KR20130014051A - Positive photosensitive resin composition, method for forming cured film, cured film, liquid crystal display device, and organic el display device - Google Patents

Abstract

식(1) 중, R¹은 수소 원자 또는 알킬기를 나타내고, L¹은 카르보닐기 또는 페닐렌기를 나타내며, R²¹～R²⁷은 각각 독립적으로, 수소 원자 또는 알킬기를 나타낸다.It aims at providing the positive photosensitive resin composition which has a high sensitivity, suppresses generation | occurrence | production of the residue at the time of image development, and can form the cured film which has the surface excellent in smoothness. The positive photosensitive resin composition of this invention has resin which has a structural unit which has a structural unit represented by Formula (1), a structural unit which has an acidic group, and a crosslinkable group, and (component B) an oxime sulfonate group. It is characterized by containing an acid generator.

In formula (1), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ²¹ to R ²⁷ each independently represent a hydrogen atom or an alkyl group.

Description

POSITIVE PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR FORMING CURED FILM, CURED FILM, LIQUID CRYSTAL DISPLAY DEVICE, AND ORGANIC EL DISPLAY DEVICE}

The present invention relates to a positive photosensitive resin composition, a method of forming a cured film, a cured film, a liquid crystal display device, and an organic EL display device.

Background Art Conventionally, in electronic components such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, organic ELs, and the like, generally, a flattening film for imparting flatness on the surface of an electronic component, and for preventing deterioration or damage of the electronic component. The photosensitive resin composition is used when forming an interlayer insulation film for maintaining a protective film or insulation. For example, a TFT type liquid crystal display element is provided with a polarizing plate on a glass substrate, forms a transparent conductive circuit layer such as indium tin oxide (ITO), and a thin film transistor (TFT), and is coated with an interlayer insulating film to form a back plate. A polarizing plate is formed on the glass substrate, and if necessary, a pattern of a black matrix layer and a color filter layer is formed. Further, a transparent conductive circuit layer and an interlayer insulating film are sequentially formed to form a top plate, and the back plate and the top plate are spacers. It is produced by enclosing the liquid crystal between the two plates to face each other.

As the photosensitive resin composition, for example, Patent Literature 1 proposes a photosensitive resin composition containing an alkali-soluble acrylic polymer binder, a quinonediazide group-containing compound, a crosslinking agent, and a photoacid generator.

Patent Literature 2 discloses a crosslinking agent, an acid generator, and itself, which are insoluble or poorly dissolved in an aqueous alkali solution, but have a protecting group capable of dissociating by the action of an acid. A positive chemically amplified resist composition is proposed which contains a resin that becomes soluble.

In patent document 3, the radiation sensitive resin composition characterized by containing an acetal structure and / or a ketal structure, resin containing an epoxy group, and an acid generator is proposed.

Patent Literature 4 discloses a step of laminating a positive photosensitive resin layer having two layers having different exposure sensitivity on a substrate such that a low-sensitivity positive photosensitive resin layer is positioned between the base and the high-sensitivity positive photosensitive resin layer. The process of exposing two layers of positive photosensitive resin layers, The process of exposing and heating the said two types of positive photosensitive resin layers, The process of developing the said two types of positive photosensitive resin layers, The positive photosensitive of two layers As a manufacturing method of the transparent cured film containing the process of post-baking a resin layer, the said positive type photosensitive resin layer contains the following (A) component, (B) component, (C) component, and (D) component. It is a positive photosensitive resin layer mentioned, The manufacturing method of the transparent cured film is disclosed.

(A) component: alkali-soluble resin

(B) component: the compound which has 2 or more vinyl ether groups in 1 molecule

(C) component: the compound crosslinking-reacts with (A) component by postbaking

(D) Component: photoacid generator

Japanese Patent Application Laid-Open No. 10-153854 Japanese Patent Application Laid-Open No. 2004-4669 Japanese Patent Application Laid-Open No. 2004-264623 International Publication No. 2008/035672 Pamphlet

When forming the cured film applied to an interlayer insulation film etc. by positive type photosensitive resin composition, high sensitivity is preferable. It is demanded that generation | occurrence | production of the residue at the time of image development is suppressed, and that the formed cured film surface is smooth. Among these, conventionally, the high sensitivity with respect to the acid generator can obtain physical properties equivalent to the calculated values, which can form high-definition patterning, in which fear of residual residue is completely eliminated. It is very preferable from the viewpoint that the smoothness of the desired cured film surface can be obtained.

However, the conventional photosensitive resin composition does not satisfy all of the sensitivity, suppression of residues, and smoothness of the cured film surface, but it is a phenomenon that further improvement is desired.

This invention is made | formed in view of the said conventional situation, and solves the following subjects.

That is, the problem to be solved by this invention is providing the positive photosensitive resin composition which has a high sensitivity, suppresses generation | occurrence | production of the residue at the time of image development, and can form the cured film which has the surface excellent in smoothness. Is in.

In addition, another problem to be solved by the present invention is a method of forming a cured film using the positive photosensitive resin composition of the present invention, a cured film formed by the method of forming the cured film, and a liquid crystal display device having the cured film; An organic EL display device is provided.

The said subject of this invention was solved by the means as described in the following <1>, <17>, <18>, <20>, <22>, or <23>. It describes below with <2>-<16>, <19>, and <21> which is preferable embodiment.

<1> (component A) Resin which has a structural unit represented by following formula (1), a structural unit which has an acidic group, and a structural unit which has a crosslinkable group, and (component B) contains an acid generator which has an oxime sulfonate group Positive type photosensitive resin composition,

(In formula (1), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ²¹ to R ²⁷ each independently represent a hydrogen atom or an alkyl group.)

<2> wherein R ¹ is a methyl group, a positive photosensitive resin composition according to the item <1>,

<3> Positive photosensitive resin composition as described in said <1> or <2> whose one or more of R < ²¹ > -R < ²⁷ > is a hydrogen atom,

<4> Positive photosensitive resin composition in any one of said <1>-<3> in which all of said R < ²¹ > -R < ²⁷ > are hydrogen atoms,

<5> wherein L ¹ is a carbonyl group, the <1> to <4> of the positive photosensitive resin composition according to any one,

<6> Positive photosensitive resin composition in any one of said <1>-<5> whose said acidic group is a carboxyl group or a phenolic hydroxyl group,

<7> Positive photosensitive resin composition as described in said <6> whose said acidic group is a carboxyl group,

<8> Positive photosensitive resin composition in any one of said <1>-<7> whose said crosslinkable group is an epoxy group or an oxetanyl group,

<9> Positive photosensitive resin composition as described in said <8> whose said crosslinkable group is an oxetanyl group,

The positive photosensitive resin composition as described in said <7> or <9> whose <10> said acidic group is a carboxy group and the said crosslinkable group is an oxetanyl group,

<11> The said component (B) is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by a following formula (OS-103), a formula (OS-104), and a formula (OS-105), said < The positive photosensitive resin composition in any one of 1>-<10>,

(In formula (OS-103)-(OS-105), R <^11> represents an alkyl group, an aryl group, or heteroaryl group, and two or more R <^12> represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom each independently. , R ¹⁶ present in plural numbers each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6)

<12> Positive photosensitive resin composition in any one of said <1>-<10> whose said component B is an oxime sulfonate compound represented by following formula (2),

(In formula (2), R <^4> represents an alkyl group or an aryl group, X respectively independently represents an alkyl group, an alkoxy group, or a halogen atom, and m shows the integer of 0-3.)

<13> The <1> containing the said component A in 40 to 95weight% of the range, and containing the said component B in the range of 0.1 to 10 weight% with respect to the total solid of a <13> positive type photosensitive resin composition. Positive type photosensitive resin composition in any one of-<12>,

The positive photosensitive resin composition in any one of said <1>-<13> which further contains a <14> crosslinking agent,

It contains the said component A in 40 to 70weight% of the range with respect to the total solid of a <15> positive type photosensitive resin composition, contains the said component B in the range of 0.1 to 10 weight%, and contains the said crosslinking agent 3 Positive type photosensitive resin composition as described in said <14> containing in 40 to 40weight% of the range,

The positive photosensitive resin composition in any one of said <1>-<15> which further contains a <16> solvent,

<17> Cured film which provided and hardened | cured at least one among light and heat about the positive photosensitive resin composition in any one of said <1>-<16>,

<18> (1) The application | coating process of apply | coating the positive photosensitive resin composition as described in said <16> on a board | substrate, (2) The solvent removal process which removes a solvent from the applied positive photosensitive resin composition, (3) Solvent removal An exposure step of exposing the positive type photosensitive resin composition to active radiation, (4) a developing step of developing the exposed positive type photosensitive resin composition with an aqueous developer, and (5) a post for thermosetting the developed positive type photosensitive resin composition. A method of forming a cured film including a baking step,

The formation method of the cured film as described in said <18> which performs the said image development process without performing heat processing after the exposure in a <19> above-mentioned exposure process,

<20> Cured film formed by the formation method of the cured film as described in said <18> or <19>,

The cured film as described in said <17> or <20> which is a <21> interlayer insulation film,

<22> A liquid crystal display device provided with the cured film as described in said <17> or <20>,

<23> The organic electroluminescence display provided with the cured film as described in said <17> or <20>.

ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which has high sensitivity, suppresses generation | occurrence | production of the residue at the time of image development, and can form the cured film which has the surface excellent in smoothness can be provided.

Moreover, according to this invention, the method of forming a cured film using the positive photosensitive resin composition of this invention, the cured film formed by the formation method of the said cured film, and the liquid crystal display device and organic electroluminescence display provided with the said cured film. Can be provided.

1 shows a configuration conceptual diagram of an example of an organic EL display device. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4. As shown in FIG.
2 shows a configuration conceptual diagram of an example of a liquid crystal display device. Typical sectional drawing of the active-matrix board | substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

(Positive photosensitive resin composition)

Hereinafter, the positive photosensitive resin composition (henceforth simply a "photosensitive resin composition") of this invention is demonstrated in detail.

Positive type photosensitive resin composition of this invention is (component A) resin which has a structural unit represented by following formula (1), a structural unit which has an acidic group, and a structural unit which has a crosslinkable group (hereinafter, "proprietary" specific resin And (component B) an acid generator having an oxime sulfonate group (hereinafter also referred to as a red "specific acid generator").

(In formula (1), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ²¹ to R ²⁷ each independently represent a hydrogen atom or an alkyl group.)

The photosensitive resin composition of this invention becomes excellent in a sensitivity by containing a specific resin and a specific acid generator. Moreover, the photosensitive resin composition of this invention can suppress the generation | occurrence | production of the residue at the time of image development, and can form the cured film which has the surface excellent in the smoothness.

Here, in this invention, when a "residue" forms the cured film of a pattern shape using the photosensitive resin composition, the residue which exists in the periphery of the said cured film edge part of the said pattern shape Means the act.

In addition, the smoothness of the cured film surface makes surface roughness Ra of the cured film surface into the index, and may also be called "surface roughness" below. In addition, surface roughness Ra of the cured film surface in this specification is the value measured by the stylus type surface roughening machine "P10" (made by Tencor Corporation).

The cured film obtained by the photosensitive resin composition of this invention can be used suitably as an interlayer insulation film, a planarization film, etc. which a liquid crystal display device and an organic electroluminescence display comprise.

When the insulating film included in the liquid crystal display device or the organic EL display device is inferior in smoothness, there is a disadvantage that the electrical resistance of the ITO electrode laminated on the insulating film is increased or the liquid crystal alignment in the liquid crystal layer laminated on the insulating film is disturbed. There is a case. In this respect, since the cured film obtained by the photosensitive resin composition of this invention is excellent in surface smoothness (it does not have surface roughness), generation | occurrence | production of such a defect is suppressed effectively.

Moreover, since the photosensitive resin composition of this invention is suppressed also about generation | occurrence | production of the residue at the time of image development, formation of the patterned cured film of a favorable shape is attained. This is particularly useful when, for example, forming a contact hole or the like.

It is preferable that the photosensitive resin composition of this invention is a chemical amplification type positive photosensitive resin composition (chemical amplification positive type photosensitive resin composition).

Hereinafter, specific resin and specific acid generator which are the characteristic components which comprise the photosensitive resin composition of this invention are demonstrated.

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In addition, the method of introducing the structural unit which the copolymer used for this invention contains may be a polymerization method, or a polymer reaction method may be sufficient as it. In the polymerization method, the monomer containing a predetermined functional group is previously synthesized, and then these monomers are copolymerized. In the polymer reaction method, after performing a polymerization reaction, the necessary functional group is introduce | transduced into a structural unit using the reactive group contained in the structural unit of the obtained copolymer. Here, as a functional group, crosslinkable groups, such as a protecting group, an epoxy group, or an oxetanyl group, and a phenolic hydroxyl group for protecting an acidic group, such as a carboxyl group or a phenolic hydroxyl group, and decomposing | disassembling in the presence of a strong acid, and freeing them, An alkali-soluble group (acidic group), such as a carboxy group, etc. can be illustrated.

(Component A) Specific Resin

The positive photosensitive resin composition of this invention contains resin which has a structural unit which has a structural unit represented by said formula (1), a structural unit which has an acidic group, and a crosslinkable group (component A).

In addition, the same structural unit may be sufficient as the structural unit which has the said acidic group, and the structural unit which has the said crosslinkable group.

In the present invention, the specific resin is alkali insoluble and alkali when the tetrahydrofuranyl group (hereinafter also referred to as a "specific acid-decomposable group") in the structural unit represented by formula (1) decomposes or dissociates. It is preferable that it is resin which becomes soluble.

Here, in this invention, "alkali-soluble" is 23 of the coating film (3 micrometers in thickness) of the said compound (resin) formed by apply | coating the solution of the said compound (resin) on a board | substrate, and heating at 90 degreeC for 2 minutes. The dissolution rate with respect to the 0.4 weight% tetramethylammonium hydroxide aqueous solution in degreeC is 0.01 micrometer / sec or more, and "alkali insoluble" means the solution of the said compound (resin) is apply | coated on a board | substrate, and it is 2 at 90 degreeC. It says that the dissolution rate with respect to the 0.4 weight% tetramethylammonium hydroxide aqueous solution in 23 degreeC of the coating film (3 micrometers in thickness) of the said compound (resin) formed by heating for minutes is said to be less than 0.01 micrometer / sec.

As for the alkali dissolution rate of specific resin in this invention, it is more preferable that it is less than 0.005 micrometer / sec. Moreover, when the specific acid-decomposable group of specific resin decomposes, it is preferable that alkali dissolution rate is 0.05 micrometer / sec or more.

It is preferable that the specific resin in this invention is an acrylic polymer.

"Acryl-type polymer" in this invention is a polymer of addition polymerization type | mold, is a polymer containing the structural unit derived from (meth) acrylic acid and / or its ester, and originates in (meth) acrylic acid and / or its ester You may have structural units other than a structural unit, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.

It is preferable to have 50 mol% or more, and, as for specific resin, to have a structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units in a polymer, ( It is especially preferable that it is a polymer which consists only of the structural unit derived from meta) acrylic acid and / or its ester.

In addition, "the structural unit derived from (meth) acrylic acid and / or its ester" is also called "acrylic structural unit." In addition, (meth) acrylic acid generically mentions methacrylic acid and acrylic acid.

Moreover, it is preferable that it is 5-110 mgKOH / g, It is more preferable that it is 20-90 mgKOH / g from a viewpoint of transparency and heat resistance transparency, and, as for the acid value of specific resin, it is more preferable that it is 30-70 mgKOH / g.

[Structural unit (a1) represented by formula (1)]

Specific resin has a structural unit represented by Formula (1) (henceforth an enemy "structural unit (a1)").

R ¹ represents a hydrogen atom or an alkyl group.

Examples of the alkyl group in R ¹ include a linear, branched, cyclic alkyl group having 1 to 20 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group And isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. In these alkyl groups, a C1-C12 linear, C3-C12 branched or C5-C10 cyclic alkyl group is preferable, A C1-C12 linear alkyl group is more preferable, A methyl group Or ethyl group is more preferred.

Especially, it is preferable that R <^1> is a hydrogen atom or a methyl group, and it is more preferable that it is a methyl group.

L ¹ represents a carbonyl group or a phenylene group, and is preferably a carbonyl group.

R ²¹ to R ²⁷ each independently represent a hydrogen atom or an alkyl group. The alkyl group in R <^21> -R <^27> is synonymous with R <^1>, and a preferable aspect is also the same.

Moreover, it is preferable that at least 1 is a hydrogen atom in R <^21> -R <^27> from a viewpoint of degradability and a synthesis | combination, and it is more preferable that all of R <^21> -R <^27> are hydrogen atoms.

In the structural unit represented by said formula (1) in this invention, the protected carboxyl group and / or protected phenolic hydroxyl group are contained.

As a carboxylic acid monomer which can form the unit represented by said Formula (1) by protecting a carboxyl group, if it can become a structural unit by protecting a carboxyl group, it can be used, For example, acrylic acid and methacrylic acid are mentioned. . Moreover, as a structural unit, the structural unit derived from the carboxylic acid in which these carboxy groups were protected is mentioned as a preferable thing.

As a monomer which has a phenolic hydroxyl group which can form the structural unit represented by said Formula (1) by protecting a phenolic hydroxyl group, as long as it can become a structural unit by protecting a phenolic hydroxyl group, it can be used. For example, hydroxy styrene, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, is mentioned as a preferable thing.

Among these, α-methyl-p-hydroxystyrene is more preferable.

A commercially available radical may be used for the radically polymerizable monomer used in order to form a structural unit (a1), and what synthesize | combined by a well-known method can also be used. For example, it can be synthesized by reacting (meth) acrylic acid with a dihydrofuran compound in the presence of an acid catalyst.

Moreover, after superposing | polymerizing with the structural unit (a2)-(a4) which mention the structural unit, the protected carboxyl group, or phenolic hydroxyl group containing monomer mentioned later, or its precursor, a carboxyl group or phenolic hydroxyl group reacts with a dihydrofuran compound It can also form by making it. In addition, the specific example of the preferable structural unit formed in this way is the same as the structural unit derived from the preferable specific example of the said radically polymerizable monomer.

As a particularly preferable thing as a structural unit (a1), the following structural unit can be illustrated.

In all the monomer units which comprise specific resin, 5-60 mol% is preferable, as for content of the monomer unit which forms a structural unit (a1), 10-50 mol% is more preferable, 10-40 mol% is especially preferable. Do. By containing a structural unit (a1) in said ratio, the photosensitive resin composition which is highly sensitive and has a wide exposure latitude can be obtained.

[Structural Unit (a2) Having an Acidic Group]

Specific resin has a structural unit (henceforth a red "structural unit (a2)") which has an acidic group.

It is preferable that the acidic group which specific resin contains is contained in specific resin by the structural unit which has 1 or more types of acidic groups chosen from a carboxyl group, a carboxylic anhydride residue, and a phenolic hydroxyl group. As structural unit (a2), it is more preferable that it is a structural unit which has a carboxyl group and / or phenolic hydroxyl group, and it is still more preferable that it is a structural unit which has a carboxyl group.

As a radically polymerizable monomer used in order to form the structural unit which has a carboxyl group, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, and crotonic acid; Unsaturated carboxylic acids, such as dicarboxylic acid, such as maleic acid, a fumaric acid, a citraconic acid, a mesaconic acid, and itaconic acid, are mentioned as a preferable thing.

Moreover, as a radically polymerizable monomer used for forming the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. are mentioned as a preferable thing, for example.

As a radically polymerizable monomer used in order to form the structural unit which has a phenolic hydroxyl group, For example, hydroxystyrenes, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, Unexamined-Japanese-Patent No. 2008-40183 The compound of Paragraph 0011-0016 of Unexamined-Japanese-Patent, the 4-hydroxybenzoic acid derivative of Paragraph 0007-0010 of Unexamined-Japanese-Patent No. 2888454, the addition reaction of 4-hydroxybenzoic acid and glycidyl methacrylate, 4 -An addition reaction product of hydroxybenzoic acid and glycidyl acrylate, etc. are mentioned as a preferable thing.

Among these, methacrylic acid, acrylic acid, the compound of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2008-40183, the 4-hydroxybenzoic acid derivatives of Paragraph 0007-0010 of Unexamined-Japanese-Patent No. 2888454, 4- The addition reactant of hydroxybenzoic acid and glycidyl methacrylate, and the addition reactant of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable, and the compounds described in paragraphs 0011 to 0016 of JP2008-40183A, Japan 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of JP 2888454, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reactants of 4-hydroxybenzoic acid and glycidyl acrylate This is particularly preferred. These structural units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of structural unit (a2), the following structural unit can be illustrated.

2-35 mol% is preferable, as for the content rate of the monomer unit which forms the structural unit (a2) which has an acidic group among all the monomer units which comprise specific resin, 5-20 mol% is more preferable, 8-12 mol% Is particularly preferred. When specific resin contains a structural unit (a2) by said ratio, high sensitivity is obtained and developability is favorable.

[Structural unit (a3) having a crosslinking group]

Specific resin has a structural unit (henceforth a red "structural unit (a3)") which has a crosslinkable group.

As a crosslinkable group, any may be used as long as it reacts with the acidic group mentioned above to form a covalent bond, and a crosslinkable group forms a covalent bond by the action of heat or light.

As a structural unit (a3) which has a crosslinkable group which reacts with an acidic group and forms a covalent bond, the structural unit which has an epoxy group or an oxetanyl group is preferable, and as a crosslinkable group forms a covalent bond by the action of heat and light, Carbon double bonds are preferred. Among these crosslinkable groups, it is preferable to react with an acid group to form a covalent bond.

It is preferable that especially a crosslinkable group is contained in specific resin as a structural unit which has an epoxy group or an oxetanyl group. As a structural unit (a3), you may contain the group of both an epoxy group and an oxetanyl group.

As a structural unit which has the said epoxy group or oxetanyl group, it is preferable that it is a structural unit which has an alicyclic epoxy group or an oxetanyl group, and it is more preferable that it is a structural unit which has an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring, and for example, a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group, a 2,3-epoxycyclopentyl group Etc. are mentioned preferably.

As a group which has an oxetanyl group, if it has an oxetane ring, there is no restriction | limiting in particular, The (3-ethyloxetan-3-yl) methyl group can be illustrated preferably.

The structural unit which has an epoxy group or an oxetanyl group should just have at least 1 epoxy group or an oxetanyl group in one structural unit, may contain 1 or more epoxy groups, 1 or more oxetanyl groups, and 2 or more epoxy groups, Or although it may have two or more oxetanyl groups, it is not specifically limited, It is preferable to have 1-3 epoxy groups and oxetanyl groups in total, It is more preferable to have 1 or 2 epoxy groups and oxetanyl groups in total, It is more preferable to have one epoxy group and an oxetanyl group.

As a specific example of the radically polymerizable monomer used for forming the structural unit which has an epoxy group, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycine (alpha)-n-propyl acrylate Dill, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxy Heptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, paragraph of Japanese Patent No. 4168443 The compound containing the alicyclic epoxy skeleton of 0031-0035, etc. are mentioned.

As an example of the radically polymerizable monomer used in order to form the structural unit which has an oxetanyl group, (meth) acrylic acid ester etc. which have the oxetanyl group of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2001-330953 are mentioned, for example. Can be mentioned.

As an example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group or an oxetanyl group, it is preferable that it is a monomer containing a methacrylic acid ester structure, and the monomer containing an acrylate ester structure.

Among these radically polymerizable monomers, the compound containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs 0011 to 0016 of Japanese Patent Laid-Open No. 2001-330953 are more preferable. It is (meth) acrylic acid ester which has an oxetanyl group, and it is a (meth) acrylic acid ester which has an oxetanyl group of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2001-330953. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyl jade). Cetane-3-yl) methyl, most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of structural unit (a3), the following structural unit can be illustrated.

10-80 mol% is preferable, as for the content rate of the monomer unit which forms the structural unit (a3) which has a crosslinkable group among all the monomer units which comprise specific resin, 15-70 mol% is more preferable, 20-65 mol % Is especially preferable. By containing the structural unit which has an epoxy group or an oxetanyl group in said ratio, the physical property of the cured film formed with the photosensitive resin composition becomes favorable.

[Other structural unit (a4)]

The specific resin may contain other structural units (a4) (hereinafter also referred to as red "structural units (a4)") within a range that does not impair the effects of the present invention.

As a radically polymerizable monomer used in order to form a structural unit (a4), the compound of Paragraph 0021-0024 of Unexamined-Japanese-Patent No. 2004-264623 is mentioned, for example (However, said structural unit (a1) Excluding (a3)).

As a preferable example of a structural unit (a4), the structural unit derived from at least 1 sort (s) chosen from the group of a hydroxyl-containing unsaturated carboxylic acid ester, an alicyclic structure containing unsaturated carboxylic acid ester, styrene, and N substituted maleimide is mentioned.

Among these, from the viewpoint of electrical characteristics improvement, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl and (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy (Meth) acrylic acid esters containing alicyclic structures such as ethyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-methylcyclohexyl (meth) acrylate, or hydrophobic such as styrene Monomers are preferred. From the viewpoint of sensitivity, (meth) acrylic acid 2-hydroxyethyl and N-substituted maleimide are preferable. Among these, (meth) acrylic acid ester which has alicyclic structure is more preferable. Moreover, styrene, such as styrene and (alpha) -methylstyrene, is preferable from a viewpoint of etching tolerance.

These structural units (a4) can be used individually by 1 type or in combination of 2 or more types.

1-50 mol% is preferable and, as for the content rate of the monomeric unit which forms a structural unit (a4) in the case of containing a structural unit (a4) among all the monomeric units which comprise specific resin, 5-40 mol% More preferably, 5-30 mol% is especially preferable.

As a suitable example of the combination of the structural unit which comprises specific resin, the structural unit derived from the radically polymerizable compound containing the acidic group protected by the specific acid-decomposable group, the structural unit derived from unsaturated carboxylic acid, and an epoxy group or an oxetanyl group are contained. The combination containing the structural unit derived from the radically polymerizable compound mentioned above is mentioned.

It is preferable that it is 1,000-100,000, and, as for the weight average molecular weight of specific resin in this invention, it is more preferable that it is 2,000-50,000. Moreover, it is preferable that the weight average molecular weight in this invention is polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

Moreover, although various methods are known about the synthesis | combining method of specific resin, For example, it contains at least the radically polymerizable monomer used for forming a structural unit (a1), a structural unit (a2), and a structural unit (a3). A radically polymerizable monomer mixture can be synthesize | combined by superposing | polymerizing using a radical polymerization initiator in the organic solvent.

Moreover, as specific resin, the temperature of about room temperature (25 degreeC)-about 100 degreeC in the absence of an acidic catalyst with 2, 3- dihydrofuran in the acid anhydride in the precursor copolymer which copolymerized unsaturated polyhydric carboxylic anhydrides. Copolymers obtained by addition at are also preferable.

As such a specific resin, for example, the air obtained by adding a molar amount of 2,3-dihydrofuran to a (meth) acrylic acid glycidyl / maleic anhydride / N-cyclohexyl maleimide / styrene copolymer to an acid anhydride group Coalescence is mentioned.

Hereinafter, although what is preferable as specific resin used by this invention is illustrated as specific resin A-P, this invention is not limited to this. In addition, the weight average molecular weight of each specific resin illustrated below is the range of 2,000-50,000.

Specific resin A: copolymer of MAA / MAMTHF / OXE-30 / HEMA (molar ratio: 10/40/30/20, acid value: 35.5 mgKOH / g)

Specific resin B: copolymer of MAA / MATHF / StOTHF / OXE-30 / HEMA (molar ratio: 10/20/14/23/33, acid value: 36.3 mgKOH / g)

Specific resin C: copolymer of MAA / AATHF / OXE-30 / HEMA (molar ratio: 10/40/35/15, acid value: 37.5 mgKOH / g)

Specific resin D: copolymer of PHS / MATHF / GMA / HEMA (molar ratio: 10/40/30/20, acid value: 38.5 mgKOH / g)

Specific resin E: copolymer of PHS / MATHF / OXE-30 / HEMA (molar ratio: 10/40/30/20, acid value: 35.4 mgKOH / g)

Specific resin F: copolymer of MAA / MATHF / GMA / HEMA (molar ratio: 12/25/30/33, acid value: 40.2 mgKOH / g)

Specific resin G: copolymer of MAA / StOTHF / OXE-30 / HEMA (molar ratio: 25/12/30/33, acid value: 43.1 mgKOH / g)

Specific resin H: copolymer of ITA / MATHF / OXE-30 / HEMA (molar ratio: 5/40/30/25, acid value: 35.8 mgKOH / g)

Specific resin I: copolymer of MAA / MATHF / OXE-30 / HEMA (molar ratio: 10/40/30/20, acid value: 36.8 mgKOH / g)

Specific resin J: copolymer of MAA / MATHF / OXE-30 / MMA / DCPM (molar ratio: 17/40/15/23/5, acid value: 69.1 mgKOH / g)

Specific resin K: copolymer of MAA / MATHF / OXE-30 / MMA / HMA (molar ratio: 16.5 / 40/10 / 23.5 / 10, acid value: 68.3 mgKOH / g)

Specific resin L: A mixture of the copolymer (molar ratio: 18/50/32) of MAA / MATHF / HEMA and the copolymer (molar ratio: 43/13/44) of MATHF / HEMA / OXE-30 (acid value: 33.6 mgKOH / g )

Specific resin M: A mixture (acid value: 35.4 mgKOH / g) of a copolymer of MAA / MATHF / HEMA (molar ratio: 18/65/17) and a copolymer of MATHF / HEMA / GMA (molar ratio: 40/13/47)

Particular resin _{N: StCO 2 H / MATHF /} OXE-30 / HEMA copolymer (molar ratio: 10/40/30/20, acid value: 35.4mgKOH / g)

Specific resin O: copolymer of MAA / MATHF / OXE-30 / HEMA / St (molar ratio: 10/35/20/25/10, acid value: 41.5 mgKOH / g)

Specific resin P: copolymer of MAA / MATHF / GMA / HEMA / St (molar ratio: 13/32/20/22/13, acid value: 61.6 mgKOH / g)

In addition, the synthesis example of each said specific resin is mentioned later. In addition, the detail of the symbol of the monomer which comprises each specific resin is as follows.

MATHF: 2-tetrahydrofuranyl methacrylate

AATHF: 2-tetrahydrofuranyl acrylate

MAMTHF: 5-methyl-2-tetrahydrofuranyl methacrylate

MAA: methacrylic acid

ITA: itaconic acid

MAEVE: 1-ethoxyethyl methacrylate

MACHVE: 1-cyclohexylethyl methacrylate

MABVE: 1-tert-butylethyl methacrylate

OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate

HEMA: hydroxyethyl methacrylate

EtMA: ethyl methacrylate

HMA: hexyl methacrylate

BzMA: benzyl methacrylate

CHMI: N-cyclohexylmaleimide

GMA: glycidyl methacrylate

St: Styrene

StCO ₂ H: styrenecarboxylic acid

StOTHF: 4- (2-tetrahydrofuranyl) styrene

PHS: 4-hydroxystyrene

DCPM: Dicyclopentanyl methacrylate

MMA: methyl methacrylate

It is preferable that content of specific resin in the photosensitive resin composition of this invention is 20-99 weight% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 40-95 weight%, It is 40-70 weight% More preferred. If content is this range, the pattern formation property at the time of image development will become favorable. In addition, solid content of the photosensitive resin composition represents the quantity except volatile components, such as a solvent.

Moreover, in the photosensitive resin composition of this invention, you may use together resin other than specific resin in the range which does not prevent the effect of this invention. However, it is preferable that content of resin other than specific resin is smaller than content of specific resin from a developable viewpoint.

(Component B) Acid Generator Having Oxime Sulfonate Group

The photosensitive resin composition of this invention contains the acid generator which has (component B) oxime sulfonate group (henceforth simply a "oxime sulfonate compound").

The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is represented by the following formula (2), the formula (OS-103), the formula (OS-104), or the formula (OS-105) described later. It is preferable that it is an oxime sulfonate compound.

X in Formula (2) each independently represents an alkyl group, an alkoxy group, or a halogen atom. The alkyl group and the alkoxy group in said X may have a substituent.

As said alkyl group in said X, a C1-C4 linear or branched alkyl group is preferable.

As an alkoxy group in said X, a C1-C4 linear or branched alkoxy group is preferable.

As a halogen atom in said X, a chlorine atom or a fluorine atom is preferable.

M in Formula (2) represents the integer of 0-3, and 0 or 1 is preferable. When m is 2 or 3, some X may be same or different.

R <^4> in Formula (2) represents an alkyl group or an aryl group, substituted with a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C5 halogenated alkyl group, a C1-C5 halogenated alkoxy group, W It is preferable that they are a phenyl group which may be substituted, a naphthyl group which may be substituted by W, or an enthranyl group which may be substituted by W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

As a specific example of a C1-C10 alkyl group in said R <^4> , A methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n -Amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As a specific example of the C1-C10 alkoxy group in said R <^4> , a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyloxy group and n-decyloxy group.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms for R ⁴ include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, and perfluoro-n- Amyl and the like.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms for R ⁴ include trifluoromethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoro-n-butoxy group, and purple Luoro-n-amyloxy group etc. are mentioned.

As a specific example of the phenyl group which may be substituted by W in said R <^4> , o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, p- (n -Propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group , m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (n-butoxy) phenyl group, p- (i-butoxy ) Phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-amyloxy ) Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, 2,4,6 -Dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6- And the like can be reflowed Rd group, a pentachlorophenyl group, a penta-bromo-phenyl group, a pentafluorophenyl group, a biphenyl group-p-.

As a specific example of the naphthyl group which may be substituted by W in said R <^4> , 2-methyl-1- naphthyl group, 3-methyl-1- naphthyl group, 4-methyl-1- naphthyl group, 5-methyl-1- Naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4- Methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group and the like.

As a specific example of the enthranyl group which may be substituted by W in said R <^4> , 2-methyl- 1-entranyl group, 3-methyl- 1-entranyl group, 4-methyl- 1-entranyl group, 5-methyl- 1- Entrayl group, 6-methyl-1-entranyl group, 7-methyl-1-entranyl group, 8-methyl-1-entranyl group, 9-methyl-1-entranyl group, 10-methyl-1-entranyl group, 1- Methyl-2-entranyl group, 3-methyl-2-entranyl group, 4-methyl-2-entranyl group, 5-methyl-2-entranyl group, 6-methyl-2-entranyl group, 7-methyl-2-entra And a vinyl group, an 8-methyl-2-entranyl group, a 9-methyl-2-entranyl group, and a 10-methyl-2-entranyl group.

In formula (2), m is 1, X is a methyl group, a substitution position of X is an ortho position, R <^4> is a C1-C10 linear alkyl group, and 7- dimethyl- 2-oxonorbornylmethyl group Or a compound which is a p-toluyl group is particularly preferable.

As a specific example of the oxime sulfonate compound represented by Formula (2), the following compound (i), compound (ii), a compound (i), a compound (i), etc. are mentioned, These compounds are used individually by 1 type. You may use it together and may use two or more types. Compound (i)-(v) can be obtained as a commercial item. Moreover, the specific example of the oxime sulfonate compound represented by other Formula (2) is given to the following.

(In formula (OS-103)-(OS-105), R <^11> represents an alkyl group, an aryl group, or heteroaryl group, and two or more R <^12> represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom each independently. , R ¹⁶ present in plural numbers each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6)

In the formulas (OS-103) to (OS-105), the alkyl group, aryl group or heteroaryl group represented by R ¹¹ may have a substituent.

In the formulas (OS-103) to (OS-105), the alkyl group represented by R ¹¹ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent which the alkyl group represented by R ¹¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

As said alkyl group represented by R <^11> in said formula (OS-103)-(OS-105), a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl Group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, etc. are mentioned. have.

Moreover, as said aryl group represented by R <^11> in said Formula (OS-103)-(OS-105), the C6-C30 aryl group which may have a substituent is preferable.

Examples of the substituent which the aryl group represented by R ¹¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, and an aminosulfo. A silyl group and an alkoxysulfonyl group are mentioned.

As an aryl group represented by R <^11> , a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

Moreover, as said heteroaryl group represented by R <^11> in the said Formula (OS-103)-(OS-105), the heteroaryl group of 4-30 total carbons which may have a substituent is preferable.

Examples of the substituent which the heteroaryl group represented by R ¹¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, and an amino group. A sulfonyl group and an alkoxysulfonyl group are mentioned.

In the formulas (OS-103) to (OS-105), the heteroaryl group represented by R ¹¹ may have at least one heteroaromatic ring, and for example, the heteroaromatic ring and the benzene ring may be condensed. do.

As the heteroaryl group represented by R ¹¹ , in the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzoimidazole ring which may have a substituent The group remove | excluding one hydrogen atom from the selected ring is mentioned.

In the formulas (OS-103) to (OS-105), R ¹² is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.

In Formulas (OS-103) to (OS-105), one or two of R ¹² present in the compound is preferably an alkyl group, an aryl group or a halogen atom, and one is an alkyl group, an aryl group or a halogen It is more preferable that it is an atom, It is especially preferable that one is an alkyl group and the remainder is a hydrogen atom.

In the formulas (OS-103) to (OS-105), the alkyl group or aryl group represented by R ¹² may have a substituent.

As a substituent which the alkyl group or aryl group represented by R <^12> may have, the group similar to the substituent which the alkyl group or aryl group in said R <^1> may have can be illustrated.

As said alkyl group represented by R <^12> in said formula (OS-103)-(OS-105), it is preferable that it is a C1-C12 alkyl group which may have a substituent, and the C1-C6 may have a substituent. It is more preferable that it is an alkyl group of.

As an alkyl group represented by R <^12> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromo Methyl group, methoxymethyl group and benzyl group are preferable, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and n-hexyl group are more preferable, and methyl group , Ethyl group, n-propyl group, n-butyl group, n-hexyl group are more preferable, and methyl group is particularly preferable.

As said aryl group represented by R <^12> in said formula (OS-103)-(OS-105), it is preferable that it is a C6-C30 aryl group which may have a substituent.

As an aryl group represented by R <^12> , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

As a halogen atom represented by R <^12> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a chlorine atom and a bromine atom are preferable.

In said formula (OS-103) (OS-105), X represents O or S, and it is preferable that it is O.

In the formulas (OS-103) to (OS-105), the ring containing X as a reduction is a 5-membered ring or a 6-membered ring.

In the formulas (OS-103) to (OS-105), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 desirable.

In the formulas (OS-103) to (OS-105), the alkyl group and alkyloxy group represented by R ¹⁶ may have a substituent.

As said alkyl group represented by R <^16> in said Formula (OS-103)-(OS-105), it is preferable that it is a C1-C30 alkyl group which may have a substituent.

Examples of the substituent which the alkyl group represented by R ¹⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

As said alkyl group represented by R <^16> in said Formula (OS-103)-(OS-105), a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl Group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

In the formulas (OS-103) to (OS-105), the alkyloxy group represented by R ¹⁶ is preferably an alkyloxy group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent which the alkyloxy group represented by R ¹⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

As said alkyloxy group represented by R <^16> in said formula (OS-103)-(OS-105), a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, trichloromethyl An oxy group or an ethoxy ethyloxy group is preferable.

Examples of the aminosulfonyl group for R ¹⁶ include a methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group, and aminosulfonyl group.

As an alkoxy sulfonyl group represented by R <^16> , a methoxy sulfonyl group, an ethoxy sulfonyl group, a propyl ox sulfonyl group, and a butyl ox sulphonyl group are mentioned.

Moreover, in said formula (OS-103) (OS-105), m represents the integer of 0-6, it is preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1, It is especially preferable that it is 0 Do.

In addition, the compound represented by the formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), (OS-110) or (OS-111), and the formula (OS-104). It is particularly preferable that the compound represented by) is a compound represented by the following formula (OS-107), and the compound represented by the formula (OS-105) is represented by the following formula (OS-108) or (OS-109). It is especially preferable that it is a compound represented by.

(In formula (OS-106)-(OS-111), R <^11> represents an alkyl group, an aryl group, or a heteroaryl group, R <^17> represents a hydrogen atom or a bromine atom, R <^18> is a hydrogen atom, C1-C8 An alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ¹⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ²⁰ represents a hydrogen atom or a methyl group Indicates)

The expression (OS-106) ~ R ¹¹ is in (OS-111), and R ¹¹ and copper in the formula (OS-103) ~ (OS -105), as a preferred aspect.

R <^17> in said Formula (OS-106) represents a hydrogen atom or a bromine atom, and it is preferable that it is a hydrogen atom.

R ¹⁸ in the formulas (OS-106) to (OS-111) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chloro It is preferable that it is a C1-C8 alkyl group, a halogen atom, or a phenyl group, It is more preferable that it is a C1-C8 alkyl group, It is more preferable that it is a C1-C6 alkyl group, It is especially preferable that it is a methyl group .

R ¹⁹ in the formulas (OS-108) and (OS-109) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R <^20> in said Formula (OS-108)-(OS-111) represents a hydrogen atom or a methyl group, and it is preferable that it is a hydrogen atom.

In addition, in the said oxime sulfonate compound, any one or a mixture may be sufficient about the three-dimensional structure (E, Z) of an oxime.

Although the following example compound is mentioned as a specific example of the oxime sulfonate compound represented by said formula (OS-103)-(OS-105), This invention is not limited to these.

As another suitable aspect of the oxime sulfonate compound which has at least one oxime sulfonate group, the compound represented by a following formula (OS-101) is mentioned.

In formula (OS-101), R ¹¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. Indicates. R ¹² represents an alkyl group or an aryl group.

X represents -O-, -S-, -NH-, -NR ^15- , -CH _2- , -CR ¹⁶ H- or -CR ¹⁶ R ^17- , R ¹⁵ to R ¹⁷ each independently represent an alkyl group Or an aryl group.

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

As R <^21> -R <^24> , a hydrogen atom, a halogen atom, or an alkyl group is preferable, Moreover, the aspect in which at least two of R <^21> -R <^24> couple | bonds with each other and forms an aryl group is also mentioned preferably. Especially, the aspect whose R <^21> -R <^24> is all hydrogen atoms is preferable from a viewpoint of a sensitivity.

All of the above substituents may further have a substituent.

It is more preferable that the compound represented by said formula (OS-101) is a compound represented by a following formula (OS-102).

In the formula ^{(OS-102), R 11} , R 12 and R ²¹ ~ R ²⁴ are each expression (OS-101), and R ^11, R ¹² and R ²¹ ~ R ²⁴ and copper in the preferred examples also shown .

Among these, the aspect whose R <^11> in a formula (OS-101) and a formula (OS-102) is a cyano group or an aryl group is more preferable, It is represented by a formula (OS-102), R <^11> is a cyano group, a phenyl group, or a naph. Most preferred is the sun, which is a tilt group.

In addition, in the said oxime sulfonate compound, about either the stereo structure (E, Z etc.) of an oxime and a benzothiazole ring, respectively, any may be sufficient as it, or a mixture may be sufficient as it.

Although the specific example (example compound b-1-b-34) of the compound represented by the formula (OS-101) which can be used suitably for this invention below is shown, this invention is not limited to this. In addition, in specific examples, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

Among the above-mentioned compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of both sensitivity and stability.

It is preferable that the photosensitive resin composition of this invention does not contain a 1, 2- quinonediazide compound as an acid generator sensitive to actinic light. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less, and its sensitivity is lower than that of the oxime sulfonate compound.

On the other hand, since the oxime sulfonate compound acts as a catalyst for deprotection of the acid group protected by the acid generated in response to actinic light, the acid produced by the action of one photon contributes to a large number of deprotection reactions, The quantum yield exceeds 1, for example, becomes a large value such as a power of 10, and it is estimated that high sensitivity can be obtained as a result of so-called chemical amplification.

In addition, since the oxime sulfonate compound has a π-conjugated system with spread, it has absorption up to the long wavelength side, and exhibits very high sensitivity not only to far ultraviolet rays (DUV) and i rays but also g rays.

By using tetrahydrofuranyl group as an acid-decomposable group in the said specific resin, the photosensitive resin composition of this invention can obtain equivalent or more acid decomposability compared with acetal or ketal. As a result, the acid-decomposable group can be surely consumed by a shorter post-baking. Moreover, by using the oxime sulfonate compound which is a radiation sensitive acid generator in combination, since the rate of sulfonic acid generation is increased, the production of acid is promoted and the decomposition of the acid-decomposable group of the resin is promoted. Moreover, the acid obtained by decomposing an oxime sulfonate compound produces | generates sulfonic acid with a small molecule | numerator, and also the diffusivity in a cured film becomes high and can be made more sensitive. Moreover, the crosslinking reaction by the crosslinkable group of specific resin also advances without clogging, and the high adhesive cured film can be obtained.

The component B may be used individually by 1 type, or may use 2 or more types together. It can also be used in combination with other specific acid generators.

In the photosensitive resin composition of this invention, it is preferable to use 0.1-10 weight% with respect to the total solid of the photosensitive resin composition, and, as for component B, it is more preferable to use 0.5-10 weight%.

&Lt; Other components >

The photosensitive resin composition of this invention can contain another component.

As another component, it is preferable to contain a development accelerator from a viewpoint of a sensitivity, and it is preferable to contain a solvent from a viewpoint of applicability | paintability, and it is preferable to contain a crosslinking agent from a viewpoint of film property.

Moreover, it is preferable that the photosensitive resin composition of this invention contains an adhesion | attachment improving agent from a viewpoint of board | substrate adhesiveness, It is preferable to contain a basic compound from a viewpoint of liquid storage stability, It is preferable to contain surfactant from a viewpoint of applicability | paintability. Do.

Moreover, as needed, the photosensitive resin composition of this invention is well-known additives, such as antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, a ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Can be added.

Further, the sensitizer is not preferably contained because heat molar occurs as the introduction amount of the low molecular weight component increases.

Hereinafter, the other component which can be contained in the photosensitive resin composition of this invention is demonstrated.

〔solvent〕

It is preferable that the photosensitive resin composition of this invention contains a solvent.

It is preferable that the photosensitive resin composition of this invention is prepared as a solution which melt | dissolved the arbitrary components of specific resin which is an essential component, a specific acid generator, and various additives in a solvent.

As a solvent used for the photosensitive resin composition of this invention, a well-known solvent can be used and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene Glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Monoalkyl ether acetates, esters, ketones, amides, lactones and the like can be exemplified.

As a solvent used for the photosensitive resin composition of this invention, For example, (1) Ethylene glycol monoalkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; (5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; (7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; (8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate; (9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; (10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;

(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate; (12) lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate; (14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxypropionate, 3-meth Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3 Other esters such as methyl-3-methoxybutylbutyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; (17) Lactones, such as (gamma) -butyrolactone, etc. are mentioned.

Moreover, as needed for these solvents, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1- Solvents, such as octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate, can also be added.

Among the above solvents, propylene glycol monoalkyl ether acetates and / or diethylene glycol dialkyl ethers are preferable, and diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferable.

These solvents can be used individually by 1 type or in mixture of 2 or more types.

It is preferable that it is 1-3,000 weight part per 100 weight part of specific resin, as for content of the solvent in the photosensitive resin composition of this invention, It is more preferable that it is 5-2,000 weight part, It is more preferable that it is 10-1,500 weight part.

[Developing accelerator]

It is preferable that the photosensitive resin composition of this invention contains a development accelerator.

As the development accelerator, any compound having a development promoting effect can be used, but it is preferably a compound having at least one group selected from the group of carboxyl group, phenolic hydroxyl group, and alkyleneoxy group, and a carboxyl group or phenolic hydroxyl group The compound which has is more preferable, and the compound which has a phenolic hydroxyl group is the most preferable.

Moreover, as molecular weight of a development accelerator, 100-2,000 are preferable, 150-1,500 are more preferable, 150-1,000 are especially preferable.

As an example of the development accelerator, as having an alkyleneoxy group, polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester , Polybutylene glycol, polyethylene glycol bisphenol A ether, polypropylene glycol bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, the compound described in Japanese Patent Application Laid-Open No. 9-222724, and the like. Can be mentioned.

Examples of the carboxyl group include compounds disclosed in Japanese Patent Application Laid-Open No. 2000-66406, Japanese Patent Application Laid-Open No. 9-6001, Japanese Patent Application Laid-Open No. 10-20501, and Japanese Patent Application Laid-Open No. 11-338150. have.

As a phenolic hydroxyl group, Unexamined-Japanese-Patent No. 2005-346024, Unexamined-Japanese-Patent No. 10-133366, Unexamined-Japanese-Patent No. 9-194415, Unexamined-Japanese-Patent No. 9-222724, The compound of Unexamined-Japanese-Patent No. 11-171810, Unexamined-Japanese-Patent No. 2007-121766, Unexamined-Japanese-Patent No. 9-297396, Unexamined-Japanese-Patent No. 2003-43679, etc. are mentioned. Among these, 2-10 phenol compounds are preferable for a benzene ring, and 2-5 phenol compounds are more suitable for a benzene ring. As a particularly preferable thing, the phenolic compound disclosed as a dissolution promoter in Unexamined-Japanese-Patent No. 10-133366 is mentioned.

The image development promoter may be used individually by 1 type, and can also use 2 or more types together.

From the viewpoint of sensitivity and residual film ratio, the addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, and more preferably 0.5 in terms of 100 parts by weight of the specific resin. It is most preferable that it is-10 weight part.

[Cross-linking system]

It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of this invention can be made a stronger film.

As a crosslinking agent, the compound which has two or more epoxy groups or oxetanyl group, the alkoxy methyl group containing crosslinking agent, or the compound which has at least 1 ethylenically unsaturated double bond can be added, for example in the molecule | numerator mentioned below.

Among these crosslinking agents, particularly preferred are compounds having two or more epoxy groups or oxetanyl groups in the molecule.

It is preferable that it is 0.05-50 weight part with respect to the total solid of the photosensitive resin composition, The addition amount of the crosslinking agent in the photosensitive resin composition of this invention is more preferable that it is 0.5-44 weight part, It is more preferable that it is 3-40 weight part. . By adding in this range, the cured film excellent in mechanical strength and solvent resistance can be obtained.

Compounds having two or more epoxy groups or oxetanyl groups in the molecule

As a specific example of the compound which has two or more epoxy groups in a molecule | numerator, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

These are available as commercial products. For example, as bisphenol-A epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan epoxy resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1055 (EPICLON1055) , DIC Co., Ltd., and the like, and examples of bisphenol F-type epoxy resins include JER806, JER807, JER4004, JER4005, JER4007, and JER4010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation). Made), LCE-21, RE-602S (above, Nihon Kayaku Co., Ltd.), etc., As a phenol novolak-type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, Japan epoxy resin Co., Ltd. product) , EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), and the like, and examples of the cresol novolac type epoxy resin include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, made by DIC Corporation), EOCN-1020 (above, made by Nihon Kayaku Co., Ltd.), etc. As the aliphatic epoxy resin, ADEKA RESIN EP -4080S, EP-4085S, EP-4088S (above, made by ADEKA Co., Ltd.), Ceroxide 2021P, Ceroxide 2081, Ceroxide 2083, Ceroxide 2085, EHPE3150, EPOLEAD PB 3600, Copper PB 4700 (The Daicel Chemical Co., Ltd. make) is mentioned above. In addition, ADEKA RESIN EP-4000S, East EP-4003S, East EP-4010S, East EP-4011S (above, made by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN -501, EPPN-502 (above, made by ADEKA Corporation), etc. are mentioned.

These may be used alone or in combination of two or more.

Preferred among these are bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenol novolac type epoxy resins. In particular, a bisphenol-A epoxy resin is preferable.

As a specific example of the compound which has two or more oxetanyl groups in a molecule | numerator, Aaronoxetane OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd. product) can be used.

In addition, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

As for the addition amount to the photosensitive resin composition of this invention of the compound which has two or more epoxy groups or oxetanyl group in a molecule | numerator, when the total amount of specific resin is 100 weight part, 1-50 weight part is preferable, and 3-30 weight part is more desirable.

-Alkoxymethyl group-containing crosslinking agent-

As the alkoxy methyl group-containing crosslinking agent, alkoxy methylated melamine, alkoxy methylated benzoguanamine, alkoxy methylated glycoluril, alkoxy methylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea into an alkoxymethyl group, respectively. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group and the like. desirable.

Among these alkoxy methyl group-containing crosslinking agents, alkoxy methylated melamine, alkoxy methylated benzoguanamine and alkoxy methylated glycoluril are mentioned as preferable crosslinking agents, and alkoxy methylated glycoluril is particularly preferable from the viewpoint of transparency.

These alkoxy methyl group containing crosslinking agents are available as a commercial item, For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (more than Mitsui Saianamid Co., Ltd.), Nikaraku MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nikaraku MS-11, Nikaraku MW-30HM, -100LM, -390 (above, Sanwa Chemical Co., Ltd.) etc. can be used preferably.

It is preferable that it is 0.05-50 weight part with respect to 100 weight part of specific resin, and, as for the addition amount of the alkoxy methyl group containing crosslinking agent at the time of using an alkoxy methyl group containing crosslinking agent for the photosensitive resin composition of this invention, it is more preferable that it is 0.5-10 weight part. By adding in this range, preferable alkali solubility at the time of image development, and the solvent resistance excellent in the film | membrane after hardening can be obtained.

A compound having at least one ethylenically unsaturated double bond

As a compound which has at least 1 ethylenically unsaturated double bond, (meth) acrylate compounds, such as monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or more (meth) acrylate, can be used suitably. have.

As monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, for example And 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like.

As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1, 9- nonane diol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxy ethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, etc. are mentioned.

As (meth) acrylate more than trifunctional, for example, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

The compound which has at least 1 ethylenically unsaturated double bond among these can be used individually by 1 type or in combination of 2 or more types.

It is preferable that it is 50 weight part or less with respect to 100 weight part of specific resin, and, as for the usage ratio of the compound which has at least 1 ethylenically unsaturated double bond in the photosensitive resin composition of this invention, it is more preferable that it is 30 weight part or less. By containing the compound which has at least 1 ethylenically unsaturated double bond in such a ratio, the heat resistance, surface hardness, etc. of the cured film obtained from the photosensitive resin composition of this invention can be improved. When adding the compound which has at least 1 ethylenically unsaturated double bond, it is preferable to add the thermal radical generating agent mentioned later.

[Adhesion improver]

It is preferable that the photosensitive resin composition of this invention contains an adhesion improving agent.

The adhesion improving agent which can be used for the photosensitive resin composition of this invention is an inorganic substance used as a board | substrate, For example, the compound which improves the adhesiveness of metals, such as silicon compounds, such as silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, etc., and an insulating film. to be. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as an adhesion improving agent used by this invention aims at the modification of an interface, It does not specifically limit, A well-known thing can be used.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? - Silane, and vinyltrialkoxysilane.

Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

These may be used alone or in combination of two or more. These materials are effective for improving adhesion with the substrate and also for adjusting the taper angle with the substrate.

0.1-20 weight part is preferable with respect to 100 weight part of specific resin, and, as for content of the adhesion | attachment improving agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

[Basic compound]

It is preferable that the photosensitive resin composition of this invention contains a basic compound.

As a basic compound, it can select arbitrarily and can use from what is used by chemically amplified resist. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, quaternary ammonium salt of carboxylic acid, etc. are mentioned.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.

As the heterocyclic amine, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4 -Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy Quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1 , 8-diazabicyclo [5.3.0] -7-undecene, and the like.

As quaternary ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexyl ammonium hydroxide, etc. are mentioned, for example. .

As quaternary ammonium salt of carboxylic acid, tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, etc. are mentioned, for example.

Although the basic compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types together, It is preferable to use 2 or more types together, It is more preferable to use 2 types together, Heterocyclic amine 2 It is more preferable to use together a species.

It is preferable that it is 0.001-1 weight part with respect to 100 weight part of specific resin, and, as for content of the basic compound in the photosensitive resin composition of this invention, it is more preferable that it is 0.002-0.2 weight part.

〔Surfactants〕

It is preferable that the photosensitive resin composition of this invention contains surfactant.

As surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferable surfactant is a nonionic surfactant.

Examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine and silicone surfactants.

It is more preferable that the photosensitive resin composition of this invention contains a fluorine-type surfactant and / or a silicone type surfactant as surfactant.

As these fluorine-type surfactant and silicone type surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226746, Unexamined-Japanese-Patent No. 61-226745, Japan-Patent No. 62-170950, Japan Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9-5988, Japanese Patent Laid-Open No. 2001-330953 The surfactant as described in each publication is mentioned, Commercially available surfactant can also be used.

As a commercially available surfactant which can be used, for example, F-Top EF301, EF303, (above, Shin Akita Chemical Co., Ltd.), Proide FC430, 431 (above, Sumitomo 3M Co., Ltd.), Megapack F171 , F173, F176, F189, R08 (above, made by DIC Corporation), Supron S-382, SC101, 102, 103, 104, 105, 106 (above, made by Asahi Glass Co., Ltd.), Poly Fox series Fluorine-type surfactants, such as (made by OMNOVA Corporation), or silicone type surfactant are mentioned. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

Moreover, the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography in the case of containing the structural unit A and structural unit B represented by following formula (1) as a surfactant, and using tetrahydrofuran (THF) as a solvent. The copolymer whose (Mw) is 1,000 or more and 10,000 or less is mentioned as a preferable example.

(In formula (1), R <^1> and R <^3> respectively independently represents a hydrogen atom or a methyl group, R <^2> represents a C1-C4 linear alkylene group, R <^4> represents a hydrogen atom or C1-C4 or less Represents an alkyl group, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing the polymerization ratio, p represents a numerical value of 10% by weight to 80% by weight, and q is 20% by weight. The numerical value of 90 weight% or more is shown, r represents the integer of 1 or more and 18 or less, n represents the integer of 1 or more and 10 or less)

It is preferable that said L is a branched alkylene group represented by following formula (2). R <^5> in Formula (2) represents a C1-C4 alkyl group, From a compatibility and wettability with respect to a to-be-coated surface, C1-C3 alkyl group is preferable, C2 or The alkyl group of 3 is more preferable.

As for the weight average molecular weight (Mw) of the said copolymer, 1,500 or more and 5,000 or less are more preferable.

These surfactant can be used individually by 1 type or in mixture of 2 or more types.

It is preferable that the addition amount of surfactant in the photosensitive resin composition of this invention is 10 weight part or less with respect to 100 weight part of specific resin, It is more preferable that it is 0.01-10 weight part, It is more preferable that it is 0.01-1 weight part. .

[Antioxidant]

The photosensitive resin composition of this invention may contain antioxidant.

As antioxidant, a well-known antioxidant can be contained. By adding antioxidant, the coloring of a cured film can be prevented, the film thickness reduction by decomposition can be reduced, and there is an advantage that it is excellent in heat resistance transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, and hydroxyls. Amine derivatives and the like. Among these, a phenolic antioxidant is especially preferable from a viewpoint of coloring of a cured film and a film thickness reduction. These may be used individually by 1 type, and may mix and use 2 or more types.

As a commercial item of a phenolic antioxidant, adecastaB AO-60, adecastab AO-80 (above, made by ADEKA Corporation), and Irganox 1098 (made by Chiba Japan Co., Ltd.) are mentioned, for example. .

It is preferable that it is 0.1-6 weight% with respect to the total solid of the photosensitive resin composition, as for content of antioxidant, it is more preferable that it is 0.2-5 weight%, It is especially preferable that it is 0.5-4 weight%. By setting it as this range, sufficient transparency of the formed film can be obtained and the sensitivity at the time of pattern formation also becomes favorable.

In addition, as an additive other than antioxidant, you may add the various ultraviolet absorbers, metal deactivator, etc. which were described in "extension of polymer additives (the daily industrial newspaper)", etc. to the photosensitive resin composition of this invention.

[Plasticizer]

The photosensitive resin composition of this invention may contain a plasticizer.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartarate, dioctyl atriate, triacetyl glycerine, and the like.

It is preferable that it is 0.1-30 weight part with respect to 100 weight part of specific resin, and, as for content of the plasticizer in the photosensitive resin composition of this invention, it is more preferable that it is 1-10 weight part.

[Thermal radical generating agent]

The photosensitive resin composition of this invention may contain the thermal radical generator, and when it contains an ethylenically unsaturated compound like the compound which has at least 1 ethylenically unsaturated double bond among the above-mentioned, it contains a thermal radical generator. It is desirable to.

As the thermal radical generator in the present invention, a known thermal radical generator can be used.

A thermal radical generating agent is a compound which generate | occur | produces a radical by the energy of heat, and starts or accelerates the polymerization reaction of a polymeric compound. By adding a thermal radical generating agent, the obtained cured film becomes tough more and heat resistance and solvent resistance may improve.

Preferable thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds and carbon halogens. The compound which has a bond, an azo compound, a bibenzyl compound, etc. are mentioned.

A thermal radical generating agent may be used individually by 1 type, and can also use 2 or more types together.

From a viewpoint of film | membrane improvement, as for content of the thermal radical generating agent in the photosensitive resin composition of this invention, 0.01-50 weight part is preferable, 0.1-20 weight part is more preferable, It is most preferable that it is 0.5-10 weight part.

[Thermal acid generator]

In this invention, in order to improve the film | membrane property etc. by low temperature hardening, you may use a thermal acid generator.

The thermal acid generator which can be used in the present invention is a compound in which an acid is generated by heat, and usually a thermal decomposition point is a compound in the range of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. It is a compound which produces low nucleophilic acid, such as a phonic acid, a carboxylic acid, and a disulfonylimide.

Examples of the acid generated by the thermal acid generator include sulfonic acid, an alkyl or arylcarboxylic acid substituted with an electron withdrawing group, and a disulfonylimide substituted with an electron withdrawing group, having a strong pKa of 2 or less. This is preferred. As an electron withdrawing group, haloalkyl groups, such as a halogen atom, such as a fluorine atom, and a trifluoromethyl group, a nitro group, and a cyano group are mentioned.

Moreover, in this invention, it is also preferable to use the sulfonic acid ester which generate | occur | produces an acid by heat, without generating an acid substantially by irradiation of exposure light.

The fact that an acid is not generated substantially by irradiation of exposure light can be judged that there is no change in spectrum by IR spectrum and NMR spectrum measurement before and after exposure of a compound.

It is preferable that it is 230-1,000, and, as for the molecular weight of sulfonic acid ester, it is more preferable that it is 230-800.

As the sulfonic acid ester that can be used in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized by, for example, reacting sulfonyl chloride or sulfonic anhydride with a corresponding polyhydric alcohol under basic conditions.

When content of the thermal acid generator to the photosensitive resin composition makes specific resin 100 weight part, 0.5-20 weight part is preferable and 1-15 weight part is more preferable.

[Acid increasing agent]

The acid increasing agent can be used for the photosensitive resin composition of this invention for the purpose of a sensitivity improvement.

The acid increasing agent which can be used for this invention is a compound which can raise an acid concentration in a reaction system by generating an acid further by an acid catalyst reaction, and is a compound which exists stably in the state in which an acid does not exist. Since one or more acids increase in one reaction, such a compound accelerates the reaction with the progress of the reaction, but since the generated acid itself induces self-decomposition, here It is preferable that it is three or less as an acid dissociation constant and pKa, and, as for the intensity | strength of the acid which generate | occur | produces, it is especially preferable that it is two or less.

As an example of an acid multiplying agent, Paragraph 0203-0223 of Unexamined-Japanese-Patent No. 10-1508, Paragraph 0016-0055 of Unexamined-Japanese-Patent No. 10-282642, and Japanese Unexamined-Japanese-Patent No. 9-512498 page 39 The compound of 12th line-2nd line of page 47 is mentioned.

As an acid increasing agent which can be used by this invention, it decompose | dissolves with the acid which generate | occur | produced from the acid generator, and pKa, such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, etc. The compound which produces | generates these 3 or less acids is mentioned.

The content of the acid increasing agent to the photosensitive resin composition is preferably 10 to 1,000 parts by weight based on 100 parts by weight of the specific acid generator, from the viewpoint of dissolution contrast between the exposed part and the unexposed part, and is 20 to 500 parts by weight. More preferably.

(Formation method of hardened film)

Next, the formation method of the cured film of this invention is demonstrated.

Although the formation method of the cured film of this invention does not have a restriction | limiting in particular except using the photosensitive resin composition of this invention, It is preferable to include the process of the following (1)-(5).

(1) Coating process of apply | coating photosensitive resin composition of this invention on board | substrate

(2) Solvent removal process which removes solvent from apply | coated photosensitive resin composition

(3) Exposure process of exposing photosensitive resin composition from which solvent was removed by actinic light

(4) A developing step of developing the exposed photosensitive resin composition with an aqueous developer

(5) Post-baking process of thermosetting the developed photosensitive resin composition

In the formation method of the cured film of this invention, after the exposure in the said exposure process, you may perform the image development process of said (4), without performing heat processing.

Moreover, you may further include the process of exposing the whole surface to the developed photosensitive resin composition before the said postbaking process.

Each step will be described below in order.

In the application | coating process of (1), it is preferable to set it as the wet film which apply | coats the photosensitive resin composition of this invention on a board | substrate, and contains a solvent.

In the solvent removal process of (2), it is preferable to form a dry coating film on a board | substrate by pressure_reduction | reduced_pressure (blowing) and / or heating from said apply | coated film | membrane, and a board | substrate.

In the exposure process of (3), it is preferable to irradiate the obtained coating film with actinic light of wavelength 300nm or more and 450nm or less. In this step, the specific acid generator decomposes and acid is generated. By the catalysis of the generated acid, the acid-decomposable group in the structural unit (a1) contained in the specific resin is decomposed to generate a carboxyl group and / or phenolic hydroxyl group.

In the region where the acid catalyst is generated, in order to accelerate the decomposition reaction, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") may be performed as necessary. PEB can promote formation of carboxyl groups and / or phenolic hydroxyl groups from acid-decomposable groups.

The acid-decomposable group in the structural unit (a1) in the specific resin has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from a specific acid generator by exposure to generate a carboxyl group and / or phenolic hydroxyl group. Therefore, it is not necessary to perform PEB. Therefore, it is preferable to perform the said developing process, without performing heat processing after an exposure process. In more detail, it is preferable to form a positive image by developing in the developing process of (4), without performing PEB after the exposure process of (3).

In addition, by performing PEB at a relatively low temperature, decomposition of the acid-decomposable group can be promoted without causing a crosslinking reaction. It is preferable that the temperature at the time of PEB is 30 degreeC or more and 130 degrees C or less, 40 degreeC or more and 110 degrees C or less are more preferable, 50 degreeC or more and 90 degrees C or less are especially preferable.

In the developing process of (4), it is preferable to develop specific resin which has advantageous carboxyl group using alkaline developing solution. A positive image can be formed by removing the exposure part area | region containing the photosensitive resin composition which has a carboxyl group and / or phenolic hydroxyl group which is easy to melt | dissolve in an alkaline developing solution.

By heating the positive image obtained in the post-baking process of (5), the carboxy group and / or produced | generated by thermal decomposition of the carboxyl group and / or phenolic hydroxyl group in the structural unit (a2), and the acid-decomposable group in the structural unit (a1), for example Alternatively, a cured film can be formed by crosslinking the phenolic hydroxyl group with the epoxy group and / or oxetanyl group in the structural unit (a3). It is preferable to heat this heating at high temperature 150 degreeC or more, It is more preferable to heat at 180-250 degreeC, It is especially preferable to heat at 200-250 degreeC. Although heating time can be suitably set according to heating temperature etc., it is preferable to set it in the range of 10 to 90 minutes.

Moreover, it is preferable to include the process of carrying out the whole surface exposure of the developed photosensitive resin composition before a postbaking process, and adding the process of irradiating an active light, preferably an ultraviolet-ray whole surface to the pattern of the developed photosensitive resin composition, The crosslinking reaction can be promoted by the acid generated by the irradiation of the actinic light.

Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

[Preparation Method of Photosensitive Resin Composition]

A solvent is mixed with the essential component of specific resin and an acid generator as needed at a predetermined ratio and by arbitrary methods, and it melt | dissolves by stirring, and prepares the photosensitive resin composition. For example, after making specific resin or acid generator into the solution which melt | dissolved in the solvent previously, respectively, these can also be mixed in a predetermined ratio and the photosensitive resin composition can be prepared. The solution of the photosensitive resin composition prepared as mentioned above can also be used for use, after filtering using a filter of 0.1 micrometer of pore diameters, etc.

An example of the suitable aspect of the photosensitive resin composition of this invention contains specific resin in 40 to 95weight% of the range with respect to the total solid of the photosensitive resin composition, and also contains 0.1-10 weight% of specific acid generators. It is the sun to contain in the range.

Moreover, the other example of the suitable aspect of the photosensitive resin composition of this invention contains specific resin in 40 to 70weight% of the range with respect to the total solid of the photosensitive resin composition, and contains 0.1 to 10 weight% of specific acid generators. It is an aspect containing in the range of and containing a crosslinking agent in 3 to 40weight% of a range.

<Application process and solvent removal process>

The desired dry coating film can be formed by apply | coating the photosensitive resin composition to a predetermined board | substrate, and removing a solvent by pressure reduction and / or heating (prebaking). As said board | substrate, the manufacture of a liquid crystal display device, for example, the polarizing plate, the glass plate etc. which provided the black matrix layer, the color filter layer as needed, and provided the transparent conductive circuit layer can be illustrated. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coating method, a spray method, a roll coating method, and a spin coating method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for large substrates. Here, a large board | substrate means the board | substrate of the magnitude | size of 1 m or more in each side.

In addition, (2) The heating conditions of a solvent removal process are a range in which an acid-decomposable group decomposes | disassembles in the structural unit (a1) in specific resin in an unexposed part, and does not make a specific resin soluble in alkaline developing solution, Although it changes also with a kind and compounding ratio, Preferably it is about 30 to 300 second at 70-120 degreeC.

Exposure process

(3) In an exposure process, actinic light of a predetermined pattern is irradiated to the board | substrate which provided the dry coating film of the photosensitive resin composition. Exposure may be performed through a mask and you may draw a predetermined pattern directly. Active rays having a wavelength of 300 nm or more and 450 nm or less can be preferably used. You may perform PEB after an exposure process as needed.

A low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, etc. can be used for exposure by actinic light.

When a mercury lamp is used, an actinic ray having a wavelength of g-line (436 nm), i-line (365 nm) and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for exposure to large areas compared to lasers.

In the case of using a laser, 343 nm and 355 nm are suitably used for a solid state (YAG) laser, 351 nm (XeF) is suitably used for an excimer laser, and 375 nm and 405 nm are suitably used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from a viewpoint of stability, cost, etc. A laser can be divided into 1 time or multiple times, and can irradiate a coating film.

The energy density per pulse of the laser is preferably 0.1 mJ / cm 2 or more and 10,000 mJ / cm 2 or less. In order to fully harden a coating film, 0.3 mJ / cm <2> or more is more preferable, 0.5 mJ / cm <2> or more is most preferable, In order not to decompose a coating film by ablation phenomenon, 1,000 mJ / cm <2> or less is more preferable, Most preferably, 100 mJ / cm <2> or less.

In addition, it is preferable that pulse width is 0.1nsec or more and 30,000nsec or less. In order not to decompose a chromatic film by the ablation phenomenon, 0.5 nsec or more is more preferable, 1 nsec or more is most preferable, In order to improve the alignment precision at the time of scanning exposure, 1,000 nsec or less is more preferable, and 50 nsec or less Most preferred.

Moreover, 1 Hz or more and 50,000 Hz or less are preferable, and, as for the frequency of a laser, 10 Hz or more and 1,000 Hz or less are more preferable.

In addition, the frequency of the laser is more preferably 10 Hz or more, more preferably 100 Hz or more, in order to shorten the exposure processing time, and more preferably 10,000 Hz or less in order to improve the alignment accuracy during scan exposure, 1,000 kPa or less is most preferred.

Compared with a mercury lamp, a laser is easy to narrow a focus, and it is preferable at the point that a mask of pattern formation in an exposure process is unnecessary, and it can cost-down.

Although there is no restriction | limiting in particular as an exposure apparatus which can be used for this invention, As what is marketed, Callisto (made by V technology), AEGIS (made by V technology), and DF2200G (Dinihon Screen Seizo Co., Ltd.) ), Etc. can be used. Moreover, the apparatus of that excepting the above is also used suitably.

Moreover, irradiation light can also be adjusted through a spectral filter, such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter, as needed.

Development Process

(4) In the developing step, the exposed portion region is removed using a basic developer to form an image pattern. As a basic compound used for a developing solution, For example, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; Aqueous solutions, such as sodium silicate and sodium metasilicate, can be used. Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the aqueous solution of the said alkalis can also be used as a developing solution.

It is preferable that pH of a developing solution is 10.0-14.0.

The developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid method, a dip method, a shower method and the like. After development, flowing water can be washed for 10 to 90 seconds to form a desired pattern.

<Post Baking Process (Crosslinking Process)>

About the pattern corresponding to the unexposed area | region obtained by image development, using heating apparatuses, such as a hotplate and oven, for a predetermined time, for example, 180-250 degreeC, for 5 to a predetermined time, for example, a hotplate If it is an oven for 60 minutes, it heat-processes for 30 to 90 minutes, decomposes the acid-decomposable group in specific resin, produces | generates a carboxyl group and / or phenolic hydroxyl group, and reacts with the crosslinkable group which is an epoxy group and / or oxetanyl group in a specific resin. By crosslinking, a protective film or an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed. In addition, when performing heat processing, transparency can also be improved by performing in nitrogen atmosphere.

Further, prior to the heat treatment, after re-exposure to the substrate on which the pattern is formed by actinic light, post-baking (re-exposure / post-baking) generates acid from the acid generator (B) present in the unexposed portion, It is preferable to function as a catalyst for promoting crosslinking.

That is, the method for forming a cured film in the present invention preferably includes the above-described step (6) for re-exposure by an actinic ray between the developing step and the post-baking step.

Although exposure in a re-exposure process may be performed by the same means as the said exposure process, in the said re-exposure process, it is preferable to perform whole surface exposure with respect to the side in which the film | membrane was formed by the photosensitive resin composition of this invention of a board | substrate. As a preferable exposure amount of a re-exposure process, it is 100-1,000mJ / cm <2>.

The cured film of this invention is a cured film obtained by hardening | curing the photosensitive resin composition of this invention, and can be used suitably as an interlayer insulation film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.

The photosensitive resin composition of this invention has the high sensitivity, the generation | occurrence | production of the residue at the time of image development is suppressed, and the cured film which has the surface excellent in smoothness is obtained, and this cured film is useful as an interlayer insulation film. . Moreover, since the interlayer insulation film formed using the photosensitive resin composition of this invention has high transparency, can form a favorable pattern shape, and also is excellent in the smoothness of the surface, it is an organic electroluminescence display and a liquid crystal display device. Useful for

The organic EL display device or liquid crystal display device to which the photosensitive resin composition of the present invention can be applied is particularly limited except that a cured film formed using the photosensitive resin composition of the present invention is used as a flattening film, a protective film, or an interlayer insulating film. Instead, various well-known organic electroluminescence display and liquid crystal display which take various structures are mentioned.

In addition, the photosensitive resin composition of this invention and the cured film of this invention can be used for various uses, without being limited to the said use. For example, in addition to the planarization film, a protective film, and an interlayer insulation film, it can be used suitably for the microlens etc. which are provided on the color filter in the spacer for keeping the thickness of the liquid crystal layer in a liquid crystal display device constant, or a solid-state image sensor.

1 shows a schematic conceptual view of an example of an organic EL display device using the photosensitive resin composition of the present invention. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4. As shown in FIG.

A glass substrate 6, an insulating film 3 made of Si ₃ N ₄ to form a bottom gate TFT (1) of the type and covering the TFT (1) state is formed. After forming a contact hole (not shown here) in the insulating film 3, a wiring 2 (1.0 μm in height) connected to the TFT 1 via the contact hole is formed on the insulating film 3. . The wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization film 4 is formed on the insulating film 3 in a state of filling the unevenness by the wiring 2.

On the planarization film 4, the bottom emission type organic electroluminescent element is formed. That is, on the planarization film 4, the 1st electrode 5 which consists of ITO is connected to the wiring 2 through the contact hole 7, and is formed. The 1st electrode 5 is corresponded to the anode of organic electroluminescent element.

The insulating film 8 of the shape which covers the periphery of the 1st electrode 5 is formed, By providing this insulating film 8, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process is formed. It can prevent.

Although not shown in FIG. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited and provided through a desired pattern mask. Subsequently, a second electrode made of Al is formed on the entire surface above the substrate, and encapsulated. An active matrix organic EL display device comprising an active glass plate and an ultraviolet curable epoxy resin to be bonded to each other to be sealed, and to which TFTs 1 for driving the organic EL elements are connected. You can get it.

2 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. This color liquid crystal display device 10 is a liquid crystal panel which has the backlight unit 12 in the back surface, and a liquid crystal panel has all arrange | positioned between two glass substrates 14 and 15 which affixed the polarizing film. Elements of the TFT 16 corresponding to the pixels are arranged. The ITO transparent electrode 19 which forms the pixel electrode through the contact hole 18 formed in the cured film 17 is wired to each element formed on the glass substrate. On the ITO transparent electrode 19, the RGB color filter 22 which has arrange | positioned the layer of the liquid crystal 20 and a black matrix is provided.

(Example)

Next, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples. In addition, "part" and "%" are basis of weights unless there is particular notice.

The symbol of each compound used by the synthesis examples of the following specific resin A-P and comparative resin R1-R12 represents the following compounds, respectively.

MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)

AATHF: 2-tetrahydrofuranyl acrylate (synthetic product)

MAMTHF: 5-methyl-2-tetrahydrofuranyl methacrylate (synthetic product)

MAA: Methacrylic acid (made by Wako Pure Chemical Industries, Ltd.)

ITA: Itakonsan (made by Wako Pure Chemical Industries, Ltd.)

MAEVE: 1-ethoxyethyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

MACHVE: 1-cyclohexylethyl methacrylate (synthetic product)

MABVE: 1-tert-butylethyl methacrylate (synthetic product)

Oxe-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Yuga Chemical Co., Ltd.)

HEMA: hydroxyethyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

V-65: 2,2'- azobis (2, 4- dimethylvaleronitrile) (made by Wako Pure Chemical Industries, Ltd.)

V-601: 2, 2- azobis (2-methylpropionic acid) dimethyl (made by Wako Pure Chemical Industries, Ltd.)

EtMA: ethyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

HMA: hexyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

Bzma: benzyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

CHMI: N-cyclohexyl maleimide (made by Wako Pure Chemical Industries, Ltd.)

GMA: glycidyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

St: Styrene (made by Wako Pure Chemical Industries, Ltd.)

StCO ₂ H: styrenecarboxylic acid

StOTHF: 4- (2-tetrahydrofuranyl) styrene (synthetic)

PHS: 4-hydroxystyrene

DCPM: dicyclopentanyl methacrylate (FA-513M, Hitachi Chemical Co., Ltd. product)

MMA: Methyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

PGMEA: methoxypropyl acetate (manufactured by Showa Denko Co., Ltd.)

HS-EDM: Hysorb EDM (diethylene glycol ethyl methyl ether, Tohogaku Kogyo Co., Ltd. product)

Synthesis Example 1 Synthesis of MATHF

50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2 mol%) of camphorsulfonic acid were mixed and cooled to 15 degreeC in the three neck flask. 41.00 g (0.585 mol) of 2, 3- dihydrofurans were dripped at this solution. Saturated sodium hydrogencarbonate aqueous solution (500 mL) was added to the reaction solution, the mixture was extracted with ethyl acetate (500 mL), and dried over magnesium sulfate. The insoluble matter was concentrated under reduced pressure after filtration at 40 ° C. or lower, and the colorless oily residue was distilled under reduced pressure to obtain 73.02 g of MATHF having a boiling point of 54 to 56 ° C./3.5 mmHg. Got it.

Synthesis Example 2 Synthesis of AATHF

42.16 g (0.585 mol) of acrylic acid and 0.27 g (0.2 mol%) of camphorsulfonic acid were mixed with the three neck flask, and it cooled to 15 degreeC. 41.00 g (0.585 mol) of 2, 3- dihydrofurans were dripped at this solution. Saturated sodium hydrogencarbonate aqueous solution (500 mL) was added to the reaction solution, the mixture was extracted with ethyl acetate (500 mL), and dried over magnesium sulfate. Insoluble matter was concentrated under reduced pressure after filtration at 40 degrees C or less, and 62.18 g of AATHF was obtained by depressurizingly distilling the residue of the colorless oily substance.

Synthesis Example 3 Synthesis of MAMTHF

50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2 mol%) of camphorsulfonic acid were mixed and cooled to 15 degreeC in the three neck flask. 49.21 g (0.585 mol) of 5-methyl-2,3-dihydrofurans were dripped at this solution. Saturated sodium hydrogencarbonate aqueous solution (500 mL) was added to the reaction solution, the mixture was extracted with ethyl acetate (500 mL), and dried over magnesium sulfate. The insolubles were concentrated under reduced pressure after filtration at 40 ° C. or lower, and 66.70 g of MAMTHF was obtained by distillation under reduced pressure of the colorless oily residue.

Synthesis Example 4: Synthesis of Specific Resin A

HS-EDM (36.86 g) was put into a three neck flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. MAA (1.72 g), MAMTHF (13.62 g), HEMA (5.21 g), OXE-30 (11.05 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution, and HS-EDM (36.86 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thereby, specific resin A was obtained. The acid value was 35.5 mgKOH / g and the weight average molecular weight was 8,200.

Synthesis Example 5: Synthesis of Specific Resin B

HS-EDM (36.07 g) was put into a three neck flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. MAA (1.72 g), MAMTHF (6.81 g), StOTHF (5.33 g), HEMA (8.59 g), OXE-30 (8.47 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution. It dissolved in HS-EDM (36.07 g) and dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thereby, specific resin B was obtained. The acid value was 36.3 mgKOH / g and the weight average molecular weight was 7,900.

Synthesis Example 6: Synthesis of Specific Resin C

HS-EDM (34.88 g) was put into a three-necked flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. MAA (1.72 g), AATHF (11.37 g), HEMA (3.90 g), OXE-30 (12.90 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution and HS-EDM (34.88 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thereby, specific resin C was obtained. The acid value was 37.5 mgKOH / g and the weight average molecular weight was 8,600.

Synthesis Example 7: Synthesis of Specific Resin D

HS-EDM (34.05 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. PHS (2.96 g), MATHF (12.49 g), HEMA (5.21 g), GMA (8.53 g), V-65 (3.34 g, 7 mol% based on monomer) was added to HS-EDM (34.05 g). It melt | dissolved and it dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin D was obtained. The acid value was 38.5 mgKOH / g and the weight average molecular weight was 7,800.

Synthesis Example 8: Synthesis of Specific Resin E

HS-EDM (37.00 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. PHS (2.96 g), MATHF (12.49 g), OXE-30 (11.05 g), HEMA (5.21 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution, and HS-EDM (37.00 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin E was obtained. The acid value was 35.4 mgKOH / g and the weight average molecular weight was 8,300.

Synthesis Example 9: Synthesis of Specific Resin F

HS-EDM (32.60g) was put into the three neck flask, and it heated up at 70 degreeC in nitrogen atmosphere. MAA (1.72 g), MATHF (12.49 g), GMA (8.53 g), HEMA (5.21 g), and V-601 (3.22 g, 7 mol% based on monomer) were added to HS-EDM (32.60 g). It melt | dissolved and it dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin F was obtained. The acid value was 40.2 mgKOH / g and the weight average molecular weight was 7,700.

Synthesis Example 10 Synthesis of Specific Resin G

HS-EDM (36.42 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. MAA (2.07 g), StOTHF (9.51 g), OXE-30 (11.05 g), HEMA (8.59 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution, and HS-EDM (33.5 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin G was obtained. The acid value was 43.1 mgKOH / g and the weight average molecular weight was 9,300.

Synthesis Example 11: Synthesis of Specific Resin H

HS-EDM (36.57 g) was put into a three neck flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. ITA (1.30 g), MATHF (12.49 g), OXE-30 (11.05 g), HEMA (6.51 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution, and HS-EDM (36.57 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin H was obtained. The acid value was 35.8 mgKOH / g and the weight average molecular weight was 8,100.

Synthesis Example 12 Synthesis of Specific Resin I

PGMEA (35.55 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. To the solution, MAA (1.72 g), MATHF (12.49 g), OXE-30 (11.05 g), HEMA (5.21 g), V-65 (3.34 g, 7 mol% based on monomer) was added to PGMEA (35.55 g). It melt | dissolved and it dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin I was obtained. The acid value was 36.8 mgKOH / g and the weight average molecular weight was 7,900.

Synthesis Example 13: Synthesis of Specific Resin J

HS-EDM (32.19 g) was put into a three neck flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. MAA (2.93 g), MATHF (12.49 g), OXE-30 (5.53 g), MMA (4.61 g), DCPM (2.04 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution. It dissolved in HS-EDM (32.19 g) and dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin J was obtained. The acid value was 69.1 mgKOH / g and the weight average molecular weight was 7,900.

Synthesis Example 14 Synthesis of Specific Resin K

HS-EDM (31.64 g) was put into the three neck flask, and it heated up at 70 degreeC in nitrogen atmosphere. MAA (2.84g), MATHF (12.49g), OXE-30 (3.68g), MMA (4.71g), HMA (3.41g), V-65 (3.34g, 7 mol% based on monomer) were added to the solution. It dissolved in HS-EDM (31.64 g) and dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin K was obtained. The acid value was 68.3 mgKOH / g and the weight average molecular weight was 9,900.

Synthesis Example 15 Synthesis of Specific Resin L

HS-EDM (31.54 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. MAA (3.10 g), MATHF (15.61 g), HEMA (8.33 g), and V-65 (3.34 g, 7 mol% based on monomer) were dissolved in HS-EDM (31.54 g) in the solution, and over 2 hours. Dropped. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. As a result, n1 was obtained. The weight average molecular weight was 7,200. In addition, HS-EDM (38.52 g) was put into a three-necked flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. In this solution, MATHF (13.42 g), OXE-30 (16.21 g), HEMA (3.38 g), V-65 (3.34 g, 7 mol% based on monomer) was dissolved in HS-EDM (38.52 g), It was dripped over two hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. As a result, n2 was obtained. The weight average molecular weight was 7,600. Specific resin L was obtained by mixing by n1 / n2 = 4/6. The acid value was 33.9 mgKOH / g.

Synthesis Example 16: Synthesis of Specific Resin M

HS-EDM (32.45g) was put into the three neck flask, and it heated up at 70 degreeC in nitrogen atmosphere. MAA (3.10 g), MATHF (20.29 g), HEMA (4.42 g), and V-65 (3.34 g, 7 mol% based on monomer) were dissolved in HS-EDM (32.45 g) in the solution, followed by 2 hours. Dropped. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. As a result, m1 was obtained. The weight average molecular weight was 8,100. In addition, HS-EDM (34.10 g) was put into a three-necked flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. In this solution, MATHF (12.49 g), GMA (13.36 g), HEMA (3.38 g), and V-65 (3.34 g, 7 mol% relative to the monomer) were dissolved in HS-EDM (34.10 g) for 2 hours. Dropped on. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This gave m2. The weight average molecular weight was 7,900. Specific resin M was obtained by mixing by m1 / m2 = 4/6. The acid value was 35.4 mgKOH / g.

Synthesis Example 17 Synthesis of Specific Resin N

HS-EDM (37.00 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. StCO ₂ H (2.96 g), MATHF (12.49 g), OXE-30 (11.05 g), MMA (5.21 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution. 37.00 g) was added dropwise over 2 hours. It stirred for 4 hours after completion | finish of dripping, and reaction was complete | finished. Thereby, specific resin N was obtained. The acid value was 68.3 mgKOH / g and the weight average molecular weight was 9,700.

Synthesis Example 18 Synthesis of Specific Resin O

HS-EDM (34.00 g) was put into a three-neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. MAA (1.72 g), MATHF (10.93 g), HEMA (5.21), OXE-30 (9.21 g), St (2.08 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution. It melt | dissolved in -EDM (34.00g) and dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, specific resin O was obtained. The acid value was 41.5 mgKOH / g and the weight average molecular weight was 10,200.

Synthesis Example 19 Synthesis of Specific Resin P

HS-EDM (30.77 g) was put into a three neck flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. MAA (2.24 g), MATHF (9.99 g), HEMA (5.21), GMA (6.25 g), St (2.71 g), V-65 (3.34 g, 7 mol% based on monomer) was added to the solution. It melt | dissolved in (30.77g) and dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thereby, specific resin P was obtained. The acid value was 61.6 mgKOH / g and the weight average molecular weight was 9,200.

Comparative Synthesis Example 1 Synthesis of Comparative Resin R1

HS-EDM (31.63 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. To the solution was added MAA (1.72 g), EtMA (9.13 g), OXE-30 (11.05 g), HEMA (5.21 g), V-65 (3.34 g, 7 mol% based on monomer) and HS-EDM (31.63 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R1. The acid value was 41.4 mgKOH / g and the weight average molecular weight was 7,500.

Comparative Synthesis Example 2 Synthesis of Comparative Resin R2

HS-EDM (34.57 g) was put into a three neck flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. MAA (1.72 g), MATHF (12.49 g), HMA (10.22 g), HEMA (5.21 g), V-65 (3.34 g, 7 mol% based on monomer) was added to HS-EDM (34.57 g). It melt | dissolved and it dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R2. The acid value was 37.9 mgKOH / g and the weight average molecular weight was 7,300.

Comparative Synthesis Example 3: Synthesis of Comparative Resin R3

HS-EDM (33.64 g) was put into a three neck flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. MAA (5.17 g), MATHF (9.99 g), OXE-30 (12.90 g), HEMA (0.78 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution, and HS-EDM (33.64 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R3. The acid value was 116.8 mgKOH / g and the weight average molecular weight was 8,200.

Comparative Synthesis Example 4 Synthesis of Comparative Resin R4

HS-EDM (34.34 g) was put into a three-necked flask, and the temperature was raised to 70 ° C. under a nitrogen atmosphere. MAA (1.72 g), MATHF (6.24 g), OXE-30 (11.05 g), HEMA (10.41 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution, and HS-EDM (34.34 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R4. The acid value was 38.1 mgKOH / g and the weight average molecular weight was 7,600.

Comparative Synthesis Example 5 Synthesis of Comparative Resin R5

HS-EDM (35.74 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. MAA (1.72 g), MAEVE (12.65 g), OXE-30 (11.05 g), HEMA (5.20 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution, and HS-EDM (35.74 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R5. The acid value was 36.6 mgKOH / g and the weight average molecular weight was 6,600.

Comparative Synthesis Example 6 Synthesis of Comparative Resin R6

HS-EDM (34.89 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. MAA (1.72 g), MACHVE (16.97 g), OXE-30 (11.05 g), HEMA (5.21 g), V-65 (3.34 g, 7 mol% based on monomer) was added to the solution, and HS-EDM (34.89 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R6. The acid value was 32.1 mgKOH / g and the weight average molecular weight was 7,200.

Comparative Synthesis Example 7 Synthesis of Comparative Resin R7

HS-EDM (32.46g) was put into the three neck flask, and it heated up at 70 degreeC under nitrogen atmosphere. MAA (1.72 g), MABVE (14.89 g), OXE-30 (11.05 g), HEMA (5.21 g), V-65 (3.34 g, 7 mol% based on monomer) were added to the solution, and HS-EDM (32.46 g). ) Was added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R7. The acid value was 34.1 mgKOH / g and the weight average molecular weight was 6,800.

Comparative Synthesis Example 8 Synthesis of Comparative Resin R8

PGMEA (70.0g) was put into the three neck flask, and it heated up at 70 degreeC in nitrogen atmosphere. MAA (30.0 g), MMA (12.0 g), HEMA (12.0 g), BzMA (6 g), and V-65 (3.34 g, 7 mol% based on monomer) were dissolved in PGMEA (70.0 g) in the solution. It was dripped over two hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R8. The acid value was 325.9 mgKOH / g and the weight average molecular weight was 7,500.

Comparative Synthesis Example 9 Synthesis of Comparative Resin R9

40 g of poly (p-hydroxystyrene) (333 mmol as p-hydroxystyrene unit) and 47 mg (0.25 mmol) of p-toluenesulfonic acid monohydrate were put into a branched flask, and it mixed with 98.3 g of PGMEA. Furthermore, 16.6 g (230 mmol) of ethyl vinyl ethers were dripped, and it was made to react at 25 degreeC for 5 hours. 100 g of methyl isobutyl ketones were added to this reaction solution, and 100 mL of ion-exchange water was added. After stirring, the organic layer portion was taken out. The organic layer was taken out and distilled under reduced pressure to obtain a PGMEA solution. The obtained liquid was a solution of a resin in which a phenolic hydroxyl group of poly (p-hydroxystyrene) was partially etherified with 1-ethoxyethyl, and this resin was analyzed by ¹ H-NMR to find 50 of the phenolic hydroxyl group. % Was 1-ethoxyethyl ether. This resin is referred to as comparative resin R9. Moreover, the acid value of this resin was 213.99 mgKOH / g.

Comparative Synthesis Example 10 Synthesis of Comparative Resin R10

HS-EDM (50.0g) was put into the three neck flask, and it heated up at 70 degreeC in nitrogen atmosphere. MACHVE (20.0 g), St (2.5 g), GMA (27.5 g), HEMA (5.0 g), and V-65 (3.5 g, 7 mol% based on monomer) were added to HS-EDM (50.0 g). It melt | dissolved and it dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R10. The acid value was 0 mgKOH / g and the weight average molecular weight was 9,700.

Comparative Synthesis Example 11: Synthesis of Comparative Resin R11

PGMEA (35.4g) was put into the three neck flask, and it heated up at 70 degreeC in nitrogen atmosphere. MAA (6.47 g), CHMI (11.77 g), HEMA (8.50 g), MMA (6.60 g), and V-65 (5.56 g, 7 mol% based on monomer) were dissolved in PGMEA (35.4 g). It dripped over two hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R11. The acid value was 126.4 mgKOH / g and the weight average molecular weight was 8,200.

Comparative Synthesis Example 12 Synthesis of Comparative Resin R12

PGMEA (43.2 g) was put into a three neck flask, and the temperature was raised to 70 ° C under a nitrogen atmosphere. To the solution, MAA (1.72 g), MATHP (19.07 g), OXE-30 (11.05 g), HEMA (5.21 g), V-65 (3.34 g, 7 mol% based on monomer) was added to PGMEA (43.2 g). It melt | dissolved and it dripped over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. This obtained the comparative resin R12. The acid value was 30.3 mgKOH / g and the weight average molecular weight was 7,700.

Synthesis Example 20 Synthesis of Oxime Sulfonate OS-2 (B4)

8.4 g (200 mmol) of NaOH and 42 g of methanol were added to a 300 mL three neck flask, and the mixture was heated and dissolved. Subsequently, after adding 5.41 g (50 mmol) of benzyl acetonitrile at 5 degreeC, 7.75 g (60 mmol) of 2-nitrothiophenes were dripped continuously. It stirred at 5 degreeC for 1 hour. 200 mL of water and 50 mL of ethyl acetate were added and stirred to the reaction container. It extracted with 200 mL of ethyl acetate, and dried over magnesium sulfate. The residue obtained by filtration and concentration was purified by column chromatography (hexane / ethyl acetate = 4/1), and 5.14 g was obtained by recrystallization from ethyl acetate. This crystal was confirmed by ¹ H-NMR to be an OS-2 intermediate. Furthermore, it confirmed that it was two types of isomer mixtures (1: 1).

2.28 g (10 mmol) of OS-2 intermediate and 20 mL of THF were added to a 100 mL three-neck flask, and 1.57 g (11 mmol) of propanesulfonyl chloride was added at 5 ° C. Still with stirring, it was added dropwise triethylamine _{(Et 3 N) 1.21g (12m㏖} ). After stirring for 2 hours at 5 ° C, 200 mL of water was added. After extraction with ethyl acetate, the mixture was dried over magnesium sulfate. Since the crude crystal was obtained by filtration and drying, 2.01g of OS-2 was obtained by performing slurry by drying in 50 mL of hexane. Purity was 98.8% by analysis by liquid column chromatography, and it was confirmed by ¹ H-NMR that the mixture was two kinds of isomers (1: 1).

¹ H-NMR (DMSO-d6, δ ppm): 7.47 to 7.38 (m, 5H), 6.22 (d, J = 6.6 Hz, 1H), 3.78 to 3.73 (m, 2H), 1.87 to 1.79 (q, J = 7.5 μs, 2H), 1.03 (t, 3H).

Synthesis Example 21 Synthesis of Oxime Sulfonate OS-16 (B5)

8.4 g (200 mmol) of NaOH and 42 g of methanol were added to a 300 mL three neck flask, and the mixture was heated and dissolved. Subsequently, after adding 6.56 g of 2-methylphenyl acetonitrile at 5 degreeC, 7.50 g of 2-nitrothiophenes were dripped continuously. It stirred at 5 degreeC for 1 hour. 200 mL of water and 50 mL of ethyl acetate were added and stirred to the reaction container. It extracted with 200 mL of ethyl acetate, and dried over magnesium sulfate. The residue obtained by filtration and concentration was purified by column chromatography (hexane / ethyl acetate = 4/1), and 5.45 g was obtained by recrystallization from ethyl acetate. This crystal was confirmed by ¹ H-NMR as an OS-16 intermediate. Furthermore, it confirmed that it was two types of isomer mixtures (1: 1).

2.42 g of OS-16 intermediate and 20 mL of THF were added to a 100 mL three neck flask, and 1.26 g of methanesulfonyl chloride were added at 5 ° C. Under stirring, 1.21 g of triethylamine was added dropwise. After stirring for 2 hours at 5 ° C, 200 mL of water was added. After extraction with ethyl acetate, the mixture was dried over magnesium sulfate. Filtration and drying gave crude crystals, so that 2.31 g of OS-16 was obtained by slurrying and drying with 50 mL of hexane. The analysis by liquid column chromatography showed the purity of 98.8%, and confirmed the product from ¹ H-NMR.

¹ H-NMR (DMSO-d 6, δ ppm): 7.45 to 7.33 (m, 5H), 6.22 (J = 6.6 Hz, 1H), 3.58 (s, 3H), 2.32 (s, 3H).

Synthesis Example 22 Synthesis of B8

1-1. Synthesis of Synthetic Intermediates B8A

2-aminobenzenethiol: 31.3 g (made by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in toluene: 100 mL (made by Wako Pure Chemical Industries, Ltd.) under room temperature (25 degreeC). Next, phenyl acetyl chloride: 40.6g (made by Tokyo Kasei Kogyo Co., Ltd.) was dripped, and it stirred for 1 hour and then made it react at 100 degreeC for 2 hours at room temperature. 500 mL of water was put into the obtained reaction liquid, the precipitated salt was dissolved, the toluene fraction was extracted, the extract liquid was concentrated with the rotary evaporator, and the synthetic intermediate B8A was obtained.

1-2. Synthesis of B8

2.25 g of the synthetic intermediate B8A obtained as described above was mixed with 10 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and then immersed in an ice bath to cool the reaction solution to 5 ° C or lower. Next, tetramethylammonium hydroxide: 4.37g (25 weight% methanol solution, the Alfa Acer company make) was dripped, and it stirred for 0.5 hour and reacted under ice bath. In addition, isopropyl nitrite: 7.03 g was added dropwise keeping the internal temperature at 20 ° C. or lower, and after completion of the dropwise addition, the reaction solution was heated to room temperature, followed by stirring for 1 hour.

Subsequently, after cooling the reaction liquid to 5 degrees C or less, p-toluene sulfonyl chloride (1.9 g) (made by Tokyo Kasei Kogyo Co., Ltd.) was thrown in, and it stirred for 1 hour, maintaining 10 degrees C or less. Then, 80 mL of water was thrown in and it stirred at 0 degreeC for 1 hour. After filtering the obtained precipitate, 60 mL of isopropyl alcohols (IPA) were thrown in, and it heated at 50 degreeC, stirred for 1 hour, and filtered and dried at the time, and 1.8g of B8 was obtained.

The ¹ H-NMR spectrum (300 MHz, heavy DMSO ((D ₃ C) ₂ S = O)) of the obtained B8 is δ = 8.2 to 8.17 (m, 1H) and 8.03 to 8.00 (m, 1H) , 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), and 2.45 (s, 3H).

It is estimated that B8 obtained from said ¹ H-NMR measurement result is 1 type of single cis or trans isomer.

Synthesis Example 23 Synthesis of B9

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixed solution was heated to 40 ° C for 2 hours to react. 4 N HCl aqueous solution (60 mL) was dripped at the reaction liquid under ice cooling, ethyl acetate (50 mL) was added and liquid-separated. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour, followed by separating an aqueous solution of 2N HCl (60 mL), separating the organic layer, and then recrystallizing the crystals with diisopropyl ether (10 mL). It filtered, dried and the ketone compound (6.5g) was obtained.

Acetic acid (7.3g) and 50weight% hydroxylamine aqueous solution (8.0g) were added and heated and refluxed to the obtained ketone compound (3.0g) and the suspension solution of methanol (30mL). After cooling, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and it heated up to room temperature and made it react for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered off, reslurried with methanol (20 mL), filtered and dried to obtain B9 (2.3 g).

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B9 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 ( dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d. 1H), 5.6 (q, 1H), 2.4 (s, 3H) and 1.7 (d, 3H).

Synthesis Example 24 Synthesis of B10

2-naphthol (20 g) was dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) were added, and the mixture was reacted at 100 ° C for 2 hours. Water (300 mL) and ethyl acetate (200 mL) were added to the reaction solution, the organic layer was concentrated, 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) were added thereto, followed by reaction for 2 hours. I was. The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a carboxylic acid crude. Then, 30 g of polyphosphoric acid was added and reacted at 170 ° C for 30 minutes. The reaction solution was poured into water (300 mL), ethyl acetate (300 mL) was added to the solution, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g) and magnesium sulfate (4.5 g) were added to the obtained ketone compound (10.0 g) and the suspension solution of methanol (100 mL), and it heated and refluxed for 24 hours. After cooling, water (150 mL) and ethyl acetate (150 mL) were added and the mixture was separated. The organic layer was separated four times with 80 mL of water, concentrated, and purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

About the obtained oxime (3.1g), sulfonation was performed like B8 and B10 (3.2g) was obtained.

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B10 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 ( dd, 1H, 7.5 (dd, 1H), 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H), 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt , 1H), 1.4 to 1.2 (m, 8H), and 0.8 (t, 3H).

Synthesis Example 25 Synthesis of B11

B11 was synthesize | combined similarly to the synthesis of B9 except having used benzenesulfonyl chloride instead of p-toluenesulfonyl chloride in the synthesis | combination of B9.

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B11 is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7- 7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d. 1H), 5.6 (q, 1H) and 1.7 (d, 3H).

(Examples 1-50, and Comparative Examples 1-14)

(1) Preparation of Photosensitive Resin Composition

After mixing each component shown in Table 1 and Table 2 into a uniform solution, it filtered using the polytetrafluoroethylene filter which has a pore size of 0.2 micrometer, and Examples 1-50 and Comparative Examples 1-14. Photosensitive resin compositions were prepared, respectively.

[Table 1]

[Table 2]

In addition, the symbol of Table 1 and Table 2 is as follows.

B1: CGI1397 (the following structure, product made in Chiba Japan)

B2: CGI1325 (the following structure, product made in Chiba Japan)

B3: CGI725 (the following structure, product made in Chiba Japan)

B4: OS-2 (synthetic)

B5: OS-16 (synthetic)

B6: 4,7-di-n-butoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate

B7: Commercial item of the composition of m / p-cresol novolak and 1,2-naphthoquinone diazide-5-sulfonic acid ester (made by Tokyo Okagyo Co., Ltd.)

B8: the following compound (synthetic product)

B9: the following compound (synthetic product)

B10: the following compound (synthetic product)

B11: the following compound (synthetic product)

C1: propylene glycol monomethyl ether acetate (methoxypropyl acetate)

C2: diethylene glycol ethyl methyl ether

D1: Adecastub AO-60 (the following structure, product made in ADEKA)

E1: JER-157S70 (polyfunctional novolak type epoxy resin (epoxy equivalent 200-220 g / eq), the Japan epoxy resin Co., Ltd. product)

H1: Megapack R-08 (perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation)

H2: W-3 (following structure)

G1: 4-dimethylaminopyridine

G2: 1,5-diazabicyclo [4.3.0] -5-nonene

F1: KBM-403 (Summer structure, Shin-Etsu Chemical Co., Ltd.)

(2) Evaluation of sensitivity

After slit-coating the photosensitive resin composition of each Example and the comparative example on the silicon wafer which has a silicon oxide film, it prebaked at 95 degreeC for 90 second on the hotplate, and formed the coating film of 3 micrometers in film thickness.

Next, it exposed using the i-line stepper (FPA-3000i5 ⁺ by Canon Corporation) through the predetermined mask. After exposure, it developed by the liquid method for 80 second with 23 weight of tetramethylammonium hydroxide aqueous solution at 23 degreeC, and then rinsed with ultrapure water for 1 minute. The optimal exposure amount at the time of resolving 10 micrometers line and space by 1: 1 by these operation was made into the sensitivity. Sensitivity was evaluated by the following evaluation criteria.

A: less than 15mJ / cm 2

B: 15-30 mJ ／ cm 2

C: 30-50mJ / cm <2>

D: exceeding 50 mJ / cm 2

(3) Evaluation of unexposed part residual film rate

The film thickness of the unexposed part after image development of the coating film formed as the evaluation of a sensitivity was measured with the stylus type film thickness meter, and the ratio of the remaining film thickness with respect to the measured initial film thickness was evaluated as a residual film rate. That is, "the unexposed part residual film ratio = film thickness after undeveloped (unexposed part) / film thickness before undeveloped (unexposed part) x 100". The higher the unexposed part residual film ratio, the better the development margin.

(4) evaluation of transparency

After slit-coating the photosensitive resin composition solution on glass substrate "Corning 1737 (made by Corning Corporation), it prebaked at 95 degreeC for 90 second on the hotplate, and formed the coating film of 3 micrometers in film thickness. The obtained coating film was exposed to a total irradiation amount of 200 mJ / cm 2 (roughness: 20 mW / cm 2) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and then the substrate was heated at 230 ° C. for 1 hour in an oven. To obtain a cured film. After heating the obtained cured film further at 230 degreeC in oven, the light transmittance was measured at the wavelength of 400-800 nm using the spectrophotometer "150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.). did. Evaluation of the transmittance | permeability in 400 nm at that time can be said that heat resistance transparency is favorable as this value is 90% or more as transparency evaluation.

(5) evaluation of heat resistance transparency

After heating the cured film obtained above in an oven for 2 hours at 230 degreeC, the light transmittance was made into the range of 400-800 nm using a spectrophotometer "150-20 type double beam (the Hitachi Seisakusho Co., Ltd. product). Measured at the wavelength. Evaluation of the transmittance | permeability in 400 nm at that time can be said that heat resistance transparency is favorable as this value is 90% or more as evaluation of heat resistance transparency.

(5) Evaluation of dielectric constant

After slit-coating the photosensitive resin composition on a bare wafer (N type low resistance) (made by SUMCO Corporation), it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the photosensitive resin composition layer of 3.0 micrometers in film thicknesses. The obtained photosensitive resin composition was exposed to a total irradiation amount of 300 mJ / cm 2 (roughness: 20 mW / cm 2) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and the substrate was heated at 220 ° C. for 1 hour in an oven. The cured film was obtained by doing this.

About this cured film, the dielectric constant was measured at the measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). The results are shown in Tables 3 and 4. It is so preferable that this value is low, and when it is 3.9 or less, it can be said that the dielectric constant of a cured film is favorable.

(6) evaluation of residue

After each photosensitive resin composition was slit-coated in the same manner as in the evaluation of the sensitivity, prebaking was carried out on a hot plate at 95 ° C. for 90 seconds to form a coating film having a film thickness of 3 μm.

The obtained coating film was exposed to an optimal exposure dose pattern in a circular shape through a mask for forming a 10 µm contact hole, and rinsed after development in the same manner as in the evaluation of sensitivity. About the residue of the edge part of the obtained circular pattern (cured film), the distance from the place where the cured film is formed to the place where a film | membrane completely disappeared was observed using the optical microscope. The evaluation criteria are as follows.

A: less than 1.0 μm

B: 1.0-2.0 µm

C: Remaining film | membrane is carried out to the outer side from 2.0 micrometers from the edge part of a cured film.

(7) evaluation of surface roughness

The cured film was formed like the evaluation of heat resistance transparency.

About the cured film after the post-baking, Ra of the surface was measured using the contact film thickness meter (touch surface roughening machine P10 by Tencor Corporation), and it evaluated according to the following evaluation criteria.

A: less than 5.0 nm

B: 5.0 nm or more and less than 10 nm

C: 10 nm or more

The evaluation result of said each evaluation in the photosensitive resin composition of Examples 1-50 and Comparative Examples 1-14 is put together in Table 3 and Table 4.

[Table 3]

[Table 4]

In addition, "-" in Table 3 and Table 4 shows that it was not able to evaluate, or it is not evaluating because the unexposed part residual film ratio is less than 80% and it is outside the practical range.

From Table 3 and Table 4, the photosensitive resin composition of each Example containing a specific resin has high sensitivity in contrast with the photosensitive resin composition of each comparative example, generation | occurrence | production of a residue is suppressed, and the surface roughness of the formed cured film also arises. It is understood that excellent results are obtained even in the evaluation of the relative dielectric constant without being excellent in transparency and heat resistance transparency.

(Example 51)

After slit coating the photosensitive resin composition solution used in Example 2 on the silicon wafer which has a silicon oxide film, it prebaked at 95 degreeC for 90 second on the hotplate, and formed the coating film of 3 micrometers in film thicknesses.

Next, the predetermined photomask was set through the 150-micrometer space | interval from the coating film, and the laser of wavelength 355nm was irradiated with the exposure amount 15mJ / cm <2>. In addition, the laser apparatus measured the exposure amount using "PE10B-V2" by OPHIR company using "AEGIS" made from V Technologies, Ltd. (wavelength 355 nm, pulse width 6 nsec). After exposure, it developed by the liquid method for 80 second with 23% of tetramethylammonium hydroxide aqueous solution at 23 degreeC, and then rinsed with ultrapure water for 1 minute. By these operations, 10 micrometers of line and space could be resolved 1: 1.

Further, except that the exposure was changed from the i-line stepper to the UV-LED light source exposure machine, the same evaluation was performed as in the above (2) evaluation of sensitivity (no PEB).

(Example 52)

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see Fig. 1).

Forming a TFT (1) of the bottom gate type on a glass substrate 6, thereby forming the insulating film 3 made of Si ₃ N ₄ in a state covering the TFT (1). Next, a contact hole (not shown here) is formed in the insulating film 3, and then the wiring 2 (1.0 mu m in height) connected to the TFT 1 via the contact hole is formed. Formed on top. This wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 was formed on the insulating film 3 in a state of filling the unevenness of the wiring 2. Formation of the planarizing film 4 on the insulating film 3 is carried out by spin-coating the photosensitive resin composition of Example 9 on a board | substrate, prebaking on a hotplate (90 degreeC x 2 minutes), and using a high pressure mercury lamp on a mask. After irradiating i line | wire (365 nm) 15mJ / cm <2> (roughness 20mW / cm <2>), it developed in alkaline aqueous solution, the pattern was formed, and it heat-processed for 60 minutes at 230 degreeC. The applicability | paintability at the time of apply | coating the said photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle and a crack were not seen in the cured film obtained after exposure, image development, and baking. In addition, the film thickness of the planarization film 4 which produced 500 nm of average level | step differences of the wiring 2 was 2,000 nm.

Next, a bottom emission type organic EL device was formed on the obtained planarization film 4. First, on the planarization film 4, the 1st electrode 5 which consists of ITO was formed by connecting to the wiring 2 through the contact hole 7. Then, the resist was apply | coated and prebaked, and it exposed and developed through the mask of a desired pattern. Using this resist pattern as a mask, pattern processing was performed by wet etching using ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (a mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The 1st electrode 5 obtained in this way is corresponded to the anode of organic electroluminescent element.

Next, the insulating film 8 of the shape which covers the periphery of the 1st electrode 5 was formed. It formed in the insulating film 8 by the method similar to the above using the photosensitive resin composition of Example 7. By providing this insulating film 8, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process can be prevented.

Moreover, the hole transport layer, the organic light emitting layer, and the electron carrying layer were sequentially deposited and provided through the desired pattern mask in the vacuum vapor deposition apparatus. Then, the 2nd electrode which consists of Al in the whole surface above a board | substrate was formed. The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix organic EL display device in which a TFT 1 for driving the organic EL element is connected to each organic EL element is obtained. When voltage was applied through the drive circuit, it was found that the display device exhibited good display characteristics and was a highly reliable organic EL display device.

(Example 53)

An organic EL display device was produced in the same manner as in Example 52, except that the photosensitive resin composition of Example 9 and the photosensitive resin composition of Example 7 were all changed to the photosensitive resin composition of Example 22. The obtained organic electroluminescence display showed favorable display characteristics, and it turned out that it is a highly reliable organic electroluminescence display.

(Example 54)

An organic EL display device was produced in the same manner as in Example 52, except that the photosensitive resin composition of Example 9 and the photosensitive resin composition of Example 7 were all changed to the photosensitive resin composition of Example 35. The obtained organic electroluminescence display showed favorable display characteristics, and it turned out that it is a highly reliable organic electroluminescence display.

(Example 55)

An organic EL display device was produced in the same manner as in Example 52 except that the photosensitive resin composition of Example 9 and the photosensitive resin composition of Example 7 were all changed to the photosensitive resin composition of Example 41. The obtained organic electroluminescence display showed favorable display characteristics, and it turned out that it is a highly reliable organic electroluminescence display.

(Example 56)

In the active matrix liquid crystal display device of FIGS. 1 and 2 of JP-A-3321003, the cured film 17 was formed as follows as an interlayer insulating film, and the liquid crystal display device of Example 17 was obtained.

That is, the cured film 17 was formed as an interlayer insulation film by the method similar to the formation method of the planarization film 4 of the organic electroluminescence display in Example 52 using the photosensitive resin composition of Example 9.

When the drive voltage was applied to the obtained liquid crystal display device, favorable display characteristics were shown and it turned out that it is a highly reliable liquid crystal display device.

1: TFT (Thin Film Transistor) 2: Wiring
3: insulating film 4: planarization film
5: first electrode 6: glass substrate
7: contact hole 8: insulating film
10: liquid crystal display device 12: backlight unit
14, 15: glass substrate 16: TFT
17: cured film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: color filter

Claims (23)

(Component A) Resin which has a structural unit represented by following formula (1), the structural unit which has an acidic group, and the structural unit which has a crosslinkable group, and
(Component B) The positive photosensitive resin composition containing the acid generator which has an oxime sulfonate group.

(In formula (1), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ²¹ to R ²⁷ each independently represent a hydrogen atom or an alkyl group.) The method of claim 1,
Positive photosensitive resin composition whose said R <^1> is a methyl group. The method according to claim 1 or 2,
Positive type photosensitive resin composition whose one or more of said R <^21> -R <^27> is a hydrogen atom. 4. The method according to any one of claims 1 to 3,
The positive photosensitive resin composition in which all of said R ²¹ to R ²⁷ are hydrogen atoms. 5. The method according to any one of claims 1 to 4,
Positive type photosensitive resin composition whose said L <^1> is a carbonyl group. The method according to any one of claims 1 to 5,
Positive type photosensitive resin composition whose said acidic group is a carboxyl group or phenolic hydroxyl group. The method according to claim 6,
The positive photosensitive resin composition whose said acidic group is a carboxyl group. 8. The method according to any one of claims 1 to 7,
The positive photosensitive resin composition whose said crosslinkable group is an epoxy group or an oxetanyl group. 9. The method of claim 8,
The positive photosensitive resin composition whose said crosslinkable group is an oxetanyl group. The method according to claim 7 or 9,
The positive type photosensitive resin composition in which the said acidic group is a carboxy group and the said crosslinkable group is an oxetanyl group. 11. The method according to any one of claims 1 to 10,
Positive type photosensitive resin composition whose said component (B) is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by a following formula (OS-103), a formula (OS-104), and a formula (OS-105).

(In formula (OS-103)-(OS-105), R <^11> represents an alkyl group, an aryl group, or heteroaryl group, and two or more R <^12> represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom each independently. , R ¹⁶ present in plural numbers each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6) 11. The method according to any one of claims 1 to 10,
Positive type photosensitive resin composition whose said component B is an oxime sulfonate compound represented by following formula (2).

(In formula (2), R <^4> represents an alkyl group or an aryl group, X respectively independently represents an alkyl group, an alkoxy group, or a halogen atom, and m shows the integer of 0-3.) 13. The method according to any one of claims 1 to 12,
Positive type photosensitive resin composition containing the said component A in the range of 40 to 95 weight% with respect to the total solid of a positive photosensitive resin composition, and containing the said component B in the range of 0.1 to 10 weight%. The method according to any one of claims 1 to 13,
Positive type photosensitive resin composition containing a crosslinking agent further. 15. The method of claim 14,
It contains the said component A in the range of 40 to 70 weight% with respect to the total solid of a positive photosensitive resin composition, contains the said component B in the range of 0.1 to 10 weight%, and contains 3 to 40 weight of the said crosslinking agent. Positive type photosensitive resin composition to contain in% of range. 16. The method according to any one of claims 1 to 15,
Positive type photosensitive resin composition containing a solvent further. The cured film which provided and hardened | cured at least one among light and the heat | fever with respect to the positive photosensitive resin composition of any one of Claims 1-16. (1) an application step of applying the positive photosensitive resin composition according to claim 16 on a substrate;
(2) a solvent removal step of removing the solvent from the applied positive photosensitive resin composition,
(3) an exposure step of exposing the positive photosensitive resin composition from which the solvent has been removed with active radiation;
(4) a developing step of developing the exposed positive photosensitive resin composition with an aqueous developer; and
(5) Post-baking process of thermosetting the developed positive photosensitive resin composition
Formation method of the cured film containing a. 19. The method of claim 18,
The formation method of the cured film which performs the said image development process, without performing heat processing after exposure in the said exposure process. The cured film formed by the formation method of the cured film of Claim 18 or 19. The method of claim 17 or 20,
Cured film which is an interlayer insulation film. The liquid crystal display device provided with the cured film of Claim 17 or 20. The organic electroluminescence display provided with the cured film of Claim 17 or 20.

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