be changed by the reduction with the hydrogen gas.

On the other hand, among the materials of the functional film in the electronic device, there is a material that releases hydrogen gas due to the manufacturing method of the material. For example, SiN or the like used as a material for a passivation film may contain ammonia gas due to its manufacturing method. Therefore, hydrogen gas generated by the decomposition of ammonia may be generated from SiN.
As described above, in an electronic element such as an organic EL element, members such as a TFT and a metal wiring may be adversely affected by the generation of hydrogen inside.

From such a problem, for example, a method of including a metal thin film as a hydrogen absorbing substance in an organic electroluminescent element (organic EL element) has been proposed (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2015-779755

However, the method described in Patent Document 1 is difficult to apply to a place where transparency is required, and a step of including a hydrogen absorbing substance is added to the manufacturing method of the electronic device, so that the manufacturing process of the electronic device is added. In addition to being complicated, it causes an increase in the manufacturing cost of electronic devices.
Therefore, there is a demand for a hydrogen barrier agent capable of imparting hydrogen barrier properties to the functional layer by blending with the functional layer originally provided in the electronic device, and a hydrogen barrier film formed by using the hydrogen barrier agent. There is.

The present invention has been made in view of the above problems, and includes a hydrogen barrier agent capable of imparting hydrogen barrier performance to various materials, a composition for forming a hydrogen barrier film containing the hydrogen barrier agent, and the above-mentioned. It is an object of the present invention to provide a hydrogen barrier membrane containing a hydrogen barrier agent, a method for producing a hydrogen barrier membrane using the above-mentioned composition for forming a hydrogen barrier membrane, and an electronic device provided with the hydrogen barrier membrane.

The present inventors prepare a composition for forming a hydrogen barrier membrane by using a compound having a specific structure having an imidazolyl group as a hydrogen barrier agent and blending the above-mentioned hydrogen barrier agent with a base material component. We have found that the above problems can be solved by forming a hydrogen barrier membrane using the above-mentioned hydrogen barrier membrane forming composition, and have completed the present invention. Specifically, the present invention provides the following.
The term "hydrogen", which is the subject of the "hydrogen barrier" performance of the present invention, means both H ₂ molecules, H radicals, ^{various components of H +} (proton), and the entire mixed component consisting of a combination of individual components. do.

（式（０）中、Ｒ^２は置換基を有してもよい芳香族基であり、Ｒ^３０は水素原子又は炭素原子数１以上４０以下の１価の置換基を示す。Ｒ^４は、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基であり、ｎは０以上３以下の整数である。）で表される化合物からなる、水素バリア剤である。 The first aspect of the present invention is the following equation (0):

(In the formula (0), R ² is an aromatic group which may have a substituent group, R ³⁰ is .R ⁴ showing a monovalent substituent having 1 or more and 40 or less carbon hydrogen atom or a carbon atom, Halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonato group, phosphino group, phosphinyl group, phosphonat group, or organic group, n is an integer of 0 or more and 3 or less. It is a hydrogen barrier agent composed of a compound represented by).

A second aspect of the present invention is a composition for forming a hydrogen barrier film, which comprises a base material component (A) and a hydrogen barrier agent (B) according to the first aspect.

A third aspect of the present invention is a hydrogen barrier membrane containing the hydrogen barrier agent according to the first aspect.

A fourth aspect of the present invention is the composition for forming a hydrogen barrier membrane according to the second aspect, wherein the base material component (A) is an alkali-soluble resin (A1) and a photopolymerizable compound (A2). A hydrogen barrier membrane comprising a cured product of a composition for forming a hydrogen barrier membrane, further comprising a photopolymerization initiator (C).

A fifth aspect of the present invention is
The composition for forming a hydrogen barrier membrane according to the second aspect, wherein the base material component (A) contains an alkali-soluble resin (A1) and a photopolymerizable compound (A2), and further, a photopolymerization initiator. To form a coating film by applying a hydrogen barrier membrane forming composition containing (C) onto a substrate.
A method for producing a hydrogen barrier membrane, which comprises exposing the coating film.

A sixth aspect of the present invention is an electronic device comprising a passivation film and a hydrogen barrier membrane according to a third or fourth aspect.

According to the present invention, a hydrogen barrier agent capable of imparting hydrogen barrier performance to various materials, a composition for forming a hydrogen barrier film containing the hydrogen barrier agent, and a hydrogen barrier film containing the above-mentioned hydrogen barrier agent. It is possible to provide a method for producing a hydrogen barrier membrane using the above-mentioned composition for forming a hydrogen barrier membrane, and an electronic element provided with the hydrogen barrier membrane.

（式（０）中、Ｒ^２は置換基を有してもよい芳香族基であり、Ｒ^３０は水素原子又は炭素原子数１以上４０以下の１価の置換基を示す。Ｒ^４は、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基であり、ｎは０以上３以下の整数である。） ≪Hydrogen barrier agent≫
The hydrogen barrier agent comprises a compound represented by the following formula (0). The hydrogen barrier agent imparts hydrogen barrier properties to various articles by being blended with various materials.

(In the formula (0), R ² is an aromatic group which may have a substituent group, R ³⁰ is .R ⁴ showing a monovalent substituent having 1 or more and 40 or less carbon hydrogen atom or a carbon atom, Halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphino group, phosphinyl group, phosphonat group, or organic group, n is an integer of 0 or more and 3 or less. be.)

In formula (0), R ² is an aromatic group which may have a substituent. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

The type of aromatic hydrocarbon group is not particularly limited as long as it does not interfere with the object of the present invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, or may be a group formed by condensing two or more aromatic hydrocarbon groups, or two or more aromatic hydrocarbon groups. May be a group formed by bonding with a single bond. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.

The type of aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. As the aromatic heterocyclic group, a pyridyl group, a frill group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isooxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable.

Substituents that the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, and a nitroso group. , Sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, and organic group. When a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent of the aromatic group is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group and the like. This organic group may contain a bond or a substituent other than the hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when forming a cyclic structure or the like.

When the aromatic group has a substituent on an adjacent carbon atom, the two substituents bonded on the adjacent carbon atom may be bonded to each other to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.

When the substituent of the aromatic group is an organic group, the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group includes an oxygen atom, a nitrogen atom, a silicon atom and the like. It may contain a bond containing a heteroatom of. Specific examples of the bond containing a hetero atom include ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond (-N = C (-R)-, -C (=). NR)-: R indicates a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.

Examples of the bond containing a hetero atom that the organic group may have include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, and an amide bond from the viewpoint of heat resistance of the compound represented by the formula (0). , Amino bond (-NR-: R indicates hydrogen atom or monovalent organic group) Urethane bond, Imino bond (-N = C (-R)-, -C (= NR)-: R is hydrogen atom or (Showing a monovalent organic group), carbonate bond, sulfonyl bond, sulfinyl bond are preferable.

When the organic group is a substituent other than the hydrocarbon group, the type of the substituent other than the hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. Specific examples of substituents other than the hydrocarbon group include halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group and alkoxy group. , Alkoxycarbonyl group, amino group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino Examples thereof include a group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, an alkyl ether group, an alkenyl ether group, an alkyl thio ether group, an alkenyl thio ether group, an aryl ether group, an aryl thio ether group and the like. The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be linear, branched or cyclic.

The substituent of the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group includes an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and 1 carbon atom. Alkoxy groups having 12 or more carbon atoms, aryloxy groups having 1 to 12 carbon atoms, arylamino groups having 1 to 12 carbon atoms, and halogen atoms are preferable.

The R ^2, the viewpoint of the effect of the present invention, a phenyl group which may have a substituent, respectively, a furyl group, a thienyl group is preferable.

（式（０−１）中、Ｒ^１は水素原子又はアルキル基であり、Ｒ^３は、置換基を有してもよいアルキレン基である。＊は結合手である。） In formula (0), R ³⁰ represents a hydrogen atom or a monovalent substituent having 1 to 40 carbon atoms. When R ³⁰ is a monovalent substituent having 1 or more and 40 or less carbon atoms, the monovalent substituent of R ³⁰ is not particularly limited, but may have 1 or more and 40 carbon atoms. Examples thereof include the following alkyl groups or π-conjugated groups having 4 to 40 carbon atoms which may have a substituent. Substituents that these alkyl groups or π-conjugated groups may have include carboxy groups, alkyloxycarbonyl groups, alkyl groups, aryl groups, halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, silyl groups and silanol groups. , Nitro group, nitroso group, sulfonato group, phosphino group, phosphinyl group, phosphonato group and the like. As R ³⁰ , an alkyl group which may have a substituent is preferable, and a monovalent group represented by the following formula (0-1) is preferable.

(In formula (0-1), R ¹ is a hydrogen atom or an alkyl group, and R ³ is an alkylene group which may have a substituent. * Is a bond.)

In formula (0-1), R ¹ is a hydrogen atom or an alkyl group. When R ¹ is an alkyl group, the alkyl group may be a straight chain alkyl group or a branched chain alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.

Specific examples of the alkyl group suitable as R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. Isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group. Examples thereof include a group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecil group, and an n-icosyl group.

In formula (0-1), R ³ is an alkylene group which may have a substituent. The substituent that the alkylene group may have is not particularly limited as long as it does not impair the object of the present invention. Specific examples of the substituent that the alkylene group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, a halogen atom and the like. The alkylene group may be a linear alkylene group or a branched chain alkylene group, and a linear alkylene group is preferable. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, further preferably 1 or more and 5 or less, and particularly preferably a methylene group. The number of carbon atoms of the alkylene group does not include the carbon atom of the substituent bonded to the alkylene group.

The alkoxy group as a substituent bonded to the alkylene group may be a linear alkoxy group or a branched chain alkoxy group. The number of carbon atoms of the alkoxy group as a substituent is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

The amino group as a substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or the dialkylamino group may be a linear alkyl group or a branched chain alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or the dialkylamino group is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

Specific examples of the alkylene group suitable as R ³ include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group and n-butane. -1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptadec-1,7-diyl group, n-octane-1,8-diyl group Group, n-nonan-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- 1,13-diyl group, n-tetradecane-1,14-diyl group, n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane-1,17-diyl group , N-octadecane-1,18-diyl group, n-nonadecane-1,19-diyl group, and n-icosan-1,20-diyl group.

Wherein (0), R ⁴ is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group , N is an integer of 0 or more and 3 or less. When n is an integer of 2 or more and 3 or less, the plurality of R ^4s may be the same or different.

When R ⁴ is an organic group, the organic group is the same as the organic group that the aromatic group may have as a substituent for ^{R 2.}

When R ⁴ is an organic group, the organic group is preferably an alkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. As the alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable. As the aromatic heterocyclic group, a pyridyl group, a frill group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isooxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable. A frill group and a thienyl group are more preferable.

When R ⁴ is an alkyl group, the bonding position of the alkyl group on the imidazole ring is preferably any of the 2-position, 4-position, and 5-position, and more preferably the 2-position. When R ⁴ is an aromatic hydrocarbon group and an aromatic heterocyclic group, the bonding position of these groups on imidazole is preferably 2-position.

Among the compounds represented by the above formula (0), the compound represented by the following formula (0-1-1) is preferable from the viewpoint of excellent effect of the present invention, and the compound represented by the following formula (0-1-1) is preferable. The compound in which R ³⁰ is of the above formula (0-1) is more preferable.

（式（０−１−１）中、Ｒ^３０、Ｒ^４、及びｎは、式（０）と同様であり、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。）

(In equation (0-1-1), R ³⁰ , R ⁴ , and n are the same as in equation (0), and R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are independent of each other. , Hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group , Ammonio group, or organic group.)

In formula (0-1-1), ^{it is preferable that at least one of R 5} , R ⁶ , R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom. It is preferable in terms of solvent solubility and the like.
When R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are organic groups, the organic group is the same as the organic group that R ² has as a substituent in the formula (0). R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably hydrogen atoms in terms of the solubility of the imidazole compound in the solvent.

Among them, at least one of ^{R 5} , R ⁶ , R ⁷ , R ⁸ and R ^{9 is preferably the following substituent, and R 9} is particularly preferably the following substituent. When R ⁹ is the following substituent, R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably hydrogen atoms.
-O-R ¹⁰
(R ¹⁰ is a hydrogen atom or an organic group.)

When R ¹⁰ is an organic group, the organic group is the same as the organic group that R ² has as a substituent in the formula (0). As R ¹⁰ , an alkyl group is preferable, an alkyl group having 1 or more and 8 or less carbon atoms is more preferable, an alkyl group having 1 or more and 3 or less carbon atoms is particularly preferable, and a methyl group is most preferable.

（式（０−１−１−１）において、Ｒ^３０、Ｒ^４、及びｎは、式（０）と同様であり、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、及びＲ^１５は、それぞれ独立に、水素原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。） Among the compounds represented by the above formula (0-1-1), the compound represented by the following formula (0-1-1-1) is preferable.

(In equation (0-1-1-1), R ³⁰ , R ⁴ , and n are the same as in equation (0), and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are respectively. Independently, hydrogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonat group, amino group, Ammonio group or organic group.)

In the formula (0-1-1-1), ^{it is preferable that at least one of R 11} , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ is a group other than a hydrogen atom.
Among the compounds represented by the formula (0-1-1-1), at least one of ^{R 11} , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is represented by the ^{above-mentioned −OR 10} It is preferably a group, and it is particularly preferable that R ¹⁵ is a group represented by ^{−OR 10.} When R ¹⁵ is a group represented by −O R ^{10 , R 11} , R ¹² , R ¹³ and R ¹⁴ are preferably hydrogen atoms.

The method for synthesizing the compound represented by the above formula (0) is not particularly limited. For example, the halogen-containing carboxylic acid derivative represented by the following formula (I) and the imidazole compound represented by the following formula (II) are reacted according to a conventional method to carry out imidazolylation, thereby carrying out the above formula (0). The compound represented by is capable of synthesizing.

（式（Ｉ）及び式（ＩＩ）中、Ｒ^２、Ｒ^３０、Ｒ^４及びｎは、式（０）と同様である。式（Ｉ）において、Ｈａｌはハロゲン原子である。）

(In the formula (I) and formula ^{(II), R 2, R} 30, R 4 and n are the same as the formula (0). In formula (I), Hal is a halogen atom.)

Preferable specific examples of the compound represented by the formula (0) include the following compounds.

≪Composition for forming hydrogen barrier membrane≫
The composition for forming a hydrogen barrier film contains a base material component (A) and the above-mentioned hydrogen barrier agent (B). Hereinafter, the components that can be contained in the hydrogen barrier membrane forming composition and the composition suitable as the hydrogen barrier membrane forming composition will be described.

<Base material component (A)>
The base material component (A) has a film-forming property that allows a film having a desired shape to be produced as it is in a composition for forming a hydrogen barrier membrane by a well-known method such as a melt processing method, or exposure, heating, and reaction with water. It is a component that imparts film-forming properties so that a film having a desired shape can be produced by a treatment such as.
The base material component (A) is not particularly limited as long as it is a material capable of imparting the desired film-forming property to the hydrogen barrier membrane-forming composition.
The base material component (A) is typically a resin material composed of a polymer compound, which is cured by cross-linking to form a polymer compound by heating or chemical modification such as intramolecular cyclization by heating. A thermocurable material, a photopolymerizable compound that can be cured by exposure, a hydrolyzable silane compound that is hydrocondensed by water in the composition or atmosphere, and the like are used.
Hydrolyzable condensable silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxylan, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldimethoxy. Examples thereof include alkoxysilane compounds such as silane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. The hydrolyzable condensable silane compound may be a partially hydrolyzed condensate of these silane compounds.

[Resin material]
Among the base material components (A), examples of the resin material include polyacetal resin, polyamide resin, polycarbonate resin, polyester resin (polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyarylate, etc.), FR-AS resin, FR. -ABS resin, AS resin, ABS resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyether ether ketone resin, fluororesin, polyimide resin, polyamideimide resin, polyamidebismaleimide resin, polyether Imid resin, polybenzoxazole resin, polybenzothiazole resin, polybenzoimidazole resin, silicone resin, BT resin, polymethylpentene, ultrahigh molecular weight polyethylene, FR-polypropylene, (meth) acrylic resin (for example, polymethylmethacrylate, etc.) , And polystyrene and the like.

When the resin material is used as the base material component (A), a method desired from a conventionally known film forming method is adopted in which a resin material in which a predetermined amount of the above-mentioned hydrogen barrier agent (B) is blended with the resin material is adopted. A hydrogen barrier membrane is produced by forming a film.
Examples of the film forming method include a melt processing method such as a T-die method (casting method), an inflation method, and a pressing method, and a casting method using a solution.
In the casting method, a solution containing a resin material and a hydrogen barrier agent (B) is applied or spilled onto a substrate to form a film composed of the solution, and then the solvent is removed from the film by a method such as heating to form a hydrogen barrier. A film is formed.
The hydrogen barrier membrane obtained by using the resin material may be subjected to stretching treatment such as uniaxial stretching or biaxial stretching, if necessary.

When the above resin material is used as the base material component (A), the composition for forming a hydrogen barrier membrane can be used as an antioxidant, an ultraviolet absorber, a flame retardant, a mold release agent, a plasticizer, a filler, if necessary. And additives such as a reinforcing material and a reinforcing material may be contained.
When the hydrogen barrier membrane forming composition is a casting composition, the hydrogen barrier membrane forming composition may contain a solvent. The type of solvent is appropriately selected according to the type of resin material.

When the hydrogen barrier membrane forming composition contains the above resin material and the hydrogen barrier agent (B), the content of the hydrogen barrier agent is based on the mass of the resin material of the hydrogen barrier membrane forming composition. It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, and particularly preferably 0.1% by mass or more and 10% by mass or less.

[Thermosetting material]
Examples of the thermosetting material include precursor materials of various thermosetting resins that have been widely used in the past. Specific examples of the thermosetting resin include phenol resin, epoxy resin, oxetane resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyimide resin, polybenzoxasol resin, polybenzimidazole resin and the like. Can be mentioned.

Further, a resin that causes an intramolecular aromatic ring formation reaction and / or a cross-linking reaction between molecules by heating is also preferably used as a thermosetting material. Hereinafter, a resin that causes an intramolecular aromatic ring formation reaction and / or a cross-linking reaction between molecules by heating is also referred to as a precursor resin.

Among these, an epoxy resin precursor and a precursor resin are particularly preferable because a hydrogen barrier membrane having excellent heat resistance, chemical resistance, mechanical properties and the like is particularly easy to form.
Hereinafter, the thermosetting material will be described as a precursor material particularly suitable as the base material component (A).

(Epoxy resin precursor)
As the epoxy resin precursor, various conventionally known epoxy compounds can be used. The molecular weight of such an epoxy compound is not particularly limited. Among the epoxy compounds, a polyfunctional epoxy compound having two or more epoxy groups in the molecule is preferable because it is easy to form a hydrogen barrier film having excellent heat resistance, chemical resistance, mechanical properties and the like.

The polyfunctional epoxy compound is not particularly limited as long as it is a bifunctional or higher functional epoxy compound. Examples of polyfunctional epoxy compounds include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; Glycidyl ester type epoxies such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxies such as tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylene diamine, and tetraglycidyl bisaminomethylcyclohexane. Resin: Heterocyclic epoxy resin such as triglycidyl isocyanurate; fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3) -Epoxy propoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxy propoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [1-[ 4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol Trifunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetrafunctional epoxy resins such as tetraglycidoxybiphenyl.

An alicyclic epoxy compound is also preferable as a polyfunctional epoxy compound in that it gives a cured product having high hardness. Specific examples of the alicyclic epoxy compound include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane and bis (3,4-epoxycyclohexylmethyl) adipate. , Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3, 4-Epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxy) Cyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, and di-2-ethylhexyl epoxycyclohexahydrophthalate, epoxy resins having a tricyclodeceneoxide group, and the following formulas (a01-1) to (a01-5). Examples thereof include compounds represented by.

（式（ａ０１−１）中、Ｚ^０１は単結合又は連結基（１以上の原子を有する二価の基）を示す。Ｒ^ａ０１〜Ｒ^ａ０１８は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。） Among the specific examples of these alicyclic epoxy compounds, the alicyclic epoxy compounds represented by the following formulas (a01-1) to (a01-5) are preferable because they give a cured product having a high hardness.

(In the formula (a01-1), Z ⁰¹ represents a single bond or a linking group (a divalent group having one or more atoms). R ^{a01 to} R ^a018 are independent hydrogen atoms, halogen atoms, and halogen atoms, respectively. It is a group selected from the group consisting of organic groups.)

Examples of the linking group Z ⁰¹ include divalent hydrocarbon groups, -O-, -O-CO-, -S-, -SO-, _{-SO 2- , -CBr 2-} , and -C (CBr ₃ ). _{2 -, - C (CF 3} ) 2 -, and ^{-R a019} -O-CO- 2 divalent group and which are selected from the group consisting of these can be exemplified a plurality bonded group.

Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 or more and 18 or less carbon atoms, a divalent alicyclic hydrocarbon group and the like. can. Examples of the linear or branched alkylene group having 1 or more and 18 or less carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group and 1,3-. Cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group and the like can be mentioned.

R ^a019 is an alkylene group having 1 or more carbon atoms and 8 or less carbon atoms, and is preferably a methylene group or an ethylene group.

(In the formula (a01-2), R ^{a01 to} R ^a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

（式（ａ０１−３）中、Ｒ^ａ０１〜Ｒ^ａ０１０は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ａ０２及びＲ^ａ０８は、互いに結合してもよい。）

(In the formula (a01-3), R ^{a01 to} R ^a010 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^a02 and R ^a08 may be bonded to each other. )

（式（ａ０１−４）中、Ｒ^ａ０１〜Ｒ^ａ０１２は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ａ０２及びＲ^ａ０１０は、互いに結合してもよい。）

(In the formula (a01-4), R ^{a01 to} R ^a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^a02 and R ^a010 may be bonded to each other. )

（式（ａ０１−５）中、Ｒ^ａ０１〜Ｒ^ａ０１２は、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。）

(In the formula (a01-5), R ^{a01 to} R ^a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

In the formulas (a01-1) to (a01-5), when R ^{a01 to} R ^a018 are organic groups, the organic group is not particularly limited as long as it does not impair the object of the present invention, and even if it is a hydrocarbon group. , A group consisting of a carbon atom and a halogen atom, or a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom together with a carbon atom and a hydrogen atom. .. Examples of halogen atoms include chlorine atom, bromine atom, iodine atom, fluorine atom and the like.

The organic group includes a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom, and a halogen atom, and a carbon atom and a hydrogen atom. , An oxygen atom, and a group consisting of a halogen atom are preferable. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. , N-Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group , N-Heptadecyl group, n-octadecyl group, n-nonadecil group, n-icosyl group and other chain alkyl groups; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n Chain alkenyl groups such as -butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; phenyl group , O-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group, And aryl groups such as phenanthryl groups; aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group and β-naphthylethyl group can be mentioned.

Specific examples of halogenated hydrocarbon groups include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2. , 2-Trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogen chain alkyl group such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , And cycloalkyl halides such as 4-bromocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group. , 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl Aryl halide groups such as groups and 4-fluorophenyl groups; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenyl It is a halogenated aralkyl group such as a methyl group, a 2-fluorophenylmethyl group, a 3-fluorophenylmethyl group, and a 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom are hydroxy chains such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Alkyl group; Cycloalkyl halide group such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3 Hydroxyaryl groups such as −dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group. Hydroxyaralkyl groups such as 2-hydroxyphenylmethyl group, 3-hydroxyphenylmethyl group, and 4-hydroxyphenylmethyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy Group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy Group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, Chain alkoxy groups such as n-nonadesyloxy group and n-icosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy Group and chain alkenyloxy group such as 3-n-butenyloxy group; phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4 Aryloxy groups such as −yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, and phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, Aralkyloxy groups such as β-naphthylmethyloxy group, α-naphthylethyloxy group, and β-naphthylethyloxy group; methoxymethyl group, ethoxymethyl group, n-propoxymethi Lu group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl Ekalkalkyl groups such as groups, 4-methoxy-n-butyl groups, 4-ethoxy-n-butyl groups, and 4-n-propoxy-n-butyl groups; methoxymethoxy groups, ethoxymethoxy groups, n-propoxymethoxy groups. , 2-Methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, Alkoxyalkoxy groups such as 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group; 2-methoxyphenyl group, 3-methoxyphenyl group, and 4- An alkoxyaryl group such as a methoxyphenyl group; an alkoxyaryloxy group such as a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group; a formyl group, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, and a hexanoyl group. An aliphatic acyl group such as a group, a heptanoyle group, an octanoyl group, a nonanoyl group, and a decanoyyl group; an aromatic acyl group such as a benzoyl group, an α-naphthoyl group, and a β-naphthoyl group; a methoxycarbonyl group, an ethoxycarbonyl group, n -Propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyl Chain alkyloxycarbonyl groups such as oxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups, α-naphthoxycarbonyl groups, and β-naphthoxycarbonyl groups; formyloxy groups, acetyloxy groups, propionyloxy groups, pigs An aliphatic acyloxy group such as a noyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoiloxy group, an octanoyloxy group, a nonanoyloxy group, and a decanoyloxy group; a benzoyloxy group, an α-naphthoyloxy group, And aromatic acyloxy groups such as β-naphthoyloxy group.

R ^{a01 to} R ^a018 are preferably groups independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, and an alkoxy group having 1 or more and 5 or less carbon atoms. In particular, it is more preferable that all of ^{R a01 to} R ^a018 are hydrogen atoms because it is easy to form a cured film having excellent mechanical properties.

Wherein ^{(a01-2) ~ (a01-5),} R a01 ~R a012 is the same as ^R a01 ^{to R A012} in formula (a01-1). In the formulas (a01-2) and (a01-4), ^{examples of the divalent groups formed when R a02} and R a010 are bonded to each other include -CH _2- and -C (CH ₃ ). ₂ − can be mentioned. In the formula (a01-3), ^{examples of the divalent group formed when R a02} and R a08 are bonded to each other include -CH _2- and -C (CH ₃ ) _2- .

Among the alicyclic epoxy compounds represented by the formula (a01-1), specific examples of suitable compounds are the following formulas (a01-1a), (a01-1b), and (a01-1c). Examples include the alicyclic epoxy compound represented, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane [= 2,2-bis (3,4-epoxycyclohexyl) propane], and the like. can.

Among the alicyclic epoxy compounds represented by the formula (a01-2), specific examples of suitable compounds include bicyclononadeene epoxides represented by the following formula (a01-2a) or dicyclononadeene epoxides. And so on.

Among the alicyclic epoxy compounds represented by the formula (a01-3), specific examples of suitable compounds include S spiro [3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6. , 2'-Oxylan] and the like.

Among the alicyclic epoxy compounds represented by the formula (a01-4), specific examples of suitable compounds include 4-vinylcyclohexenedioxide, dipentenedioxide, limonene dioxide, and 1-methyl-4- (3-). Methyloxylan-2-yl) -7-oxabicyclo [4.1.0] heptane and the like can be mentioned.

Among the alicyclic epoxy compounds represented by the formula (a01-5), specific examples of suitable compounds include 1,2,5,6-diepoxycyclooctane and the like.

[Precursor resin]
As the base material component (A), a precursor resin which is a resin that causes an intramolecular aromatic ring formation reaction and / or a cross-linking reaction between molecules by heating is preferable.

According to the intramolecular aromatic ring formation reaction, the structure of the molecular chain constituting the resin is rigidized, and a hydrogen barrier membrane having excellent heat resistance and mechanical properties can be formed. Among the intramolecular aromatic ring forming reactions, preferred reactions include, for example, the reactions represented by the following formulas (I) to (VI). The reaction in the following formula is only an example of an aromatic ring forming reaction, and the structure of the resin used as the base material component (A) that causes an intramolecular aromatic ring forming reaction by heating is described in the following formula. It is not limited to the structure of the precursor polymer shown in.

(A resin having a group selected from a hydroxyl group, a carboxylic acid anhydride group, a carboxyl group, and an epoxy group in the molecule)
According to the cross-linking reaction between molecules, the molecular chains constituting the resin are cross-linked with each other to form a three-dimensional cross-linked structure. Therefore, when a resin having a group selected from a hydroxyl group, a carboxylic acid anhydride group, a carboxyl group, and an epoxy group in the molecule, which causes a cross-linking reaction by heating, is used as the base material component (A), it has heat resistance. And a hydrogen barrier film having excellent mechanical properties can be obtained.

When a resin having a hydroxyl group is used, the action of the dehydration condensing agent causes cross-linking between the molecules contained in the resin by dehydration condensation between the hydroxyl groups. Further, since the hydroxyl group contains an active hydrogen atom and is highly reactive, it reacts with various cross-linking agents to give a cured product containing the cross-linked resin.

When a resin having a carboxylic acid anhydride group is used, the carboxy groups generated by hydrolysis of the acid anhydride group are dehydrated and condensed by the action of a dehydration condensing agent to crosslink. Further, since the acid anhydride group itself is also highly reactive, for example, by using a cross-linking agent such as a polyol having two or more hydroxyl groups and a polyamine having two or more amino groups, a cured product containing the cross-linked resin can be obtained. give.

When a resin having a carboxy group is used, the action of the dehydration condensing agent causes cross-linking between the molecules contained in the resin by dehydration condensation between the carboxy groups. It is also possible to carry out cross-linking using a cross-linking agent having a functional group capable of reacting with a carboxy group such as an isocyanate group.

When a resin having an epoxy group is used, if necessary, a well-known curing accelerator or the like is used to cause cross-linking between the molecules contained in the resin by a polyaddition reaction between the epoxy groups.

Examples of the resin having a hydroxyl group in the molecule include novolak resin. The novolak resin is not particularly limited, but is obtained by subjecting 1 mol of phenols to a condensation reaction of a condensing agent such as formaldehyde or paraformaldehyde at a ratio of 0.5 mol or more and 1.0 mol or less under an acidic catalyst. The resulting resin is preferred.

Examples of phenols include cresols such as phenol, o-cresol, m-cresol, p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3 , 4-Xylenol, Xylenols such as 3,5-Xylenol; Ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, Alkylphenols such as o-butylphenol, m-butylphenol, p-butylphenol, p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol, 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone , Hydroquinone monomethyl ether, pyrogallol, fluoroglycinol and other polyhydric phenols; alkylresolvin, alkylcatechol, alkylquil hydroquinone and other polyhydric phenols (alkyl polyhydric phenols contain 1 carbon atom of alkyl group) (4 or less), α-naphthol, β-naphthol, hydroxydiphenyl, bisphenol A and the like. These phenols can be used alone or in combination of two or more.

Among the phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. By adjusting the blending ratio of both, various properties such as sensitivity and heat resistance as a photoresist can be adjusted. The blending ratio of m-cresol and p-cresol is not particularly limited, but m-cresol / p-cresol = 3/7 or more and 8/2 or less (mass ratio) is preferable. If the ratio of m-cresol is less than the above lower limit value, the sensitivity may decrease, and if it exceeds the above upper limit value, the heat resistance may decrease.

Examples of the acidic catalyst used in the production of novolak resin include inorganic acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid and phosphite, and organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate and paratoluenesulfonic acid. , Metal salts such as zinc acetate and the like. These acidic catalysts can be used alone or in combination of two or more.

The mass average molecular weight of the novolak resin in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1000 or more and 50,000 or less.

The resin having a carboxylic acid anhydride group in the molecule has an unsaturated double bond containing one or more monomers selected from maleic anhydride, citraconic anhydride, and itaconic anhydride. A copolymer obtained by polymerizing a mixture of monomers is preferable. As such a polymer, a styrene-maleic acid copolymer is preferable.

Examples of the resin having a carboxy group in the molecule include a resin obtained by hydrolyzing an acid anhydride group in the resin having a carboxylic acid anhydride group in the molecule, (meth) acrylic acid, crotonic acid, and malein. A copolymer obtained by polymerizing a mixture of monomers having an unsaturated double bond, which comprises one or more monomers selected from acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. preferable.

The epoxy group-containing resin having an epoxy group in the molecule will be described in detail later.

Among compounds that cause intramolecular aromatic ring formation reaction and intermolecular cross-linking reaction by such heating, it is easy to form a hydrogen barrier film having excellent heat resistance. Therefore, polyamic acid and polybenzoxazole precursors Molecules, polybenzothiazole precursors, polybenzimidazole precursors, styrene-maleic acid copolymers, and epoxy group-containing resins are preferred. Hereinafter, these resins will be described.

[Polyimide resin precursor]
Examples of the polyimide resin precursor include polyamic acid, which is formed in the presence of an imidizing agent, if necessary, after forming a hydrogen barrier membrane forming composition containing polyamic acid as the base material component (A). When the film is heated, a hydrogen barrier membrane containing a polyimide resin and having excellent heat resistance is formed.

The molecular weight of the polyamic acid is preferably 5,000 or more and 30,000 or less, and more preferably 10,000 or more and 20,000 or less, as a mass average molecular weight. When a polyamic acid having a mass average molecular weight within such a range is used, it is easy to form a hydrogen barrier membrane having excellent heat resistance.
Suitable polyamic acids include, for example, polyamic acids composed of structural units represented by the following formula (A1).

（式（Ａ１）中、Ｒ^ａ０２０は４価の有機基であり、Ｒ^ａ０２１は２価の有機基であり、ｎ^ａは式（Ａ１）で表される構成単位の繰り返し数である。）

(In the formula ^{(A1), R} a020 is a tetravalent organic ^{group, R A021} represents a divalent organic group, ^{n a} is the number of repetitions of structural units represented by the formula (A1).)

In the formula (A1), the ^{number of carbon atoms of R a020} and R ^a021 is preferably 2 or more and 50 or less, and more preferably 2 or more and 30 or less. R ^a020 and R ^a021 may be an aliphatic group, an aromatic group, or a group combining these structures, respectively. The tetravalent aromatic group is the same as that of ^{Ra022 described later.} R ^a020 and R ^a021 may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to the carbon atom and the hydrogen atom. When R ^a020 and R a021 contain an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, the nitrogen atom, or the sulfur atom is a nitrogen-containing heterocyclic group, ^{-CONH-, -NH-, -N = N-,} -CH = N -, - COO - , - O -, - CO -, - SO -, - SO 2 -, - S-, and a group selected from ^-S-S-, the ^{R A020} and ^{R A021} It may be included, and is included in ^{R a020} and R ^a021 _{as a group selected from -O-, -CO-, -SO-, -SO 2-} , -S-, and -S-S-. More preferred.

The polyamic acid is usually prepared by reacting a tetracarboxylic dianhydride component with a diamine component. Hereinafter, a method for producing a tetracarboxylic dianhydride component, a diamine component, and a polyamic acid used for preparing a polyamic acid will be described.

（式（ａ１−１）中、Ｒ^ａ０２０は式（Ａ１）のＲ^ａ０２０と同様である。） (Tetracarboxylic dianhydride component)
The tetracarboxylic dianhydride component, which is a raw material for synthesizing the polyamic acid, is not particularly limited as long as it can form a polyamic acid by reacting with the diamine component. The tetracarboxylic dianhydride component can be appropriately selected from the tetracarboxylic dianhydride components that have been conventionally used as a raw material for synthesizing polyamic acids. The tetracarboxylic acid dianhydride component may be aromatic tetracarboxylic acid dianhydride or aliphatic tetracarboxylic acid dianhydride, and for example, tetra represented by the following formula (a1-1). Carous acid dianhydride is mentioned, and aromatic tetracarboxylic acid dianhydride is preferable. Two or more kinds of tetracarboxylic dianhydride components may be used in combination.

(In the formula ^{(a1-1), R a020} is the same as ^{R A020} of formula (A1).)

Suitable specific examples of aromatic tetracarboxylic acid dianhydrides include pyromellitic acid dianhydrides, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydrides, 2,3,3', 4'. -Biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid anhydride, and 3,3', 4,4'-diphenylsulfone Examples thereof include tetracarboxylic acid dianhydride. Among these, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the viewpoint of price, availability and the like. In addition, those listed in the photosensitive composition of the fifth aspect may be selected.

（式（ａ１−２）中、Ｒ^ａ０２１は式（Ａ１）のＲ^ａ０２１と同様である。） (Diamine component)
The diamine component, which is a raw material for synthesizing the polyamic acid, is not particularly limited as long as the polyamic acid can be formed by reacting with the tetracarboxylic dianhydride component. The diamine component can be appropriately selected from diamines conventionally used as a synthetic raw material for polyamic acids. For example, a diamine component represented by the following formula (a1-2) or a diamine ^{giving Y d} described later may be used. Can be mentioned. The diamine component may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferable. Two or more kinds of diamine components may be used in combination.

(In the formula ^{(a1-2), R a021} is the same as ^{R A021} of formula (A1).)

Suitable specific examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis ( Trifluoromethyl) biphenyl, 3,3'-diaminodiphenyl sulphon, 4,4'-diaminodiphenyl sulphon, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino) Phenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulphon, bis [4- (3-aminophenoxy) phenyl] sulphon, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -9H-fluorene, Examples thereof include 9,9-bis (4-amino-3-methylphenyl) -9H-fluorene and 4,4'-[1,4-phenylenebis (1-methylethane-1,1-diyl)] dianiline. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the viewpoint of price, availability, and the like. In addition, those listed in the photosensitive composition of the fifth aspect may be selected.

(Manufacturing method of polyamic acid)
A polyamic acid can be obtained by reacting the tetracarboxylic dianhydride component and the diamine component described above in a solvent capable of dissolving both of them. The amount of the tetracarboxylic dianhydride component and the diamine component used in synthesizing the polyamic acid is not particularly limited. It is preferable to use 0.50 mol or more and 1.50 mol or less of the diamine component, more preferably 0.60 mol or more and 1.30 mol or less, and 0.70 mol or less, with respect to 1 mol of the tetracarboxylic acid dianhydride component. It is particularly preferable to use more than 1 mol and 1.20 mol or less.

Solvents that can be used for the synthesis of polyamic acids include, for example, N, N, N', N'-tetramethylurea, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide. , Hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, and aproton polar organic solvents such as γ-butyrolactone, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, Examples thereof include glycol ethers such as propylene glycol monoalkyl ether acetate and propylene glycol monoalkyl ether propionate. Two or more of these solvents can be used in combination. Among these, it is preferable to use N, N, N', N'-tetramethylurea.

The amount of the solvent used in synthesizing the polyamic acid is not particularly limited as long as the polyamic acid having a desired molecular weight can be synthesized. Typically, the amount of the solvent used is preferably 100 parts by mass or more and 4000 parts by mass or less, and 150 parts by mass or more, based on 100 parts by mass in total of the amount of the tetracarboxylic acid dianhydride component and the amount of the diamine component. More preferably, it is 2000 parts by mass or less.

The temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature of the tetracarboxylic dianhydride component and the diamine component is preferably −5 ° C. or higher and 150 ° C. or lower, more preferably 0 ° C. or higher and 120 ° C. or lower, and particularly preferably 0 ° C. or higher and 70 ° C. or lower. preferable. The time for reacting the tetracarboxylic acid dianhydride component with the diamine component varies depending on the reaction temperature, but is typically preferably 1 hour or more and 50 hours or less, and more preferably 2 hours or more and 40 hours or less. It is particularly preferable that the time is 5 hours or more and 30 hours or less.

According to the above method, a solution or paste of polyamic acid can be obtained. Such a solution or paste may be used as it is for preparing a composition for forming a hydrogen barrier membrane. Further, the solid polyamic acid obtained by removing the solvent from the solution or paste of the polyamic acid may be used for preparing the composition for forming a hydrogen barrier membrane.

[Polybenzoxazole precursor]
Polybenzoxazole precursors are typically produced by reacting an aromatic diaminediol with a dicarbonyl compound of a particular structure. Hereinafter, the aromatic diamine diol, the dicarbonyl compound, the solvent used for the synthesis of the polybenzoxazole precursor, and the method for producing the polybenzoxazole precursor will be described.

（式（ａ０２）中、Ｒ^ａ０２２は１以上の芳香環を含む４価の有機基であり、式（ａ０２）で表される芳香族ジアミンジオールに含まれる２組のアミノ基と水酸基との組み合わせに関して、それぞれの組み合わせでは、アミノ基と水酸基とは、Ｒ^ａ０２２に含まれる芳香環上の隣接する２つの炭素原子に結合している。） (Aromatic diamine diol)
As the aromatic diamine diol, those conventionally used for the synthesis of polybenzoxazole can be used without particular limitation. As the aromatic diamine diol, it is preferable to use a compound represented by the following formula (a02). The aromatic diamine diol may be used alone or in combination of two or more.

(In the formula (a02), R ^a022 is a tetravalent organic group containing one or more aromatic rings, and is a combination of two sets of amino groups and a hydroxyl group contained in the aromatic diamine diol represented by the formula (a02). In each combination, the amino group and the hydroxyl group are bonded to two adjacent carbon atoms on the aromatic ring contained in ^Ra022.)

In the formula (a02), R ^a022 is a tetravalent organic group containing one or more aromatic rings, and the number of carbon atoms thereof is preferably 6 or more and 50 or less, and more preferably 6 or more and 30 or less. R ^a022 may be an aromatic group, and two or more aromatic groups contain an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, or a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom. It may be a group attached via a binding that contains. ^Bonds containing heteroatoms such as oxygen atom, sulfur atom, and nitrogen atom contained in R a022 include -CONH-, -NH-, -N = N-, -CH = N-, -COO-,-. O -, - CO -, - SO -, - SO 2 -, - S-, and -S-S-, and the like, -O -, - CO -, - SO -, - SO 2 -, - S -And -SS- are preferable.

The ^{aromatic ring contained in Ra022} may be an aromatic heterocycle. The aromatic ring bonded to the amino group and the hydroxyl group in ^{Ra022 is preferably a benzene ring.} When ^{the ring bonded to the amino group and the hydroxyl group in R a022} is a fused ring containing two or more rings, the ring bonded to the amino group and the hydroxyl group in the condensed ring is preferably a benzene ring.

（式（ａ０２−１）中、Ｘ^０１は、炭素原子数１以上１０以下のアルキレン基、炭素原子数１以上１０以下のフッ素化アルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、及び単結合からなる群より選択される１種である。式（ａ０２−２）〜（ａ０２−５）中、Ｙ^０１は、それぞれ、同一でも異なっていてもよく、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、及び単結合からなる群より選択される１種である。） Preferable examples of R ^a022 include groups represented by the following formulas (a02-1) to (a02-9).

(In the formula (a02-1), X ⁰¹ is an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, −O−, −S−, −SO−, −. _{SO 2 -, - CO -,} - COO -, -. CONH-, and in which one selected from the group consisting of single bond formula ^{(a02-2) ~ (a02-5),} Y 01 , respectively , The same or different, is one selected from the group consisting of _{-CH 2-} , -O-, -S-, -SO-, -SO _{2-, -CO-, and a single bond.} )

The groups represented by the above formulas (a02-1) to (a02-9) may have one or more substituents on the aromatic ring. Preferable examples of the substituent are a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a carbon atom number. A fluorinated alkoxy group of 1 or more and 6 or less is preferable. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

Specific examples of the compound represented by the above formula (a02) include 2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, and 2,5-diamino-3-3. Fluoro-1,4-benzenediol, 2,5-diamino-3,6-difluoro-1,4-benzenediol, 2,6-diamino-1,5-dihydroxynaphthalene, 1,5-diamino-2,6 -Dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5-dihydroxynaphthalene, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'- Diamino-4,4'-dihydroxybiphenyl, 2,3'-diamino-3,2'-dihydroxybiphenyl, 3,4'-diamino-4,3'-dihydroxybiphenyl, 4,4'-diamino-3,3 '-Dihydroxy-6,6'-ditrifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, 2,3'-diamino-3,2'- Dihydroxy-6,6'-ditrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy- 5,5'-Ditrifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 2,3'-diamino-3,2'-dihydroxy-5,5 5'-Ditrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, bis (4-amino-3-hydroxyphenyl) methane, bis (3-amino) -4-Hydroxyphenyl) methane, 3,4'-diamino-4,3'-dihydroxydiphenylmethane, bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) methane, bis (3-amino-4- Hydroxy-6-trifluoromethylphenyl) methane, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenylmethane, bis (4-amino-3-hydroxyphenyl) difluoromethane, bis (3-Amino-4-hydroxyphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxydiphenyldifluoromethane, bis (4-amino-3-hydroxy-6-triflu) Oromethylphenyl) difluoromethane, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl Difluoromethane, bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) ether, 3,4'-diamino-4,3'-dihydroxydiphenyl ether, bis (4-amino-) 3-Hydroxy-6-trifluoromethylphenyl) ether, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) ether, 3,4'-diamino-4,3'-dihydroxy-6,6' -Ditrifluoromethyldiphenyl ether, bis (4-amino-3-hydroxyphenyl) ketone, bis (3-amino-4-hydroxyphenyl) ketone, 3,4'-diamino-4,3'-dihydroxydiphenylketone, bis ( 4-Amino-3-hydroxy-6-trifluoromethylphenyl) ketone, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) ketone, 3,4'-diamino-4,3'-dihydroxy- 6,6'-Ditrifluoromethyldiphenylketone, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2- (3- (3-) Amino-4-hydroxyphenyl) -2- (4'-amino-3'-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) propane, 2,2 -Bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) propane, 2- (3-amino-4-hydroxy-6-trifluoromethylphenyl) -2- (4'-amino-3'- Hydroxy-6'-trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) Hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (3-amino-4-hydroxyphenyl) -2- (4'-amino-3'-hydroxyphenyl) Hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexa Fluoropropane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-6-trifluoromethylphenyl) -2- ( 4'-Amino-3'-Hydroxy-6'-Trifluoromethylphenyl) Hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) Hexafluoropropane, Bis (4) -Amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 3,4'-diamino-4,3'-dihydroxydiphenyl sulfone, bis (4-amino-3-hydroxy-6) -Trifluoromethylphenyl) sulfone, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) sulfone, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl Sulfone, bis (4-amino-3-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfide, 3,4'-diamino-4,3'-dihydroxydiphenyl sulfide, bis (4-amino- 3-Hydroxy-6-trifluoromethylphenyl) sulfide, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) sulfide, 3,4'-diamino-4,3'-dihydroxy-6,6' -Ditrifluoromethyldiphenylsulfide, (4-amino-3-hydroxyphenyl) 4-amino-3-hydroxyphenylbenzoate, (3-amino-4-hydroxyphenyl) 3-amino4-hydroxyphenylbenzoate, (3-amino -4-Hydroxyphenyl) 4-amino-3-hydroxyphenylbenzoate, (4-amino-3-hydroxyphenyl) 3-amino-4-hydroxyphenylbenzoate, N- (4-amino-3-hydroxyphenyl) 4- Amino-3-hydroxybenzamide, N- (3-amino-4-hydroxyphenyl) 3-amino4-hydroxyphenylbenzamide, N- (3-amino-4-hydroxyphenyl) 4-amino-3-hydroxyphenylbenzamide, N- (4-amino-3-hydroxyphenyl) 3-amino-4-hydroxyphenylbenzamide, 2,4'-bis (4-amino-3-hydroxyphenoxy) biphenyl, 2,4'-bis (3-amino) − 4-Hydroxyphenoxy) biphenyl, 4,4'-bis (4-amino-3-hydroxyphenoxy) biphenyl, 4,4'-bis (3-amino-4-hydroxyphenoxy) biphenyl, di [4- (4- (4- (4- (4- (4-)4-hydroxyphenoxy) biphenyl) Amino-3-hydroxyphenoxy) phenyl] ether, di [4- (3-amino-4-hydroxyphenoxy) phenyl] ether, 2,4'-bis (4-amino-3-hydroxyphenoxy) benzophenone, 2,4 '-Bis (3-amino-4-hydroxyphenoxy) benzophenone, 4,4'-bis (4-amino-3-hydroxyphenoxy) benzophenone, 4,4'-bis (3-amino-4-hydroxyphenoxy) benzophenone , 2,4'-bis (4-amino-3-hydroxyphenoxy) octafluorobiphenyl, 2,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 4,4'-bis (4-4'-bis) Amino-3-hydroxyphenoxy) octafluorobiphenyl, 4,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 2,4'-bis (4-amino-3-hydroxyphenoxy) octafluorobenzophenone , 2,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobenzophenone, 4,4'-bis (4-amino-3-hydroxyphenoxy) octafluorobenzophenone, 4,4'-bis (3-amino-4-hydroxyphenoxy) Amino-4-hydroxyphenoxy) octafluorobenzophenone, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) ) Phenyl] propane, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexa Fluoropropane, 2,8-diamino-3,7-dihydroxydibenzofuran, 2,8-diamino-3,7-dihydroxyfluorene, 2,6-diamino-3,7-dihydroxyxanthene, 9,9-bis- (4) Examples thereof include −amino-3-hydroxyphenyl) fluorene and 9,9-bis- (3-amino-4-hydroxyphenyl) fluorene.

Of these, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferred.

(Dicarbonyl compound)
As a raw material for synthesizing the polybenzoxazole precursor, a dicarbonyl compound represented by the following formula (a03) is used together with the aromatic diamine diol described above. A polybenzoxazole precursor can be obtained by condensing the above-mentioned aromatic diaminediol with the dicarbonyl compound represented by the following formula (a03).

（式（ａ０３）中、Ｒ^ａ０２３は２価の有機基であり、Ａ^０は水素原子又はハロゲン原子を表す。）

(In the formula ^{(a03), R A023} represents a divalent organic group, ^{A 0} represents a hydrogen atom or a halogen atom.)

^{R a023} in the formula (a03) may be an aromatic group, an aliphatic group, or a group in which an aromatic group and an aliphatic group are combined. ^Ra023 is preferably a group containing an aromatic group and / or an alicyclic group from the viewpoint of good heat resistance, mechanical properties, chemical resistance and the like of the obtained polybenzoxazole resin. The ^{aromatic group contained in Ra023} may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

Ra ⁰²³ may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to the carbon atom and the hydrogen atom. When R a023 contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, the nitrogen atom, or the sulfur atom is a nitrogen-containing heterocyclic group, ^{-CONH-, -NH-, -N = N-, -CH =.} It may be included in ^Ra023 as a group selected from N-, -COO-, -O-, -CO-, -SO-, -SO _2- , -S-, and -S-S-. -O -, - CO -, - SO -, - SO 2 -, - S-, and a group selected from ^-S-S-, and more preferably contained in ^{R A023.}

Wherein (a03), one of the two A ⁰ is a hydrogen atom, the other is may be a halogen atom, or two A ⁰ are both hydrogen atoms, two A ⁰ are both a halogen atom It is preferable to have it. When A ⁰ is a halogen atom, chlorine, bromine, and iodine are preferable as ^{A 0, and chlorine is more preferable.}

（式（Ａ２）中、Ｒ^ａ０２２及びＲ^ａ０２３は、式（ａ０２）及び式（ａ０３）と同様であり、ｎ^１は式（Ａ２）で表される単位の繰り返し数である。） As dicarbonyl compound represented by the formula (a03), if two A ⁰ is used both dialdehyde compound is a hydrogen atom, polybenzoxazole precursor represented by the following formula (A2) is produced.

(In the formula (A2), R ^a022 and R ^a023 are the same as those in the formula (a02) and the formula (a03), and n ¹ is the number of repetitions of the unit represented by the formula (A2).)

（式（Ａ３）中、Ｒ^ａ０２２及びＲ^ａ０２３は、式（ａ０２）及び式（ａ０３）と同様であり、ｎ^２は式（Ａ３）で表される単位の繰り返し数である。） As dicarbonyl compound represented by the formula (a03), if two A ⁰ is used both dihalide dicarboxylic acid is a halogen atom, polybenzoxazole precursor represented by the following formula (A3) is produced.

(In the formula (A3), R ^a022 and R ^a023 are the same as those in the formula (a02) and the formula (a03), and n ² is the number of repetitions of the unit represented by the formula (A3).)

Hereinafter, the dialdehyde compound and the dicarboxylic acid dihalide, which are suitable compounds as the dicarbonyl compound, will be described.

（式（ａ２−Ｉ）中、Ｒ^ａ０２３は、式（ａ０３）と同様である。） (Dialdehyde compound)
The dialdehyde compound used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (a02-I). One type of dialdehyde compound may be used alone, or two or more types may be used in combination.

(In the formula (a2-I), R ^a023 is the same as the formula (a03).)

（上記式中、Ｘ^０２は、炭素原子数１以上１０以下のアルキレン基、炭素原子数１以上１０以下のフッ素化アルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、及び単結合からなる群より選択される１種である。Ｘ^０２が複数である場合、複数のＸ^０２は同一でも異なっていてもよい。Ｙ^０２は、それぞれ、同一でも異なっていてもよく、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、及び単結合からなる群より選択される１種である。ｐ^０及びｑ^０は、それぞれ０以上３以下の整数である。） ^Examples of the aromatic group or aromatic ring-containing group suitable as Ra203 in the formula (a2-I) include the following groups.

(In the above formula, X ⁰² is an alkylene group having 1 or more and 10 or less carbon atoms, a fluorinated alkylene group having 1 or more and 10 or less carbon atoms, -O-, -S-, -SO-, -SO _2- , -CO -, - COO -, - CONH-, and if one is a ^{.X 02} selected from the group consisting of a single bond is more, a plurality of ^{X 02} good be the same or different ^{.Y 02} Are the same or different, respectively, and are _{selected from the group consisting of -CH 2-} , -O-, -S-, -SO-, -SO _2- , -CO-, and a single bond. P ⁰ and q ⁰ are integers of 0 or more and 3 or less, respectively.)

（上記式中、Ｘ^０２は、炭素原子数１以上１０以下のアルキレン基、炭素原子数１以上１０以下のフッ素化アルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、及び単結合からなる群より選択される１種である。Ｘ^０２が複数である場合、複数のＸ^０２は同一でも異なっていてもよい。Ｙ^０２は、それぞれ、同一でも異なっていてもよく、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、及び単結合からなる群より選択される１種である。Ｚ^０は、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−、及び−ＣＨ＝ＣＨ−からなる群より選択される１種である。ｐ^０は、それぞれ０以上３以下の整数である。） ^Examples of the alicyclic group or the alicyclic-containing group suitable as R a023 in the formula (a2-I) include the following groups.

(In the above formula, X ⁰² is an alkylene group having 1 or more and 10 or less carbon atoms, a fluorinated alkylene group having 1 or more and 10 or less carbon atoms, -O-, -S-, -SO-, -SO _2- , -CO -, - COO -, - CONH-, and if one is a ^{.X 02} selected from the group consisting of a single bond is more, a plurality of ^{X 02} good be the same or different ^{.Y 02} Are the same or different, respectively, and are _{selected from the group consisting of -CH 2-} , -O-, -S-, -SO-, -SO _2- , -CO-, and a single bond. .Z ⁰ is _{the, -CH 2 -, - CH 2} CH 2 -, and -CH = CH- .p ⁰ is one selected from the group consisting of each is 0 to 3 integer .)

The aromatic ring or alicyclic ring contained in the group suitable as ^{Ra023 may have one or more substituents on the ring.} Preferable examples of the substituent are a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a carbon atom number. Examples thereof include 1 or more and 6 or less fluorinated alkoxy groups. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

When the dialdehyde compound represented by the formula (a2-I) is an aromatic dialdehyde, suitable examples thereof include benzenedialdehydes, pyridinedialdehydes, pyrazinedialdehydes, pyrimidindialdehydes, and naphthalene. Dialdehydes, biphenyldialdehydes, diphenylether dialdehydes, diphenylsulfonedialdehydes, diphenylsulfide dialdehydes, bis (formylphenoxy) benzenes, [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde , 2,2-Bis [4- (formylphenoxy) phenyl] propanes, bis [4- (formylphenoxy) phenyl] sulfides, bis [4- (formylphenoxy) phenyl] sulfones, and fluorinated aldehydes. Can be mentioned.

Specific examples of benzenedialdehydes include phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 3-fluorophthalaldehyde, 4-fluorophthalaldehyde, 2-fluoroisophthalaldehyde, 4-fluoroisophthalaldehyde, 5-fluoroisophthalaldehyde, 2 -Fluoroterephthalaldehyde, 3-trifluoromethylphthalaldehyde, 4-trifluoromethylphthalaldehyde, 2-trifluoromethylisophthalaldehyde, 4-trifluoromethylisophthalaldehyde, 5-trifluoromethylisophthalaldehyde, 2-trifluoromethyl Examples thereof include terephthalaldehyde, 3,4,5,6-tetrafluorophthalaldehyde, 2,4,5,6-tetrafluoroisophthalaldehyde, and 2,3,5,6-tetrafluoroterephthalaldehyde.

Specific examples of pyridine dialdehydes include pyridine-2,3-dialdehyde, pyridine-3,4-dialdehyde, and pyridine-3,5-dialdehyde.
Specific examples of pyrazine dialdehydes include pyrazine-2,3-dialdehyde, pyrazine-2,5-dialdehyde, pyrazine-2,6-dialdehyde and the like.
Specific examples of pyrimidine dialdehydes include pyrimidine-2,4-dialdehyde, pyrimidine-4,5-dialdehyde, pyrimidine-4,6-dialdehyde and the like.

Specific examples of naphthalenedialdehydes include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene-3,7-dialdehyde, 2,3. 4,6,7,8-Hexafluoronaphthalene-1,5-dialdehyde, 2,3,4,5,6,8-hexafluoronaphthalene-1,6-dialdehyde, 1,3,4,5 7,8-Hexafluoronaphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-2,6-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene-2,6-dialdehyde, 1- Trifluoromethylnaphthalene-3,7-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene-3,7-dialdehyde, 1-trifluoromethyl-2,4,5,6,8-pentafluoronaphthalene -3,7-Dialdehyde, 1-bis (trifluoromethyl) methoxy-2,4,5,6,8-pentafluoronaphthalene-3,7-dialdehyde, 1,5-bis (trifluoromethyl)- 2,4,6,8-Tetrafluoronaphthalene-3,7-dialdehyde, and 1,5-bis [bis (trifluoromethyl) methoxy] -2,4,6,8-tetrafluoronaphthalene-3,7 -Dialdehyde and the like can be mentioned.

Specific examples of the biphenyl dialdehydes include biphenyl-2,2'-dialdehyde, biphenyl-2,4'-dialdehyde, biphenyl-3,3'-dialdehyde, biphenyl-4,4'-dialdehyde, 6,6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-2,4'-dialdehyde, 6,6'-difluorobiphenyl-3,3'-dialdehyde, 6,6 6'-Difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-4,4'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-2,2'-dialdehyde, 6, 6'-Ditrifluoromethylbiphenyl-2,4'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-3,3'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-3,4'-di Examples thereof include aldehydes and 6,6'-ditrifluoromethylbiphenyl-4,4'-dialdehydes.

Specific examples of diphenyl ether dialdehydes include diphenyl ether-2,4'-dialdehyde, diphenyl ether-3,3'-dialdehyde, diphenyl ether-3,4'-dialdehyde, and diphenyl ether-4,4'-dialdehyde. And so on.

Specific examples of the diphenylsulfone dialdehydes include diphenylsulfone-3,3'-dialdehyde, diphenylsulfone-3,4'-dialdehyde, diphenylsulfone-4,4'-dialdehyde and the like.

Specific examples of the diphenylsulfide dialdehydes include diphenylsulfide-3,3'-dialdehyde, diphenylsulfide-3,4'-dialdehyde, diphenylsulfide-4,4'-dialdehyde and the like.

Specific examples of diphenylketone dialdehydes include diphenylketone-3,3'-dialdehyde, diphenylketone-3,4'-dialdehyde, diphenylketone-4,4'-dialdehyde and the like.

Specific examples of bis (formylphenoxy) benzenes include 1,3-bis (3-formylphenoxy) benzene, 1,4-bis (3-formylphenoxy) benzene, and 1,4-bis (4-formylphenoxy). ) Benzene and the like.

Specific examples of [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehydes include 3,3'-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, 3,4'-. Examples thereof include [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, and 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde.

Specific examples of 2,2-bis [4- (formylphenoxy) phenyl] propane include 2,2-bis [4- (2-formylphenoxy) phenyl] propane and 2,2-bis [4- (3). -Formyl phenoxy) phenyl] propane, 2,2-bis [4- (4-formyl phenoxy) phenyl] propane, 2,2-bis [4- (3-formyl phenoxy) phenyl] hexafluoropropane, and 2,2 -Bis [4- (4-formylphenoxy) phenyl] hexafluoropropane and the like can be mentioned.

Specific examples of bis [4- (formylphenoxy) phenyl] sulfides include bis [4- (3-formylphenoxy) phenyl] sulfide and bis [4- (4-formylphenoxy) phenyl] sulfide. ..

Specific examples of the bis [4- (formylphenoxy) phenyl] sulfone include bis [4- (3-formylphenoxy) phenyl] sulfone and bis [4- (4-formylphenoxy) phenyl] sulfone. ..

Specific examples of the fluorene-containing aldehyde include fluorene-2,6-dialdehyde, fluorene-2,7-dialdehyde, dibenzofuran-3,7-dialdehyde, 9,9-bis (4-formylphenyl) fluorene, and the like. Examples thereof include 9,9-bis (3-formylphenyl) fluorene and 9- (3-formylphenyl) -9- (4'-formylphenyl) fluorene.

Further, diphenylalcandialdehyde or diphenylfluoroalcandialdehyde represented by the following formula can also be suitably used as an aromatic dialdehyde compound.

Further, a compound having an imide bond represented by the following formula can also be suitably used as an aromatic dialdehyde compound.

When the dicarbonyl compound represented by the formula (a2-I) is an alicyclic dialdehyde containing an alicyclic group, suitable examples thereof include cyclohexane-1,4-dialdehyde and cyclohexane-1,3. -Dialdehyde, bicyclo [2.2.1] heptane-2,5-dialdehyde, bicyclo [2.2.2] octane-2,5-dialdehyde, bicyclo [2.2.2] octa-7- En-2,5-dialdehyde, bicyclo [2.2.1] heptane-2,3-dialdehyde, bicyclo [2.2.1] hepta-5-ene-2,3-dialdehyde, tricyclo [5] 2.1.0 ^2,6 ] Decane-3,4-dialdehyde, tricyclo [5.2.1.0 ^2,6 ] Deca-4-ene-8,9-dialdehyde, perhydronaphthalene-2 , 3-Dialdehyde, Perhydronaphthalene-1,4-Dialdehyde, Perhydronaphthalene-1,6-Dialdehyde, Perhydro-1,4-methanonaphthalene-2,3-Dialdehyde, Perhydro-1,4- Metanonaphthalene-2,7-dialdehyde, perhydro-1,4-methanonaphthalene-7,8-dialdehyde, perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dialdehyde, perhydro-1 , 4: 5,8-dimethanonaphthalene-2,7-dialdehyde, perhydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dialdehyde, bicyclohexyl-4,4' -Dialdehyde, dicyclohexyl ether-3,4'-dialdehyde, dicyclohexylmethane-3,3'-dialdehyde, dicyclohexylmethane-3,4'-dialdehyde, dicyclohexylmethane-4,4'-dialdehyde, dicyclohexyldifluoro Methan-3,3'-dialdehyde, dicyclohexyldifluoromethane-3,4'-dialdehyde, dicyclohexyldifluoromethane-4,4'-dialdehyde, dicyclohexylsulfone-3,3'-dialdehyde, dicyclohexylsulfon-3, 4'-dialdehyde, dicyclohexylsulfone-4,4'-dialdehyde, dicyclohexylsulfide-3,3'-dialdehyde, dicyclohexylsulfide-3,4'-dialdehyde, dicyclohexylsulfide-4,4'-dialdehyde, Dicyclohexylketone-3,3'-dialdehyde, dicyclohexylketone-3,4'-dialdehyde, dicyclohexylketone-4,4'-di Aldehyde, 2,2-bis (3-formylcyclohexyl) propane, 2,2-bis (4-formylcyclohexyl) propane, 2,2-bis (3-formylcyclohexyl) hexafluoropropane, 2,2-bis (4) -Formylcyclohexyl) hexafluoropropane, 1,3-bis (3-formylcyclohexyl) benzene, 1,4-bis (3-formylcyclohexyl) benzene, 1,4-bis (4-formylcyclohexyl) benzene, 3,3 '-[1,4-Cyclohexylenebis (1-methylethylidene)] biscyclohexanecarbaldehyde, 3,4'-[1,4-cyclohexylenebis (1-methylethylidene)] biscyclohexanecarbaldehyde, 4,4 '-[1,4-Cyclohexylene bis (1-methylethylidene)] biscyclohexanecarbaldehyde, 2,2-bis [4- (3-formylcyclohexyl) cyclohexyl] propane, 2,2-bis [4- (4) -Formylcyclohexyl) cyclohexyl] propane, 2,2-bis [4- (3-formylcyclohexyl) cyclohexyl] hexafluoropropane, 2,2-bis [4- (4-formylphenoxy) cyclohexyl] hexafluoropropane, bis [ 4- (3-formylcyclohexyloxy) cyclohexyl] sulfide, bis [4- (4-formylcyclohexyloxy) cyclohexyl] sulfide, bis [4- (3-formylcyclohexyloxy) cyclohexyl] Formilcyclohexyloxy) cyclohexyl] sulfone, 2,2'-bicyclo [2.2.1] heptane-5,6'-dialdehyde, 2,2'-bicyclo [2.2.1] heptane-6,6' -Dialdehyde, 1,3-diformyladamantan and the like can be mentioned.

Among the dialdehyde compounds described above, isophthalaldehyde is preferable because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole precursor that gives a polybenzoxazole resin having excellent heat resistance and mechanical properties.

（式（ａ２−ＩＩ）中、Ｒ^ａ０２３は、式（ａ０３）と同様であり、Ｈａｌはハロゲン原子である。） (Dicarboxylic acid dihalide)
The dicarboxylic acid dihalide used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (a2-II). As the dicarboxylic acid dihalide, one type may be used alone, or two or more types may be used in combination.

(In the formula (a2-II), R ^a023 is the same as the formula (a03), and Hal is a halogen atom.)

In the formula (a2-II), as Hall, chlorine, bromine, and iodine are preferable, and chlorine is more preferable.

As a suitable compound as the compound represented by the formula (a2-II), a compound in which the two aldehyde groups of the above-mentioned compound as a suitable example of the dialdehyde compound are replaced with a halocarbonyl group, preferably a chlorocarbonyl group. Can be mentioned.

Among the dicarboxylic acid dihalides described above, terephthalic acid dichloride is selected because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole precursor that gives a polybenzoxazole resin having excellent heat resistance and mechanical properties. preferable.

（式（ａ０４）中、Ｒ^ａ０２４及びＲ^ａ０２５は、それぞれ独立に炭素原子数１以上３以下のアルキル基であり、Ｒ^ａ０２６は下式（ａ０４−１）又は下式（ａ０４−２）：

で表される基である。式（ａ０４−１）中、Ｒ^ａ０２７は、水素原子又は水酸基であり、Ｒ^ａ０２８及びＲ^ａ０２９は、それぞれ独立に炭素原子数１以上３以下のアルキル基である。式（ａ０４−２）中、Ｒ^ａ０３０及びＲ^ａ０３１は、それぞれ独立に水素原子、又は炭素原子数１以上３以下のアルキル基である。） (solvent)
The solvent used for preparing the polyimide resin precursor or the polybenzoxazole precursor is not particularly limited, and can be appropriately selected from the solvents conventionally used for preparing the polyimide resin precursor or the polybenzoxazole precursor. As the solvent used for preparing the polyimide resin precursor or the polybenzoxazole precursor, it is preferable to use a solvent containing the compound represented by the following formula (a04).

(In the formula (a04), R ^a024 and R ^a025 are each independently alkyl groups having 1 or more and 3 or less carbon atoms, and R ^a026 is the following formula (a04-1) or the following formula (a04-2):

It is a group represented by. In the formula (a04-1), R ^a027 is a hydrogen atom or a hydroxyl group, and R ^a028 and R ^a029 are independently alkyl groups having 1 or more and 3 or less carbon atoms. In the formula (a04-2), R ^a030 and R ^a031 are independently hydrogen atoms or alkyl groups having 1 or more and 3 or less carbon atoms. )

When the polybenzoxazole precursor is synthesized using a solvent containing the compound represented by the above formula (a04), the resin for heating the polybenzoxazole precursor even when the polybenzoxazole precursor is heat-treated at a low temperature. It is possible to produce a polybenzoxazole resin having excellent mechanical properties such as tensile elongation and chemical resistance while suppressing a decrease in transparency due to coloring.

Further, when the polybenzoxazole precursor synthesized by using a solvent containing the compound represented by the above formula (a04) is heated to produce a polybenzoxazole resin, the swelling on the surface of the polybenzoxazole resin causes swelling. Occurrence of defects such as cracks and foaming can be suppressed. Therefore, when a film containing a polybenzoxazole precursor synthesized by using a solvent containing the compound represented by the above formula (a04) is heated to produce a polybenzoxazole resin film, cracks, blister, and pins are produced. It is easy to manufacture a film with excellent appearance without defects such as holes.

Among the compounds represented by the formula (a04), ^{specific examples of the case where R a026} is a group represented by the formula (a04-1) include N, N, 2-trimethylpropionamide, N-ethyl, N. , 2-Dimethylpropionamide, N, N-diethyl-2-methylpropionamide, N, N, 2-trimethyl-2-hydroxypropionamide, N-ethyl-N, 2-dimethyl-2-hydroxypropionamide, and Examples thereof include N, N-diethyl-2-hydroxy-2-methylpropionamide.

Among the compounds represented by the formula (a04), ^{specific examples of the case where R a026} is a group represented by the formula (a04-2) include N, N, N', N'-tetramethylurea and N. , N, N', N'-tetraethylurea and the like.

Particularly preferred examples of the compound represented by the formula (a4) include N, N, 2-trimethylpropionamide, and N, N, N', N'-tetramethylurea. The boiling point of N, N, 2-trimethylpropionamide under atmospheric pressure is 175 ° C, and the boiling point of N, N, N', N'-tetramethylurea under atmospheric pressure is 177 ° C. Thus, N, N, 2-trimethylpropionamide, and N, N, N', N'-tetramethylurea can dissolve aromatic diaminediols, dicarbonyl compounds, and the polybenzoxazole precursors produced. It has a relatively low boiling point in various solvents. Therefore, a polybenzoxazole precursor synthesized using a solvent containing at least one selected from N, N, 2-trimethylpropionamide and N, N, N', N'-tetramethylurea is used. When the polybenzoxazole resin is formed, the solvent is unlikely to remain in the produced polybenzoxazole resin when the polybenzoxazole precursor is heated, and the tensile elongation of the obtained polybenzoxazole resin is unlikely to decrease. ..

Furthermore, N, N, 2-trimethylpropionamide, and N, N, N', N'-tetramethylurea are substances of very high concern under the REACH regulation in the EU (European Union). It is also useful in that it is a substance with low toxicity, as it is not designated as a substance of very high concern (Substance of Very High Concern).

When the solvent used for preparing the polybenzoxazole precursor contains a compound represented by the formula (a04), the content of the compound represented by the formula (a04) in the solvent is preferably 70% by mass or more, preferably 80% by mass. % Or more is more preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.

When the solvent contains a compound represented by the formula (a04), examples of the organic solvent that can be used together with the compound represented by the formula (a04) include N, N-dimethylformamide, N, N-dimethylacetamide, and the like. Nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; γ-butyrolactone , Γ-Valerolactone, δ-Valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and esters such as -n-butyl acetate; dioxane, and Cyclic ethers such as tetrahydrofuran; cyclic esters such as ethylene carbonate and propylene carbonate; aromatic hydrocarbons such as toluene and xylene; sulfoxides such as dimethyl sulfoxide.

(Method for producing polybenzoxazole precursor)
The polybenzoxazole precursor is produced by reacting the above-mentioned aromatic diaminediol with a dicarbonyl compound in a solvent according to a well-known method. Hereinafter, as typical examples of the method for producing a polybenzoxazole precursor, a production method when the dicarbonyl compound is a dialdehyde compound and a production method when the dicarbonyl compound is a dicarboxylic acid halide will be described.

-Reaction between aromatic diaminediol and dialdehyde compound The reaction between aromatic diaminediol and dialdehyde compound is a Schiff base formation reaction and can be carried out according to a well-known method. The reaction temperature is not particularly limited, but is usually preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 20 ° C. or higher and 160 ° C. or lower, and particularly preferably 100 ° C. or higher and 160 ° C. or lower.

The reaction between the aromatic diaminediol and the dialdehyde compound may be carried out by adding an entrainer to the solvent and reflux dehydration. The entrainer is not particularly limited, and is appropriately selected from an organic solvent that forms an azeotropic mixture with water and forms a two-phase system with water at room temperature. Preferable examples of entrainers include esters such as isobutyl acetate, allyl acetate, -n-propyl propionate, isopropyl propionate, -n-butyl propionate, and isobutyl propionate; dichloromethyl ether, ethyl isoamyl ether, and the like. Ethers; ketones such as ethylpropyl ketone; aromatic hydrocarbons such as toluene.

The reaction time of the aromatic diaminediol and the dialdehyde compound is not particularly limited, but is typically about 2 hours or more and 72 hours or less.

The amount of the dialdehyde compound used in producing the polybenzoxazole precursor is preferably 0.5 mol or more and 1.5 mol or less, preferably 0.7 mol or more, with respect to 1 mol of the aromatic diaminediol. More preferably, it is 1.3 mol or less.

The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diaminediol and the dialdehyde compound proceeds well. Typically, a solvent having a mass of 1 to 40 times or more, preferably 1.5 to 20 times or less of the total mass of the aromatic diamine diol and the mass of the dialdehyde compound is used. ..

The reaction between the aromatic diaminediol and the dialdehyde compound is preferably carried out until the number average molecular weight of the produced polybenzoxazole precursor is 1000 or more and 20000 or less, preferably 1200 or more and 5000 or less.

-Reaction between aromatic diaminediol and dicarboxylic acid dihalide The reaction temperature for reacting aromatic diaminediol and dicarboxylic acid dihalide is not particularly limited, but is usually preferably -20 ° C or higher and 150 ° C or lower, and -10 ° C or higher and 150 ° C. The following is more preferable, and -5 ° C. or higher and 70 ° C. or lower is particularly preferable. Hydrogen halides are by-produced in the reaction of aromatic diaminediols with dicarboxylic acid dihalides. In order to neutralize such hydrogen halide, an organic base such as triethylamine, pyridine, and N, N-dimethyl-4-aminopyridine, or an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide is used as a reaction solution. A small amount may be added therein.

The reaction time of the aromatic diaminediol and the dicarboxylic acid dihalide is not particularly limited, but is typically about 2 hours or more and 72 hours or less.

The amount of the dicarboxylic acid dihalide used in producing the polybenzoxazole precursor is preferably 0.5 mol or more and 1.5 mol or less, and 0.7 mol or more, with respect to 1 mol of the aromatic diaminediol. More preferably, it is 1.3 mol or less.

The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diaminediol and the dicarboxylic acid dihalide proceeds well. Typically, a solvent having a mass of 1 to 40 times, preferably 1.5 to 20 times or less the total mass of the aromatic diamine diol and the mass of the dicarboxylic acid dihalide is used. ..

The reaction between the aromatic diaminediol and the dicarboxylic acid dihalide is preferably carried out until the number average molecular weight of the produced polybenzoxazole precursor is 1000 or more and 20000 or less, preferably 1200 or more and 5000 or less.

A solution of the polybenzoxazole precursor can be obtained by the method described above. When preparing the composition for forming a hydrogen barrier membrane, the solution of the polybenzoxazole precursor may be used as it is. Polybenzoxazole obtained by removing at least a part of the solvent from the solution of the polybenzoxazole precursor at a low temperature under reduced pressure so as not to convert the polybenzoxazole precursor into the polybenzoxazole resin. The precursor paste or solid can also be used to prepare a composition for forming a hydrogen barrier membrane.

[Polybenzothiazole precursor]
Polybenzothiazole precursors are typically produced by reacting an aromatic diaminedithiol with a dicarbonyl compound of a particular structure. As the aromatic diaminedithiol, a compound in which the hydroxyl group of the aromatic diaminediol used in the synthesis of the polybenzoxazole precursor is replaced with a mercapto group can be used. As the dicarbonyl compound, a compound similar to the compound used for the synthesis of the polybenzoxazole precursor can be used.

When synthesizing a polybenzothiazole precursor by reacting an aromatic diaminedithiol with a dicarbonyl compound, the reaction method, reaction conditions, etc. are as follows. Is the same as the case of synthesizing.

[Polybenzimidazole precursor]
Polybenzimidazole precursors are typically produced by reacting an aromatic tetraamine with a dicarboxylic acid dihalide. As the aromatic tetraamine, a compound in which the hydroxyl group of the aromatic diaminediol used in the synthesis of the polybenzoxazole precursor is replaced with an amino group can be used. As the dicarboxylic acid dihalide, a compound similar to the compound used for the synthesis of the polybenzoxazole precursor can be used.

When synthesizing a polybenzimidazole precursor by reacting an aromatic tetraamine with a dicarboxylic acid dihalide, the reaction method, reaction conditions, etc. are as follows. It is the same as the case of synthesizing.

[Styrene-maleic acid copolymer]
The type of styrene-maleic acid copolymer is not particularly limited as long as it does not impair the object of the present invention. The copolymerization ratio (mass ratio) of styrene / maleic acid in the styrene-maleic acid copolymer is preferably 1/9 or more and 9/1 or less, more preferably 2/8 or more and 8/1 or less, and 1/1 or more. 8/1 or less is particularly preferable. The molecular weight of the styrene-maleic acid copolymer is not particularly limited, but the polystyrene-equivalent mass average molecular weight is preferably 1000 or more and 100,000 or less, and more preferably 5000 or more and 12000 or less.

[Epoxy group-containing resin]
When the epoxy group-containing resin is used as the base material component (A), the epoxy groups of the epoxy group-containing resin are crosslinked by heating in the presence of a curing agent or a curing accelerator as needed. As a result, a cured product having excellent heat resistance and mechanical properties can be obtained. The epoxy group-containing resin is not particularly limited as long as it is a resin composed of molecules having an epoxy group.

The epoxy group-containing resin may be a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group. The epoxy group-containing resin is obtained by introducing an epoxy group into a polymer having a reactive functional group such as a hydroxyl group, a carboxyl group, or an amino group by using a compound having an epoxy group such as epichlorohydrin. You may. Since it is easy to obtain, prepare, adjust the amount of epoxy groups in the polymer, etc., the polymer having an epoxy group is a single amount containing a monomer having an epoxy group or a monomer having an epoxy group. A polymer obtained by polymerizing a body mixture is preferable.

Preferred examples of the epoxy group-containing resin are novolak epoxy resins such as phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol AD novolac type epoxy resin. A ring-type aliphatic epoxy resin such as an epoxie of a dicyclopentadiene type phenol resin; an aromatic epoxy resin such as an epoxie of a naphthalene type phenol resin can be mentioned.

Further, among the epoxy group-containing resins, since it is easy to prepare and the physical properties of the hydrogen barrier film can be easily adjusted, it is possible to use a homopolymer of a (meth) acrylic acid ester having an epoxy group or an epoxy. A copolymer of a (meth) acrylic acid ester having a group and another monomer is preferable.

The (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group, which will be described later, even if it is a (meth) acrylic acid ester having a chain aliphatic epoxy group. There may be. Further, the (meth) acrylic acid ester having an epoxy group may contain an aromatic group. Among the (meth) acrylic acid esters having an epoxy group, an aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group and an aliphatic (meth) acrylic acid ester having an alicyclic epoxy group are preferable. Aliphatic (meth) acrylic acid esters having an alicyclic epoxy group are more preferable, and from the viewpoint of patterning properties, an aliphatic (meth) having an alicyclic epoxy group having a polycyclic structure in the ring structure of the alicyclic epoxy group ( Meta) epoxides are more preferred.

Examples of (meth) acrylic acid esters containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxyphenyl (meth) acrylate. , 4-Glysidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate and the like.

Examples of aliphatic (meth) acrylic acid esters having a chain aliphatic epoxy group include ester groups (-O-CO-) such as epoxyalkyl (meth) acrylates and epoxyalkyloxyalkyl (meth) acrylates. ), A (meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to an oxy group (−O−) can be mentioned. The chain aliphatic epoxy group contained in such a (meth) acrylic acid ester may contain one or more oxy groups (−O−) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and particularly preferably 3 or more and 10 or less.

Specific examples of the aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth). ) Acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, 6-glycidyloxy-n-hexyl (meth) acrylate and other epoxyalkyloxyalkyl (meth) acrylates can be mentioned.

Specific examples of the aliphatic (meth) acrylic acid ester having an alicyclic epoxy group include compounds represented by the following formulas (a05-1) to (a05-15). Among these, the compounds represented by the following formulas (a05-1) to (a05-5) are preferable, and the compounds represented by the following formulas (a05-1) to (a05-2) are more preferable. Further, with respect to each of these compounds, the binding site of the oxygen atom of the ester group to the alicyclic is not limited to the position shown here, and may contain a partial position isomer.

In the above formula, R ^a032 represents a hydrogen atom or a methyl group, R ^a033 represents a divalent aliphatic saturated hydrocarbon group having 1 or more and 6 or less ^{carbon atoms, and R a034} represents 2 having 1 or more and 10 or less carbon atoms. It indicates a valent hydrocarbon group, and t ⁰ indicates an integer of 0 or more and 10 or less. As R ^a033 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a034 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group and a cyclohexylene group are preferable.

As the polymer having an epoxy group, either a homopolymer of a (meth) acrylic acid ester having an epoxy group or a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer is used. However, the content of the unit derived from the (meth) acrylic acid ester having an epoxy group in the polymer having an epoxy group is, for example, 1 to 100% by mass, and 10% by mass or more and 90% by mass. The following is preferable, 30% by mass or more and 80% by mass or less is more preferable, and 50% by mass or more and 75% by mass or less is particularly preferable.

When the polymer having an epoxy group is a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer, the other monomer has an unsaturated carboxylic acid and an epoxy group. Examples thereof include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds can be used alone or in combination of two or more. (Meta) acrylic acid having an epoxy group from the viewpoint of storage stability of the composition for forming a hydrogen barrier membrane and chemical resistance of a hydrogen barrier membrane formed using the composition for forming a hydrogen barrier membrane to alkalis and the like. The copolymer of the ester and the other monomer preferably does not contain a unit derived from the unsaturated carboxylic acid.

Examples of unsaturated carboxylic acids include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.

Examples of (meth) acrylic acid esters having no epoxy group include direct methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and t-octyl (meth) acrylate. Chained or branched alkyl (meth) acrylates; chloroethyl (meth) acrylates, 2,2-dimethylhydroxypropyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates, trimethylolpropane mono (meth) acrylates, benzyls. Examples thereof include (meth) acrylates and furfuryl (meth) acrylates; (meth) acrylic acid esters having a group having an alicyclic skeleton. Among the (meth) acrylic acid esters having no epoxy group, the (meth) acrylic acid ester having a group having an alicyclic skeleton is preferable.

In a (meth) acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like.

Examples of the (meth) acrylic acid ester having a group having an alicyclic skeleton include compounds represented by the following formulas (a06-1) to (a06-8). Among these, the compounds represented by the following formulas (a06-3) to (a06-8) are preferable, and the compounds represented by the following formulas (a06-3) or (a06-4) are more preferable.

In the above formula, R ^a035 represents a hydrogen atom or a methyl group, Ra ⁰³⁶ represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a037 represents a hydrogen atom or a carbon atom number. Indicates an alkyl group of 1 or more and 5 or less. As R ^a036 , a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a037 , a methyl group and an ethyl group are preferable.

Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide. , N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate; allyloxyethanol; And so on.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, and hydroxy. Aliphatic vinyl ethers such as ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4 − Vinyl aryl ethers such as dichlorophenyl ethers, vinyl naphthyl ethers and vinyl anthranyl ethers; and the like.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl. Examples thereof include phenylacetate, vinylacetate acetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene. Alkylstyrene such as ethoxymethylstyrene and acetoxymethylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo Examples thereof include styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, halostyrene such as 2-bromo-4-trifluoromethylstyrene and 4-fluoro-3-trifluoromethylstyrene; and the like.

The molecular weight of the epoxy group-containing resin is not particularly limited as long as it does not impair the object of the present invention, but the polystyrene-equivalent mass average molecular weight is preferably 3,000 or more and 30,000 or less, and 5,000 or more and 15,000 or less. More preferred.

When the above thermosetting material is used as the base material component (A), the composition for forming a hydrogen barrier membrane may contain a curing agent, a curing accelerator, a dehydration condensing agent, an antioxidant, an ultraviolet absorber, as necessary. It may contain additives and reinforcing materials such as flame retardants, mold release agents, plasticizers, fillers, and reinforcing materials.
Further, in order to facilitate film formation, the composition for forming a hydrogen barrier membrane may contain a solvent. The type of solvent is appropriately selected according to the type of thermosetting material.

When the composition for forming a hydrogen barrier membrane contains the above-mentioned heat-curable material and the hydrogen barrier agent (B), the content of the hydrogen barrier agent is the mass of the heat-curable material of the composition for forming a hydrogen barrier membrane. On the other hand, 0.01% by mass or more and 30% by mass or less is preferable, 0.05% by mass or more and 20% by mass or less is more preferable, and 0.1% by mass or more and 10% by mass or less is particularly preferable.

As the composition for forming a hydrogen barrier membrane, a photosensitive composition known as a so-called photoresist composition is also preferable, in addition to the composition containing the base material component (A) described above. By adding a predetermined amount of the above-mentioned hydrogen barrier agent (B) to various conventionally known photosensitive compositions, a photosensitive hydrogen barrier film forming composition can be obtained.
Conventionally known photosensitive compositions include various photocurable compounds, alkali-soluble resins, resins whose solubility in alkali is increased by exposure, and the like as the base material component (A).
The photosensitive hydrogen barrier membrane forming composition may be a negative type photosensitive composition that is insoluble in the developing solution by exposure, or a positive type photosensitive composition that is solubilized in the developing solution by exposure. It may be a thing.
Hereinafter, suitable photosensitive compositions will be described.

(1) Photosensitive composition of the first aspect The photosensitive composition of the first aspect is a hydrogen barrier together with an alkali-soluble resin (A1), a photopolymerizable compound (A2), and a photopolymerization initiator (C). It is a negative type photosensitive composition containing the agent (B) and an organic solvent.
In the photosensitive composition of the first aspect, the alkali-soluble resin (A1) and the photopolymerizable compound (A2) correspond to the base material component (A).

The alkali-soluble resin (A1) in the photosensitive composition of the first aspect is not particularly limited, and conventionally known alkali-soluble resins can be used. The alkali-soluble resin (A1) may have an ethylenically unsaturated group or may not have an ethylenically unsaturated group.
In the present specification, the alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) to form a resin film having a thickness of 1 μm on the substrate and having a thickness of 2.38% by mass. A resin that dissolves in a film thickness of 0.01 μm or more when immersed in an aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute.

As the alkali-soluble resin (A1) having an ethylenically unsaturated group, for example, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used. ..

Among them, the resin represented by the following formula (a-1) is preferable. The resin represented by this formula (a-1) is preferable in that it has high photocurability.

In the formula ^{(a-1), X} a represents a group represented by the following formula (a-2).

In the above formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 or more and 6 or less carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group. shows, ^{W a} represents a group represented by a single bond or the following formula (a-3).

Further, in the above formula ^{(a-1), Y} a represents the residue obtained by removing dicarboxylic acid anhydride from the acid anhydride group (-CO-O-CO-). Examples of dicarboxylic acid anhydrides are phthalic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro. Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, biphenyl ether tetracarboxylic acid dianhydride and the like.
Further, in the above equation (a-1), m represents an integer of 0 or more and 20 or less.

As the alkali-soluble resin (A1) having an ethylenically unsaturated group, a (meth) acrylic acid is reacted with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid. Obtained polyester (meth) acrylate; Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F Type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin , Epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as an amine epoxy resin or a dihydroxybenzene type epoxy resin with (meth) acrylic acid can also be used.
In addition, in this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" means both acrylate and methacrylate.

On the other hand, as the alkali-soluble resin (A1) having no ethylenically unsaturated group, a resin obtained by copolymerizing an unsaturated carboxylic acid with another unsaturated compound can be used. As the other unsaturated compound, it is preferable to use at least one selected from an epoxy group-containing unsaturated compound and an alicyclic group-containing unsaturated compound.

Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids; Be done. Among these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerizability, alkali solubility of the obtained resin, easy availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound include an epoxy group-containing unsaturated compound having no alicyclic group and an epoxy group-containing unsaturated compound having an alicyclic group.
Examples of the epoxy group-containing unsaturated compound having an alicyclic group include compounds represented by the above formulas (a05-1) to (a05-15).
Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl ( Epoxide alkyl (meth) acrylates such as meta) acrylates; 2-glycidyloxyethyl (meth) acrylates, 3-glycidyloxy-n-propyl (meth) acrylates, 4-glycidyloxy-n-butyl (meth) acrylates, 5- Epoxide alkyloxyalkyl (meth) acrylates such as glycidyloxy-n-pentyl (meth) acrylate, 6-glycidyloxy-n-hexyl (meth) acrylate; glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, Α-alkylacrylic acid epoxyalkyl esters such as α-n-butylacrylic acid glycidyl, α-ethylacrylic acid 6,7-epoxyheptyl; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl Glysidyl ethers such as glycidyl ether; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoint of copolymerization reactivity, strength of resin after curing, etc. Glysidyl ethers, m-vinylbenzyl glycidyl ethers, and p-vinylbenzyl glycidyl ethers are preferred.
These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the above-mentioned formulas (a06-1) to (a06-8).

It is also preferable to further polymerize other compounds other than the above with respect to the unsaturated carboxylic acid. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, maleimides and the like. These compounds can be used alone or in combination of two or more.

Examples of (meth) acrylic acid esters include linear or branched chains such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and t-octyl (meth) acrylate. Alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethyl propane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meta) acrylate; and the like.

Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, and N. Examples thereof include -methyl-N-phenyl (meth) acrylamide and N-hydroxyethyl-N-methyl (meth) acrylamide.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and the like. Can be mentioned.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether and hydroxyethyl vinyl ether. , Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and other alkyl vinyl ethers; vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4-di Vinyl aryl ethers such as chlorophenyl ethers, vinyl naphthyl ethers and vinyl anthranyl ethers; and the like can be mentioned.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl chloride. Examples thereof include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy. Alkylstyrene such as methylstyrene and acetoxymethylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Examples thereof include halostyrene such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene.

Examples of maleimides include carbons such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nn-pentylmaleimide, and Nn-hexylmaleimide. N-substituted maleimide with an alkyl group having 1 to 10 atoms; N-substituted with an alicyclic group having 3 to 20 carbon atoms such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, and N-cycloheptylmaleimide. Maleimide: N-arylmaleimide N-substituted with an aryl group having 6 to 20 carbon atoms such as N-phenylmaleimide, N-α-naphthylmaleimide, N-β-naphthylmaleimide; N-benzylmaleimide, N-phenethyl Examples thereof include N-aralkylmaleimide N-substituted with an aralkyl group having 7 or more and 20 or less carbon atoms such as maleimide.

Further, a copolymer having at least a structural unit derived from an unsaturated carboxylic acid and a structural unit having a polymerizable site with a photopolymerizable compound (A2) described later, or a structural unit derived from an unsaturated carboxylic acid. A copolymer having at least a structural unit derived from an unsaturated compound containing an epoxy group and a structural unit having a polymerizable site with a photopolymerizable compound (A2) described later is also suitable as the alkali-soluble resin (A1). Can be used.
When these alkali-soluble resins are used, it is possible to form a hydrogen barrier membrane having excellent mechanical strength and adhesion to a substrate.

The copolymer having a structural unit having a polymerizable site with the photopolymerizable compound (A2) is the above-mentioned (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters. , Styrenes, maleimides, etc. may further have one or more constituent units.

The structural unit having a polymerizable moiety with the photopolymerizable compound (A2) preferably has an ethylenically unsaturated group as a polymerizable moiety with the photopolymerizable compound (A2). A copolymer having such a structural unit can be prepared by reacting at least a part of the carboxyl groups contained in the unsaturated carboxylic acid homopolymer with an epoxy group-containing unsaturated compound.
Alternatively, the unsaturated carboxylic acid can be reacted with at least a part of the epoxy group in the polymer having the structural unit derived from the unsaturated carboxylic acid and the structural unit derived from the unsaturated compound containing an epoxy group. A copolymer having a structural unit having a polymerizable site with the photopolymerizable compound (A2) can be prepared.

The proportion of the structural unit derived from the unsaturated carboxylic acid in the alkali-soluble resin (A1) is preferably 3% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 25% by mass or less. preferable. The proportion of the structural unit derived from the epoxy group-containing unsaturated compound is preferably 30% by mass or more and 95% by mass or less, and more preferably 50% by mass or more and 90% by mass or less. The proportion of the structural unit derived from the alicyclic group-containing unsaturated compound is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 25% by mass or less. It is more preferably mass% or more and 20 mass% or less. By setting the above range, it is possible to improve the adhesion of the photosensitive composition to the substrate and the strength of the photosensitive composition after curing, while making the alkali solubility of the obtained resin appropriate.

The mass average molecular weight of the alkali-soluble resin (A1) is preferably 1000 or more and 40,000 or less, and more preferably 2000 or more and 30,000 or less. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

The content of the alkali-soluble resin (A1) is preferably 5% by mass or more and 80% by mass or less, and is 15% by mass or more and 50% by mass or less, based on the solid content of the photosensitive composition of the first aspect. Is more preferable. Within the above range, the developability tends to be easily balanced.

Examples of the photopolymerizable compound (A2) in the photosensitive composition of the first aspect include a monofunctional monomer and a polyfunctional monomer.
Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and N-methylol ( Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-Methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, Glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Examples thereof include tetrafluoropropyl (meth) acrylate and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylpropantri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Ellisritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxipolyethoxyphenyl) propane, 2-hydroxy-3 -(Meta) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin poly Glycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, ( Examples thereof include polyfunctional monomers such as meth) acrylamide methylene ether and condensates of polyhydric alcohol and N-methylol (meth) acrylamide, and triacrylic formal. These polyfunctional monomers can be used alone or in combination of two or more.

The content of the photopolymerizable compound (A2) is preferably 1% by mass or more and 30% by mass or less, and 5% by mass or more and 20% by mass or less, based on the solid content of the photosensitive composition of the first aspect. More preferably. Within the above range, it tends to be easy to balance sensitivity, developability, and resolution.

The photopolymerization initiator (C) in the photosensitive composition of the first aspect is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specifically, as the photopolymerization initiator (C), 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etanone, 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime), (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1) -Methylethoxy) -2-methylphenyl] methanone O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide , 4-Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2- Ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propandion-2- (O-ethoxycarbonyl) oxime, o- Methyl benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-Methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumenehydroperoxide, 2 − Mercaptobe Nzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone , P-Dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, Pentyl-4-dimethylaminobenzoate, 9-phenylaclysine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) Propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methyl) Phenyl-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (tric) Loromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4) -Methoxy) Phenyl-s-Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-) Bromo-4-methoxy) styrylphenyl-s-triazine and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more.

Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. Among the oxime-based photopolymerization initiators, particularly preferable ones are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] etanone oxime and etanone. , 1- [9-ethyl-6- (pyrrole-2-ylcarbonyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), and 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)].

（Ｒ^ｃ１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、
ｎ１は０以上４以下の整数であり、
ｎ２は０、又は１であり、
Ｒ^ｃ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、
Ｒ^ｃ３は、水素原子、又は炭素原子数１以上６以下のアルキル基である。） As the photopolymerization initiator, it is also preferable to use an oxime compound represented by the following formula (c1).

(R ^c1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group.
n1 is an integer of 0 or more and 4 or less,
n2 is 0 or 1,
R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent.
R ^c3 is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms. )

In the formula (c1), R ^c1 is not particularly limited as long as it does not interfere with the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a benzoyloxy which may have a substituent. A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent. A naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, an amino group, 1 , Or an amino group substituted with 2 organic groups, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like. When n1 is an integer of 2 or more and 4 or less, R ^c1 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further possessed by the substituent.

When R ^c1 is an alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^c1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples thereof include an n-decyl group and an isodecyl group. When R ^c1 is an alkyl group, the alkyl group may contain an ether bond (−O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c1 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group and n. -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (−O−) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples of the case where R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Specific examples of the case where R ^c1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group and the like.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and n. -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^c1 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^c1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, the number of carbon atoms is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. When R ^c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples of the case where R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, ^Rc1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiazazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Examples thereof include isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline and the like. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. , Saturated aliphatic acyl group having 2 or more and 20 or less carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, and 7 or more carbon atoms which may have a substituent. A phenylalkyl group of 20 or less, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group which may have a substituent and has 11 or more and 20 or less carbon atoms, and Heterocyclyl groups and the like can be mentioned. Specific examples of these suitable organic groups are the same as for R ^c1 . Specific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group, and an n-. Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naftylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c1} further have a substituent, the substituents include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, alkyl group with 1 to 6 carbon atoms Examples thereof include a monoalkylamino group having, a dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c1} further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 4 or less. When ^{the phenyl group, the naphthyl group, and the heterocyclyl group contained in R c1} have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c1 , alkyl groups having 1 to 6 carbon atoms and 1 carbon atom have 1 or less carbon atoms because they are chemically stable, have few steric obstacles, and facilitate the synthesis of oxime ester compounds. A group selected from the group consisting of an alkoxy group having 6 or more carbon atoms and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, an alkyl having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable. ..

Position R ^c1 is bonded to the phenyl group, the phenyl group R ^c1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group In addition, the 4th or 5th position is preferable, and the 5th position is more preferable. Further, n1 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. When R ^c2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 or more and 6 or less carbon atoms.

In R ^c2 , the substituent contained in the phenyl group or the carbazolyl group is not particularly limited as long as it does not impair the object of the present invention. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon atom. Cycloalkyl group with 3 to 10 carbon atoms, cycloalkoxy group with 3 to 10 carbon atoms, saturated aliphatic acyl group with 2 to 20 carbon atoms, alkoxycarbonyl group with 2 to 20 carbon atoms, carbon atom It has a saturated aliphatic acyloxy group having a number of 2 or more and 20 or less, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, and a substituent. A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 or more and 20 or less carbon atoms. It has a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent. It may have a naphthoyloxy group, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl which may have a substituent. Examples thereof include an amino group substituted with a group, an amino group, 1 or 2 organic groups, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a cyclo having 3 to 10 carbon atoms. An alkyl group, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, and a benzoyl group which may have a substituent. , A phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 or more and 20 or less carbon atoms, a naphthyl group which may have a substituent, and a substituent. May have a naphthoyl group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent and may have 11 or more and 20 or less carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclyl group which may have a substituent. Examples thereof include a heterocyclylcarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl group or the carbazolyl group may have are an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. For phenylalkyl groups which may have groups, naphthylalkyl groups which may have substituents, heterocyclyl groups which may have substituents, and amino groups substituted with one or two organic groups. , R ^c1 .

In R ^c2 , an alkyl having 1 to 6 carbon atoms as an example of a substituent when the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent. Group; alkoxy group with 1 to 6 carbon atoms; saturated aliphatic acyl group with 2 to 7 carbon atoms; alkoxycarbonyl group with 2 to 7 carbon atoms; saturated aliphatic acyl group with 2 to 7 carbon atoms It is selected from the group consisting of an acyloxy group; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group. A benzoyl group substituted with a group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; piperazin- 1-Il group; halogen; nitro group; cyano group can be mentioned. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. It is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c2, the group represented by the following formula (c2) or (c3) is preferable, and the group represented by the following formula (c2) is more preferable, from the viewpoint that a photopolymerization initiator having excellent sensitivity can be easily obtained. , A group represented by the following formula (c2), in which A is S, is particularly preferable.

（Ｒ^ｃ４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎ３は、０以上４以下の整数である。）

(R ^c4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, A is S or O, and n3 is an integer of 0 or more and 4 or less. Is.)

（Ｒ^ｃ５及びＲ^ｃ６は、それぞれ、１価の有機基である。）

(R ^c5 and R ^c6 are monovalent organic groups, respectively.)

^{When R c4} in the formula (c2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. ^{A preferred example of the case where R c4} is an organic group in the formula (c2) is an alkyl group having 1 or more and 6 or less carbon atoms; an alkoxy group having 1 or more and 6 or less carbon atoms; and 2 or more and 7 or less carbon atoms. Saturated aliphatic acyl group; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; 1 to 6 carbon atoms A benzoyl group substituted with a group selected from the group consisting of the following alkyl groups, morpholin-1-yl groups, piperazin-1-yl groups, and phenyl groups; mono having an alkyl group having 1 to 6 carbon atoms. Alkylamino group; dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms; morpholin-1-yl group; piperazin-1-yl group; halogen; nitro group; cyano group.

In R ^c4 , it is substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group. Benzoyl group; nitro group is preferable, and benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferable.

Further, in the formula (c2), n3 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. If n3 is 1, binding position of R ^c4, to the bond to the phenyl group R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.

^{R c5} in the formula (c3) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples of R ^c5 are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and 2 carbon atoms. It may have an alkoxycarbonyl group of 20 or more, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent. A phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent. Examples thereof include a naphthylalkyl group having 11 or more and 20 or less carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ^c5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

^{R c6} in the formula (c3) is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of a group suitable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Examples include heterocyclyl groups which may be used. Among these groups, a phenyl group which may have a substituent is more preferable as R ^{c6, and a 2-methylphenyl group is particularly preferable.}

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms and 1 carbon atom. An alkoxy group having 6 or more carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and a carbon atom number. Monoalkylamino group having 1 or more and 6 or less alkyl groups, dialkylamino group having 1 or more and 6 or less carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and Examples include a cyano group. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. It is preferably 1 or more and 4 or less. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c4} , R ^c5 , or R ^c6 has a plurality of substituents, the plurality of substituents may be the same or different.

^{R c3} in the formula (c1) is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms. As R ^c3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

The oxime ester compound represented by the formula (c1) can be synthesized, for example, according to the following scheme 1 when p is 0. Specifically, an aromatic compound represented by the following formula (c1-1) is acylated by a Friedelcrafts reaction using a halocarbonyl compound represented by the following formula (c1-2), and the following formula is used. A ketone compound represented by (c1-3) was obtained, and the obtained ketone compound (c1-3) was oximeized with hydroxylamine to obtain an oxime compound represented by the following formula (c1-4), followed by the formula. The hydroxy group in the oxime compound of (c1-4) can be acylated to obtain an oxime ester compound represented by the following formula (c1-7). Examples of the acylating agent include acid anhydrides ((R ^c3 CO) ₂ O) represented by the following formula (c1-5) or acid halides (R ^c3 COHal, Hal) represented by the following formula (c1-6). Is a halogen.) Is preferably used. In the following formula (c1-2), H is a halogen, and in the following formulas (c1-1), (c1-2), (c1-3), (c1-4), and (c1-7). , R ^c1 , R ^c2 , R ^c3 , and n1 are the same as in equation (c1).

<Scheme 1>

The oxime ester compound represented by the formula (c1) can be synthesized, for example, according to the following scheme 2 when n2 is 1. Specifically, the ketone compound represented by the following formula (c2-1) is nitrite ester represented by the following formula (c2-2) in the presence of hydrochloric acid (RONO and R have 1 or more carbon atoms and 6). The following alkyl group) is reacted to obtain a ketooxime compound represented by the following formula (c2-3), and then the hydroxy group in the ketooxime compound represented by the following formula (c2-3) is acylated. , An oxime ester compound represented by the following formula (c2-6) can be obtained. As the acylating agent, an acid anhydride represented by the following formula (c2-4) ((R ^c3 CO) ₂ O) or an acid halide represented by the following formula (c2-5) (R ^c3 COHal, Hal) Is a halogen.) Is preferably used. In the following formulas (c2-1), (c2-3), (c2-4), (c2-5), and (c2-6), R ^c1 , R ^c2 , R ^c3 , and n1 are formulas. It is the same as (c1).

<Scheme 2>

Further, in the oxime ester compound represented by the formula (c1), n2 is 1, R ^c1 is ^{a methyl group, and R c1} is paralyzed with respect to the methyl group bonded to the benzene ring to which ^{R c1 is bonded.} In the case of binding to the position, for example, the compound represented by the following formula (c2-7) can be synthesized by oximeization and acylation in the same manner as in Scheme 1. In the following formula (c2-7), R ^c2 is the same as the formula (c1).

Among the oxime ester compounds represented by the formula (c1), the following PI-1 to PI-42 are particularly suitable compounds.

An oxime ester compound represented by the following formula (c4) is also preferable as a photopolymerization initiator.

（Ｒ^ｃ７は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｃ８及びＲ^ｃ９は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ８とＲ^ｃ９とは相互に結合して環を形成してもよく、Ｒ^ｃ１０は１価の有機基であり、Ｒ^ｃ１１は、水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基であり、ｎ４は０以上４以下の整数であり、ｎ５は０又は１である。）

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^c8 and R ^c9 are a chain alkyl group which may have a substituent and a cyclic organic group which may have a substituent, respectively. It is a group or a hydrogen atom, and R ^c8 and R ^c9 may be bonded to each other to form a ring, R ^c10 is a monovalent organic group, and R ^c11 has a hydrogen atom and a substituent. It is an alkyl group having 1 or more and 11 or less carbon atoms, or an aryl group which may have a substituent, n4 is an integer of 0 or more and 4 or less, and n5 is 0 or 1.)

Here, as the oxime compound for producing the oxime ester compound of the formula (c4), the compound represented by the following formula (c5) is suitable.

（Ｒ^ｃ７、Ｒ^ｃ８、Ｒ^ｃ９、Ｒ^ｃ１０、ｎ４、及びｎ５は、式（ｃ４）と同様である。）

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4, and n5 are the same as in the formula (c4).)

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 is attached to a 6-membered aromatic ring on the fluorene ring in the formula (c4), which is different from the 6-membered aromatic ring attached to the group represented by _{− (CO) n5-.} In the formula (c4), the ^{binding position of R c7} with respect to the fluorene ring is not particularly limited. When the compound represented by the formula (c4) has 1 or more R ^{c7 , one of the 1 or more R c7} is a fluorene ring because the compound represented by the formula (c4) can be easily synthesized. It is preferable to bind to the 2-position of the inside. If R ^c7 is more, a plurality of R ^c7 is independently in may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as it does not interfere with the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a benzoyloxy which may have a substituent. A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent. It has a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like.

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^c7 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples thereof include an n-decyl group and an isodecyl group. When R ^c7 is an alkyl group, the alkyl group may contain an ether bond (−O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^c7 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c7 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group and n. -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^c7 is an alkoxy group, the alkoxy group may contain an ether bond (−O−) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples of the case where R ^c7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Specific examples of the case where R ^c7 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group and the like.

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^c7 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and n. -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^c7 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^c7 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^c7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. When R ^c7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples of the case where R ^c7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c7 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, ^Rc7 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclyl carbonyl group, the heterocyclyl group contained in the heterocyclyl carbonyl group is the same as when R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and the like. Saturated aliphatic acyl group having 2 or more and 21 or less carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, and 7 or more and 20 carbon atoms which may have a substituent. The following phenylalkyl groups, naphthyl groups which may have substituents, naphthoyl groups which may have substituents, naphthylalkyl groups which may have substituents and have 11 to 20 carbon atoms, and heterocyclyl. The group etc. can be mentioned. Specific examples of these suitable organic groups are the same as for R ^c7 . Specific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group, and an n-. Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naftylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c7} further have a substituent, the substituents include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, alkyl group with 1 to 6 carbon atoms Examples thereof include a monoalkylamino group having, a dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like. When ^{the phenyl group, naphthyl group, and heterocyclyl group contained in R c7} further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 4 or less. When ^{the phenyl group, the naphthyl group, and the heterocyclyl group contained in R c7} have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, as R ^c7 , a nitro group or ^{a group represented by R c12-} CO- tends to improve the sensitivity and is preferable. R ^c12 is not particularly limited as long as it does not interfere with the object of the present invention, and can be selected from various organic groups. Examples of a suitable group as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Heterocyclyl groups may be mentioned. Among these groups, 2-methylphenyl group, thiophen-2-yl group, and α-naphthyl group are particularly preferable as R ^c12.
Further, when R ^c7 is a hydrogen atom, the transparency tends to be good, which is preferable. If R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b) described later, the transparency tends to be better.

In the formula (c4), R ^c8 and R ^c9 are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. R ^c8 and R ^c9 may be coupled to each other to form a ring. Among these groups, as R ^c8 and R ^c9 , a chain alkyl group which may have a substituent is preferable. When R ^c8 and R ^c9 are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

When R ^c8 and R ^c9 are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. preferable. Specific examples of cases where R ^c8 and R ^c9 are chain alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-Pentyl group, Isopentyl group, sec-Pentyl group, tert-Pentyl group, n-Hexyl group, n-Heptyl group, n-octyl group, Isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Examples thereof include a group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when R ^c8 and R ^c9 are alkyl groups, the alkyl group may contain an ether bond (−O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c8 and R ^c9 are chain alkyl groups having substituents, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. .. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as it does not impair the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as in the preferred example when ^{R c7 is a cycloalkyl group.} Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like. Specific examples of the heterocyclyl group are the same as in the preferred example when ^{R c7 is a heterocyclyl group.} When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of preferred substituents depends on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When R ^c8 and R ^c9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^c8 and R ^c9 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ^c8 and R ^c9 are chain alkyl groups.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, whether the aromatic hydrocarbon group is a phenyl group or a group formed by bonding a plurality of benzene rings via carbon-carbon bonds. , It is preferable that the group is formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.

When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, Examples thereof include a tetracyclododecyl group and an adamantyl group.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, such monocyclic rings, or between such monocyclic rings and a benzene ring. Is a heterocyclyl group condensed with. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done.

R ^c8 and R ^c9 may be coupled to each other to form a ring. The group consisting of the ring formed by ^{R c8} and R ^{c9 is preferably a cycloalkylidene group.} When R ^c8 and R ^c9 are combined to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

When ^{the group formed by combining R c8} and R ^c9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that may be fused with a cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine. Rings, pyrazine rings, pyrimidine rings and the like can be mentioned.

Among the R ^c8 and R ^c9 described above, examples of suitable groups include groups represented by the ^{formula −A 1} −A ^2. In the formula, A ¹ is a linear alkylene group and A ² is an alkoxy group, a cyano group, a halogen atom, an alkyl halide group, a cyclic organic group, or an alkoxycarbonyl group.

The ^{number of carbon atoms of the linear alkylene group of A 1} is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is an alkyl halide group, the halogen atom contained in the alkyl halide group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The alkyl halide group may be linear or branched, and is preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as those of the cyclic organic group that ^{R c8} and R ^{c9 have as substituents.} When A ² is an alkoxycarbonyl group, examples of alkoxycarbonyl groups are similar to the alkoxycarbonyl groups that ^{R c8} and R ^{c9 have as substituents.}

Suitable specific examples of R ^c8 and R ^c9 are alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl. Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n Cyanoalkyl groups such as −pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl Phyl groups such as groups, 4-phenyl-n-butyl groups, 5-phenyl-n-pentyl groups, 6-phenyl-n-hexyl groups, 7-phenyl-n-heptyl groups, and 8-phenyl-n-octyl groups. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy Carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy Carbonyl ethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-etoki An alkoxycarbonylalkyl group such as a sicarbonyl-n-heptyl group and an 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5- Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4- Bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-tri Examples thereof include a fluoropropyl group and an alkyl halide group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among the above-mentioned suitable groups as R ^c8 and R ^c9 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group and 2-phenylethyl group. 2-Cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,5,5,5-hepta It is a fluoro-n-pentyl group.

Examples of suitable organic groups for R ^c10 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups and substituents ^{, as in R c7.} A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent. A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group which may have a group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like. Specific examples of these groups are similar to those described for ^{R c7.} Further, as R ^c10 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained ^{in R c7 may have.}

Among the organic groups, R ^c10 includes an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthio which may have a substituent on the aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is the most preferable. preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups that may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

^As the ^{R c10,} a group represented by -A 3 ^{-CO-O-A 4} are also preferred. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group is preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

Preferred examples of A ^4, the number 1 to 10 alkyl group carbon atoms, having 7 or more carbon atoms and 20 or less aralkyl group, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific preferable examples of A ⁴ is methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, n- pentyl group, n- hexyl Examples thereof include a group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group and the like.

Preferable specific examples of the group represented by −A ³ −CO—O—A ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n. -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group and the like.

（式（ｃ４ａ）及び（ｃ４ｂ）中、Ｒ^ｃ１３及びＲ^ｃ１４はそれぞれ有機基であり、ｎ６は０以上４以下の整数であり、Ｒ^ｃ１３及びＲ^ｃ１４がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１３とＲ^ｃ１４とが互いに結合して環を形成してもよく、ｎ７は１以下８以下の整数であり、ｎ８は１以上５以下の整数であり、ｎ９は０以上（ｎ８＋３）以下の整数であり、Ｒ^ｃ１５は有機基である。） ^Having described ^{R c10,} as the ^{R c10,} preferably a group represented by the following formula (C4a) or (C4b).

(In formulas (c4a) and (c4b), R ^c13 and R ^c14 are organic groups, respectively, n6 is an integer of 0 or more and 4 or less, and R ^c13 and R ^c14 are present at adjacent positions on the benzene ring. In this case, R ^c13 and R ^c14 may be combined with each other to form a ring, n7 is an integer of 1 or less and 8 or less, n8 is an integer of 1 or more and 5 or less, and n9 is 0 or more (n8 + 3). It is the following integer, and R ^c15 is an organic group.)

Examples of organic groups for ^{R c13} and R ^{c14 in} formula (c4a) are similar to ^{R c7.} As R ^c13 , an alkyl group or a phenyl group is preferable. When R ^c13 is an alkyl group, the number of carbon atoms thereof is preferably 1 or less and 10 or more, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (c4a) in which R ^c13 and R ^c14 form a ring include a naphthalene-1-yl group and 1,2,3,4-. Examples thereof include a tetrahydronaphthalene-5-yl group. In the above formula (c4a), n6 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (c4b), R ^c15 is an organic group. ^Examples of the organic group include groups similar to the organic group described for R c7. Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the above formula (c4b), n8 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (c4b), n9 is 0 or more (n8 + 3) or less, an integer of 0 or more and 3 or less is preferable, an integer of 0 or more and 2 or less is more preferable, and 0 is particularly preferable. In the above formula (c4b), n7 is an integer of 1 or more and 8 or less, an integer of 1 or more and 5 or less is preferable, an integer of 1 or more and 3 or less is more preferable, and 1 or 2 is particularly preferable.

In the formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As the ^{substituent which may be possessed when R c11} is an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. Further, ^{as the substituent which may be possessed when R c7} is an aryl group, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

In the formula (c4), as R ^c11 , a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified. Of these, a methyl group or a phenyl group is more preferable.

The compound represented by the formula (c4) has an oxime group (> C = N-OH) contained in the compound represented by the above formula (c5) represented by> C = NO-COR ^c11. Manufactured by a method comprising the step of converting to an oxime ester group. R ^c11 are the same as ^{R c11} in formula (c4).

The conversion of the oxime group (> C = N-OH) ^{to the oxime ester group represented by> C = NO-COR c11} is carried out by using the compound represented by the above formula (c5) and an acylating agent. It is done by reacting.
The acylating agent to give the acyl group represented by -COR ^{c11, (R c11} _CO) or an acid anhydride represented by ₂ ^O, R c11 COHal (Hal is a halogen atom) include acid halide represented by Be done.

The compound represented by the general formula (c4) can be synthesized, for example, according to the following scheme 3 when n5 is 0. In Scheme 3, a fluorene derivative represented by the following formula (c3-1) is used as a raw material. When R ^c7 is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (c3-1) is replaced with a fluorene derivative in which the 9-position is ^{substituted with R c8} and R ^c9 by a well-known method. It can be obtained by introducing a substituent R ^c7. The fluorene derivative in which the 9-position is ^{substituted with R c8} and R ^c9 is, for example, an alkali metal hydroxide as described in JP-A-06-234668 when ^{R c8} and R ^{c9 are alkyl groups.} It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotonic polar organic solvent. Further, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By carrying out the alkylation reaction, 9,9-alkyl substituted fluorene can be obtained.

^{An acyl group represented by -CO-R c10} is introduced into the fluorene derivative represented by the formula (c3-1) by a Friedel-Crafts acylation reaction, and the fluorene derivative represented by the formula (c3-3) is obtained. can get. The acylating agent for introducing an acyl group represented by -CO-R ^{c10 may be a halocarbonyl compound or an acid anhydride.} As the acylating agent, a halocarbonyl compound represented by the formula (c3-2) is preferable. In formula (c3-2), H is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction or by protecting and deprotecting other positions at the acylated position. can.

^{Next, the group represented by -CO-R c10} in the obtained fluorene derivative represented by the formula (c3-3) is converted into a group represented by -C (= N-OH) -R ^c10. The oxime compound represented by the formula (c3-4) is obtained. The method for converting the group represented by -CO-R ^c10 to the group represented by -C (= N-OH) -R ^c10 is not particularly limited, but oxime formation with hydroxylamine is preferable. The oxime compound of the formula (c3-4) and the acid anhydride ((R ^c11 CO) ₂ O) represented by the following formula (c3-5), or the acid halide represented by the following formula (c3-6) ( R ^c11 COHal and Hal are halogen atoms.) To obtain a compound represented by the following formula (c3-7).

In the formulas (c3-1), (c3-2), (c3-3), (c3-4), (c3-5), (c3-6), and (c3-7), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^c11 are the same as in the formula (c4).

^{Further, in Scheme 3, R c10} contained in each of the formula (c3-2), the formula (c3-3), and the formula (c3-4) may be the same or different. ^{That is, R c10} in the formulas (c3-2), formula (c3-3), and formula (c3-4) may undergo chemical modification in the synthetic process represented as Scheme 3. Examples of chemical modifications include esterification, etherification, acylation, amidation, halogenation, substitution of hydrogen atoms in amino groups with organic groups, and the like. The ^{chemical modifications that R c10} may undergo are not limited to these.

<Scheme 3>

The compound represented by the formula (c4) can be synthesized, for example, according to the following scheme 4 when n5 is 1. In Scheme 4, a fluorene derivative represented by the following formula (c4-1) is used as a raw material. Table fluorene derivative represented by the formula (C4-1) carries out the same method as in Scheme 3, the compound represented by the formula (c3-1), with _-CO-CH ^{2 -R c10} by Friedel-Crafts reaction It is obtained by introducing the acyl group to be used. As the acylating agent, a carboxylic acid halide represented by the formula (c3-8): Hal-CO-CH _2- R ^{c10 is preferable. Next, the methylene group existing between the R c10} and the carbonyl group in the compound represented by the formula (c4-1) is oxime-ized to obtain the keto-oxime compound represented by the following formula (c4-3). The method for oxime-forming the methylene group is not particularly limited, but the nitrite ester represented by the following general formula (c4-2) in the presence of hydrochloric acid (RONO and R are alkyl groups having 1 to 6 carbon atoms). Is preferred. Next, the ketooxime compound represented by the following formula (c4-3) and the acid anhydride (R ^c11 CO) ₂ O) represented by the following formula (c4-4), or the following formula (c4-5). The acid halide (R ^c11 COHal, Hal is a halogen atom) is reacted with the acid halide (R c11 COHal, Hal is a halogen atom) to obtain a compound represented by the following formula (c4-6). In the following formulas (c4-1), (c4-3), (c4-4), (c4-5), and (c4-6), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^c11 is the same as the equation (c4).
When n5 is 1, there is a tendency that the generation of foreign substances in the pattern formed by using the photosensitive composition containing the compound represented by the formula (c4) can be further reduced.

^{Further, in Scheme 4, R c10} contained in each of the formula (c3-8), the formula (c4-1), and the formula (c4-3) may be the same or different. ^{That is, R c10} in the formulas (c3-8), formula (c4-1), and formula (c4-3) may undergo chemical modification in the synthetic process represented as Scheme 4. Examples of chemical modifications include esterification, etherification, acylation, amidation, halogenation, substitution of hydrogen atoms in amino groups with organic groups, and the like. The ^{chemical modifications that R c10} may undergo are not limited to these.

<Scheme 4>

Preferable specific examples of the compound represented by the formula (c4) include the following PI-43 to PI-83.

The content of the photopolymerization initiator is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the solid content of the photosensitive composition of the first aspect. Within the above range, sufficient heat resistance and chemical resistance can be obtained, the coating film forming ability can be improved, and curing defects can be suppressed.

The photosensitive composition of the first aspect contains the hydrogen barrier agent (B) as described above. When this compound is contained in a photosensitive composition, a pattern having hydrogen barrier performance can be formed.

The content of the hydrogen barrier agent (B) is preferably 0.5 parts by mass or more and 95 parts by mass or less, and 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the photopolymerization initiator. More preferred. Within the above range, a hydrogen barrier film having excellent hydrogen barrier properties can be formed, and good micropatterning characteristics can be obtained while obtaining good developability.

The photosensitive composition of the first aspect may further contain a colorant. By containing a colorant, it is preferably used for forming a color filter in an image display device such as a liquid crystal display or an organic EL display. Further, the photosensitive composition of the first aspect is preferably used as a black matrix forming application in a color filter, for example, by containing a light-shielding agent as a colorant.

The colorant is not particularly limited, but for example, a compound classified as Pigment in the Color Index (CI; The Society of Dyers and Colorists), specifically, the following. It is preferable to use a pigment having a color index (CI) number.

C. I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53. , 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 , 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180. 185;
C. I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the number is described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46. , 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 , 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 , 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215 , 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only the number is described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , 66;
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37;
C. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26, C.I. I. Pigment Brown 28;
C. I. Pigment Black 1, C.I. I. Pigment Black 7.

When the colorant is a light-shielding agent, it is preferable to use a black pigment as the light-shielding agent. Examples of black pigments include metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, composite oxides, metal sulfides, metal sulfates and metal carbonates. , Various pigments regardless of organic or inorganic substances can be mentioned. Among these, it is preferable to use carbon black having a high light-shielding property.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light-shielding properties. Further, resin-coated carbon black may be used.

Since resin-coated carbon black has lower conductivity than carbon black without resin coating, it produces a highly reliable and low power consumption display with less current leakage when used as a black matrix for liquid crystal display. can.

Further, in order to adjust the color tone of carbon black, the above organic pigment may be appropriately added as an auxiliary pigment.

Further, a dispersant may be further used in order to uniformly disperse the colorant in the photosensitive composition. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

Further, the inorganic pigment and the organic pigment may be used alone or in combination, but when they are used in combination, 10 parts by mass of the organic pigment is used with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferably used in the range of 20 parts by mass or more and 80 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less.

The content of the colorant may be appropriately determined according to the use of the photosensitive composition of the first aspect, but as an example, with respect to 100 parts by mass of the solid content of the photosensitive composition of the first aspect. It is preferably 5 parts by mass or more and 70 parts by mass or less, and more preferably 25 parts by mass or more and 60 parts by mass or less.
In particular, when the black matrix is formed using the photosensitive composition of the first aspect, the light-shielding agent in the photosensitive composition is used so that the OD value per 1 μm of the black matrix film thickness is 4 or more. It is preferable to adjust the amount. When the OD value per 1 μm film thickness in the black matrix is 4 or more, sufficient display contrast can be obtained when used in the black matrix of a liquid crystal display.

The colorant is preferably added to the photosensitive composition after being prepared as a dispersion liquid dispersed at an appropriate concentration using a dispersant.

Examples of the organic solvent in the photosensitive composition of the first aspect include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol mono. Ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , Dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; Lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanemethyl, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl pro Pionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , Methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone , N, N-dimethylformamide, N, N-dimethylacetamide, amides such as solvents represented by the above formula (a04) and the like. These organic solvents can be used alone or in combination of two or more.

Among the above organic solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-methoxybutyl acetate, N-methylpyrrolidone , N, N-dimethylformamide, N, N-dimethylacetamide, and amides such as the solvent represented by the formula (a04) are the alkali-soluble resin (A1), the photopolymerizable compound (A2), and the light. It is preferable because it exhibits excellent solubility in the polymerization initiator (C) and the hydrogen barrier agent (B).

The content of the organic solvent is preferably such that the solid content concentration of the photosensitive composition of the first aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

The photosensitive composition of the first aspect may contain various additives, if necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion accelerator, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, a thermal polymerization inhibitor, a defoaming agent, a surfactant and the like.
In addition, as optional additives, 1- (N, N-di (2-ethylhexyl) amino) methyl-1H-benzotriazole, 1- (N, N-di (2-ethylhexyl) amino) methyl-1H-methyl Benzotriazole derivatives such as benzotriazole, carboxybenzotriazole, benzotriazole, methylbenzotriazole, dihydroxypropylbenzotriazole, and bisaminomethylbenzotriazole may be used alone or in combination of two or more.
The amount of the various additives added may be appropriately adjusted in the range of, for example, 0.001% by mass and 10% by mass or less, preferably 0.1% by mass or more and 5% by mass or less, based on the entire composition. ..

(2) Photosensitive composition of the second aspect The photosensitive composition of the second aspect is a positive photosensitive composition. When the photosensitive composition of the second aspect is a chemically amplified positive photosensitive composition, an acid generator that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as a photoacid generator) and It contains a resin whose solubility in alkali is increased by the action of an acid (hereinafter, also referred to as a photosensitive resin). The photosensitive resin composition may contain components such as an alkali-soluble resin, an acid diffusion inhibitor, and an organic solvent, if necessary. Examples of the photosensitive composition of the second aspect include a positive photosensitive composition containing a quinonediazide group-containing compound and an alkali-soluble resin such as a novolak phenol resin (for example, a novolak resin (C1) described later).

The film thickness of the resist pattern formed by using the photosensitive composition of the second aspect is not particularly limited. The photosensitive composition of the second aspect is preferably used for forming a thick-film resist pattern. Specifically, the film thickness of the resist pattern formed by using the photosensitive composition of the second aspect is preferably 10 μm or more, more preferably 10 μm or more and 150 μm or less, particularly preferably 20 μm or more and 120 μm or less, and particularly preferably. Is most preferably 20 μm or more and 80 μm or less.

Hereinafter, the essential or arbitrary components contained in the photosensitive composition of the second aspect and the method for producing the photosensitive resin composition will be described.

The photoacid generator is a compound that generates an acid by irradiation with active light or radiation, and is not particularly limited as long as it is a compound that directly or indirectly generates an acid by light.
Hereinafter, suitable examples of the photoacid generator preferably used in the photosensitive composition of the second aspect will be described.

A first example of a suitable photoacid generator is a compound represented by the following formula (a1).

In the above formula (a1), X ^1a represents a sulfur atom or an iodine atom having a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1a is an ^{organic group bonded to X 1a} , which includes an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, and an alkyl group having 1 to 30 carbon atoms. Represents an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, and R ^1a is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio. At least one selected from the group consisting of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens. It may be replaced with a seed. The number of R ^1a is g + h (g-1) + 1, and R ^1a may be the same or different from each other. Also, directly with each other two or more ^{R 1a,} or _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2a -, - CO -, - COO -, - CONH- , An alkylene group having 1 or more and 3 or less carbon atoms or a phenylene group may be bonded to form a ring structure containing ^{X 1a.} R ^2a is an alkyl group having 1 or more and 5 or less carbon atoms or an aryl group having 6 or more and 10 or less carbon atoms.

X ^2a has a structure represented by the following formula (a2).

In the above formula (a2), X ^4a contains an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms. Represented, X ^4a is composed of an alkyl having 1 to 8 carbon atoms, an alkoxy having 1 to 8 carbon atoms, an aryl, hydroxy, cyano, and nitro groups having 6 to 10 carbon atoms, and a halogen. It may be replaced with at least one selected. X ^5a is _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2a -, - CO -, - COO -, - CONH-, carbon atom number of 1 to 3 alkylene Represents a group or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h + 1 ^X4a and the h ^X5a may be the same or different, respectively. R ^2a is the same as the above definition.

X ^3a- is a counterion of onium, and examples thereof include a fluorinated alkylfluorophosphate anion represented by the following formula (a17) and a borate anion represented by the following formula (a18).

In the above formula (a17), R ^3a represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. j indicates the number thereof, and is an integer of 1 or more and 5 or less. The j R ^3a may be the same or different.

In the above formula (a18), R ^{4a to} R ^7a independently represent a fluorine atom or a phenyl group, and a part or all of the hydrogen atoms of the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. It may be replaced with at least one of the above.

Examples of the onium ion in the compound represented by the above formula (a1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, and bis [4- (diphenylsulfonio) phenyl] sulfide. Bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-) Chlorophenylthio) Phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -Thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-Benzoylphenylthio) Phenyldiphenylsulfonium, diphenylphenacilsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacilsulfonium, phenyl [4- (4-Biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetophenylthio) phenyl] diphenylsulfonium, octadecylmethylphenacylsulfonium , Diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- Examples thereof include (2-hydroxytetradecyloxy) phenylphenyl iodonium, 4-isopropylphenyl (p-tolyl) iodonium, 4-isobutylphenyl (p-tolyl) iodonium, and the like.

Among the onium ions in the compound represented by the above formula (a1), preferable onium ions include sulfonium ions represented by the following formula (a19).

In the above formula (a19), R ^8a is independently composed of a hydrogen atom, an alkyl, a hydroxy, an alkoxy, an alkylcarbonyl, an alkylcarbonyloxy, an alkyloxycarbonyl, a halogen atom, and an aryl, an arylcarbonyl, which may have a substituent. Represents a group selected from the group. X ^2a represents the same meaning as ^{X 2a} in the formula (a1).

Specific examples of the sulfonium ion represented by the above formula (a19) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4-. (4-Benzoylphenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4) Examples thereof include −acetophenylthio) phenyl] diphenylsulfonium and diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium.

In the fluorinated alkylfluorophosphate anion represented by the above formula (a17), R ^3a represents an alkyl group substituted with a fluorine atom, and the preferable number of carbon atoms is 1 or more and 8 or less, and the more preferable number of carbon atoms is 1 or more. It is 4 or less. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclopentyl. , Cycloalkyl groups such as sikuhexyl, and the proportion of the hydrogen atom of the alkyl group substituted with a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of the fluorine atom is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by the above formula (a1) decreases.

Particularly preferable R ^3a is a linear or branched perfluoroalkyl group having 1 or more and 4 or less carbon atoms and a fluorine atom substitution rate of 100%. Specific examples thereof include CF ₃ and CF ₃ CF. _{2, (CF 3) 2 CF} , CF 3 CF 2 CF 2, CF 3 CF 2 CF 2 CF 2, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, is _{(CF 3)} 3 C Can be mentioned. The number j of R ^3a is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among these, [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , or [((CF 3) 2 CF) CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ is particularly preferable.

Specific preferred examples of the borate anion represented by the formula (a18), tetrakis (pentafluorophenyl) borate _{([B (C 6 F 5} ) 4] -), tetrakis [(trifluoromethyl) phenyl] borate ( [B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro (pentafluorophenyl) borate ([(C) ₆ F ₅ ) BF ₃ ] ^- ), tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ) and the like. Among these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

A second example of a suitable photoacid generator is 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2. -(2-Frill) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl ] -S-Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-) 5-propoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4 -Bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-[ 2- (3,5-Dimeth Xyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1 , 3,5-Triazine, 2- (3,4-Methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, Tris (1,3-dibromopropyl) -1, Halogen-containing triazine compounds such as 3,5-triazine and tris (2,3-dibromopropyl) -1,3,5-triazine, and tris (2,3-dibromopropyl) isocyanurate and the like according to the following formula (a3). Examples thereof include the represented halogen-containing triazine compounds.

In the above formula (a3), R ^9a , R ^10a , and R ^11a each independently represent an alkyl halide group.

Third examples of suitable photoacid generators include α- (p-toluenesulfonyloxyimine) -phenylacetonitrile, α- (benzenesulfonyloxyimine) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimine). Imino) -2,6-dichlorophenyl acetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenyl acetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile, and the following containing an oxime sulfonate group Examples thereof include a compound represented by the formula (a4).

In the above formula (a4), R ^12a represents a monovalent, divalent or trivalent organic group, and R ^13a is a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. It represents a compound group, and n represents the number of repeating units of the structure in parentheses.

In the above formula (a4), the aromatic compound group indicates a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aryl group such as a phenyl group or a naphthyl group, or a frill group. , Heteroaryl groups such as thienyl group can be mentioned. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like on the ring. Further, R ^13a is particularly preferably an alkyl group having 1 or more and 6 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. In particular, a ^{compound in which R 12a} is an aromatic compound group and R ^13a is an alkyl group having 1 to 4 carbon atoms is preferable.

As the photoacid generator represented by the above formula (a4), when n = 1, R ^12a is any of a phenyl group, a methyl phenyl group, and a methoxy phenyl group, and R ^13a is a compound having a methyl group. Specifically, α- (methylsulfonyloxyimino) -1-phenyl acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p) -Methylphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-ylidene] (o-tolyl) acetonitrile and the like can be mentioned. When n = 2, the photoacid generator represented by the above formula (a4) specifically includes a photoacid generator represented by the following formula.

A fourth example of a suitable photoacid generator is an onium salt having a naphthalene ring in the cation portion. By "having a naphthalene ring", it means having a structure derived from naphthalene, and it means that the structure of at least two rings and their aromaticity are maintained. This naphthalene ring has substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and a linear or branched alkoxy group having 1 to 6 carbon atoms. May be good. The structure derived from the naphthalene ring may be a monovalent group (one free valence) or a divalent group (two free valences) or more, but it may be a monovalent group. Desirable (however, at this time, the free valence shall be counted except for the portion bonded to the above substituent). The number of naphthalene rings is preferably 1 or more and 3 or less.

As the cation portion of the onium salt having a naphthalene ring in such a cation portion, a structure represented by the following formula (a5) is preferable.

In the above formula (a5), ^{at least one of R 14a} , R ^15a , and R ^16a represents a group represented by the following formula (a6), and the rest are linear or branched with 1 to 6 carbon atoms. Represents an alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14a , R ^15a , and R ^16a is a group represented by the following formula (a6), and the remaining two are independently linear or branched with 1 to 6 carbon atoms. It is an alkylene group of, and these ends may be bonded to form a cyclic.

In the above formula (a6), R ^17a and R ^18a are independently hydroxyl groups, linear or branched alkoxy groups having 1 to 6 carbon atoms, or linear or branched having 1 to 6 carbon atoms, respectively. It represents a branched alkyl group, and R ^19a represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent. l and m each independently represent an integer of 0 or more and 2 or less, and l + m is 3 or less. However, ^{when there are a plurality of R 17a} , they may be the same or different from each other. Further, ^{when a plurality of R 18a} exist, they may be the same or different from each other.

Of the above R ^14a , R ^15a , and R ^16a , the number of groups represented by the above formula (a6) is preferably one from the viewpoint of compound stability, and the rest is directly formed with 1 or more and 6 or less carbon atoms. It is a chain or branched alkylene group, and these ends may be bonded to form a cyclic group. In this case, the above two alkylene groups form a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group and the like.

The substituents that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms, and a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms. Alkoxy group and the like can be mentioned.

Suitable examples of these cation portions include those represented by the following formulas (a7) and (a8), and a structure represented by the following formula (a8) is particularly preferable.

The cation portion may be an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the viewpoint of acid generation efficiency and the like.

Therefore, as an anion portion of an onium salt having a naphthalene ring in the cation portion, an anion capable of forming a sulfonium salt is desirable.

The anion portion of such a photoacid generator is a fluoroalkyl sulfonic acid ion or an aryl sulfonic acid ion in which a part or all of hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkyl sulfonic acid ion may be linear, branched or cyclic with 1 or more and 20 or less carbon atoms, and has 1 or more and 10 or less carbon atoms from the bulkiness of the generated acid and its diffusion distance. Is preferable. In particular, branched or annular ones are preferable because they have a short diffusion distance. Moreover, since it can be synthesized at low cost, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like can be mentioned as preferable ones.

Examples of the aryl group in the aryl sulfonic acid ion include an aryl group having 6 to 20 carbon atoms, an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferable ones include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group and the like.

In the above fluoroalkyl sulfonic acid ion or aryl sulfonic acid ion, the fluorination rate when a part or all of hydrogen atoms is fluorinated is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. The following is particularly preferable, in which all hydrogen atoms are replaced with fluorine atoms because the acid strength becomes stronger. Specific examples thereof include trifluoromethanesulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

Among these, preferred anion portions include those represented by the following formula (a9).

In the above formula (a9), R ^20a is a group represented by the following formulas (a10), (a11), and (a12).

In the above equation (a10), x represents an integer of 1 or more and 4 or less. Further, in the above formula (a11), R ^21a is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, or a linear or branched alkyl group having 1 or more and 6 or less carbon atoms. Represents an alkoxy group in the form, and y represents an integer of 1 or more and 3 or less. Among these, trifluoromethanesulfonate and perfluorobutane sulfonate are preferable from the viewpoint of safety.

Further, as the anion portion, those containing nitrogen represented by the following formulas (a13) and (a14) can also be used.

The formula (a13), (a14) in, X ^a represents a linear or branched alkylene group having at least one hydrogen atom is substituted with a fluorine atom, the number of carbon atoms of the alkylene group 2 to 6 It is preferably 3 or more and 5 or less, and most preferably the number of carbon atoms is 3. Further, Y ^a and Z ^a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms of the alkyl group is 1 or more and 10 or less. It is preferably 1 or more and 7 or less, and more preferably 1 or more and 3 or less.

X ^a number of carbon atoms of the alkylene group, or Y ^a, soluble enough in organic solvents the number of carbon atoms in the alkyl group of Z ^a is less preferred because it is excellent.

Further, an alkylene group or Y ^a of X ^a, the alkyl groups of Z ^a, the larger the number of hydrogen atoms substituted with fluorine atoms is large, preferred because the acid strength increases. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably all hydrogen atoms are fluorine. It is an atomically substituted perfluoroalkylene group or perfluoroalkyl group.

Preferred as an onium salt having a naphthalene ring in such a cation portion include compounds represented by the following formulas (a15) and (a16).

Sixth examples of suitable photoacid generators include bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenyl). Sulfonyl) Bissulfonyldiazomethanes such as diazomethane; p-toluenesulfonic acid 2-nitrobenzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, nitrobenzyltosylate, dinitrobenzyltosylate, nitrobenzylsulfonate, nitrobenzylcarbo Nitrobenzyl derivatives such as nat, dinitrobenzylcarbonate; pyrogalloltrimesylate, pyrogalloltritosylate, benzyltosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide , N-Methylsulfonyloxyphthalimide and other sulfonic acid esters; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethane Sulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluo Onium salts such as lomethanesulfonate; benzointosylates such as benzointosylate and α-methylbenzointosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzylcarbonate and the like can be mentioned.

（式（ｃ−５）中、Ｒ^２２ａは、１価の有機基であり、Ｒ^２３ａ、Ｒ^２４ａ、Ｒ^２５ａ、及びＲ^２６ａ、それぞれ独立に、水素原子又は１価の有機基であり、Ｒ^２３ａとＲ^２４ａと、Ｒ^２４ａとＲ^２５ａと、又はＲ^２５ａとＲ^２６ａとは、それぞれ互いに結合して環を形成してもよい。） When used in combination with the hydrogen barrier agent (B), a particularly preferable photoacid generator includes a naphthalic acid derivative represented by the following formula (c-5).

(In formula (c-5), R ^22a is a monovalent organic group, and R ^23a , R ^24a , R ^25a , and R ^26a are independently hydrogen atoms or monovalent organic groups, and R ^23a and R ^24a , R ^24a and R ^25a , or R ^25a and R ^26a may be coupled to each other to form a ring.)

The organic group as R ^22a is not particularly limited as long as it does not interfere with the object of the present invention. The organic group may be a hydrocarbon group and may contain a hetero atom such as an O, N, S, P or halogen atom. Further, the structure of the organic group may be linear, branched, cyclic, or a combination of these structures.

Suitable organic groups as R ^22a include an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, and 6 carbon atoms which may have a substituent. An aryl group having 20 or less, an aralkyl group having 7 or more and 20 or less carbon atoms which may have a substituent, an alkylaryl group having 7 or more and 20 or less carbon atoms which may have a substituent, and camphor-10- Il group and the following formula (c-5a):
−R ^27a − (O) _a −R ^28a − (O) _b −Y ¹ −R ^29a ... (c-5a)
(In the formula (c-5a), Y ¹ is a single bond or an alkanediyl group having 1 or more and 4 or less carbon atoms. R ^27a and R ^28a are each having the number of carbon atoms which may be substituted with halogen atoms. An alkanediyl group of 2 or more and 6 or less, or an arylene group having 6 or more and 20 or less ^{carbon atoms which may be substituted with a halogen atom. R 29a} has 1 or more and 18 or less carbon atoms which may be substituted with a halogen atom. Alkyl group, alicyclic hydrocarbon group having 3 to 12 carbon atoms, aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, and 7 carbon atoms which may be substituted with a halogen atom. 20 or less aralkyl groups. A and b are 0 or 1, respectively, and at least one of a and b is 1.)
The group represented by is mentioned.

When ^{the organic group as R 22a} has a halogen atom as a substituent, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

When ^{the organic group as R 22a} is an alkyl group having 1 or more and 18 or less carbon atoms substituted with an alkylthio group, the alkylthio group preferably has 1 or more and 18 or less carbon atoms.
Alkylthio groups having 1 to 18 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group and n-pentylthio. Group, isopentylthio group, tert-pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group , N-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, And n-octadecylthio groups.

When ^{the organic group as R 22a} is an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, the aliphatic hydrocarbon group is unsaturated. It may contain a double bond.
The structure of the aliphatic hydrocarbon group is not particularly limited, and may be linear, branched, cyclic, or a combination of these structures.

Preferable examples of the case where the organic group as R ^22a is an alkenyl group include an allyl group and a 2-methyl-2-propenyl group.

Preferable examples of the case where the organic group as R ^22a is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an isobutyl group. , N-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-hexane-2-yl group, n-hexane-3-yl group, n-heptyl group, n-heptan-2-yl group , N-Heptane-3-yl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, n Examples thereof include -undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group.

When ^{the organic group as R 22a} is an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like. Cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, and adamantan Can be mentioned. As the alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons is preferable.

Preferable examples of the case where the organic group as R ^22a is an aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group and a heptafluoro. -N-propyl group, 3-bromopropyl group, nonafluoro-n-butyl group, tridecafluoro-n-hexyl group, heptadecafluoro-n-octyl group, 2,2,2-trifluoroethyl group, 1, 1-difluoroethyl group, 1,1-difluoro-n-propyl group, 1,1,2,2-tetrafluoro-n-propyl group, 3,3,3-trifluoro-n-propyl group, 2,2 , 3,3,3-pentafluoro-n-propyl group, 2-norbornyl-1,1-difluoroethyl group, 2-norbornyltetrafluoroethyl group, and 3-adamantyl-1,1,2,2- Examples include a tetrafluoropropyl group.

Preferable examples of the case where the organic group as R ^22a is an aliphatic hydrocarbon group substituted with an alkylthio group are a 2-methylthioethyl group, a 4-methylthio-n-butyl group, and a 2-n-butylthio. Ethyl groups can be mentioned.

A preferred example of the case where the organic group as R ^22a is an aliphatic hydrocarbon group substituted with a halogen atom and an alkylthio group is a 3-methylthio-1,1,2,2-tetrafluoro-n-propyl group. Can be mentioned.

Preferable examples of the case where the organic group as R ^22a is an aryl group include a phenyl group, a naphthyl group and a biphenylyl group.

Preferable examples of the case where the organic group as R ^22a is an aryl group substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group and a trichlorophenyl group.

Preferable examples of the case where the organic group as R ^22a is an aryl group substituted with an alkylthio group include a 4-methylthiophenyl group, a 4-n-butylthiophenyl group, a 4-n-octylthiophenyl group, and 4 Examples include the -n-dodecylthiophenyl group.

A preferred example of the case where the organic group as R ^22a is an aryl group substituted with a halogen atom and an alkylthio group is a 1,2,5,6-tetrafluoro-4-methylthiophenyl group, 1,2,5. , 6-Tetrafluoro-4-n-butylthiophenyl group, 1,2,5,6-tetrafluoro-4-n-dodecylthiophenyl group.

Preferable examples of the case where the organic group as R ^22a is an aralkyl group include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group and a triphenylmethyl group.

Preferable examples of the case where the organic group as R ^22a is an aralkyl group substituted with a halogen atom include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyltetrafluoroethyl group and 2- (pentafluorophenyl). ) Ethyl group can be mentioned.

A preferred example of the case where the organic group as R ^22a is an aralkyl group substituted with an alkylthio group is a p-methylthiobenzyl group.

A preferred example of the case where the organic group as R ^22a is an aralkyl group substituted with a halogen atom and an alkylthio group is a 2- (2,3,5,6-tetrafluoro-4-methylthiophenyl) ethyl group. Can be mentioned.

Preferable examples of the case where the organic group as R ^22a is an alkylaryl group include 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, and the like. 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-octylphenyl group, 4- (2-ethyl -N-Hexyl) Phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3, 5-Dimethylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 2,6-di-tert-butylphenyl group, 2,4-di-tert- Pentylphenyl group, 2,5-di-tert-pentylphenyl group, 2,5-di-tert-octylphenyl group, 2-cyclohexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,4 Examples thereof include 5-trimethylphenyl group, 2,4,6-trimethylphenyl group and 2,4,6-triisopropylphenyl group.

The group represented by the formula (c-5a) is an ether group-containing group.
In the formula (c-5a), as the alkanediyl group of 1 to 4 carbon atoms represented by ^{Y 1,} a methylene group, ethane-1,2-diyl, ethane-1,1-diyl group, propane -1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2- The diyl group is mentioned.
In the formula (c-5a), ^{examples of the alkanediyl group having 2 or more and 6 or less carbon atoms represented by R 27a} or R ^28a include an ethane-1,2-diyl group, a propane-1,3-diyl group, and a propane. -1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group, pentane-1,5- Diyl group, pentane-1,3-diyl group, pentane-1,4-diyl group, pentane-2,3-diyl group, hexane-1,6-diyl group, hexane-1,2-diyl group, hexane- Examples thereof include 1,3-diyl group, hexane-1,4-diyl group, hexane-2,5-diyl group, hexane-2,4-diyl group, and hexane-3,4-diyl group.

In the formula (c-5a), when R ^27a or R ^28a is an arcandyl group having 2 or more and 6 or less carbon atoms substituted with a halogen atom, the halogen atoms include chlorine atom, bromine atom and iodine atom. And a fluorine atom. Examples of halogen-substituted alkanediyl groups include tetrafluoroethane-1,2-diyl group, 1,1-difluoroethane-1,2-diyl group, 1-fluoroethane-1,2-diyl group, 1,2-Difluoroethane-1,2-diyl group, hexafluoropropane-1,3-diyl group, 1,1,2,2, -tetrafluoropropane-1,3-diyl group, 1,1,2, Included are 2,-tetrafluoropentane-1,5-diyl groups.

^{Examples of cases where R 27a} or R ^28a is an arylene group in the formula (c-5a) include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a 2,5-dimethyl-. 1,4-phenylene group, biphenyl-4,4'-diyl group, diphenylmethane-4,4'-diyl group, 2,2,-diphenylpropane-4,4'-diyl group, naphthalene-1,2-diyl Group, Naphthalene-1,3-diyl group, Naphthalene-1,4-Diyl group, Naphthalene-1,5-Diyl group, Naphthalene-1,6-Diyl group, Naphthalene-1,7-Diyl group, Naphthalene-1 , 8-Diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group.

In the formula (c-5a), when R ^27a or R ^28a is an arylene group substituted with a halogen atom, the halogen atom includes a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the arylene group substituted with a halogen atom include 2,3,5,6-tetrafluoro-1,4-phenylene group.

In the formula (c-5a), ^{the alkyl group having 1 to 18 carbon atoms which may have a branch represented by R 29a} includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-. Butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-hexane-2-yl group, n-hexane-3-yl Group, n-heptyl group, n-heptane-2-yl group, n-heptane-3-yl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group , N-nonyl group, isononyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n -Octadecyl group is mentioned.

In the formula (c-5a), when R ^29a is an alkyl group having 1 or more and 18 or less carbon atoms substituted with a halogen atom, the halogen atom includes a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Can be mentioned. Examples of alkyl groups substituted with halogen atoms include trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, nonafluoro-n-butyl group, tridecafluoro-n-hexyl group, heptadecafluoro. -N-octyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoro-n-propyl group, 1,1,2,2-tetrafluoro-n-propyl Groups include 3,3,3-trifluoro-n-propyl group, 2,2,3,3,3-pentafluoro-n-propyl group and 1,1,2,2-tetrafluorotetradecyl group. ..

In the formula (c-5a), when R ^29a is an alicyclic hydrocarbon group having 3 or more and 12 or less carbon atoms, an example of an alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group. Cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane. , Bicyclo [2.2.2] octane, and adamantan. As the alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons is preferable.

In formula (c-5a), when R ^29a is an aryl group, an aryl halide group, an aralkyl group, or a halogenated aralkyl group, suitable examples of these groups are the same as when ^{R 22a is these groups.} Is.

Among the groups represented by the formula (c-5a), a preferable group is a group ^{represented by R 27a in} which the carbon atom bonded to the sulfur atom is replaced with a fluorine atom. The number of carbon atoms of such a suitable group is preferably 2 or more and 18 or less.

As R ^22a , a perfluoroalkyl group having 1 to 8 carbon atoms is preferable. Further, a camphor-10-yl group is also preferable as ^{R 22a} because it is easy to form a high-definition resist pattern.

In formula (c-5), R ^{23a to} R ^26a are hydrogen atoms or monovalent organic groups. Further, R ^23a and R ^24a , R ^24a and R ^25a , or R ^25a and R ^26a may be coupled to each other to form a ring. For example, ^{an acenaphthene skeleton may be formed by combining R 25a} and R ^26a to form a 5-membered ring together with a naphthalene ring.

The monovalent organic group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or a halogen atom, and may have a branch. An alkoxy group having 4 to 18 carbon atoms. Heterocyclyloxy group; Alkylthio group having 4 to 18 carbon atoms which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or a halogen atom and may have a branch; Heterocyclylthio Group; is preferred.
Further, a group in which a methylene group at an arbitrary position not adjacent to the oxygen atom of the alkoxy group is substituted with −CO− is also preferable.
A group in which the alkoxy group is interrupted by an -O-CO- bond or an -O-CO-NH- bond is also preferable. The left end of the -O-CO- bond and the -O-CO-NH- bond is the side of the alkoxy group close to the naphthalic acid matrix.
Further, an alkylthio group having 4 to 18 carbon atoms which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom and may have a branch is also preferable as ^{R 23a to} R ^26a.
A group in which the methylene group at an arbitrary position not adjacent to the sulfur atom of the alkylthio group is substituted with −CO− is also preferable.
A group in which the alkylthio group is interrupted by an -O-CO- bond or an -O-CO-NH- bond is also preferable. The left end of the -O-CO- bond and the -O-CO-NH- bond is the side of the alkylthio group close to the naphthalic acid matrix.

As R ^{23a to} R ^26a , R ^23a is an organic group and R ^{24a to} R ^26a are hydrogen atoms, or R ^24a is an organic group and R ^23a , R ^25a , and R ^26a are hydrogen atoms. Is preferable. Further, R ^{23a to} R ^26a may be all hydrogen atoms.

Examples of cases where R ^{23a to} R ^26a are unsubstituted alkoxy groups include n-butyloxy group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group and isopentyloxy group. tert-Pentyloxy group, n-hexyloxy group, n-heptyloxy group, isoheptyloxy group, tert-heptyloxy group, n-octyloxy group, isooctyloxy group, tert-octyloxy group, 2-ethylhexyl group , N-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group Examples thereof include a group, an n-heptadecyloxy group and an n-octadecyloxy group.

Examples of cases where R ^{23a to} R ^26a are unsubstituted alkylthio groups include n-butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group, n-pentylthio group, isopentylthio group and tert. -Pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n- Examples thereof include decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group and n-octadecylthio group. ..

When R ^{23a to} R ^26a are an alkoxy group or an alkylthio group substituted with an alicyclic hydrocarbon group, cyclopropane is an example of an alicyclic hydrocarbon constituting the main skeleton of an alicyclic hydrocarbon group. , Cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2. 2.2] Octane and Adamantane can be mentioned. As the alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons is preferable.

When R ^{23a to} R ^26a are an alkoxy group or an alkylthio group substituted with a heterocyclic group, or when R ^{23a to} R ^26a are heterocyclyloxy groups, the complex constituting the main skeleton of the heterocyclic group or heterocyclyloxy group. Examples of rings include pyrrol, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isooxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isooxazolidine, isothiazolidine. , Piperidine, piperazine, morpholin, thiomorpholin, chroman, thiochroman, isochroman, isothiochroman, indolin, isoindolin, pyrindin, indridin, indol, indazole, purine, quinolidine, isoquinolin, quinoline, naphthylidine, phthalazine, quinoxalin, quinazoline, Synnoline, pteridine, aclysine, perimidine, phenanthroline, carbazole, carboline, phenazine, antilysine, thiazazole, oxadiazol, triazine, triazole, tetrazole, benzoimidazole, benzoxazole, benzothiazole, benzothiazazole, benzofloxane, naphthoimidazole, Examples include benzotriazole and tetraazainden. Further, among these heterocycles, a saturated heterocycle obtained by hydrogenating a ring having a conjugated bond is also preferable.
As the heterocyclic group substituting the alkoxy group or the alkylthio group, or the heterocyclic group contained in the heterocyclyloxy group, a group obtained by removing one hydrogen atom from the above heterocycle is preferable.

Examples of cases where R ^{23a to} R ^26a are alkoxy groups containing an alicyclic hydrocarbon group include cyclopentyloxy group, methylcyclopentyloxy group, cyclohexyloxy group, fluorocyclohexyloxy group, chlorocyclohexyloxy group, and cyclohexylmethyl. Oxy group, methylcyclohexyloxy group, norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, 1-cyclohexyl Butyloxy group, adamantyloxy group, menthyloxy group, n-butylcyclohexyloxy group, tert-butylcyclohexyloxy group, bornyloxy group, isobornyloxy group, decahydronaphthyloxy group, dicyclopentadienoxy group, 1 -Cyclohexylpentyloxy group, methyladamantyloxy group, adamantylmethyloxy group, 4-pentylcyclohexyloxy group, cyclohexylcyclohexyloxy group, adamantylethyloxy group, dimethyladamantyloxy group.

Examples of cases where R ^{23a to} R ^26a are heterocyclyloxy groups include a tetrahydrofuranyloxy group, a furfuryloxy group, a tetrahydrofurfuryloxy group, a tetrahydropyranyloxy group, a butyrolactonyloxy group, and an indolyloxy group. The group is mentioned.

Examples of cases where R ^{23a to} R ^26a are alkylthio groups containing an alicyclic hydrocarbon group include a cyclopentylthio group, a cyclohexylthio group, a cyclopentylmethylthio group, a norbornylthio group, and an isonorbornylthio group.

Examples of cases where R ^{23a to} R ^26a are heterocyclylthio groups include a furfurylthio group and a tetrahydrofuranylthio group.

Examples of cases where R ^{23a to} R ^26a are groups in which the methylene group at an arbitrary position not adjacent to the oxygen atom of the alkoxy group is substituted with -CO- are 2-ketobutyl-1-oxy group and 2-ketopentyl. -1-oxy group, 2-ketohexyl-1-oxy group, 2-ketoheptyl-1-oxy group, 2-ketooctyl-1-oxy group, 3-ketobutyl-1-oxy group, 4-ketopentyl-1-oxy group , 5-ketohexyl-1-oxy group, 6-ketoheptyl-1-oxy group, 7-ketooctyl-1-oxy group, 3-methyl-2-ketopentan-4-oxy group, 2-ketopentan-4-oxy group, Examples thereof include 2-methyl-2-ketopentane-4-oxy group, 3-ketoheptane-5-oxy group and 2-adamantanone-5-oxy group.

Examples of cases where R ^{23a to} R ^26a are groups in which a methylene group at an arbitrary position not adjacent to the sulfur atom of the alkylthio group is substituted with -CO- are 2-ketobutyl-1-thio group and 2-ketopentyl. -1-thio group, 2-ketohexyl-1-thio group, 2-ketoheptyl-1-thio group, 2-ketooctyl-1-thio group, 3-ketobutyl-1-thio group, 4-ketopentyl-1-thio group , 5-Kethexyl-1-thio group, 6-ketoheptyl-1-thio group, 7-ketooctyl-1-thio group, 3-methyl-2-ketopentan-4-thio group, 2-ketopentan-4-thio group, Examples thereof include 2-methyl-2-ketopentane-4-thio group and 3-ketoheptane-5-thio group.

Preferable examples of the naphthalic acid derivative represented by the formula (c-5) include the following compounds.

Examples of other photoacid generators include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, and bis (1). , 1-Dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis ( 3-Methylphenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (4-tert-butylphenylsulfonyl) diazomethane, etc. Bissulfonyldiazomethanes; 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane, 2-methanesulfonyl-2-methyl- (p-) Sulfonylcarbonyl alkanes such as methylthio) propiophenone, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1 -Methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (1) , 1-Dimethylethylsulfonyl) -3,3-dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo-1- (p-toluenesulfonyl) -3,3- Dimethyl-2-butanone, 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p-toluenesulfonyl) -3-methyl-2-butanone, 2-diazo- Cyclohexyl 2- (p-toluenesulfonyl) acetate, 2-diazo-2-benzenesulfonylacetic acid-tert-butyl, 2-diazo-2-methanesulfonylacetic acid isopropyl, 2-diazo-2-benzenesulfonylacetic acid cyclohexyl, 2-diazo -2- (p-toluenesulfonyl) acetate-tert-butyl Sulfonylcarbonyldiazomethanes such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl and the like. Derivatives: Pyrogalol methanesulphonic acid ester, Pyrogalol benzenesulphonic acid ester, Pyrogarol p-toluenesulphonic acid ester, Pyrogalol p-methoxybenzenesulphonic acid ester, Pyrrobacterrol mesitylene sulphonic acid ester, Pyrrobacterrol benzyl sulfonic acid ester, Glutton Alkyl methanesulfonic acid ester, alkyl benzoate benzenesulfonic acid ester, alkyl dicedate p-toluenesulfonic acid ester, alkyl gallate (alkyl group has 1 to 15 carbon atoms) p-methoxy Examples thereof include esters of polyhydroxy compounds such as benzene sulfonic acid ester, mesityrene sulfonic acid ester of alkyl gallate, and benzyl sulfonic acid ester of alkyl gallate, and aliphatic or aromatic sulfonic acid.
These photoacid generators can be used alone or in combination of two or more.

This photoacid generator may be used alone or in combination of two or more. The content of the photoacid generator is preferably 0.1% by mass or more and 10% by mass or less, and 0.5% by mass or more and 3% by mass, based on the total mass of the photosensitive composition of the second aspect. More preferably, it is% or less. By setting the amount of the photoacid generator in the above range, it is easy to prepare the photosensitive composition of the second aspect, which has good sensitivity, is a uniform solution, and is excellent in storage stability.

The resin whose solubility in alkali is increased by the action of acid is not particularly limited, and any resin whose solubility in alkali is increased by the action of acid can be used. Among them, it is preferable to contain at least one resin selected from the group consisting of novolak resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3).

[Novolak resin (B1)]
As the novolak resin (B1), a resin containing a structural unit represented by the following formula (b1) can be used.

In the above formula (b1), R ^1b represents an acid dissociative dissolution inhibitory group, and R ^2b and R ^3b each independently represent a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms.

Examples of the ^{acid dissociative dissolution inhibitor group represented by R 1b} include a group represented by the following formulas (b2) and (b3), a linear, branched or cyclic alkyl having 1 to 6 carbon atoms. It is preferably a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrafuranyl group, or a trialkylsilyl group.

In the above formulas (b2) and (b3), R ^4b and R ^5b each independently represent a hydrogen atom or a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, and R ^6b is carbon. Represents a linear, branched, or cyclic alkyl group having 1 or more and 10 or less atoms, and R ^7b represents a linear, branched, or cyclic alkyl group having 1 or more and 6 or less carbon atoms. Represents 0 or 1.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. .. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

Here, as the acid dissociative dissolution inhibitory group represented by the above formula (b2), specifically, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, Examples thereof include isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid dissociative dissolution inhibitory group represented by the above formula (b3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include those having 1 or more and 6 or less carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
As the polyhydroxystyrene resin (B2), a resin containing a structural unit represented by the following formula (b4) can be used.

In the above formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, and R ^9b represents an acid dissociative dissolution inhibitory group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

As the ^{acid dissociative dissolution inhibitor represented by R 9b} , the same acid dissociative dissolution inhibitor as those exemplified in the above formulas (b2) and (b3) can be used.

Further, the polyhydroxystyrene resin (B2) can contain another polymerizable compound as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-. Methacrylic acid derivatives having carboxy groups and ester bonds such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meta) acrylic acid alkyl esters such as (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, (Meta) acrylic acid aryl esters such as benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, Vinyl group-containing aromatic compounds such as α-methylhydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile, methacrylonitrile and the like Examples thereof include nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide; and the like.

[Acrylic resin (B3)]
As the acrylic resin (B3), a resin containing a structural unit represented by the following formulas (b5) to (b7) can be used.

In the above formulas (b5) to (b7), R ^10b and R ^{14b to} R ^19b are independently hydrogen atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, fluorine atoms, or fluorine atoms, respectively. Represents a linear or branched fluorinated alkyl group ^{having 1 or more and 6 or less carbon atoms, and R 11b to} R ^13b are independently linear or branched alkyl groups having 1 or more and 6 or less carbon atoms. Represents a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms or an aliphatic cyclic group having 5 to 20 carbon atoms, and R ^12b and R ^13b are bonded to each other, and both are bonded to each other. A hydrocarbon ring having 5 or more and 20 or less carbon atoms may be formed together with the bonded carbon atom, and Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, and p. Represents an atom of 0 or more and 4 or less, and q represents 0 or 1.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Can be mentioned. The fluorinated alkyl group is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a fluorine atom.
Specific examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, a group obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Can be mentioned. In particular, a group obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have a substituent) is preferable.

When the R ^12b and R ^13b do not bond with each other to form a hydrocarbon ring ^{, the carbon atoms of the R 11b} , R ^12b , and R ^13b are high in contrast and have good resolution, depth of focus, and the like. It is preferably a linear or branched alkyl group having a number of 2 or more and 4 or less. The R ^15b , R ^16b , R ^18b , and R ^19b are preferably hydrogen atoms or methyl groups.

The R ^12b and R ^13b may form an aliphatic cyclic group having 5 or more and 20 or less carbon atoms together with the carbon atom to which both are bonded. Specific examples of such an aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group is mentioned. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Further, ^{when the aliphatic cyclic group formed by R 12b} and R ^13b has a substituent on its ring skeleton, examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, and an oxygen atom (= O). ), And linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (= O) is particularly preferable.

The Y ^b is an aliphatic cyclic group or an alkyl group, and examples thereof include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. .. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The basis etc. can be mentioned. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferable.

Further, when ^{the aliphatic cyclic group of Y b} has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxy group, a cyano group and an oxygen atom (= O). Examples thereof include a linear or branched alkyl group having 1 or more and 4 or less carbon atoms. As the polar group, an oxygen atom (= O) is particularly preferable.

When Y ^b is an alkyl group, it is preferably a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, preferably 6 or more and 15 or less. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, and a 1-isopropoxy. Ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -Ethoxy-1-methylethyl group and the like can be mentioned.

As a preferable specific example of the structural unit represented by the above formula (b5), the structural unit represented by the following formulas (b5-1) to (b5-33) can be mentioned.

In the above formulas (b5-1) to (b5-33), R ^20b represents a hydrogen atom or a methyl group.

As a preferable specific example of the structural unit represented by the above formula (b6), the structural unit represented by the following formulas (b6-1) to (b6-25) can be mentioned.

In the above formulas (b6-1) to (b6-25), R ^20b represents a hydrogen atom or a methyl group.

As a preferable specific example of the structural unit represented by the above formula (b7), the structural unit represented by the following formulas (b7-1) to (b7-15) can be mentioned.

In the above formulas (b7-1) to (b7-15), R ^20b represents a hydrogen atom or a methyl group.

Further, the acrylic resin (B3) is a resin composed of a copolymer containing a structural unit derived from a polymerizable compound having an ether bond with respect to the structural units represented by the above formulas (b5) to (b7). Is preferable.

Examples of the polymerizable compound having an ether bond include a radically polymerizable compound such as a (meth) acrylic acid derivative having an ether bond and an ester bond, and specific examples thereof include 2-methoxyethyl (meth) acrylate. , 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Examples thereof include acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. The polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Further, the acrylic resin (B3) can contain other polymerizable compounds as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic polymerizable compounds.

Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Methacrylic acid derivatives having carboxy groups and ester bonds such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) (Meta) acrylic acid alkyl esters such as acrylates and cyclohexyl (meth) acrylates; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylates and 2-hydroxypropyl (meth) acrylates; phenyl ( (Meta) acrylic acid aryl esters such as meta) acrylates and benzyl (meth) acrylates; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene , Hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl group-containing aromatic compounds; vinyl acetate and other vinyl group-containing aliphatic compounds; butadiene, isoprene and other conjugated diolefins; Binitrile group-containing polymerizable compounds such as bnitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide; and the like can be mentioned.

Examples of the polymerizable compound include (meth) acrylic acid esters having an acid-non-dissociating aliphatic polycyclic group, vinyl group-containing aromatic compounds, and the like. As the acid non-dissociative aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group and the like are particularly preferable in terms of being easily available industrially. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of the (meth) acrylic acid esters having an acid-non-dissociating aliphatic polycyclic group include (meth) acrylics given the structural units of the following formulas (b8-1) to (b8-5). Acid esters can be exemplified.

In the above formulas (b8-1) to (b8-5), R ^21b represents a hydrogen atom or a methyl group.

Among the above photosensitive resins, it is preferable to use an acrylic resin (B3). Among such acrylic resins (B3), a structural unit represented by the above formula (b5), a structural unit derived from (meth) acrylic acid, and a configuration derived from (meth) acrylic acid alkyl esters. It is preferably a copolymer having a unit and a constituent unit derived from (meth) acrylic acid aryl esters.

Such a copolymer is preferably a copolymer represented by the following formula (b9).

In the above formula (b9), R ^22b represents a hydrogen atom or a methyl group, R ^23b represents a linear or branched alkyl group having 2 to 4 carbon atoms, and X ^b is a bond to which it is bonded. ^Represents a hydrocarbon ring having 5 or more and 20 or less carbon atoms formed together with the carbon atoms, and R 24b is a linear or branched alkyl group having 1 or more and 6 or less carbon atoms or 1 or more carbon atoms. Represents an alkoxyalkyl group of 6 or less, and R ^25b represents an aryl group having 6 or more and 12 or less carbon atoms.

Further, in the copolymer represented by the above formula (b9), s, t, u, and v represent the molar ratio of each constituent unit, s is 8 mol% or more and 45 mol% or less, and t is 10. It is mol% or more and 65 mol% or less, u is 3 mol% or more and 25 mol% or less, and v is 6 mol% or more and 25 mol% or less.

The polystyrene-equivalent mass average molecular weight of the photosensitive resin is preferably 10,000 or more and 600,000 or less, more preferably 20,000 or more and 400,000 or less, and further preferably 30,000 or more and 300,000 or less. By setting such a mass average molecular weight, sufficient strength of the photosensitive resin layer can be maintained without deteriorating the peelability from the substrate surface, and further, swelling of the profile and occurrence of cracks during plating can be prevented. Can be done.

Further, the photosensitive resin is preferably a resin having a dispersity of 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting such a dispersion degree, it is possible to avoid problems such as stress resistance to the desired plating and the tendency of the metal layer obtained by the plating treatment to swell.

The content of the resin is preferably 5% by mass or more and 60% by mass or less with respect to the total mass of the photosensitive composition of the second aspect.

The photosensitive composition of the second aspect preferably further contains an alkali-soluble resin in order to improve crack resistance.
The alkali-soluble resin is preferably at least one resin selected from the group consisting of novolak resin (C1), polyhydroxystyrene resin (C2), and acrylic resin (C3).

[Novolak resin (C1)]
The novolak resin is obtained, for example, by adding and condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes under an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-Xylenol, 2,4-Xylenol, 2,5-Xylenol, 2,6-Xylenol, 3,4-Xylenol, 3,5-Xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples thereof include trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, fluoroxylenol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like.
The catalyst at the time of the addition condensation reaction is not particularly limited, but for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

The flexibility of the novolak resin can be further improved by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes. Is.

The mass average molecular weight of the novolak resin (C1) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 1000 or more and 50,000 or less.

[Polyhydroxystyrene resin (C2)]
Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (C2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like.
Further, the polyhydroxystyrene resin (C2) is preferably a copolymer with the styrene resin. Examples of the styrene-based compound constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene and the like.

The mass average molecular weight of the polyhydroxystyrene resin (C2) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 1000 or more and 50,000 or less.

[Acrylic resin (C3)]
The acrylic resin (C3) preferably contains a structural unit derived from a polymerizable compound having an ether bond and a structural unit derived from a polymerizable compound having a carboxy group.

Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, and phenoxypolyethylene glycol ( Examples thereof include (meth) acrylic acid derivatives having ether bonds and ester bonds such as meta) acrylates, methoxypolypropylene glycol (meth) acrylates, and tetrahydrofurfuryl (meth) acrylates. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Examples of the polymerizable compound having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Examples of compounds having a carboxy group and an ester bond such as ethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid; and the like can be exemplified. The polymerizable compound having a carboxy group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

The mass average molecular weight of the acrylic resin (C3) is not particularly limited as long as it does not impair the object of the present invention, but is preferably 50,000 or more and 800,000 or less.

When the total content of the photosensitive resin and the alkali-soluble resin is 100 parts by mass, the content of the alkali-soluble resin is preferably 0 parts by mass or more and 80 parts by mass or less, and more preferably 0 parts by mass or more and 60 parts by mass or less. By setting the content of the alkali-soluble resin in the above range, the crack resistance tends to be improved and the film loss during development tends to be prevented.

The photosensitive resin composition of the second aspect preferably further contains an acid diffusion control agent in order to improve the retention stability of the film made of the photosensitive composition. As the acid diffusion control agent, a nitrogen-containing compound (D1) is preferable, and if necessary, an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof (D2) can be contained.

[Nitrogen-containing compound (D1)]
Examples of the nitrogen-containing compound (D1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine and n-hexylamine. , N-Heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propion Amide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benz Imidazole, 4-methylimidazole, 8-oxyquinolin, aclysine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholin, 4-methylmorpholin, piperazin, 1,4- Examples thereof include dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, pyridine and the like. These may be used alone or in combination of two or more.

The nitrogen-containing compound (D1) is usually used in a range of 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the photosensitive resin and the alkali-soluble resin, and is 0 parts by mass or more and 3 parts by mass or less. It is particularly preferable to use it in a range.

[Organic carboxylic acid, or phosphorus oxo acid or derivative thereof (D2)]
Among the organic carboxylic acids, phosphorus oxo acids or derivatives thereof (D2), the organic carboxylic acids are specifically malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like. , Particularly salicylic acid is preferred.

Phosphate oxo acids or derivatives thereof include phosphoric acids such as phosphoric acid, di-n-butyl ester of phosphoric acid, diphenyl ester of phosphoric acid and derivatives such as esters thereof; phosphonic acid, dimethyl phosphonic acid ester, phosphonic acid- Phosphoric acids such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives such as their esters; such as phosphinic acid such as phosphinic acid, phenylphosphinic acid and their esters. Derivatives; etc. Of these, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

The organic carboxylic acid, or the oxo acid of phosphorus or a derivative thereof (D2) is usually used in a range of 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the photosensitive resin and the alkali-soluble resin. , It is particularly preferable to use in the range of 0 parts by mass or more and 3 parts by mass or less.

Further, in order to form and stabilize the salt, it is preferable to use the same amount of the organic carboxylic acid, or the oxo acid of phosphorus or its derivative (D2) as that of the nitrogen-containing compound (D1).

The photosensitive composition of the second aspect contains an organic solvent. The type of the organic solvent is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected and used from the organic solvents conventionally used in the positive photosensitive resin composition.

Specific examples of the organic solvent include the solvents mentioned in the photosensitive composition of the first aspect, as well as ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, and the like. Polyhydric alcohols such as diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether and derivatives thereof. Cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methoxypropionic acid Methyl, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3- Examples thereof include esters such as methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; and the like. These may be used alone or in combination of two or more.

The content of the organic solvent is not particularly limited as long as it does not impair the object of the present invention. When the photosensitive composition is used in a thick film application in which the thickness of the photosensitive resin layer obtained by a spin coating method or the like is 10 μm or more, the solid content concentration of the photosensitive resin composition is 30% by mass or more and 55% by mass. It is preferable to use an organic solvent in the range of% or less.

The photosensitive composition of the second aspect may further contain a polyvinyl resin in order to improve plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinylmethyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. Can be mentioned. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

Further, the photosensitive composition of the second aspect further contains an adhesion aid in order to improve the adhesiveness between the hydrogen barrier membrane formed by using the photosensitive composition and the substrate, particularly the metal substrate. May be good.

In addition, the photosensitive composition of the second aspect may further contain a surfactant in order to improve coatability, defoaming property, leveling property and the like. Specific examples of surfactants include BM-1000 and BM-1100 (all manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, and Megafuck F183 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.). ), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Commercially available fluorine-based surfactants such as Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) are listed. However, it is not limited to these.

The second photosensitive composition may further contain an acid, an acid anhydride, or a high boiling point solvent in order to fine-tune the solubility in a developing solution.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxymonocarboxylics such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycaterous acid, 3-hydroxycaterous acid, 4-hydroxycaterous acid, 5-hydroxyisophthalic acid, silingic acid, etc. Acids; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic Polyvalent carboxylic acids such as acids, butanetetracarboxylic acids, trimellitic acids, pyromellitic acids, cyclopentanetetracarboxylic acids, butanetetracarboxylic acids, 1,2,5,8-naphthalenetetracarboxylic acids; itaconic anhydride, anhydrous Succinic acid, citraconic anhydride, dodecenyl succinic anhydride, tricarbanyl anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic acid anhydride, Acid anhydrides such as cyclopentanetetracarboxylic acid dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis anhydride trimeritat, glycerintris anhydride trimeritate; etc. can.

Specific examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and benzyl. Ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, capric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , Propylene carbonate, phenylcellosolveacetate and the like.

The photosensitive composition of the second aspect may further contain a sensitizer in order to improve the sensitivity.

The content of the hydrogen barrier agent (B) is preferably 0.01% by mass or more and 30% by mass or less with respect to the mass of the resin corresponding to the base material component (A) in the photosensitive composition of the second aspect. It is more preferably 0.05% by mass or more and 20% by mass or less, and particularly preferably 0.1% by mass or more and 10% by mass or less. Within the above range, a pattern having hydrogen barrier performance can be obtained while obtaining good developability.

(3) Photosensitive composition of the third aspect The photosensitive composition of the third aspect contains an alkali-soluble resin having a phenolic hydroxyl group, an acid crosslinkable substance, a photoacid generator, a hydrogen barrier agent (B), and a hydrogen barrier agent (B). It is a negative photosensitive composition containing an organic solvent.

As the alkali-soluble resin having a phenolic hydroxyl group in the photosensitive composition of the third aspect, for example, a polyhydroxystyrene resin can be used.
The polyhydroxystyrene-based resin has at least a structural unit derived from hydroxystyrene.
Here, "hydroxystyrene" refers to hydroxystyrene, one in which the hydrogen atom bonded to the α-position of hydroxystyrene is substituted with another substituent such as a halogen atom, an alkyl group, or an alkyl halide group, and derivatives thereof. The concept includes the hydroxystyrene derivative (monomer) of.
In the "hydroxystyrene derivative", at least a benzene ring and a hydroxyl group bonded to the benzene ring are maintained. For example, the hydrogen atom bonded to the α-position of hydroxystyrene is a halogen atom or an alkyl group having 1 to 5 carbon atoms. , A device substituted with another substituent such as an alkyl halide group, or a benzene ring to which a hydroxyl group of hydroxystyrene is bonded, further bonded to an alkyl group having 1 or more and 5 or less carbon atoms, or a bond of this hydroxyl group. It is intended to include those in which one or more and two or less hydroxyl groups are further bonded to the benzene ring (at this time, the total number of hydroxyl groups is 2 or more and 3 or less).
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and the like, and a fluorine atom is preferable.
The "α-position of hydroxystyrene" refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The structural unit derived from this hydroxystyrene is represented by, for example, the following formula (b-1).

In the above formula (b-1), R ^b1 represents a hydrogen atom, an alkyl group, a halogen atom, or an alkyl halide group, R ^b2 represents an alkyl group having 1 or more and 5 or less carbon atoms, and p is 1 or more and 3 or more. The following integers are indicated, and q indicates an integer of 0 or more and 2 or less.

The alkyl group of R ^b1 preferably has 1 or more carbon atoms and 5 or less carbon atoms. Further, a linear or branched alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like are preferable. Can be mentioned. Among these, a methyl group is industrially preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
The alkyl halide group is a group in which a part or all of the hydrogen atoms of the above-mentioned alkyl group having 1 or more and 5 or less carbon atoms is substituted with a halogen atom. Among these, an alkyl group in which all hydrogen atoms are substituted with fluorine atoms is preferable. Further, a linear or branched alkyl fluorinated group is preferable, a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group and the like are more preferable, and a trifluoromethyl group (-CF ₃ ) is preferable. Is the most preferable.
As R ^b1 , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

^Examples of the alkyl group having 1 or more carbon atoms and 5 or less carbon atoms in R b2 include the same groups as in the case of ^{R b1.}
q is an integer of 0 or more and 2 or less. Among these, 0 or 1 is preferable, and industrially, it is particularly preferable to be 0.
The substitution position of R ^b2 may be any of the ortho position, the meta position, and the para position when q is 1, and any substitution position can be combined when q is 2.
p is an integer of 1 or more and 3 or less, and is preferably 1.
When p is 1, the hydroxyl group substitution position may be any of the ortho position, the meta position, and the para position, but the para position is preferable because it is easily available and inexpensive. Further, when p is 2 or 3, any substitution position can be combined.

The structural unit represented by the above formula (b-1) can be used alone or in combination of two or more.

The proportion of the constituent units derived from hydroxystyrene in the polyhydroxystyrene-based resin is preferably 60 mol% or more and 100 mol% or less, preferably 70 mol% or more, with respect to all the constituent units constituting the polyhydroxystyrene-based resin. It is more preferably 100 mol% or less, and further preferably 80 mol% or more and 100 mol% or less. By setting the content within the above range, appropriate alkali solubility can be obtained when the photosensitive composition is prepared.

The polyhydroxystyrene-based resin preferably further has a structural unit derived from styrene.
Here, the "structural unit derived from styrene" is defined to include a structural unit formed by cleaving the ethylenic double bond of styrene and a styrene derivative (however, hydroxystyrene is not included).
The "styrene derivative" is a derivative in which the hydrogen atom bonded to the α-position of styrene is replaced with another substituent such as a halogen atom, an alkyl group or an alkyl halide group, and the hydrogen atom of the phenyl group of styrene is carbon. It is defined to include a derivative or the like substituted with a substituent such as an alkyl group having 1 or more and 5 or less atoms.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and the like, and a fluorine atom is preferable.
The "α-position of styrene" refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The structural unit derived from this styrene is represented by, for example, the following formula (b-2). In the formula, R ^b1 , R ^b2 , and q are synonymous with the above formula (b-1).

^{Examples of R b1} and R ^b2 include groups similar to R ^b1 and R ^b2 of the above formula (b-1), respectively.
q is an integer of 0 or more and 2 or less. Among these, 0 or 1 is preferable, and industrially, it is particularly preferable to be 0.
The substitution position of R ^b2 may be any of the ortho position, the meta position, and the para position when q is 1, and any substitution position can be combined when q is 2.

The structural unit represented by the above formula (b-2) can be used alone or in combination of two or more.

The ratio of the constituent units derived from styrene in the polyhydroxystyrene-based resin is preferably 40 mol% or less, more preferably 30 mol% or less, based on all the constituent units constituting the polyhydroxystyrene-based resin. It is preferably 20 mol% or less, and more preferably 20 mol% or less. Within the above range, an appropriate alkali solubility can be obtained when the photosensitive composition is prepared, and the balance with other constituent units is also improved.

The polyhydroxystyrene-based resin may have a structural unit derived from hydroxystyrene or a structural unit other than the structural unit derived from styrene. More preferably, the polyhydroxystyrene-based resin is a polymer composed of only a structural unit derived from hydroxystyrene, or a copolymer composed of a structural unit derived from hydroxystyrene and a structural unit derived from styrene.

The mass average molecular weight of the polyhydroxystyrene resin is not particularly limited, but is preferably 1500 or more and 40,000 or less, and more preferably 2000 or more and 8000 or less.

Further, as the alkali-soluble resin having a phenolic hydroxyl group, a novolak resin can also be used. This novolak resin can be obtained by addition-condensing phenols and aldehydes in the presence of an acid catalyst.

Examples of phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4. Xylenols such as -xylenol, 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol , P-butylphenol, alkylphenols such as p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol, 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, Polyhydric phenols such as fluoroglycinol; Alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, alkylhydroquinone (the number of carbon atoms of the alkyl group contained in the alkyl polyhydric phenols is 1 or more and 4 or less); α -Naftor, β-naphthol, hydroxydiphenyl, bisphenol A and the like can be mentioned. These phenols can be used alone or in combination of two or more.
Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various characteristics such as sensitivity can be adjusted by adjusting the blending ratio of both.

Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. These aldehydes can be used alone or in combination of two or more.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid and phosphite; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfate and paratoluenesulfonic acid; and metal salts such as zinc acetate. Be done. These acid catalysts can be used alone or in combination of two or more.

Specific examples of the novolak resin thus obtained include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, and phenol-naphthol / formaldehyde condensed novolak resin.

The mass average molecular weight of the novolak resin is not particularly limited, but is preferably 1000 or more and 30,000 or less, and more preferably 3000 or more and 25,000 or less.

Further, as the alkali-soluble resin having a phenolic hydroxyl group, a phenol-xylylene glycol condensed resin, a cresol-xylylene glycol condensed resin, a phenol-dicyclopentadiene condensed resin or the like can also be used.

The content of the alkali-soluble resin having a phenolic hydroxyl group is preferably 20% by mass or more and 80% by mass or less, and 35% by mass or more and 65% by mass or less, based on the solid content of the photosensitive composition of the third aspect. Is more preferable. Within the above range, the developability tends to be easily balanced.

The acid-crosslinking substance in the photosensitive composition of the third aspect is not particularly limited, and conventionally known acid-crosslinking substances can be used.

Specific examples of the acid-crosslinkable substance include amino resins having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, acetoguanamine resin, benzoguanamine resin, glycoluryl-formaldehyde resin, succinylamide-formaldehyde resin, and ethylene. Urea-formaldehyde resin and the like can be mentioned. These acid-crosslinking substances are melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluryl, succinylamide, and ethyleneurea, which are reacted with formalin in boiling water to form methylol, or they are further reacted with a lower alcohol to form an alkoxyl. It can be easily obtained by converting to. Practically, it can be obtained as a melamine resin such as Nicarac MX-750, Nicarac MW-30, Nicarac MW100LM, and a urea resin such as Nicarac MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). In addition, benzoguanamine resins such as Cymel 1123 and Cymel 1128 (manufactured by Mitsui Sianad Co., Ltd.) can also be obtained as commercially available products.

Further, a benzene compound having an alkoxyl group such as 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, and 1,4-bis (sec-butoxymethoxy) benzene. Phenol compounds having a hydroxyl group or an alkoxyl group such as 2,6-dihydroxymethyl-p-tert-butylphenol can also be used.
These acid-crosslinkable substances can be used alone or in combination of two or more.

The content of the acid-crosslinkable substance is preferably 5 parts by mass or more and 50 parts by mass or less, and more preferably 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. preferable. Within the above range, the curability and patterning characteristics of the photosensitive composition are improved.

The photoacid generator in the photosensitive composition of the third aspect is not particularly limited, and conventionally known photoacid generators can be used. Preferred photoacid generators include the photoacid generators described for the second photosensitive composition.

The content of the photoacid generator is preferably 0.05 parts by mass or more and 30 parts by mass or less, and 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. Is more preferable. Within the above range, the curability of the photosensitive composition becomes good.

The photosensitive composition of the third aspect contains the hydrogen barrier agent (B) as described above. When this compound is contained in a photosensitive composition, a pattern having hydrogen barrier performance can be formed.

The content of the hydrogen barrier agent (B) is preferably 0.01% by mass or more and 30% by mass or less with respect to the mass of the resin corresponding to the base material component (A) in the photosensitive composition of the third aspect. It is more preferably 0.05% by mass or more and 20% by mass or less, and particularly preferably 0.1% by mass or more and 10% by mass or less. Within the above range, a pattern having hydrogen barrier performance can be obtained while obtaining good developability.

The photosensitive composition of the third aspect may further contain a compound having 4 or more phenolic hydroxyl groups and a molecular weight of less than 2000.

Specifically, such compounds include various benzophenone compounds such as tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, and heptahydroxybenzophenone, as well as bis [2-hydroxy-3- (2'-hydroxy-5'). -Methylbenzyl) -5-methylphenyl] methane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3, 4-Dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, Bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-4-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-4-methylphenyl) -3,4-dihydroxyphenylmethane Hydroxyaryl compounds such as 4-hydroxy-2,3,5-trimethylphenyl) -3,4-dihydroxyphenylmethane; 2- (2,3,4-trihydroxyphenyl) -2- (2', 3' , 4'-Trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2', 4'-dihydroxyphenyl) propane and other bis (hydroxyphenyl) alkane compounds; poly with a molecular weight of less than 2000 Polyhydroxy such as (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), poly (α-methyl-p-hydroxystyrene), poly (4-hydroxy-3-methylstyrene) Phenyl compounds; and the like. These benzophenone-based compounds, hydroxyaryl-based compounds, bis (hydroxyphenyl) alkane-based compounds, and polyhydroxystyrene-based compounds may have substituents other than hydroxyl groups.
These compounds can be used alone or in combination of two or more.

The content of the compound having 4 or more phenolic hydroxyl groups and having a molecular weight of less than 2000 is preferably 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin having phenolic hydroxyl groups. Within the above range, the tapering phenomenon when the photosensitive composition is patterned can be suppressed.

Examples of the organic solvent in the photosensitive composition of the third aspect include the organic solvent exemplified in the photosensitive composition of the first aspect.
The content of the organic solvent is preferably such that the solid content concentration of the photosensitive composition of the third aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.
The photosensitive composition of the third aspect may contain the above-mentioned various additives, if necessary, like the photosensitive composition of the first aspect.

(4) Photosensitive composition of the fourth aspect The photosensitive composition of the fourth aspect contains a photosensitive polyimide precursor, a photopolymerizable compound, a photopolymerization initiator, a hydrogen barrier agent (B), and an organic solvent. It is a negative type photosensitive composition contained.

The photosensitive polyimide precursor in the photosensitive composition of the fourth aspect has, for example, a structural unit represented by the following formula (d-1), and has an acid functional group and a photosensitive group in the molecule. The resin to have can be used.

In the above formula (d-1), X ^d represents an atom-free tetravalent organic group having an unshared electron pair in the skeleton connecting two amide groups bonded to ^{X d , and Y d} is bonded to ^{Y d.} In the skeleton connecting the two amide groups, an atom-free divalent organic group having an unshared electron pair is shown, and R ^d1 and R ^d2 independently represent a hydroxyl group or a monovalent organic group, respectively.

In ^{the definition of X d} and Y ^d , "a skeleton connecting two amide groups" means a skeleton consisting only of atoms constituting a chain of bonds connecting two amide bonds. Therefore, atoms such as hydrogen atoms and fluorine atoms that exist as terminals and do not form a chain of bonds connecting two amide bonds are not included in the above "skeleton". However, when the skeleton contains atoms constituting a ring (aromatic ring or aliphatic ring), all the atoms constituting the ring are defined as being included in the above "skeleton". For example, when the chain of the bond connecting the two amide bonds contains a benzene ring or a cyclohexyl ring, the above "skeleton" includes six carbon atoms constituting the benzene ring or the cyclohexyl ring itself. Substituents and hydrogen atoms bonded to the benzene ring and cyclohexyl ring are not included in the "skeleton" here.

Therefore, when a carbonyl bond is present on the skeleton, only the carbon atom in the carbonyl group constitutes the chain connecting the two amide groups, so that the oxygen atom in the carbonyl group forms the "skeleton". Do not configure. Regarding the 2,2-propyridene bond and the hexafluoro-2,2-propyridene bond, only the carbon atom existing in the center (2nd position) constitutes the skeleton, and the carbon atoms (1st or 3rd position) at both ends form the skeleton. It does not constitute the above "skeleton". Examples of "atoms having unshared electron pairs" include oxygen atoms, nitrogen atoms, sulfur atoms and the like, while "atoms without unshared electron pairs" include carbon atoms, silicon atoms and the like. Be done.

In the photosensitive polyimide precursor, it ^{is preferable that X d} does not contain an atom having an unshared electron pair in the skeleton as described above because swelling during alkaline development is small. For ^{the same reason, it is preferable that Y d} does not contain an atom having an unshared electron pair in the skeleton.

^{Further, if the photosensitive polyimide precursor has Y d2} containing a silicon atom as a part instead ^{of Y d} in the constituent unit, for example, a photosensitive polyimide precursor containing a siloxane bond, the substrate adhesion is higher. Is preferable because it can be imparted. In this case, the ratio is preferably 1 mol% or more and 20 mol% or less of all the diamine residues forming the photosensitive polyimide precursor.

^{The X d} and Y ^d in the above formula (d-1) include aromatic groups such as alkyl groups and cycloalkyl groups having 4 or more and 20 or less carbon atoms, and benzene rings and naphthalene rings having 6 or more and 20 or less carbon atoms. It is preferable that two or more and ten or less of the rings and these aromatic rings are bonded via a single bond, an alkylene group, a fluorinated alkylene group, a carbonyl group, or the like. Further, these may have a substituent such as a hydrocarbon group, a halogenated hydrocarbon group, or a halogen atom on the aromatic ring. Among these X ^d and Y ^d , it is preferable that the atom directly bonded to the atom constituting the skeleton is also an “atom having no unshared electron pair” because of its high effect. It should be noted that this definition excludes those in which an oxygen atom is directly bonded to a carbon atom constituting the skeleton and a group in which a fluorine atom is bonded to a carbon atom constituting the skeleton, such as a carbonyl group. Further, X ^d and Y ^d preferably do not contain a fluorine atom.

Examples of the acid functional group contained in the molecule of the photosensitive polyimide precursor include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and the like, and a carboxyl group is preferable. Further, as the photosensitive group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyl group, a methacryloxy group and the like containing an ethylenically unsaturated bond are preferable, and an acryloyl group, a methacryloyl group, an acryloyl group and a methacryloyl group are more preferable. preferable.

In the photosensitive polyimide precursor, the acid functional group is present as having R ^d1 or R ^d1 in the structural unit of the above formula (d-1) as a hydroxyl group (that is, forming a carboxyl group), or Y ^d. It is preferably present in the diamine residue indicated by. Further, the photosensitive group is a side chain represented by ^{R d1} or R ^d2 in the above formula (d-1) ^{, or a diamine residue represented by Y d} , for example, an aromatic ring of a diamine residue having an aromatic ring. It is preferably present as a group to be attached.

In R ^d1 and R ^d2 , examples of the monovalent organic group having a photosensitive group include those represented by the following formula.

In the above formula, R ^d3 and R ^d4 independently represent a monovalent hydrocarbon group having 1 to 6 ^{carbon atoms, and R d5} represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ^d6 represents a hydrogen atom or a methyl group.

Further, in R ^d1 and R ^d2 , examples of the monovalent organic group having no photosensitive group include an alkoxy group or an alkylamino group having 1 to 15 carbon atoms.

The photosensitive polyimide precursor preferably has a structural unit represented by the above formula (d-1) of 50 mol% or more and 100 mol% or less, and only the structural unit represented by the above formula (d-1) is used. It is more preferable to have a structural unit represented by the above formula (d-1) and a structural unit in which Y ^d in the above formula (d-1) is a divalent organic group containing a silicon atom. ..

The photosensitive polyimide precursor can be obtained from a compound having a tetracarboxylic dianhydride, a diamine, and a photosensitive group as a material, and various known production methods can be applied.

Examples of the tetracarboxylic acid dianhydride ^{give X d} , for example, pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 1,2,5,6. -Naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylene Tetracarboxylic acid dianhydride, m-terphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride , 4,4'-Hexafluoroisopropyridene diphthalic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride and the like. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

Examples of the diamine that gives Y ^d include 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2', 6,6'-. Tetramethyl-4,4'-diaminobiphenyl, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-(or 3,4-, 3,3'-, 2,4-, 2,2'-) diaminodiphenylmethane, p-xylylene diamine, m-xylylene diamine, 4,4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylene -Bis- (2,6-diisopropylaniline), 1,5,-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethyl-4, 4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 2,2'-hexafluorodimethyl-4,4'-diaminobiphenyl, 3,3'-hexafluorodimethyl-4,4'- Diaminobiphenyl, 4,4'-hexafluoroisopropyridene dianiline, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,3,5,6 -Tetramethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4,6-trimethyl-1,3- Preferred are phenylenediamine, 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, 2,2-hexafluorodimethyl-4,4'-diaminobiphenyl and the like. These diamines can be used alone or in combination of two or more.

Further, Y ^d may have at least one phenolic hydroxyl group or a carboxyl group as an acid functional group as long as it is a bifunctional amine that does not contain an atom having an unshared electron pair in the skeleton connecting the amino groups. .. For example, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, 4,4 '-Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl, 1,3-diamino-4-hydroxybenzene, 1,3 -Diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) hexa Preferred examples are fluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-carboxyphenyl) methane, 4,4'-diamino-2,2'-dicarboxybiphenyl and the like. Is listed as. These are used alone or in combination of two or more with diamine.

^{Further, as a diamine that gives Y 2d} containing a silicon atom, an aliphatic diamine such as diaminopolysiloxane represented by the following formula (d-2) can be mentioned.

In the above equation (d-2), s, t, and u each independently represent an integer of 1 or more and 10 or less.
When this aliphatic diamine is used, the blending amount thereof is preferably 20 mol% or less of the total diamine from the viewpoint of less swelling during development and heat resistance of the formed film.

To obtain a polyimide precursor having a photosensitive group, for example, a compound having an ethylenically unsaturated bond and an amino group or a quaternized salt group thereof is a polyamic acid carboxyl group and an amino group or quaternized thereof. Examples thereof include a method of forming a polyimide precursor having an ion-bonded form at the base portion of the salt, a method of introducing an ethylenically unsaturated bond into the side chain via a covalent bond such as an ester bond and an amide bond, and the like.

Among these, a photosensitive polyimide precursor (polyamic acid ester) in which an ethylenically unsaturated bond is introduced by an ester bond is particularly suitable for alkaline development. When an ethylenically unsaturated bond is introduced by an ester bond, the amount of the compound having an ethylenically unsaturated bond introduced is that of a polyamic acid from the viewpoint of achieving both alkali solubility, curability, heat resistance and reactivity. It is preferable that the amount is 85 mol% or more and 25 mol% or less with respect to the total amount of the carboxyl group, and the rest is the carboxyl group as it is (that is, the polyamic acid partial ester).

Examples of compounds that introduce an ethylenically unsaturated bond via an ester bond include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4 -Hydroxybutyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, dicaprolactone 2- (methacryloyloxy) ethyl ester, caprolactone 2- ( Acryloyloxy) ethyl ester, dicaprolactone 2- (acryloyloxy) ethyl ester and the like can be mentioned.

The mass average molecular weight of the photosensitive polyimide precursor is preferably 5000 or more and 80,000 or less.

The content of the photosensitive polyimide precursor is preferably 40% by mass or more and 95% by mass or less, and 55% by mass or more and 90% by mass or less, based on the solid content of the photosensitive composition of the fourth aspect. Is more preferable. Within the above range, the developability tends to be easily balanced.

Examples of the photopolymerizable compound in the photosensitive composition of the fourth aspect include the photopolymerizable compounds exemplified in the photosensitive composition of the first aspect.
The content of the photopolymerizable compound is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the photosensitive polyimide precursor. Within the above range, it tends to be easy to balance sensitivity, developability, and resolution.

Examples of the photopolymerization initiator in the photosensitive composition of the fourth aspect include the photopolymerization initiator exemplified in the photosensitive composition of the first aspect.
The content of the photopolymerization initiator is preferably 0.01 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the photosensitive polyimide precursor. Within the above range, sufficient heat resistance and chemical resistance can be obtained, the coating film forming ability can be improved, and curing defects can be suppressed.

The photosensitive composition of the fourth aspect contains the hydrogen barrier agent (B) as described above. When this compound is contained in a photosensitive composition, a pattern having hydrogen barrier performance can be formed.

The content of the hydrogen barrier agent (B) is preferably 0.01% by mass or more and 30% by mass or less with respect to the mass of the resin corresponding to the base material component (A) in the photosensitive composition of the fourth aspect. It is more preferably 0.05% by mass or more and 20% by mass or less, and particularly preferably 0.1% by mass or more and 10% by mass or less. Within the above range, a pattern having hydrogen barrier performance can be obtained while obtaining good developability.

Examples of the organic solvent in the photosensitive composition of the fourth aspect include the organic solvent exemplified in the photosensitive composition of the first aspect. Among these, a solvent containing the compound represented by the formula (a04) or a polar solvent that completely dissolves the produced polyimide is preferable, and N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide. , Dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric acid triamide, γ-butyl lactone and the like.
The content of the organic solvent is preferably such that the solid content concentration of the photosensitive composition of the fourth aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.
The photosensitive composition of the fourth aspect may contain the above-mentioned various additives, if necessary, like the photosensitive composition of the first aspect.

(5) Photosensitive composition of the fifth aspect The photosensitive composition of the fifth aspect contains a polyimide precursor, a hydrogen barrier agent (B), and an organic solvent. Further, it is preferable to contain a photosensitizer.

As the polyimide precursor in the photosensitive composition of the fifth aspect, for example, a polyamic acid having a structural unit represented by the following formula (e-1) can be used.

In the above formula (e-1), R ^e1 represents a tetravalent organic group, R ^e2 represents a divalent organic group, and R ^e3 and R ^e4 represent a hydrogen atom or a monovalent organic group.

When R ^e3 and R ^e4 are monovalent organic groups, they are represented by, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and C _x H _{2 x} OC _y H _{2y + 1 containing an ether bond thereof.} The structure to be used can be mentioned.
As the polyimide precursor, ^{a polyamic acid in which Re 3} and ^{Re 4} are hydrogen atoms is preferably used from the viewpoint of alkali developability.

Although the ^{tetravalent value of Re1} indicates only the valence for binding to the acid, it may have an additional substituent. Similarly, divalent R ^e2 shows only valence for bonding with the amine, which may have further substituents other.

The polyamic acid is obtained by reacting a tetracarboxylic acid dianhydride with a diamine, and is given in the above formula (e-1) from the viewpoint of imparting excellent heat resistance and dimensional stability to the finally obtained polyimide. It is preferable that R ^e1 or R ^e2 is an aromatic group, and it is more preferable that R ^e1 and R ^e2 are aromatic groups. ^{At this time, in R e1} of the above formula (e-1), even if the four groups ((−CO−) ₂ (−COOH) ₂ ^{) bonded to the R e1} are bonded to the same aromatic ring. Often, they may be attached to different aromatic rings. Similarly, in the ^{R e2} of the formula (e-1), 2 is bonded to the ^{R e2} radicals _{((-NH-) 2)} may be bonded to the same aromatic ring, different aromatic rings May be combined with.

The polyamic acid represented by the above formula (e-1) may be composed of a single structural unit or two or more kinds of structural units.

As a method for producing a polyimide precursor, a conventionally known method can be applied. For example, (1) a method for synthesizing polyamic acid as a precursor from tetracarboxylic acid dianhydride and diamine, and (2) reacting tetracarboxylic acid dianhydride with a monovalent alcohol, an amino compound, an epoxy compound, or the like. Examples thereof include, but are not limited to, a method of synthesizing a polyimide precursor by reacting a synthesized carboxylic acid of an ester acid or an amic acid monomer with a diamino compound or a derivative thereof.

Examples of the tetracarboxylic acid dianhydride applicable to the reaction for obtaining the polyimide precursor include ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclobutane tetracarboxylic acid dianhydride, and methylcyclobutanetetra. Aliphatic tetracarboxylic acid dianhydrides such as carboxylic acid dianhydrides and cyclopentanetetracarboxylic acid dianhydrides; pyromellitic acid dianhydrides, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydrides, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3', 3,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid Dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 2,3', 3,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 6,6'- Biphenyltetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3, 4-Dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3) −Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 3-Hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [( 3,4-dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2,1,2) -Dicarboxy) phenoxy] phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1) , 2-Dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4'-bis [4- (1) , 2-Dicarboxy) phenoxy] biphenyl dianhydride, 4,4'-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-di) Carboxy) Fe Noxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] Phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfonate dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} Sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] Phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1, 1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,1,1,3,3,3-hexafluoro-2,2- Bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride , 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8-Phenantren tetracarboxylic hydride, pyridinetetracarboxylic hydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride Anhydrides, aromatic tetracarboxylic dianhydrides such as p-terphenyl-3,3', 4,4'-tetracarboxylic hydride and the like can be mentioned.
These acid dianhydrides can be used alone or in combination of two or more.

Examples of diamines applicable to the reaction for obtaining a polyimide precursor include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl Sulfur, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane , 3,4'-Diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-amino) Benzene) propane, 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1, 3,3,3-Hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di ( 3-Aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane , 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene Aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3) -Amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) Benzene, 1,3-bi Sulfone (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-Ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-Bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-amino) Phenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ 4- (3-Aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3- Bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1, 4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4' -Bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4-( 4-Amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone , 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibi Phenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis (3-aminophenoxy) -3,3,3', 3' Aromatic amines such as -tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) -3,3,3', 3'-tetramethyl-1,1'-spirobiindane; 1 , 3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω- Bis (4-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis [2- (aminomethoxy) ethyl] ether, bis [ 2- (2-Aminoethoxy) ethyl] ether, bis [2- (3-aminopropoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-) Aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7 Aliphatic amines such as −diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane; 1,2-diaminocyclohexane, 1,3-Diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) ) Cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bi Examples thereof include alicyclic diamines such as su (aminomethyl) bicyclo [2.2.1] heptane. In addition, a diamine obtained by substituting a part or all of the hydrogen atoms on the aromatic ring of the diamine with a substituent selected from the group consisting of a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group is also used. can do.
These diamines can be used alone or in combination of two or more.

The content of the polyimide precursor is preferably 50% by mass or more and 99% by mass or less, and more preferably 70% by mass or more and 95% by mass or less, based on the solid content of the photosensitive composition of the fifth aspect. preferable. Within the above range, the coating film forming ability can be improved.

The photosensitive composition of the fifth aspect contains the hydrogen barrier agent (B) as described above. When this compound is contained in a photosensitive composition, a pattern having hydrogen barrier performance can be formed.

The content of the hydrogen barrier agent (B) is preferably 0.01 parts by mass or more and 40 parts by mass or less, preferably 0.05 parts by mass or more and 30 parts by mass or less, and 0 by mass with respect to 100 parts by mass of the polyimide precursor. .1 part by mass or more and 20 parts by mass or less is more preferable, and 0.2 parts by mass or more and 10 parts by mass or less is particularly preferable. Within the above range, good micropatterning characteristics can be obtained while obtaining good developability.

Examples of the organic solvent in the photosensitive composition of the fifth aspect include the organic solvent exemplified in the photosensitive composition of the first aspect. Among these, polar solvents such as propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, toluene and the like. Aromatic hydrocarbons of the above, and mixed solvents thereof are preferable.
The content of the organic solvent is preferably such that the solid content concentration of the photosensitive composition of the fifth aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

When the photosensitive composition of the fifth aspect is a positive photosensitive composition, it is preferable to further contain a photoacid generator as the photosensitive agent. Examples of the photoacid generator include quinonediazide group-containing compounds in addition to the compounds described above in the photosensitive composition of the second aspect. Examples of the quinone diazide group-containing compound include an orthoquinone diazido compound and a diazonaphthoquinone compound. For example, a complete esterified product or a partially esterified product of a phenol compound (also referred to as a phenolic hydroxyl group-containing compound) and a naphthoquinone diazido sulfonic acid compound; ortho. Orthoquinone diazide compounds (among others, 1,1-bis (4-hydroxyphenyl) -1- [4- {1-( 4-Hydroxyphenyl) -1-methylethyl} phenyl] ethane] and an ester compound obtained by the reaction of 1-naphthoquinone-2-diazide-5-sulfonyl chloride) are preferable.

Other components such as thermal cross-linking agent, silicon-containing compound, non-polymerizable binder polymer, solvent, elastomer, dissolution accelerator, dissolution inhibitor, surfactant or leveling agent, thermoacid generator, etc. are contained as necessary. be able to.

The thermal cross-linking agent is not particularly limited except that it is a compound that is cross-linked or polymerized in the heat treatment step after development, but may be a compound having a methylol group, an alkoxymethyl group, an epoxy group or a vinyl ether group in the molecule. preferable. For example, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,3,5-benzenetrimethanol, 4,4'-biphenyldimethanol, 2,6-pyridine. Compounds with methylol groups such as dimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 4,4'-methylenebis (2,6-dialkoxymethylphenol); 1,4-bis (methoxymethyl) Benzene, 1,3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl, 2 , Methyl 6-naphthalenedicarboxylate, compounds having an alkoxymethyl group such as 4,4'-methylenebis (2,6-dimethoxymethylphenol); methylol melamine compounds such as hexamethylol melamine and hexabutanol melamine, hexamethoxymelamine and the like. Amethyl melamine compound, alkoxymethyl glycol uryl compound such as tetramethoxymethyl glycol uryl, methylol benzoguanamine compound, methylol urea compound such as dimethylol ethyleneurea; cyano compound such as dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid; 1,4- Isocyanate compounds such as phenylenedi isocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, Epoxy group-containing compounds such as bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol novolac resin type epoxy resin; N, N'-1,3-phenylenedi maleimide, N, N'-methyl dimaleimide Maleimide compounds and the like, but are not limited thereto. These thermal cross-linking agents can be used alone or in combination of two or more.

Examples of the silicon-containing compound include a silicon-containing resin, a silicon-containing resin precursor, and a silane coupling agent, and a silane coupling agent is preferable, and 1- (2-pyridyl) -3- [3- (trimethoxysilyl). A ureido group-containing silane coupling agent such as propyl] urea and 1- (3-pyridyl) -3- [3- (triethoxysilyl) propyl] urea is more preferable.

When the photosensitive composition of the fifth aspect is a negative type photosensitive composition, it is preferable to further contain a photobase generator as the photosensitive agent. The photobase generator is not particularly limited, but a compound similar to the oxime ester compound described above in the photosensitive composition of the first aspect is preferably used.

The negative photosensitive composition may contain other components similar to those of the positive photosensitive composition, if necessary.
The ratio of each component other than the hydrogen barrier agent (B) in the photosensitive composition of the fifth aspect is as follows.
The content of the polyimide precursor is preferably 50% by mass or more, more preferably 60% by mass or more and 90% by mass or less, based on the total solid content of the photosensitive composition.
The content of the photosensitizer is preferably 3 parts by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyimide precursor from the viewpoint of sensitivity and the like.
When the heat cross-linking agent is contained, the content is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyimide precursor.
When the silane compound is contained, the content is preferably 0.1 part by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyimide precursor.
The solid content concentration of the photosensitive composition is preferably 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and further preferably 5% by mass or more and 15% by mass or less.
The photosensitive composition of the fifth aspect may contain the above-mentioned various additives, if necessary, like the photosensitive composition of the first aspect.

(6) Photosensitive composition of the sixth aspect The photosensitive composition of the sixth aspect contains an epoxy compound, a hydrogen barrier agent (B), and an organic solvent.

Examples of the epoxy compound in the photosensitive composition of the sixth aspect include a bisphenol A type epoxy resin derived from bisphenol A and epichlorohydrin, a bisphenol F type epoxy resin derived from bisphenol F and epichlorohydrin, and a bisphenol S type. Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, Biphenyl type epoxy resin, fluorene type epoxy resin, polyfunctional type epoxy resin such as trifunctional type epoxy resin and tetrafunctional type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantin type epoxy resin, isocyanurate type epoxy Examples thereof include resins and aliphatic chain epoxy resins. These epoxy compounds may be halogenated or hydrogenated.
Examples of commercially available epoxy compounds include JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, Epicron 830, EXA835LV manufactured by Japan Epoxy Resin Co., Ltd. , HP4032D, HP820, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., Serokiside series manufactured by Daicel (2021, 2021P, 2083, 2085, 3000, etc.), Epoxy series, EHPE series, Nippon Steel YD series, YDF series, YDCN series, YDB series manufactured by Kagaku Co., Ltd., phenoxy resin (polyhydroxypolyether synthesized from bisphenols and epichlorohydrin, which has epoxy groups at both ends; YP series, etc.), manufactured by Nagase ChemteX Corporation. Denacol series, Epolite series manufactured by Kyoeisha Chemical Co., Ltd., etc., but are not limited to these.
These epoxy compounds can be used alone or in combination of two or more.

The content of the epoxy compound is preferably 55% by mass or more and 99% by mass or less, and more preferably 70% by mass or more and 95% by mass or less, based on the solid content of the photosensitive composition of the sixth aspect. .. Within the above range, the coating film forming ability can be improved.

The photosensitive composition of the sixth aspect contains the above-mentioned hydrogen barrier agent (B). Since the hydrogen barrier agent (B) is a compound containing an imidazole ring, it accelerates the curing of the epoxy compound when exposed, and gives the photosensitive composition good patterning properties and hydrogen barrier performance.

The content of the hydrogen barrier agent (B) is preferably 0.01 part by mass or more and 30 parts by mass or less, more preferably 0.05 part by mass or more and 20 parts by mass or less, and 0 by mass with respect to 100 parts by mass of the epoxy compound. .1 part by mass or more and 10 parts by mass or less is particularly preferable. Within the above range, patterning characteristics and hydrogen barrier performance can be obtained.

Examples of the organic solvent in the photosensitive composition of the sixth aspect include the organic solvent exemplified in the photosensitive composition of the first aspect. Among these, polar solvents such as propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, toluene and the like. Aromatic hydrocarbons of the above, and mixed solvents thereof are preferable.
The content of the organic solvent is preferably such that the solid content concentration of the photosensitive composition of the sixth aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

The photosensitive composition of the sixth aspect may contain the above-mentioned various additives, if necessary, like the photosensitive composition of the first aspect.

The epoxy group-containing polycarboxylic acid resin according to the sixth aspect described later is said to be consumed by the reaction of all the epoxy groups with "monocarboxylic acid having an alcoholic hydroxyl group" and "polybasic acid anhydride". However, it also corresponds to the epoxy resin in the photosensitive composition of the sixth aspect in that it usually has a residual epoxy group. In this respect, the epoxy group-containing polycarboxylic acid resin in the photosensitive composition of the sixth aspect may be used as the epoxy resin in the photosensitive composition of the sixth aspect. In the present specification, among the epoxy resins in the photosensitive composition of the sixth aspect, resins other than the epoxy group-containing polycarboxylic acid resin in the photosensitive composition of the sixth aspect are referred to as non-carboxylic acid-modified epoxy resins. be.

(7) Photosensitive composition of the seventh aspect The photosensitive composition of the seventh aspect is a negative containing an epoxy group-containing polycarboxylic acid resin, a photoacid generator, a hydrogen barrier agent (B), and an organic solvent. It is a type photosensitive composition.

The epoxy group-containing polycarboxylic acid resin in the photosensitive composition of the seventh aspect has, for example, an epoxy compound having two or more epoxy groups in one molecule and one or more alcoholic hydroxyl groups in one molecule. A resin obtained by further reacting a polybasic acid anhydride with a reaction product obtained by reacting with a monocarboxylic acid can be used.

Examples of the epoxy compound having two or more epoxy groups in one molecule include novolak type epoxy resin, bisphenol type epoxy resin, trisphenol methane type epoxy resin, tris (2,3-epoxypropyl) isocyanurate, and biphenyldi. Examples thereof include glycidyl ether, alicyclic epoxy resin, and copolymerized epoxy resin.

The novolak type epoxy resin is obtained by reacting novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenol, and alkylphenol with formaldehyde under an acidic catalyst with epichlorohydrin and methylepicrolhydrin. Epoxy resin and the like can be mentioned. Commercially available products include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1027, EPPN-201, BREN-S (all manufactured by Nippon Kayaku Co., Ltd.); DEN-431, DEN-439 (all Dow. (Manufactured by Chemical Corporation); N-730, N-770, N-865, N-665, N-673, VH-4150 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.) and the like.

Examples of the bisphenol type epoxy resin include an epoxy resin obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabrom bisphenol A with epichlorohydrin and methylepicrolhydrin, and diglycidyl of bisphenol A and bisphenol F. Examples thereof include an epoxy resin obtained by reacting a condensate of ether and the above bisphenol with epichlorohydrin or methylepicrolhydrin. Examples of commercially available products include Epicoat 1004, Epicoat 1002, Epicoat 4002, Epicoat 4004 (all manufactured by Yuka Shell Epoxy Co., Ltd.) and the like.

Examples of the trisphenol methane type epoxy resin include an epoxy resin obtained by reacting trisphenol methane or triscresol methane with epichlorohydrin or methyl epichlorohydrin. Examples of commercially available products include EPPN-501 and EPPN-502 (both manufactured by Nippon Kayaku Co., Ltd.).

Examples of the alicyclic epoxy resin include celloxide 2021 manufactured by Daicel Chemicals, Epomic VG-3101 manufactured by Mitsui Chemicals, E-1031S manufactured by Oleochemical Shell Epoxy, EPB-13 and EPB manufactured by Nippon Soda. -27 and the like can be mentioned. The copolymerized epoxy resin includes CP-50M and CP-50S manufactured by Nippon Oil & Fats Co., Ltd., which are copolymers of glycidyl methacrylate, styrene, and α-methylstyrene, or the common weight of glycidyl methacrylate and cyclohexylmaleimide. Coalescence and the like can be mentioned.

Particularly preferable examples of the epoxy resin having two or more epoxy groups in one of these molecules include, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol methane type epoxy resin and the like. Be done. In particular, a polycondensate of α-hydroxyphenyl-ω-hydropoly (biphenyldimethylene-hydroxyphenylene) and 1-chloro-2,3-epoxypropane, and α-2,3-epoxypropoxyphenyl-ω-hydropoly { 2- (2,3-epoxypropoxy) -benzylidene-2,3-epoxypropoxyphenylene} is preferable.

Examples of monocarboxylic acids having one or more alcoholic hydroxyl groups in one molecule include hydroxymonocarboxylic acids such as dimethylol propionic acid, dimethylol acetic acid, dimethylol butyric acid, dimethylol valerate, dimethylol caproic acid, and hydroxypivalic acid. Can be mentioned. Among these, a monocarboxylic acid having 1 to 5 alcoholic hydroxyl groups in one molecule is preferable.

Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Can be mentioned.

The reaction between the epoxy compound and the monocarboxylic acid is preferably 0.1 mol or more and 0.7 mol or less, and 0.2 mol or more and 0.5 mol or less, based on 1 equivalent of the epoxy group of the epoxy compound. Is more preferable. In this reaction, it is preferable to use an organic solvent that does not react with an epoxy compound or a polybasic acid anhydride and has no hydroxyl group or carboxyl group. In addition, catalysts (eg, triphenylphosphine, benzyldimethylamine, trialkylammonium chloride, triphenylstibine, etc.) can be used to accelerate the reaction. When a catalyst is used, the one in which the catalyst is inactivated by using an organic peroxide or the like after the reaction is completed is preferable because it is stable and has good storage stability. The amount of the reaction catalyst used is preferably 0.1% by mass or more and 10% by mass or less with respect to the reaction mixture, and the reaction temperature is preferably 60 ° C. or more and 150 ° C. or less. Thereby, a reaction product of the epoxy compound and the monocarboxylic acid can be obtained.

In the reaction between this reaction product and the polybasic acid anhydride, an amount of the polybasic acid anhydride having an acid value of 50 mgKOH / g or more and 150 mgKOH / g or less of the finally obtained epoxy group-containing polycarboxylic acid resin is reacted. Is preferable. The reaction temperature is preferably 60 ° C. or higher and 150 ° C. or lower. In this way, an epoxy group-containing polycarboxylic acid resin can be obtained.

These epoxy group-containing polycarboxylic acid resins can be used alone or in combination of two or more.

The content of the epoxy group-containing polycarboxylic acid resin is preferably 30% by mass or more and 80% by mass or less, preferably 40% by mass or more and 70% by mass or less, based on the solid content of the photosensitive composition of the seventh aspect. More preferably. Within the above range, the coating film forming ability can be improved.

Examples of the photoacid generator in the photosensitive composition of the seventh aspect include the photoacid generator exemplified in the photosensitive composition of the second aspect.
The content of the photoacid generator is preferably 0.5% by mass or more and 30% by mass or less, and 1% by mass or more and 20% by mass or less, based on the solid content of the photosensitive composition of the seventh aspect. Is more preferable. Within the above range, the curability of the photosensitive composition becomes good.

The photosensitive composition of the seventh aspect contains the hydrogen barrier agent (B) as described above. When this compound is contained in a photosensitive composition, a pattern having hydrogen barrier performance can be formed.

The content of the hydrogen barrier agent (B) is preferably 0.01% by mass or more and 30% by mass or less with respect to the mass of the resin corresponding to the base material component (A) in the photosensitive composition of the seventh aspect. It is more preferably 0.05% by mass or more and 20% by mass or less, and particularly preferably 0.1% by mass or more and 10% by mass or less. Within the above range, a pattern having hydrogen barrier performance can be obtained while obtaining good developability.

The photosensitive composition of the seventh aspect may further contain a sensitizer. As the sensitizer, for example, an anthracene compound having an alkoxy group at the 9-position and the 10-position (9,10-dialkoxy-anthracene derivative) is preferable. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms. The 9,10-dialkoxy-anthracene derivative may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, a sulfonic acid alkyl ester group, and a carboxylic acid alkyl ester group. Examples of the alkyl group in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester group include an alkyl group having 1 to 4 carbon atoms. The substitution position of these substituents is preferably 2-position.

Examples of the 9,10-dialkoxy-anthracene derivative include 9,10-dimethoxy-anthracene, 9,10-diethoxy-anthracene, 9,10-dipropoxy-anthracene, 9,10-dimethoxy-2-ethyl-anthracene, and the like. 9,10-diethoxy-2-ethyl-anthracene, 9,10-dipropoxy-2-ethyl-anthracene, 9,10-dimethoxy-2-chloro-anthracene, 9,10-dimethoxyanthracene-2-sulfonic acid methyl ester, Examples thereof include 9,10-diethoxyanthracene-2-sulfonic acid methyl ester and 9,10-dimethoxyanthracene-2-carboxylic acid methyl ester.

For these compounds, an anthraquinone derivative is treated with a reducing agent such as zinc powder, hydrosulfite, palladium-carbon, and sodium borohydride in an alkaline aqueous solution to obtain a 9,10-dihydroxyanthracene derivative, and then dimethyl. Sulfate ester such as sulfuric acid and diethylsulfate, toluene sulfonic acid ester such as methyl toluene sulfonate, ethyl toluene sulfonate, propyl toluene sulfonic acid, monoethylene glycol ester of toluene sulfonic acid, or methyl benzene sulfonic acid, ethyl benzene sulfonate, benzene It is obtained by alkoxylating the 9th and 10th positions with a benzenesulfonic acid ester such as propyl sulfonate.

These sensitizers can be used alone or in combination of two or more.

The content of the sensitizer is preferably 0.1 or more and 6 or less, and more preferably 0.2 or more and 4 or less in terms of molar ratio with respect to the photoacid generator. Within the above range, the sensitivity and curability of the photosensitive composition are improved.

The photosensitive composition of the seventh aspect may further contain a modifying component for adjusting moisture resistance, heat resistance, adhesion and the like. The modified component itself may be cured by heat, ultraviolet rays, or the like, or may react with the residual hydroxyl group, carboxyl group, or the like of the epoxy group-containing polycarboxylic acid resin by heat, ultraviolet rays, or the like. Specifically, an epoxy compound having one or more epoxy groups in one molecule, a melamine derivative (for example, hexamethoxymelamine, hexabutoxydated melamine, condensed hexamethoxymelamine, etc.), and a bisphenol A-based compound (for example, tetramethylol). Bisphenol A etc.), oxazoline compounds and the like can be mentioned.

Epoxy compounds having one or more epoxy groups in one molecule include Epicoat 1009 and 1031 (all manufactured by Yuka Shell Co., Ltd.), Epicron N-3050, and N-7050 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.). , DER-642U, DER-673MF (all manufactured by Dow Chemical Co., Ltd.) and the like; bisphenol A type epoxy resin such as ST-2004, ST-2007 (all manufactured by Toto Kasei Co., Ltd.); -2004, YDF-2007 (all manufactured by Toto Kasei Co., Ltd.) and other bisphenol F type epoxy resins; SR-BBS, SR-TBA-400 (all manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), YDB-600, YDB-715 (all manufactured by Sakamoto Pharmaceutical Co., Ltd.) Brominated bisphenol A type epoxy resin such as EPPN-201, EOCN-103, EOCN-1020, BREN (all manufactured by Nippon Kayakusha), etc. Novorak type epoxy resin; Dainippon Ink and Chemicals Co., Ltd. Novolak type epoxy resin of bisphenol A such as Epicron N-880 manufactured by Dainippon Ink and Chemicals Co., Ltd .; Rubber-modified epoxy resin such as Epicron TSR-601 manufactured by Dainippon Ink and Chemicals Co., Ltd. and R-1415-1 manufactured by ACR Co., Ltd .; Bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd. and Epicron EXA-1514 manufactured by Dainippon Ink and Chemicals Co., Ltd .; Diglycidyl terephthalate such as Plummer DGT manufactured by Nippon Yushi Co., Ltd .; Triglycidyl isocyanurate; Bisphenol type epoxy resin such as YX-4000 manufactured by Yuka Shell Co., Ltd .; Bisphenol type epoxy resin such as YL-6056 manufactured by Yuka Shell Co., Ltd .; Cyclic epoxy resin; etc.

The content of the modifying component is preferably 50% by mass or less, more preferably 30% by mass or less, based on the solid content of the photosensitive composition of the seventh aspect.

The photosensitive composition of the seventh aspect is made of barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, mica, etc. in order to further improve properties such as adhesion and hardness. It may contain a known filler.
The content of the filler is preferably 60% by mass or less, and more preferably 5% by mass or more and 40% by mass or less, based on the solid content of the photosensitive composition of the sixth aspect.

The photosensitive composition of the seventh aspect further comprises a colorant such as phthalocyanine blue, phthalocyanine green, disazo yellow, crystal violet, titanium oxide, carbon black, a thickener such as ultrafine silica, montmorillonite, and a silicone-based polymer. , Defoaming agents such as fluoropolymers and / or additives such as leveling agents and adhesion imparting agents such as silane coupling agents may be contained.

Examples of the organic solvent in the photosensitive composition of the seventh aspect include the organic solvent exemplified in the photosensitive composition of the first aspect.
The content of the organic solvent is preferably such that the solid content concentration of the photosensitive composition of the seventh aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

The photosensitive composition of the seventh aspect may contain the above-mentioned various additives, if necessary, like the photosensitive composition of the first aspect.

<Method for preparing photosensitive composition>
The photosensitive composition is prepared by mixing each of the above components with a stirrer. In addition, you may filter using a membrane filter or the like so that the prepared photosensitive composition becomes uniform.

≪Manufacturing method of hydrogen barrier membrane≫
By using the composition for forming a hydrogen barrier membrane containing the hydrogen barrier agent (B) described above, a hydrogen barrier membrane containing the hydrogen barrier agent (B) can be formed.

The composition for forming a hydrogen barrier film contains a polyacetal resin, a polyamide resin, a polycarbonate resin, a polyester resin (polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyarylate, etc.), FR-AS resin, etc. as the base material component (A). FR-ABS resin, AS resin, ABS resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyether ether ketone resin, fluororesin, polyimide resin, polyamideimide resin, polyamidebismaleimide resin, poly Etherimide resin, polybenzoxazole resin, polybenzothiazole resin, polybenzoimidazole resin, silicone resin, BT resin, polymethylpentene, ultrahigh molecular weight polyethylene, FR-polypropylene, (meth) acrylic resin (for example, polymethylmethacrylate, etc.) ), And in the case of containing a resin material such as polystyrene, the method for forming the hydrogen barrier film is as described above.

When the composition for forming a hydrogen barrier membrane contains a thermosetting material as a base material component (A), the composition for forming a hydrogen barrier membrane is formed into a film by a method such as coating, and then the formed film is formed. A hydrogen barrier membrane can be formed by heating and curing at a temperature corresponding to the type of curable material.

When the composition for forming a hydrogen barrier membrane is the above-mentioned various photosensitive compositions, typically
To form a coating film by applying a composition for forming a hydrogen barrier film onto a substrate,
A hydrogen barrier membrane is produced by a method comprising exposing the coating film.

More specifically, first, a coating film is formed by an appropriate coating method. For example, the photosensitive composition is applied onto the substrate using a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater, and dried. The coating film can be formed by allowing the coating film to be formed.
The drying method is not particularly limited, and for example, (1) a method of prebaking on a hot plate at a temperature of 80 ° C. or higher and 120 ° C. or lower, preferably 90 ° C. or higher and 100 ° C. or lower for 60 seconds or longer and 120 seconds or lower. (2) A method of leaving it at room temperature for several hours or more and several days or less, (3) a method of putting it in a warm air heater or an infrared heater for several tens of minutes or more and several hours or less to remove the solvent. ..

Next, the coating film is exposed by irradiating the coating film with electromagnetic waves in a regioselective manner. When the photosensitive composition is a negative type photosensitive composition that is cured by exposure, the entire surface of the coating film may be exposed.
When the exposure is regioselective, the electromagnetic waves may be irradiated through a positive or negative mask or may be directly irradiated. Exposure dose varies depending on the composition of the photosensitive composition, preferably for example, about 5 mJ / cm ² or more 500 mJ / cm ² or less.

When the exposure is applied to the entire coating film, the exposed coating film can be used as it is as a hydrogen barrier film.
When the exposure is performed regioselectively, the coated film after the exposure is developed with a developing solution to obtain a hydrogen barrier membrane patterned in a desired shape.
The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developing solution include organic developing solutions such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

It is preferable to post-bake the patterned hydrogen barrier membrane after development at about 200 ° C. or higher and 250 ° C. or lower.

The hydrogen barrier membrane formed as described above is used without particular limitation in various applications requiring shielding of hydrogen gas, and is particularly preferably used in an electronic device described later.

Since the hydrogen barrier membrane can suppress the permeation of hydrogen gas having a small molecular weight and a small molecular size, it can also suppress the permeation of a gas having a molecular size larger than that of hydrogen. Examples of such a gas include nitrogen gas, oxygen gas, ozone gas, water vapor, carbon monoxide gas, carbon dioxide gas, nitrogen oxide gas, sulfur oxide gas and the like.

≪Electronic element≫
The hydrogen barrier film formed by using the composition for forming a hydrogen barrier film described above is preferably used in an electronic device provided with a passivation film.
The passivation film is a film provided to protect a functional layer such as a semiconductor layer from ions, gas, etc., physical damage, and the like.

The electronic device is not particularly limited, but an organic electronic device including an organic conductive layer, an organic semiconductor layer, an organic light emitting layer, or the like is preferable.
Preferable specific examples of the electronic element include a light emitting element such as an LED element and an organic EL element, a semiconductor element, a solar cell element, and a solid-state imaging element.

The passivation film includes, for example, metal oxides, metal nitrides, metal carbides, metal oxide nitrides, metal oxide carbides and the like. More specifically, oxides, nitrides, carbides, oxynitrides, acid carbides and the like containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta. Is preferably used.
Among these materials, oxides, nitrides, or oxynitrides of metals selected from Si, Al, In, Sn, Zn, and Ti are preferable, and oxides or nitrides of Si or Al are more preferable. In particular, silicon nitride (Si nitride) is preferable.
These may contain other elements as secondary components. For example, silicon nitride may contain hydrogen to be hydrogenated silicon, and may further contain oxygen to be hydrogenated silicon nitride.
The Si oxide film or nitride film may be an oxide film or a nitride film obtained by firing a coating film of a silicon-containing polymer-containing composition such as polysilazane, polysiloxane, polysiloxazan, or polysilane. ..
From the viewpoint of the protective performance of the passivation film, the passivation film preferably contains silicon nitride (SiN).

The passionation film described above may contain hydrogen gas or a compound capable of generating hydrogen gas such as ammonia and amines, depending on the raw material and the production method thereof.
Passivation membranes containing silicon nitride are particularly prone to generate hydrogen gas.

On the other hand, electronic devices often include a TFT to drive the device like an organic EL device. Further, the electronic element is often provided with wiring made of a metal such as copper.
The function of the TFT may be impaired by the reduction reaction due to the contact with the hydrogen gas, and the electrical characteristics of the metal wiring may be changed by the reduction with the hydrogen gas.

However, when the electronic device includes a hydrogen barrier membrane together with a passivation film,
The hydrogen gas generated from the passivation membrane can be shielded by the hydrogen barrier membrane, and the occurrence of adverse effects on the members affected by the hydrogen gas can be suppressed.
The hydrogen barrier membrane is preferably provided between an object such as a TFT that is to be protected from hydrogen and a source of hydrogen.
When hydrogen existing in the external environment of the electronic device may invade the object to be protected in the electronic device, a hydrogen barrier agent is added to the hard coat layer provided on the surface where the electronic device comes into contact with the external environment. It may be a hydrogen barrier membrane.
Further, when protecting a protected object such as a TFT in an electronic element from hydrogen generated from a film that is a hydrogen generating source such as a passivation film, a hydrogen barrier is provided between the film that is a hydrogen generating source and the protected object. It is preferable that a film is formed. In this case, for example, the flattening film may be a hydrogen barrier membrane.

As described above, in an electronic device provided with a passivation film, if a hydrogen barrier membrane is provided, it is possible to protect members such as TFTs and metal wirings that may be adversely affected by hydrogen, and an electronic device with high operational reliability can be manufactured. be able to.

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

[Example 1]
12 parts by mass of alkali-soluble resin having the following structure, 6 parts by mass of dipentaerythritol hexaacrylate, 1.0 part by mass of photopolymerization initiator having the following structure, surface conditioner (BYK-310, polyester-modified polydimethylsiloxane, big chemie) (Manufactured by Japan Co., Ltd.) 0.04 parts by mass and 2.0 parts by mass of a hydrogen barrier agent having the following structure were dissolved in a mixed solvent to obtain a processable composition.

As the mixed solvent, a mixed solvent consisting of 45 parts by mass of propylene glycol monomethyl ether, 30 parts by mass of diethylene glycol monomethyl ether, and N, N, N', N'-tetramethylurea was used.

The structure of the alkali-soluble resin, the structure of the photopolymerization initiator, and the structure of the hydrogen barrier agent are described below. For the alkali-soluble resin, the number at the lower right of each structural unit is the content (mass%) of each structural unit in the resin.

The obtained photosensitive composition was applied onto a SiN substrate (a laminate having a SiN layer on a silicon wafer) with a spin coater, and then the coating film was prebaked at 105 ° C. for 100 seconds. The prebaked coating film was exposed to the entire surface (ghi line broadband) at an exposure amount of 50 mJ / cm ^{2 using an ultraviolet curing machine to cure the coating film.} The coated film after exposure was post-baked at 230 ° C. for 20 minutes to obtain a cured film having a film thickness of 2.0 μm.

For a SiN substrate provided with a cured film, the silicon wafer side is heated, and a component having a molecular weight of 1 (hydrogen radical or hydrogen ion) generated from the surface of the cured film by a thermal deposition spectrometry (TDS) method and a molecular weight. The amount of the component 2 (hydrogen gas) and the component (water vapor) having a molecular weight of 18 were measured.
The heating at the time of measuring the amount of gas generated was carried out by raising the temperature from 50 ° C. to 280 ° C. at a rate of 10 ° C./min. Heating was terminated when the temperature reached 280 ° C.
Table 1 shows the amount of these gases generated (peak intensity).

[Comparative Example 1]
For the SiN substrate on which the cured film is not formed, a component having a molecular weight of 1 (hydrogen radical or hydrogen ion), a component having a molecular weight of 2 (hydrogen gas), and a component having a molecular weight of 18 (water vapor) are used in the same manner as in Example 1. The amount of gas generated was measured.
Table 1 shows the amount of these gases generated (peak intensity).
The amount of gas generated is the amount of gas generated from the SiN surface.

[Comparative Example 2]
A photosensitive composition was obtained in the same manner as in Example 1 except that a hydrogen barrier agent was not used. Using the obtained photosensitive composition, a cured film was formed on the SiN substrate in the same manner as in Example 1.
With respect to the SiN substrate provided with the cured film, the amount of a component having a molecular weight of 1 (hydrogen radical or hydrogen ion), a component having a molecular weight of 2 (hydrogen gas), and a component having a molecular weight of 18 (water vapor) are generated in the same manner as in Example 1. Was measured.
Table 1 shows the amount of these gases generated (peak intensity).

[Comparative Example 3]
A photosensitive composition was obtained in the same manner as in Example 1 except that a commercially available molecular sieve powder was added to the photosensitive composition so that the ratio in the solid content was 20% by mass and dispersed so as to be uniform. rice field. Using the obtained photosensitive composition, a cured film was formed on the SiN substrate in the same manner as in Example 1.
With respect to the SiN substrate provided with the cured film, the amount of a component having a molecular weight of 1 (hydrogen radical or hydrogen ion), a component having a molecular weight of 2 (hydrogen gas), and a component having a molecular weight of 18 (water vapor) are generated in the same manner as in Example 1. Was measured.
Table 1 shows the amount of these gases generated (peak intensity).

According to the comparison between Example 1 and Comparative Examples 1 and 2, when a cured film is formed on a SiN substrate using a photosensitive composition containing a hydrogen barrier agent having a predetermined structure, the gas generated from SiN It can be seen that the permeation can be effectively suppressed by the cured film.
On the other hand, according to the comparison between Comparative Example 3 and Comparative Examples 1 and 2, even if a material capable of adsorbing hydrogen gas or water such as a molecular sieve is added to the cured film formed by using the photosensitive composition, even if a material capable of adsorbing hydrogen gas or water is added. It can be seen that the permeation of gas generated from SiN can hardly be suppressed by the cured film.

<Examples 2 to 4, Comparative Examples 4 to 5>
[Example 2]
A composition for forming a hydrogen barrier membrane was obtained in the same manner as in Example 1 except that a resin in which the epoxy group-containing structural unit of the alkali-soluble resin of Example 1 was replaced with a structural unit derived from glycidyl methacrylate was used.

[Comparative Example 4]
A film-forming composition for comparison was obtained in the same manner as in Example 2 except that the hydrogen barrier agent having the above structure was not used.

[Example 3]
A hydrogen barrier membrane was formed in the same manner as in Example 1 except that a resin in which the epoxy group-containing structural unit of the alkali-soluble resin of Example 1 was replaced with a structural unit derived from 3,4-epoxycyclohexylmethylmethacrylate was used. The composition for use was obtained.

[Comparative Example 5]
A film-forming composition for comparison was obtained in the same manner as in Example 3 except that the hydrogen barrier agent having the above structure was not used.

[Example 4]
A composition for forming a hydrogen barrier film was obtained in the same manner as in Example 1 except that the amount of the hydrogen barrier agent added in Example 1 was 0.6 parts by mass.

Each of the obtained compositions was coated on a SiN substrate (a laminate having a SiN layer on a silicon wafer), and then the coating film was prebaked at 80 ° C. for 100 seconds. The prebaked coating film was exposed to the entire surface (ghi line broadband) at an exposure amount of 50 mJ / cm ^{2 using an ultraviolet curing machine to cure the coating film.} The coated film after exposure was post-baked at 230 ° C. for 20 minutes to obtain a cured film having a film thickness of 2.0 μm. The cured films 2 to 4 and the comparative cured films 4 to 5, respectively.
When the amount of each gas generated was compared with respect to the obtained SiN substrate provided with each cured film in the same manner as in Example 1, the cured films 2 to 3 according to the examples were found to be from the corresponding comparative cured films 4 to 5. However, the permeation of gas could be effectively suppressed. Further, also in the cured film 4 according to the example, the permeation of gas could be suppressed more effectively than in Comparative Example 2.

<Examples 5 to 6, Comparative Examples 6 to 7>
[Example 5]
As a base material component, 100 parts by mass of a compound represented by the following formula (A-2), 1 part by mass of a curing agent represented by the following formula (a1-2-1), and 10 parts by mass of hydrogen having the above structure. A composition for forming a hydrogen barrier film was obtained by mixing with a barrier agent.

[Comparative Example 6]
A film-forming composition for comparison was obtained in the same manner as in Example 5 except that the hydrogen barrier agent having the above structure was not used.

[Example 6]
For forming a hydrogen barrier membrane in the same manner as in Example 5, except that the compound represented by the following formula (A-3) is 100 parts by mass instead of the compound represented by the above formula (A-2). The composition was obtained.

[Comparative Example 7]
A film-forming composition for comparison was obtained in the same manner as in Example 6 except that the hydrogen barrier agent having the above structure was not used.

After each of the obtained compositions is coated on a SiN substrate (a laminate having a SiN layer on a silicon wafer), the entire surface is exposed (ghi line broadband) at ^{an exposure amount of 50 mJ / cm 2 using an ultraviolet curing machine.} , A cured film having a film thickness of about 2.0 μm was obtained. The cured films 5 to 6 and the comparative cured films 6 to 7, respectively.
When the amount of each gas generated was compared with respect to the obtained SiN substrate provided with each cured film in the same manner as in Example 1, the cured films 5 to 6 according to the examples were found to be from the corresponding comparative cured films 6 to 7. However, the permeation of gas could be effectively suppressed.

<Examples 7 to 8 and Comparative Examples 8 to 9>
[Example 7]
As a base material component, 100 parts by mass of a mixed resin component (mass ratio (A-3) :( A-4) = 70:30) represented by the following formula (A-3) and the following formula (A-4). , 5 parts by mass of a curing agent (naphthalic acid derivative) represented by the following formula (a1-2-2), 15 parts by mass of a hydrogen barrier agent having the above structure, and 700 parts by mass of propylene glycol monomethyl ether acetate are mixed. Then, a composition for forming a hydrogen barrier membrane was obtained.

[Comparative Example 8]
A film-forming composition for comparison was obtained in the same manner as in Example 7 except that the hydrogen barrier agent having the above structure was not used.

[Example 8]
As the base material component, the mixed resin component is represented by the following formula (A-5) and the following formula (A-6) (mass ratio (A-5) :( A-6) = 70:30). A composition for forming a hydrogen barrier film was obtained in the same manner as in Example 7 except that the portion was 100 parts by mass.

[Comparative Example 9]
A film-forming composition for comparison was obtained in the same manner as in Example 8 except that the hydrogen barrier agent having the above structure was not used.
Each of the obtained compositions was coated on a SiN substrate (a laminate having a SiN layer on a silicon wafer), and then the coating film was prebaked at 80 ° C. for 120 seconds. The prebaked coating film was exposed to the entire surface (ghi line broadband) at an exposure amount of 50 mJ / cm ^{2 using an ultraviolet curing machine to cure the coating film.} The coated film after exposure was baked at 100 ° C. for 20 minutes to obtain a cured film having a film thickness of 2.0 μm. The cured films 7 to 8 and the comparative cured films 8 to 9, respectively.
When the amount of each gas generated was compared with respect to the obtained SiN substrate provided with each cured film in the same manner as in Example 1, the cured films 7 to 8 according to the examples were found to be from the corresponding comparative cured films 8 to 9. However, the permeation of gas could be effectively suppressed.

Claims (8)

Equation (0):

(In formula (0), R ² is an aromatic group which may have a substituent and
R ³⁰ is expressed by the following equation (0-1):

(In formula (0-1), R ¹ is a hydrogen atom or an alkyl group, and R ³ is an alkylene group which may have a substituent. * Is a bond.)
It is a monovalent group represented by.
R ⁴ is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonat group, or an organic group, and n is 0 or more and 3 It is the following integer. )
A hydrogen barrier agent consisting of a compound represented by. A composition for forming a hydrogen barrier film, which comprises the base material component (A) and the hydrogen barrier agent (B) according to claim 1. The base material component (A) contains an alkali-soluble resin (A1) and a photopolymerizable compound (A2).
The composition for forming a hydrogen barrier film according to claim 2, further comprising a photopolymerization initiator (C). A hydrogen barrier membrane containing the hydrogen barrier agent (B) according to claim 1. A hydrogen barrier membrane comprising a cured product of the composition for forming a hydrogen barrier membrane according to claim 3. The composition for forming a hydrogen barrier film according to claim 3 is applied onto a substrate to form a coating film.
A method for producing a hydrogen barrier membrane, which comprises exposing the coating film. An electronic device comprising a passivation film and the hydrogen barrier membrane according to claim 4 or 5. The electronic device according to claim 7, further comprising a TFT.