KR20130033314A - Photosensitive resin composition, method of producing cured film, cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

PURPOSE: A photosensitive resin composition, a hardened film using the same, a manufacturing method thereof, an organic EL display device and a liquid crystal display device are provided to be able to manufacture a photosensitive resin composition having high chemical resistance after curing and a very high sensitivity by obtaining a hardened film with low transparency decline in heating. CONSTITUTION: A photosensitive resin composition comprises a resin with the acetal structure in which the alkali solubility is changed with the acid action, a photo acid generator, a cross-linking agent, and a solvent. The cross-linking agent includes a block isocyanate compound. The parent structure of the block isocyanate compound is the burette structure. The isocyanate functional group of the block isocyanate compound is blocked by a blocking agent selected from the group consisting of oxime compound, lactam compound, phenol compound, alcohol compound, amine compound, activated methylene compound, pyrazole compound, mercaptan compound, imidazole compound, and imide compound. The photo acid generator is oxime sulfonate compound. A liquid crystal display device(10) uses the photosensitive resin composition.

Description

Photosensitive resin composition, the method of forming a cured film, a cured film, an organic EL display apparatus, and a liquid crystal display device {PHOTOSENSITIVE RESIN COMPOSITION, METHOD OF PRODUCING CURED FILM, CURED FILM, ORGANIC EL DISPLAY DEVICE, AND LIQUID CRYSTAL DISPLAY DEVICE}

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

More specifically, it relates to a positive photosensitive resin composition suitable for the formation of planarization films, protective films and interlayer insulating films of electronic components such as organic EL displays, liquid crystal displays, integrated circuit devices, solid-state imaging devices, and a method of forming a cured film using the same. will be.

A patterned interlayer insulating film is formed in an organic EL display device, a liquid crystal display device, or the like. The photosensitive resin composition is widely used for the formation of this interlayer insulation film in that the number of steps for obtaining the required pattern shape is small and sufficient flatness is obtained.

In addition to the physical properties of the cured film which is excellent in insulation, solvent resistance, heat resistance, and indium tin oxide (ITO) sputterability, the interlayer insulating film in the said display apparatus is desired. For this reason, it is tried to use acrylic resin excellent in transparency as a film formation component.

On the other hand, a microlens having a lens diameter of about 3 to 100 µm as an imaging system of an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state imaging device, or an optical fiber connector, or a microlens array in which these microlenses are regularly arranged Is being used.

To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment to be used as a lens, or by using a melt-flowed lens pattern as a mask and dry etching to form a lens. And a method for transferring the same is known. The photosensitive resin composition is widely used for formation of the said lens pattern.

As such a photosensitive resin composition, Unexamined-Japanese-Patent No. 10-26829, Unexamined-Japanese-Patent No. 2004-264623, and Unexamined-Japanese-Patent No. 2008-3532 are mentioned, for example.

Various chemical liquids, such as an etching liquid, a peeling liquid, and N-methylpyrrolidone (NMP), are used for manufacture of such display apparatuses, and resistance to these chemical liquids becomes essential. For example, Japanese Unexamined Patent Application Publication No. 2008-3532 discloses an invention relating to improvement in resistance to MEA (monoethanolamine) as a stripping solution, but does not describe improvement in resistance to other chemicals, particularly NMP.

The problem to be solved by the present invention is to provide a photosensitive resin composition having a very high sensitivity by obtaining a cured film having high chemical resistance after curing and small transparency drop even when heated.

Further, another object of the present invention is to provide a cured film using the photosensitive resin composition, a method for producing the same, an organic EL display device having the cured film, and a liquid crystal display device.

The said subject of this invention was solved by the means as described in the following <1>, <11>, <15>, <17>, or <18>. It describes below with <2>-<10>, <12>-<14>, and <16> which is preferable embodiment.

<1> (component A) Resin which has an acetal structure and whose alkali solubility changes by the action of an acid, (component B) photoacid generator, (component C) crosslinking agent, and (component D) solvent, Comprising: Is a block isocyanate compound, and the parent structure of the block isocyanate compound is a photosensitive resin composition,

<2> The isocyanate group of the block isocyanate compound according to <1>, wherein an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and already Photosensitive resin composition characterized by blocking with a blocking agent selected from the group consisting of a de-based compound,

<3> The <1> or <2>, wherein the block isocyanate compound is tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) Photosensitive resin composition characterized by blocking the isocyanate group of the multimer which has a burette structure obtained by multiplying the compound selected from the group which consists of a blocking agent,

<4> The photosensitive resin composition in any one of <1>-<3> whose content of the said block isocyanate compound is 0.1-8 mass% with respect to the total solid content of the photosensitive resin composition,

<5> Photosensitive resin composition in any one of <1>-<4> whose component A is a polymer which has a structural unit (a1) which has a residue by which the carboxyl group was protected by the acetal structure,

<6> Photosensitive resin composition in any one of <1>-<5> whose component A is a polymer which has a structural unit (a2) which has a carboxyl group or a phenolic hydroxyl group,

<7> Photosensitive resin composition in any one of <1>-<6> whose component B is an oxime sulfonate compound,

<8> Photosensitive resin composition in any one of <1>-<7> whose component A is a polymer which has a structural unit which has a crosslinkable group (a3),

<9><8> method, (a3) cross-linking group contained in the structural unit having a crosslinking group is an epoxy group, an oxetanyl group, and a -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms in Photosensitive resin composition, characterized in that at least one selected from the group consisting of

<10> Photosensitive resin composition in any one of <1>-<9> which further contains antioxidant,

<11> (1) The application process of applying the photosensitive resin composition in any one of said <1>-<10> on a board | substrate, (2) The solvent removal process of removing a solvent from the applied photosensitive resin composition, (3) An exposure step of exposing the photosensitive resin composition from which the solvent has been removed by actinic light, (4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition. A method of forming a cured film comprising a step,

<12> The method for forming a cured film according to <11>, comprising a step of exposing the entire surface of the photosensitive resin composition developed after the developing step and before the post-baking step.

<13> The method for forming a cured film according to <11>, which does not include a step of exposing the entire surface of the photosensitive resin composition developed after the developing step and before the post-baking step.

<14> The method for forming a cured film according to any one of <11> to <13>, further comprising (6) a dry etching step of performing dry etching on the substrate having a cured film obtained by thermosetting.

<15> Cured film formed by the method in any one of said <11>-<14>,

<16> The cured film as described in <15> which is an interlayer insulation film,

<17> The organic electroluminescence display provided with the cured film as described in said <15> or <16>,

<18> The liquid crystal display device provided with the cured film as described in said <15> or <16>.

(Effects of the Invention)

According to this invention, the cured film with high chemical-resistance after hardening and small transparency fall even if it heats was obtained, and the photosensitive resin composition which has very high sensitivity was able to be provided.

Moreover, according to this invention, the cured film using the said photosensitive resin composition, its manufacturing method, the organic electroluminescence display provided with the said cured film, and the liquid crystal display device were provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows the structure of an example of the organic electroluminescent display which applied the cured film using the photosensitive resin composition of this invention as an insulating film and a planarization film.
It is typical sectional drawing which shows the structure which shows an example of the liquid crystal display device which applied the cured film using the photosensitive resin composition of this invention.

Hereinafter, the present invention will be described in detail.

In addition, description of "lower limit-an upper limit" shows "lower limit or more and an upper limit or less" in the specification, and description of "upper limit-lower limit" represents "upper limit or less, lower limit or more". That is, the numerical range including an upper limit and a lower limit is shown.

In addition, "resin which (component A) has an acetal structure and whose alkali solubility changes by the action of an acid", etc. is also called "component A" etc. only, and "the structural unit which has a residue by which the carboxyl group was protected by the acetal structure a1) ”and the like are also simply referred to as“ structural unit (a1) ”or the like.

In addition, when both or one of "acrylate" and "methacrylate" are referred to as "(meth) acrylate", and when referring to both or both of "acryl" and "methacryl", it is "(meth) acryl And may be described respectively.

(Photosensitive resin composition)

The photosensitive resin composition of this invention has the (component A) acetal structure, and contains resin in which alkali solubility changes by the action of an acid, (component B) photoacid generator, (component C) crosslinking agent, and (component D) solvent The component C contains a block isocyanate compound, and the parent structure of the block isocyanate compound is a burette structure.

In general, each chemical liquid such as etching liquid, peeling liquid, and N-methylpyrrolidone (NMP) used in the manufacture of display devices differs in the principle of operation to the cured film, penetration, and the like, and the improvement in resistance to certain chemical liquids is different. Since the resistance to chemical liquids is not improved, in particular, as a result of earnestly examining the chemical liquid resistance to NMP, the present invention has been considered. In addition, by using the photosensitive resin composition of this invention as an unexpected effect, it became possible to manufacture the high quality display apparatus without a display nonuniformity.

Moreover, it is preferable that it is a positive photosensitive resin composition, and, as for the photosensitive resin composition of this invention, it is more preferable that it is a chemically amplified positive photosensitive resin composition (chemical amplification positive photosensitive resin composition).

In addition, in this specification, the heat exposure after exposure (Post Exposure Baking) may be called PEB.

Hereinafter, each component which comprises the photosensitive resin composition is 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.

(Component A) Resin which has an acetal structure and changes alkali solubility by action of an acid.

The photosensitive resin composition of this invention has resin (component A) acetal structure, and contains resin in which alkali solubility changes by the action of an acid.

Moreover, it is preferable that component A is a polymer which has a structural unit (a1) which has a structural unit (a1) which has a residue in which a carboxyl group was protected by the acetal structure, a carboxyl group, or a phenolic hydroxyl group.

In addition, the component A may contain structural units other than the said structural unit (a1) and a structural unit (a2).

Component A is a resin in which alkali solubility is changed by the action of an acid, and has a structural unit (a1) having a moiety in which a carboxyl group is protected by an acetal structure, and is a resin that becomes alkali-soluble when the acetal structure is decomposed. desirable.

In addition, "alkali-soluble" in this invention is 23 degreeC 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 mass% tetramethylammonium hydroxide aqueous solution in is said to be 0.01 micrometer / sec or more, and "alkali insoluble" is a solution of the said compound (resin) apply | coated on a board | substrate, and it is 90 minutes at 90 degreeC The dissolution rate with respect to the 0.4 mass% tetramethylammonium hydroxide aqueous solution in 23 degreeC of the coating film (3 micrometers in thickness) of the said compound (resin) formed by heating is less than 0.01 micrometer / sec, Preferably it is 0.005 micrometer / sec I say less than.

In addition, "alkali solubility changes by the effect | action of an acid" means that the dissolution rate with respect to the 0.4 mass% tetramethylammonium hydroxide aqueous solution in 23 degreeC changes before and after making an acid react.

It is preferable that component A is an acrylic polymer.

"Acryl-type polymer" in this invention is addition polymerization type resin, is a polymer containing the structural unit derived from (meth) acrylic acid or its ester, and structural units other than the structural unit derived from (meth) acrylic acid or its ester For example, you may have a structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. Moreover, you may include all the structural units derived from (meth) acrylic acid and its ester.

It is preferable that component A is 50 mol% or more with respect to the whole monomeric unit in component A, and, as for the component unit derived from (meth) acrylic acid or its ester, it is more preferable that it is 80 mol% or more, (meth) acrylic acid or its ester It is especially preferable that it is a polymer which consists only of the monomeric unit derived from.

In addition, "the monomer unit derived from (meth) acrylic acid and / or its ester" is also called "acrylic-type monomer unit." In addition, (meth) acrylic acid shall mean methacrylic acid and / or acrylic acid.

The "acetal structure" in the present invention shall include both the acetal structure and the ketal structure in consultation unless otherwise specified.

The component A may have an acetal structure or a ketal structure, or may have both an acetal structure and a ketal structure.

It is preferable that it is a structure represented by following formula (I) as an acetal structure.

R ¹ and R ² each independently represent a hydrogen atom, a straight or branched alkyl group or a cycloalkyl group. Provided that at least one of R ¹ and R ² represents an alkyl group or a cycloalkyl group.

R ³ represents a linear or branched alkyl group, a cycloalkyl group or an aralkyl group.

R ¹ or R ² and R ³ may be connected to form a cyclic ether.

In addition, the broken-line part in Formula (I) shows the coupling position with another structure.

The alkyl group in R ¹ and R ² in formula (I) is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group as R ¹ and R ² is preferably a cycloalkyl group having 3 to 6 carbon atoms.

The alkyl group in R ³ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The cycloalkyl group as R ³ is preferably a cycloalkyl group having 3 to 10 carbon atoms.

The aralkyl group in R ³ is preferably an aralkyl group having 7 to 10 carbon atoms.

When R ¹ or R ² and R ³ connect to form a cyclic ether, it is preferable that R ¹ or R ² and R ³ connect to form an alkylene chain having 2 to 5 carbon atoms.

The alkyl group, cycloalkyl group, and aralkyl group in R ³ may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom, and the carbon number of the substituent is preferably 6 or less.

Formula (I) according to, R ¹ and R ² is one, for example, as the R ⁷ in the structure of the acetal ester carboxylic acids (-COOR ⁷⁾ hydrogen atom, 1-methoxyethyl group, 1-ethoxy Ethyl group, 1-n-propoxyethyl group, 1-i-propoxyethyl group, 1-n-butoxyethyl group, 1-i-butoxyethyl group, 1-sec-butoxyethyl group, 1-t-butoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-norbornyloxyethyl group, 1-bornyloxyethyl, 1-benzyloxyethyl group, 1-phenethyloxyethyl group, cyclohexyl (methoxy) methyl group, Cyclohexyl (ethoxy) methyl group, cyclohexyl (n-propoxy) methyl group, cyclohexyl (i-propoxy) methyl group, cyclohexyl (cyclohexyloxy) methyl group, cyclohexyl (benzyloxy) methyl group, (alpha) -methoxy Benzyl group, α-ethoxybenzyl group, α-n-propoxybenzyl group, α-i-propoxybenzyl group, α-cyclohexyloxybenzyl group, α-benzyloxybenzyl group, 2-phenyl-1-me Methoxyethyl group, 2-phenyl-1-ethoxy Cyethyl group, 2-phenyl-1-n-propoxyethyl group, 2-phenyl-1-i-propoxyethyl group, 2-phenyl-1-cyclohexyloxyethyl group, 2-phenyl-1-benzyloxyethyl group, 2- Tetrahydrofuranyl group, 2-tetrahydropyranyl group, etc. are mentioned.

Formula (I) R ¹ and R ² both are Examples of R ⁸ in the structure ketal ester (-COOR ⁸⁾ of the carboxylic acid rather than hydrogen atoms, 1-methyl-1-methoxyethyl group, 1-In Methyl-1-ethoxyethyl group, 1-methyl-1-n-propoxyethyl group, 1-methyl-1-i-propoxyethyl group, 1-methyl-1-n-butoxyethyl group, 1-methyl-1- i-butoxyethyl group, 1-methyl-1-sec-butoxyethyl group, 1-methyl-1-t-butoxyethyl group, 1-methyl-1-cyclopentyloxyethyl group, 1-methyl-1-cyclohexyloxy Ethyl group, 1-methyl-1-norbornyloxyethyl group, 1-methyl-1-bornyloxyethyl group, 1-methyl-1-benzyloxyethyl group, 1-methyl-1-phenethyloxyethyl group, 1-cyclohexyl -1-methoxyethyl group, 1-cyclohexyl-1-ethoxyethyl group, 1-cyclohexyl-1-n-propoxyethyl group, 1-cyclohexyl-1-i-propoxyethyl group, 1-cyclohexyl-1 -Cyclohexyloxyethyl group, 1-cyclohexyl-1-benzyloxyethyl group, 1-phenyl-1-methoxyethyl group, 1-phenyl-1-ethoxyethyl group, 1- Neyl-1-n-propoxyethyl group, 1-phenyl-1-i-propoxyethyl group, 1-phenyl-1-cyclohexyloxyethyl group, 1-phenyl-1-benzyloxyethyl group, 1-benzyl-1-me Methoxyethyl group, 1-benzyl-1-ethoxyethyl group, 1-benzyl-1-n-propoxyethyl group, 1-benzyl-1-i-propoxyethyl group, 1-benzyl-1-cyclohexyloxyethyl group, 1- Benzyl-1-benzyloxyethyl group, 2-methyl2-tetrahydrofuranyl group, 2-methyl-2-tetrahydropyranyl group, 1-methoxycyclopentyl group, 1-methoxy-cyclohexyl group, etc. may be mentioned. .

In an acetal ester structure or a ketal ester structure of the said carboxylic acid, an acetal ester structure is more preferable from a process stability viewpoint. Acetal ester structure of carboxylic acids (-COOR ⁷⁾ Preferred R ⁷ as 1-ethoxyethyl group, 1-cyclohexyl-oxy group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl groups are preferred, and the sensitivity in the In view of the above, 1-ethoxyethyl group and 1-cyclohexyloxyethyl group are particularly preferable.

<Structural unit (a1) having a residue in which a carboxyl group is protected by an acetal structure>

It is preferable that component A has at least structural unit (a1) which has a residue by which the carboxyl group was protected by the acetal structure.

As a compound used for forming a structural unit (a1), if a carboxyl group is protected and it can become the compound used for forming a structural unit (a1), it can be used. As a compound which has a carboxyl group, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid, (alpha) -methyl- p-carboxy styrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid, and acrylic acid and methacrylic acid are particularly preferred. Moreover, as a structural unit (a1), the structural unit derived from the carboxylic acid in which these carboxyl groups were protected by the acetal structure is mentioned as a preferable thing.

As a preferable specific example of the radically polymerizable monomer used in order to form a structural unit (a1), for example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1 -Methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-i-butoxyethyl acrylate, 1- ( 2-ethylhexyloxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1-cyclo Hexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl Methacrylate, 1-benzyloxyethyl acrylate, methacrylic acid tetrahydro-2H-pyran-2-yl, And the like can be mentioned methacrylic acid tetrahydro -2H- pyran-2-yl methacrylate, tetrahydrofuran-2-yl, tetrahydrofuran-2-yl acrylate. Among them, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-yl acrylate, 1-cyclohexyloxyethyl methacrylate, and 1 Cyclohexyloxyethyl acrylate is particularly preferred. These structural units (a1) can be used individually by 1 type or in combination of 2 or more types.

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, as long as it is a monomer represented by following formula (II), it can synthesize | combine by reacting (meth) acrylic acid with a vinyl ether compound in presence of an acidic catalyst, as shown below.

In Formula (II), R <^6> represents a hydrogen atom or a methyl group, and R <^5> is synonymous with R <^3> in Formula (I).

In addition, the structural unit (a1) can also be formed by reacting a carboxyl group with a vinyl ether compound after polymerizing with the structural units (a2) to (a5) described later and the precursor thereof. 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 for the structural unit (a1), the structural unit represented by following formula (5) is preferable.

In formula (5), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 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 having 1 to 4 carbon atoms. Indicates.

As a preferable specific example of a structural unit (a1), the following structural unit (a1-1)-(a1-8) can be illustrated. Among these, especially preferable are structural units represented by (a1-1)-(a1-4), (a1-7), and (a1-8).

When the polymer containing the structural unit (a1) does not include the structural unit (a3) having a substantially crosslinkable group, the content rate of the monomer unit forming the structural unit (a1) is a polymer containing the structural unit (a1). 20-100 mol% is preferable and 30-90 mol% is more preferable.

When the polymer containing the structural unit (a1) contains the structural unit (a3), the content rate of the monomer unit forming the structural unit (a1) is in the polymer containing the structural unit (a1) and the structural unit (a3). 3-70 mol% is preferable from a viewpoint of a sensitivity, and 10-60 mol% is more preferable. Moreover, especially when the said acid-decomposable group in the said structural unit (a1) is a structural unit which is a protective carboxyl group in which the carboxyl group was protected by the form of acetal, the content rate of the monomeric unit which forms a structural unit (a1) is 20-50 mol%. It is preferable and 30-45 mol% is more preferable.

<Structural unit (a2) which has a carboxyl group or phenolic hydroxyl group>

It is preferable that component A has at least a structural unit (a2) which has a carboxyl group or phenolic hydroxyl group, and it is more preferable to have a structural unit (a2-1) which has a carboxyl group at least.

As a structural unit (a2-1) which has a carboxyl group, For example, the structure derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in molecules, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, etc. A unit is mentioned.

What is illustrated below is used as an unsaturated carboxylic acid used in order to acquire the structural unit (a2-1) which has a carboxyl group.

That is, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. can be illustrated.

Moreover, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. can be illustrated as unsaturated dicarboxylic acid.

Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to acquire the structural unit (a2-1) which has a carboxyl group. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester of polyhydric carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl) and succinic acid mono (2-methacryl) Royloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, etc. are mentioned.

In addition, the unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the both terminal dicarboxy polymers, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. Can be.

As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.

Especially, in order to form the structural unit (a2-1) which has a carboxyl group from a developable viewpoint, it is preferable to use acrylic acid and methacrylic acid, and it is more preferable to use methacrylic acid.

In addition, the structural unit (a2-1) which has a carboxyl group can also be obtained by making the structural unit and hydroxyl acid anhydride which have a hydroxyl group react.

As an acid anhydride, a well-known thing can be used, Specifically, Dibasic acid anhydrides, such as maleic anhydride, succinic anhydride, itaconic acid anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, chloric anhydride; Acid anhydrides, such as trimellitic anhydride, a pyromellitic dianhydride, a benzophenone tetracarboxylic anhydride, a biphenyl tetracarboxylic anhydride, are mentioned. In these, phthalic anhydride, tetrahydro phthalic anhydride, or succinic anhydride is preferable from a developable viewpoint.

As a radically polymerizable monomer used in order to form the structural unit (a2-2) which has a phenolic hydroxyl group, For example, hydroxystyrenes, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, Japan Of the compounds described in paragraphs 0011 to 0016 of JP 2008-40183 A, the 4-hydroxybenzoic acid derivatives of paragraphs 0007 to 0010 of JP 2888454 A, 4-hydroxybenzoic acid and glycidyl methacrylate The addition reaction product, addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, etc. are mentioned as a preferable thing.

Among the radically polymerizable monomers used to form the structural unit (a2), methacrylic acid, acrylic acid, the compounds described in paragraphs 0011 to 0016 of JP 2008-40183 A, and paragraphs 0007 to 0010 of JP 2888454 A. The 4-hydroxybenzoic acid derivatives described above, the addition reactant of 4-hydroxybenzoic acid and glycidyl methacrylate, and the addition reactant of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable, but from the viewpoint of transparency, methacryl Acids and acrylic acids are particularly preferred. These structural units can be used individually by 1 type or in combination of 2 or more types.

It is preferable to introduce a structural unit (a2) in the range in which component A is not alkali-soluble. When component A has a structural unit (a2), it is preferable that the content rate of the monomer unit which forms a structural unit (a2) among all the monomer units which comprise component A is 2-20 mol%, and 2-15 mol% is furthermore It is preferable and 3-15 mol% is especially preferable. By containing a structural unit (a2) in the said ratio, high sensitivity is obtained and developability is also favorable.

<Structural unit (a3) having a crosslinker >>

Component A may have a structural unit (a3) which has a crosslinking group. The crosslinking group is not particularly limited as long as it is a group causing a curing reaction by heat treatment. In the form of structural units having a preferred cross-linking Examples of the epoxy group, oxetanyl group, -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) groups represented by and an ethylenically unsaturated group selected from the group consisting of there may be mentioned a structural unit comprising one, at least, an epoxy group, an oxetanyl group, and a -NH-CH ₂ -OR at least selected from the groups represented by (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) It is preferable that it is 1 type. Especially, it is more preferable that component A contains the structural unit containing at least 1 of an epoxy group and an oxetanyl group, and it is especially preferable to include the structural unit containing an oxetanyl group. In more detail, the following are mentioned.

<< structural unit (a3-1) which has an epoxy group and / or an oxetanyl group >>

It is preferable that component A contains the structural unit (structural unit (a3-1)) which has an epoxy group and / or an oxetanyl group. The three-membered ring cyclic ether group is also called an epoxy group, and the four-membered ring cyclic ether group is also called an oxetanyl group. As a structural unit (a3-1) which has the said epoxy group and / or oxetanyl group, it is preferable that it is a structural unit which has an alicyclic epoxy group and / or oxetanyl group, and it is more preferable that it is a structural unit which has an oxetanyl group.

The structural unit (a3-1) which has the said epoxy group and / or oxetanyl group should just have at least 1 epoxy group or oxetanyl group in one structural unit, and at least 1 epoxy group and 1 or more oxetanyl group, two Although it may have the above epoxy group or two or more oxetanyl groups, it is not specifically limited, It is preferable to have 1-3 epoxy groups and / or oxetanyl groups in total, One epoxy group and / or oxetanyl group in total or It is more preferable to have two, and it is still more preferable to have one epoxy group or oxetanyl group.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycine (alpha)-n-propyl acrylate, for example. Dyl, α-n-butylacrylic acid glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4 -Epoxycyclohexylmethyl, alpha -ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Japanese Patent The compound containing the alicyclic epoxy skeleton of Paragraph No. 0031 of Unexamined-Japanese-Patent No. 0031-0035, etc. are mentioned.

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

As a specific example of the radically polymerizable monomer used in order to form the structural unit (a3-1) which has the said epoxy group and / or oxetanyl group, it is preferable that it is a monomer containing a methacrylic acid ester structure, and a monomer containing an acrylic ester structure. Do.

More preferred among these monomers are compounds containing alicyclic epoxy skeletons described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and oxetanyl groups described in paragraphs 0011 to 0016 of Japanese Patent Laid-Open No. 2001-330953. It is (meth) acrylic acid ester which has, and especially preferable is (meth) acrylic acid ester which has the oxetanyl group of Paragraph No. 0011 of Unexamined-Japanese-Patent No. 2001-330953-0016. Preferred among these are methacrylic acid glycidyl, acrylic acid 3,4-epoxycyclohexylmethyl, methacrylic acid 3,4-epoxycyclohexylmethyl, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic Acid (3-ethyloxetan-3-yl) methyl, most preferred is 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 structural unit (a3-1) which has the said epoxy group and / or oxetanyl group, Paragraph No. 0053 of Unexamined-Japanese-Patent No. 2011-215590-description of 0055 can be considered into consideration.

The following structural unit can be illustrated as a preferable specific example of structural unit (a3-1) which has the said epoxy group and / or oxetanyl group. R represents a hydrogen atom or a methyl group.

In the present invention, an oxetanyl group is preferable from the viewpoint of sensitivity. Moreover, an alicyclic epoxy group and an oxetanyl group are preferable from a viewpoint of transmittance | permeability (transparency). As mentioned above, in this invention, as an epoxy group and / or an oxetanyl group, an alicyclic epoxy group and an oxetanyl group are preferable, and an oxetanyl group is especially preferable.

<< structural unit (a3-2) which has an ethylenically unsaturated group >>

The structural unit (a3-2) which has an ethylenically unsaturated group is mentioned as one of the structural units (a3) which have the said crosslinking group (henceforth "a structural unit (a3-2)"). As a structural unit (a3-2) which has the said ethylenically unsaturated group, the structural unit which has an ethylenically unsaturated group in a side chain is preferable, The structural unit which has an ethylenically unsaturated group at the terminal, and has a C3-C16 side chain, The structural unit which has a side chain represented by following formula (a3-2-1) is more preferable.

(In formula (a3-2-1), R ³⁰¹ represents a C1-C13 divalent linking group, R ³⁰² represents a hydrogen atom or a methyl group, and * is connected to the main chain of the structural unit (a3) having a crosslinking group). Indicates a site)

R ³⁰¹ is a C1-C13 divalent linking group, and may include an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and may include a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond. In addition, the divalent linking group may have substituents, such as a hydroxyl group and a carboxyl group, in arbitrary positions. Specific examples of R ³⁰¹ include the following divalent linking groups.

Among the side chains represented by the formula (a3-2-1), an aliphatic side chain containing a divalent linking group represented by R ³⁰¹ is preferable.

In addition, description of Paragraph No. 0077-0090 of Unexamined-Japanese-Patent No. 2011-215580 can be considered about the structural unit (a3-2) which has an ethylenically unsaturated group.

_{<< - NH-CH 2 -OR (} R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a structural unit (a3-3) having a group represented by >>

The copolymer used in the present invention is also preferably a structural unit (a3-3) having a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having structural unit (a3-3), hardening reaction can be raise | generated by loose | gentle heat processing, and the cured film excellent in various characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Moreover, although an alkyl group may be any of a linear, branched or cyclic alkyl group, it is preferable that it is a linear or branched alkyl group. The structural unit (a3-3) is more preferably a structural unit having a group represented by the following formula (a3-3-1).

In the formula, R ³³¹ represents a hydrogen atom or a methyl group, and R ³³² represents an alkyl group having 1 to 20 carbon atoms.

R ³³² is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Moreover, although an alkyl group may be any of a linear, branched or cyclic alkyl group, it is preferable that it is a linear or branched alkyl group.

As a specific example of R <^332> , a methyl group, an ethyl group, n-butyl group, i-butyl group, a cyclohexyl group, or n-hexyl group is mentioned. Of these, an i-butyl group, an n-butyl group, or a methyl group is preferable.

<< preferable form of structural unit (a3) >>

When the polymer containing the structural unit (a3) does not substantially include the structural unit (a1), the monomer unit forming the structural unit (a3) of all the monomer units constituting the polymer containing the structural unit (a3) 5-90 mol% is preferable and, as for content, 20-80 mol% is more preferable.

When the polymer containing the said structural unit (a3) contains the said structural unit (a1), content of the monomer unit which forms a structural unit (a3) among all the monomer units which comprise the polymer containing a structural unit (a3) is 3-70 mol% is preferable from a viewpoint of a sensitivity, and 10-60 mol% is more preferable.

In the present invention, the content of the monomer unit forming the structural unit (a3) among all the monomer units constituting the component A is preferably 3 to 70 mol%, more preferably 10 to 60 mol%, regardless of which form. Do.

If it is in the said numerical range, transparency of the cured film obtained from the photosensitive resin composition, and ITO sputter resistance will become favorable.

<Other structural unit (a4)>

The component A may have structural units (a4) other than the said structural units (a1)-(a3) in the range which does not prevent the effect of this invention.

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

Among these, from the viewpoint of electrical characteristics improvement, (meth) acrylic acid esters containing alicyclic structures such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate, methyl (meth) acrylate and ethyl (meth) acrylate (Meth) acrylic-acid alkylester which does not contain alicyclic structures, such as propyl (meth) acrylic acid and n-butyl (meth) acrylate, is preferable. In addition, methyl (meth) acrylate is preferable from the viewpoint of transparency. Moreover, styrene, such as styrene and (alpha) -methylstyrene, is preferable from a viewpoint of etching tolerance. Moreover, the structural unit which has hydroxyl groups or alkyleneoxy groups other than a phenolic hydroxyl group is also preferable from a viewpoint of a sensitivity improvement.

Although component A may have one type or two or more types of structural unit (a4), it is not necessary to have it, but it does not have, ie, component A consists of a structural unit selected from the group which consists of structural units (a1)-(a3). It is preferable that it is resin.

It is preferable that the content rate of the monomeric unit which forms a structural unit (a4) among all the monomeric units which comprise component A is 0-40 mol%. When the component A has a structural unit (a4), 1-40 mol% is preferable and, as for the content rate of the monomeric unit which forms a structural unit (a4) among all the monomeric units which comprise component A, 5-30 mol% is more preferable. 5-25 mol% is especially preferable.

It is preferable that the weight average molecular weight of component A is 1,000-50,000, It is more preferable that it is 2,000-30,000, It is still more preferable that it is 3,000-20,000. In addition, the weight average molecular weight in this invention is polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

Moreover, as a method of introducing each structural unit which component A has, a polymerization method may be sufficient, a polymer reaction method may be sufficient, and these two methods may be used together.

In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. That is, a radically polymerizable monomer mixture containing a structural unit (a1), a structural unit (a2), a structural unit (a3), and a radically polymerizable monomer used for forming the structural unit (a4) as needed is an organic solvent. It can synthesize | combine by superposing | polymerizing using a medium radical polymerization initiator.

In the polymer reaction method, necessary functional groups are introduced into the structural unit using a reactive group included in the structural unit of the copolymer obtained after the polymerization reaction.

It is preferable that content of the component A in the photosensitive resin composition of this invention is 20-99 mass% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 25-97 mass%, It is 30-95 mass% 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 shows the quantity except volatile components, such as a solvent. Component A can be used individually by 1 type or in combination of 2 or more types for photosensitive resin composition.

As the photosensitive resin composition of this invention, you may have the polymer component different from the component A separately. When including the polymer component different from the component A, it is preferable that the compounding quantity of the said polymer component is 80 mass% or less in all the polymer components, It is more preferable that it is 70 mass% or less, It is further more preferable that it is 60 mass% or less.

As a structural unit of a polymer component different from the component A, the structural unit (a2) which has a carboxyl group or phenolic hydroxyl group mentioned above, the structural unit (a3) which has a crosslinkable group, etc. are illustrated, and is comprised in the range which does not prevent the effect of this invention. You may have structural units (a4) other than a unit (a2) and a structural unit (a3).

In particular, when component A is resin which does not have a structural unit (a3) which has the said crosslinking group, it is preferable that the photosensitive resin composition of this invention further contains resin which has a structural unit (a3) which has a crosslinking group, and it is a carboxyl group or a phenol. It is more preferable to further contain resin which has a structural unit (a2) which has a hydroxyl group, and a structural unit (a3) which has a crosslinking group.

As such a polymer, resin which has a carboxyl group in a side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54-25957, Japanese Patent Publication 59-53836, Japan Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like described in each publication of Japanese Patent Application Laid-Open No. 59-71048 The acid cellulose derivative which has the thing, the thing which added the acid anhydride to the polymer which has a hydroxyl group, etc. are mentioned, The high molecular polymer which has a (meth) acryloyl group in a side chain is also mentioned as a preferable thing.

For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, Japanese Patent Laid-Open No. 7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropylacrylate / polymethylmethacrylate macromonomer described in Japanese Patent Application Laid-Open / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macro monomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macro monomer / benzyl Methacrylate / methacrylic acid copolymer, and the like.

In addition, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 11-174224 The well-known high molecular compound of Unexamined-Japanese-Patent No. 2000-56118, Unexamined-Japanese-Patent No. 2003-233179, Unexamined-Japanese-Patent No. 2009-52020, etc. can be used.

One type of these polymers may be included and they may be included two or more types.

SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Satoma), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, BASF Corporation), etc. can also be used.

(Component B) Photoacid Generator

The photosensitive resin composition of this invention contains the (component B) photoacid generator.

As the (component B) photoacid generator used in the present invention, a compound which is sensitive to actinic light having a wavelength of 300 nm or more, preferably having a wavelength of 300 to 450 nm and generates an acid is preferable, but the chemical structure is not limited. Moreover, if it is a compound which sensitizes actinic light of wavelength 300nm or more and generate | occur | produces acid also by using together with a sensitizer about the photo-acid generator which does not directly react to actinic light of wavelength 300nm or more, it can use preferably in combination with a sensitizer.

As the photoacid generator used in the present invention, a photoacid generator for generating an acid having an acid dissociation constant (pKa) of 4 or less is preferable, and a photoacid generator for generating an acid having a pKa of 3 or less is more preferable.

In addition, about pKa, a value can be calculated | required by a well-known measuring method, a well-known calculation method, and / or a literature value.

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidesulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from a viewpoint of high sensitivity. These photoacid generators can be used individually by 1 type or in combination of 2 or more types.

The following can be illustrated as these specific examples.

2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6- as trichloromethyl-s-triazines Trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl)- Bis (4,6-trichloromethyl) -s-triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) Ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaph Ethyl) -bis (4,6-trichloromethyl) -s-triazine and the like.

As diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium tri Fluoroacetate, Phenyl-4- (2'-hydroxy-1'-tetradecaoxy) phenyliodoniumtrifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodine Nium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'- tetradecaoxy) phenyl iodonium p-toluenesulfonate, and the like.

As triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsul Phonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, and the like.

Tetramethylammoniumbutyltris (2,6-difluorophenyl) borate, tetramethylammoniumhexyltris (p-chlorophenyl) borate, tetramethylammoniumhexyltris (3-trifluoromethylphenyl as quaternary ammonium salts ) Borate, benzyldimethylphenylammoniumbutyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammoniumhexyltris (p-chlorophenyl) borate, benzyldimethylphenylammoniumhexyltris (3-trifluoro Methylphenyl) borate and the like.

Diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like.

Trifluoromethylsulfonyloxybicyclo [2.2.1] -hepto-5-ene-dicarboxyimide, succinimidetrifluoromethylsulfonate, phthalimide trifluoromethylsulfonate as an imide sulfonate derivative , N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidepropanesulfonate and the like.

It is preferable that the photosensitive resin composition of this invention contains the oxime sulfonate compound which has at least one oxime sulfonate residue represented by following formula (1) as a (component B) photoacid generator. In addition, the broken line portion shows the bonding position with other chemical structures.

As a compound which has at least one oxime sulfonate residue represented by said Formula (1), the oxime sulfonate compound represented by a following formula (OS-3), a formula (OS-4), or a formula (OS-5) Is preferably.

(In formula (OS-3)-(OS-5), R <^1> represents an alkyl group, an aryl group, or heteroaryl group, and two or more R <^2> represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom each independently, A plurality of R ⁶ 's 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, and m is 0 Represents an integer of -6)

The alkyl group, aryl group, or heteroaryl group represented by R ¹ in the formulas (OS-3) to (OS-5) may have a substituent.

It is preferable that it is a C1-C30 alkyl group which may have a substituent as said alkyl group represented by R <^1> in said Formula (OS-3)-(OS-5).

Examples of the substituent which the alkyl group represented by R ¹ 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 <^1> in said formula (OS-3)-(OS-5), 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. .

Moreover, as an aryl group represented by R <^1> in said Formula (OS-3)-(OS-5), the C6-C30 aryl group which may have a substituent is preferable.

Substituents which may have an aryl group represented by R ¹ are halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, sulfonic acid group, aminosulfonyl group And an alkoxysulfonyl group.

As the aryl group represented by R ¹ , a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group are preferable.

Moreover, as a heteroaryl group represented by R <^1> in said Formula (OS-3)-(OS-5), the heteroaryl group of 4-30 total carbons which may have a substituent is preferable.

Substituents which may have a heteroaryl group represented by R ¹ are halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, sulfonic acid group, aminosulfo A silyl group and an alkoxysulfonyl group are mentioned.

The heteroaryl group represented by R ¹ in the formulas (OS-3) to (OS-5) may be at least one heteroaromatic ring, and for example, the heteroaromatic ring and the benzene ring may be condensed.

The heteroaryl group represented by R ¹ is selected from 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 a ring is mentioned.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.

In the formulas (OS-3) to (OS-5), one or two of R ² 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 atom. It is more preferable that it is more preferable that one is an alkyl group and the remainder is a hydrogen atom.

The alkyl group or aryl group represented by R ² in the formulas (OS-3) to (OS-5) may have a substituent.

As a substituent which the alkyl group or aryl group represented by R <^2> 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 <^2> in said Formula (OS-3)-(OS-5), it is preferable that it is a C1-C12 alkyl group which may have a substituent, and the C1-C6 alkyl group which may have a substituent is preferable. It is more preferable that is.

Examples of the alkyl group represented by R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group and bromomethyl 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, methyl group, The ethyl group, n-propyl group, n-butyl group and n-hexyl group are more preferable, and a methyl group is especially preferable.

As an aryl group represented by R <^2> in said Formula (OS-3)-(OS-5), it is preferable that it is a C6-C30 aryl group which may have a substituent.

As an aryl group represented by R <^2> , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

Examples of the halogen atom represented by R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.

In said formula (OS-3)-(OS-5), X represents O or S, and it is preferable that it is O.

In the formulas (OS-3) to (OS-5), the ring containing X as a reduction is a 5-membered ring or a 6-membered ring.

In formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is preferably 2.

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.

It is preferable that it is a C1-C30 alkyl group which may have a substituent as said alkyl group represented by R <^6> in said Formula (OS-3)-(OS-5).

Examples of the substituent which the alkyl group represented by R ⁶ 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.

Examples of the alkyl group represented by R ⁶ in the formulas (OS-3) to (OS-5) include 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.

It is preferable that it is a C1-C30 alkyloxy group which may have a substituent as said alkyloxy group represented by R <^6> in said Formula (OS-3)-(OS-5).

Examples of the substituent which the alkyloxy group represented by R ⁶ 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.

Examples of the alkyloxy group represented by R ⁶ in the formulas (OS-3) to (OS-5) include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, and a trichloromethyloxy group. Or an ethoxyethyloxy group is preferable.

Examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group, and aminosulfonyl group.

Examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

Moreover, in said formula (OS-3)-(OS-5), 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 .

Moreover, it is especially preferable that the compound represented by said Formula (OS-3) is a compound represented by following formula (OS-6), (OS-10), or (OS-11), The said formula (OS-4) It is particularly preferable that the compound represented by the formula is a compound represented by the following formula (OS-7), and the compound represented by the formula (OS-5) is represented by the following formula (OS-8) or formula (OS-9) It is particularly preferred that it is a losing compound.

(In formula (OS-6)-(OS-11), R <^1> represents an alkyl group, an aryl group, or a heteroaryl group, R <^7> represents a hydrogen atom or a bromine atom, R <^8> is a hydrogen atom and 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 ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ¹⁰ represents a hydrogen atom or a methyl group Indicates)

The expression (OS-6) ~ R ¹ in (OS-11) is R ¹ and agreed in the formula (OS-3) ~ (OS -5), as a preferred form.

R <^7> in said Formula (OS-6) represents a hydrogen atom or a bromine atom, and it is preferable that it is a hydrogen atom.

R ⁸ in the formulas (OS-6) to (OS-11) 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 still more preferable that it is a C1-C6 alkyl group, It is especially preferable that it is a methyl group .

R ⁹ in the formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R <^10> in said Formula (OS-8)-(OS-11) 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 stereo structure (E, Z) of an oxime.

Although the following exemplary compound is mentioned as a specific example of the oxime sulfonate compound represented by said formula (OS-3)-a formula (OS-5), This invention is not limited to these.

As a preferable another aspect of the oxime sulfonate compound which has at least one oxime sulfonate group represented by said formula (1), the compound represented by a following formula (OS-1) is mentioned.

In formula (OS-1), R ¹ 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 ² represents an alkyl group or an aryl group.

X represents -O-, -S-, -NH-, -NR ^5- , -CH _2- , -CR ⁶ H-, or -CR ⁶ R ^7- , R ⁵ to R ⁷ is an alkyl group, or 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, and an alkyl group are preferable, Moreover, the form which at least 2 of R <^21> -R <^24> couple | bonds with each other and forms an aryl group is also mentioned preferably. Especially, the form in which 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-1) is a compound represented by a following formula (OS-2).

The expression (OS-2) ^{of, R 1, R 2, R} 21 ~ R 24 is ^{R 1, R 2, R 21} ~ R 24 and agree in each expression (OS-1), preferred examples same again Do.

Among these, the form whose R <^{1> in a} formula (OS-1) and a formula (OS-2) is a cyano group or an aryl group is more preferable, It is represented by a formula (OS-2), R <^1> is a cyano group and a phenyl group Or a naphthyl group is most preferred.

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

Although the specific example (example compound b-1-b-34) of the compound represented by the formula (OS-1) which can be used suitably for this invention below is shown, this invention is not limited to this. In the 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.

One of the preferable forms of the compound which has at least one oxime sulfonate residue represented by Formula (1) is a compound represented by following formula (2-1). The compound represented by the formula (2-1) is a compound in which R ^2A and R ^1A in the formula (2) are bonded to form a 5-membered ring.

(In formula (2-1), R <^3A> represents a C1-C8 alkyl group, p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group, or a nonafluorobutyl group, and X represents an alkyl group, an alkoxy group, or a halogen. An atom, t represents an integer of 0 to 3, and when t is 2 or 3, a plurality of X may be the same or different)

The C1-C8 alkyl group and nonafluorobutyl group in R <^3A> of said Formula (2-1) may be linear, or may have a branch. Moreover, it is preferable that it is 1-4, and, as for carbon number of the alkyl group in said R <^3A> , it is more preferable that it is 1-3.

In addition, although the binding position of a camphoryl group and a sulfur atom in R <^3A> is not restrict | limited, It is preferable that it is 10-position. That is, the camphoryl group is preferably a 10-camphoryl group.

R ^3A in the formula (2-1) is preferably a methyl group, n-propyl group, n-octyl group, p-toluyl group or camphoryl group, and n-propyl group, n-octyl group, p-toluyl group Or it is more preferable that it is a camphoryl group, It is further more preferable that it is n-propyl group or p-toluyl group.

As an alkyl group represented by X, a C1-C4 linear or branched alkyl group is preferable.

As the alkoxy group represented by X, a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable.

As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.

As t, 0 or 1 is preferable.

In formula (2-1), t is 1, X is a methyl group, X is a substituted position ortho-position, R <^3A> is a linear alkyl group of 1-10 carbon atoms, and 7,7- dimethyl- 2-oxonorbor Particularly preferred are compounds which are a methylmethyl group or a p-toluyl group.

Specific examples of the oxime sulfonate compound represented by the formula (2-1) include the following compounds (i), (ii), (iii) and (iv) Two or more types may be used in combination. Compound (i)-(iv) can be obtained as a commercial item.

It can also be used in combination with other specific photoacid generators.

As a compound which has at least one oxime sulfonate residue represented by Formula (1), it is preferable that it is a compound represented by following formula (2-2).

(In formula (2-2), R <^4A> represents a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a nitro group, and L shows the integer of 0-5.) ^5A is substituted with 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, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, and substituted with W Or an anthranyl group which may be substituted with a naphthyl group which may be present, or 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, or a carbon atom having 1 to 5 carbon atoms. Halogenated alkyl group or halogenated alkoxy group having 1 to 5 carbon atoms)

As R ^5A in Formula (2-2), a methyl group, an ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group, or pentafluorophenyl group is preferable, and it is especially preferable that they are a methyl group, an ethyl group, n-propyl group, n-butyl group, or p-tolyl group.

As the halogen atom represented by R ^4A , a fluorine atom, a chlorine atom or a bromine atom is preferable.

As the alkyl group having 1 to 4 carbon atoms represented by R ^4A , a methyl group or an ethyl group is preferable.

As the alkoxy group having 1 to 4 carbon atoms represented by R ^4A , a methoxy group or an ethoxy group is preferable.

As L, 0-2 are preferable and 0-1 are especially preferable.

As a preferable aspect of the compound contained in the compound represented by Formula (2-2) among the compounds which have at least 1 oxime sulfonate residue represented by Formula (1), R <^4A> is a phenyl group or 4 in Formula (2-2). It is a form which represents a methoxyphenyl group and R <^5A> represents a methyl group, an ethyl group, n-propyl group, n-butyl group, or 4-tolyl group.

Hereinafter, although the especially preferable example of the compound contained in the compound represented by Formula (2-2) among the compound which has at least one oxime sulfonate residue represented by Formula (1) is shown, this invention is limited to these. It is not.

α- (methylsulfonyloxyimino) benzyl cyanide (R ^4A = phenyl group, R ^5A = methyl group)

α- (ethylsulfonyloxyimino) benzyl cyanide (R ^4A = phenyl group, R ^5A = ethyl group)

α- (n-propylsulfonyloxyimino) benzyl cyanide (R ^4A = phenyl group, R ^5A = n-propyl group)

α- (n-butylsulfonyloxyimino) benzyl cyanide (R ^4A = phenyl group, R ^5A = n-butyl group)

α- (4-toluenesulfonyloxyimino) benzyl cyanide (R ^4A = phenyl group, R ^5A = 4-tolyl group)

α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^4A = 4-methoxyphenyl group, R ^5A = methyl group)

α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^4A = 4-methoxyphenyl group, R ^5A = ethyl group)

α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^4A = 4-methoxyphenyl group, R ^5A = n-propyl group)

α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^4A = 4-methoxyphenyl group, R ^5A = n-butyl group)

α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^4A = 4-methoxyphenyl group, R ^5A = 4-tolyl group)

It is preferable that the photosensitive resin composition of this invention does not contain a 1, 2- quinonediazide compound as a photoacid generator (component B) sensitive to actinic light. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by sequential fluorescence chemical 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 the 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 many deprotection reactions, both The yield exceeds 1, for example, becomes a large value such as a power of 10, and it is estimated that high sensitivity is obtained as a result of so-called chemical amplification.

In the photosensitive resin composition of this invention, it is preferable to use 0.1-10 mass parts with respect to 100 mass parts of component A, and, as for the (component B) photoacid generator, it is more preferable to use 0.5-10 mass parts.

(Component C) Crosslinking Agent

The photosensitive resin composition of this invention contains the (component C) crosslinking agent.

Moreover, the (component C) crosslinking agent in the photosensitive resin composition of this invention is characterized by including the block isocyanate compound whose parent structure is a biuret structure.

When the block isocyanate compound is deprotected at the time of post-baking, an isocyanate group is formed, and when the active hydrogen compound, for example, component A has a structural unit (a4), the hydroxyl group, and component A is a structural unit (a1) When it has a structural unit (a2), it is estimated that it reacts with a carboxyl group or phenolic hydroxyl group, and forms a crosslinked structure.

Moreover, the photosensitive resin composition of this invention may contain the compound which has two or more epoxy groups or oxetanyl group in a molecule, the alkoxy methyl group containing crosslinking agent, and / or the compound which has at least 1 ethylenically unsaturated double bond, etc. as a component C. good.

Block isocyanate compound

The block isocyanate compound in the photosensitive resin composition of this invention is a block isocyanate compound whose parent structure is a biuret structure. As a block isocyanate type compound in this invention, it is preferable that it is a compound which has two or more block isocyanate groups in 1 molecule from a sclerosis | hardenability viewpoint.

In addition, the block isocyanate group in this invention is group which can produce an isocyanate group by heat, For example, group which protected the isocyanate group by making a blocking agent react with an isocyanate group can be illustrated preferably. Moreover, it is preferable that the said block isocyanate group is group which can produce an isocyanate group by the heat of 90 degreeC-250 degreeC.

As an isocyanate compound used for synthesis | combination of the parent structure of a block isocyanate compound, as long as it has 2 or more isocyanate groups in 1 molecule, what kind of thing may be sufficient as it, and what is necessary is just an aliphatic, alicyclic, or aromatic polyisocyanate, for example, 2, 4- tolylene di Isocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexa Methylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexanediisocyanate, 2,2'-diethyl Ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p- Silylene diisocyanate, methylenebis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylenedi isocyanate, 3,3'-methyleneditolylene-4,4'-diisocyanate, 4,4'-diphenylether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenation Isocyanate compounds, such as 1, 4- xylylene diisocyanate, and the compound of the prepolymer type skeleton derived from these compounds can be used preferably. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are especially preferable.

The biuret structure is a structure represented by the following formula (bi), preferably a structure represented by the following formula (bi-1), and more preferably a structure represented by the following formula (bi-2). In addition, in a following formula, a broken line part is a coupling part with another structure.

(In formula (bi-1) and formula (bi-2), R <^1> , R <^2> and R <^3> respectively independently represent residues other than the isocyanate group of aliphatic, alicyclic, or aromatic diisocyanate, R <^4> and R ⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group)

As the aliphatic, cycloaliphatic or aromatic diisocyanate to be used, a diisocyanate among the aliphatic, cycloaliphatic or aromatic polyisocyanates described above can be preferably used.

There is no restriction | limiting in particular as a formation method of the burette structure in a block isocyanate compound, Although what is necessary is just to form by a well-known method, For example, it can form easily by trimerization of an isocyanate compound.

Examples of the block agent forming the block structure of the block isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds and the like. Can be mentioned. Among these, the blocking agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, and a pyrazole compound is especially preferable.

As said oxime compound, an oxime and a keto oxime are mentioned, Specifically, an acetoxime, a form aldoxin sim, a cyclohexane oxime, a methyl ethyl ketone oxime, a cyclohexanone oxime, a benzophenone oxime, an acetoxime, etc. can be illustrated. .

(Epsilon) -caprolactam, (gamma) -butyrolactam, etc. can be illustrated as said lactam compound.

As said phenolic compound, phenol, naphthol, cresol, xylenol, a halogen substituted phenol, etc. can be illustrated.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate, and the like.

As said amine compound, a primary amine and a secondary amine can be mentioned, Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may be sufficient, and aniline, diphenylamine, ethyleneimine, polyethyleneimine, etc. can be illustrated. .

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, and the like.

Pyrazole, methylpyrazole, dimethyl pyrazole, etc. can be illustrated as said pyrazole compound.

Alkyl mercaptan, an aryl mercaptan, etc. can be illustrated as said mercaptan compound.

The block isocyanate compound whose parent structure used for the photosensitive resin composition of this invention is a biuret structure can be obtained as a commercial item, For example, Dulanate 17B-60PX, 17B-60P (above, Asahi Kasei Chemicals make) Can be mentioned.

In the photosensitive resin composition of this invention, it is preferable that the block isocyanate compound whose mother structure is a biuret structure is 0.1-8 mass% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 0.2-7 mass%, 0.5-5 It is most preferable that it is mass%. You may use 2 or more types together.

-Alkoxymethyl group-containing crosslinking agent-

Moreover, in the photosensitive resin composition of this invention, a known crosslinking agent can be used other than the said block isocyanate, For example, an alkoxy methyl group containing crosslinking agent can be used preferably.

Specific examples of the alkoxymethyl group-containing crosslinking agent include alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like. These are obtained by converting the metyrol groups of methirolated melamine, methirolized benzoguanamine, methirolized glycoluril, or methirolated urea to an alkoxymethyl group, respectively.

It does not specifically limit about the kind of this alkoxy methyl group, For example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group etc. are mentioned, A methoxymethyl group is especially the point of view of the generation amount of outgas. desirable.

Among these alkoxymethyl group-containing crosslinking agents, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferred alkoxymethyl group-containing crosslinking agents, and alkoxymethylated melamine is particularly preferable from the viewpoint of chemical resistance effect.

These alkoxymethyl 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.), Nikarak MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nikarak MS-11, Nikarak MW-30HM, -100LM, -390 (above, acid and chemicals make), etc. can be used preferably.

When the photosensitive resin composition of this invention contains an alkoxy methyl group containing crosslinking agent, it is preferable that the addition amount of the alkoxy methyl group containing crosslinking agent in the photosensitive resin composition of this invention is 0.1-10 mass% with respect to the total solid of the photosensitive resin composition, and is 0.2 It is more preferable that it is-7 mass%, and it is most preferable that it is 0.5-5 mass%.

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

It is preferable that the photosensitive resin composition of this invention contains the compound which has two or more epoxy groups or oxetanyl group in a molecule as component C.

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 compound, etc. are mentioned. The aliphatic epoxy compound is a resin having a linear and / or branched carbon chain and an epoxy group, in which an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, or the like may be bonded to the carbon chain in addition to a hydrogen atom. The aliphatic epoxy compound is particularly preferably a linear and / or branched carbon chain, a hydrogen atom, a resin composed of an epoxy group, or a resin in which a hydroxyl group is substituted for the resin. 1-4 are preferable and, as for the number of an epoxy group, 2 or 3 is more preferable.

These are available as commercial products. For example, as a bisphenol-A epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON 1050, EPICLON 1055 (EPICLON 10 55) , DIC Co., Ltd.) and the like, and as bisphenol F type epoxy resins, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Co., Ltd. product) ), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), and the like, and phenol novolac type epoxy resins include JER152, JER154, JER157S70, and JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation) and the like, and examples of cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, and 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 Nippon Kayaku Co., Ltd.), and aliphatic epoxy As resin, ADEKA RESIN EP- 4080S, copper EP-4085S, copper EP-4088S (above, made by ADEKA Co., Ltd.), as the aliphatic epoxy compound, ceoxide 2021P, ceoxide 2081, ceoxide 2083, ceoxide 2085, EHPE3150, EPOLEAD PB 3600, and copper PB 4700 (Above, Daicel Kagaku Kogyo Co., Ltd.) etc. are mentioned. 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.

Moreover, as an aliphatic epoxy compound, the compound represented by a following formula (X-1) is mentioned.

(In formula (X-1), A represents a linear or branched hydrocarbon group, may have a hydroxyl group as a substituent, and n represents the integer of 1-4.)

1-20 are preferable, as for carbon number of A in Formula (X-1), 1-15 are more preferable, 2-10 are more preferable, and 2-6 are especially preferable.

N in Formula (X-1) represents the integer of 1-4, and 2 or 3 is preferable.

As an aliphatic epoxy compound, it is more preferable that it is a compound represented by a following formula (X-2).

(In formula (X-2), A 'represents a linear or branched hydrocarbon group, may have a hydroxyl group as a substituent, and n represents the integer of 1-4.)

1-18 are preferable, as for carbon number of A 'in Formula (X-2), 1-13 are more preferable, and 2-8 are more preferable.

N in Formula (X-2) represents the integer of 1-4, and 2 or 3 is preferable.

Aliphatic epoxy compounds which can be preferably used in the present invention include Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX- 841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-321L, EX-850L, EX-211L, EX-946L, EX-946L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (above, Nagase Chemtex Co., Ltd.), YH-300, YH-301, YH-302, YH-315 , YH-324, YH-325 (above, Shin-Nitetsu Kagaku Co., Ltd.), etc. are mentioned.

Among these, the trimetholol propane triglycidyl ether or neopentyl glycol diglycidyl ether shown below is especially preferable. Among these, EX-321, EX-321L, EX-211, and EX-211L (above, Nagase Chemtex Co., Ltd.) correspond to these.

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

Among these, an epoxy resin and an aliphatic epoxy compound are mentioned preferably, A bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, and an aliphatic epoxy compound are mentioned more preferable, Bisphenol-A type Epoxy resins and aliphatic epoxy compounds are particularly preferred.

As a specific example of the compound which has two or more oxetanyl groups in a molecule | numerator, Aaronoxetane OXT-121, OXT-221, OX-S ', 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.

When using the compound which has two or more epoxy groups or oxetanyl group in a molecule | numerator in the photosensitive resin composition of this invention, the addition amount of the compound which has two or more epoxy groups or oxetanyl group in a molecule | numerator to the photosensitive resin composition is 100 mass parts of component A 0.1-50 mass parts is preferable with respect to, 0.5-30 mass parts is more preferable, and 1-10 mass parts is more preferable.

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 preferably. .

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-nonanediol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, etc. are mentioned.

As (meth) acrylate more than trifunctional, for example, trimethol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra ( Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

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

When using the compound which has one ethylenically unsaturated double bond in the photosensitive resin composition of this invention, the use ratio of the compound which has at least 1 ethylenically unsaturated double bond in the photosensitive resin composition of this invention is 100 mass parts of component A. It is preferable that it is 50 mass parts or less with respect to, and it is more preferable that it is 30 mass parts 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 generator mentioned later.

(Component D) Solvent

The photosensitive resin composition of this invention contains the (component D) solvent.

It is preferable that the photosensitive resin composition of this invention is prepared as the liquid which melt | dissolved or disperse | distributed the arbitrary components of component A-component C which are essential components, and the various additives mentioned later which are preferable components in the (component D) solvent.

As a (component D) 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, etc. can be illustrated.

Examples of the (component D) solvent used in the photosensitive resin composition of the present invention include (1) ethylene glycol mono, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Alkyl ethers; (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, ethyl propionate n-propyl, propionic acid isopropyl, n-butyl propionate, propionic acid Aliphatic carboxylic acid esters such as isobutyl, methyl 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-methoxypropionmethyl, 3-meth Oxypropionethyl, 3-ethoxypropionmethyl, 3-ethoxypropionethyl, 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; (16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; Lactone, such as (17) (gamma) -butyrolactone, etc. are mentioned.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, capronic acid, caprylic acid, and 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, diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate are particularly preferable.

The solvent which can be used for this invention can use together single 1 type or 2 types or more.

It is preferable that content of the (component D) solvent in the photosensitive resin composition of this invention is 50-3,000 mass parts per 100 mass parts of component A, It is more preferable that it is 100-2,000 mass parts, It is still more preferable that it is 150-1,500 mass parts Do.

&Lt; Other components >

The photosensitive resin composition of this invention may use the said component A-component D as an essential component, and may contain other arbitrary components. Optional components include (component E) sensitizer, (component F) basic compound, (component G) surfactant, (component H) adhesion improving agent, (component I) development accelerator, (component J) antioxidant, (component K) Plasticizer, (component L) thermal radical generator, (component M) thermal acid generator, (component N) acid increasing agent, ultraviolet absorber, thickener, organic or inorganic precipitation inhibitor, etc. are mentioned. The additive which can be used by this invention is not limited to these, Various additives well-known in the said field can be used.

As another component, it is preferable that the photosensitive resin composition of this invention contains a (component H) adhesion improving agent from a viewpoint of board | substrate adhesiveness, and it is preferable to contain a (component F) basic compound from a viewpoint of liquid storage stability, and is coatable It is preferable to contain (component G) surfactant (fluorine type surfactant, silicone type surfactant, etc.) from a viewpoint.

Moreover, it is preferable to contain a (component I) development accelerator from a viewpoint of a sensitivity. Moreover, it is preferable to add a (component E) sensitizer from a viewpoint of a sensitivity.

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

(Component E) sensitizer

It is preferable that the photosensitive resin composition of this invention contains the (component E) photosensitizer.

By containing a photosensitizer, it is effective for the improvement of exposure sensitivity, and it is especially effective when an exposure light source is g and h-ray mixed lines.

As the photosensitizer, anthracene derivatives, acridon derivatives, thioxanthone derivatives, coumarin derivatives, basestyryl derivatives and distyrylbenzene derivatives are preferable.

Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.

As the acridon derivative, acridon, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone, and N-ethyl-2-methoxyacridone are preferable.

As a thioxanthone derivative, thioxanthone, diethyl thioxanthone, 1-chloro-4- propoxy thioxanthone, and 2-chloro thioxanthone are preferable.

As coumarin derivatives, coumarin-1, coumarin-6H, coumarin-110, and coumarin-102 are preferable.

Examples of the base styryl derivatives include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole and 2- (4-dimethylaminostyryl) naphthothiazole. .

Examples of the distyrylbenzene derivatives include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.

Among these, an anthracene derivative is preferable and 9,10- dialkoxy anthracene (C1-C6 of an alkoxy group) is more preferable.

The following is mentioned as a specific example of a photosensitizer. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of total content of component A and the component B, and, as for content of the photosensitizer in the photosensitive resin composition of this invention, it is more preferable that it is 0.5-10 mass parts. If content of a photosensitizer is 0.1 mass part or more, desired sensitivity will be easy to be obtained, and if it is 10 mass parts or less, transparency of a coating film will be easy to be ensured.

(Component F) Basic Compound

It is preferable that the photosensitive resin composition of this invention contains a (component F) basic compound from a viewpoint of liquid storage stability.

It can be used selecting arbitrarily as a basic compound 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 amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, Triethanolamine, dicyclohexylamine, dicyclohexyl methylamine, etc. are mentioned.

As aromatic amine, aniline, benzylamine, N, N- dimethylaniline, diphenylamine, etc. are mentioned, for example.

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, N-cyclohexyl-N '-[2- (4-morpholinyl) Ethyl] thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7-undecene, etc. are mentioned.

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.

The basic compounds usable in the present invention may be used singly or in combination of two or more kinds.

It is preferable that it is 0.001-1 mass part with respect to 100 mass parts of component A, and, as for content of the (component F) basic compound in the photosensitive resin composition of this invention, it is more preferable that it is 0.002-0.2 mass part.

(Component G) Surfactant (fluorine type surfactant, silicone type surfactant, etc.)

It is preferable that the photosensitive resin composition of this invention contains (component G) surfactant (fluorine-type surfactant, silicone type surfactant, etc.).

As the surfactant, a copolymer (3) containing the constituent unit A and the constituent unit B shown below may be mentioned as a preferable example. The weight average molecular weight (Mw) of the copolymer is preferably 1,000 or more and 10,000 or less, and more preferably 1,500 or more and 5,000 or less. The weight average molecular weight is a value of polystyrene conversion measured by gel permeation chromatography.

In the copolymer (3), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a straight alkylene group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or 1 to 4 carbon atoms. An alkyl group is represented, L represents a C3-C6 alkylene group, p and q are the mass percentages which show a polymerization ratio, p represents the numerical value of 10 mass% or more and 80 mass% or less, q is 20 mass% The numerical value of 90 mass% 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.

L in the constituent unit B is preferably an alkylene group represented by the following formula (4).

In formula (4), R <^25> represents a C1-C4 alkyl group, A C1-C3 alkyl group is preferable from a compatible point and wettability with respect to a to-be-coated surface, and a C2-C3 alkyl group is more preferable. .

Moreover, it is preferable that the sum (p + q) of p and q is p + q = 100, ie, 100 mass%.

As examples of fluorine-based surfactants and silicone-based surfactants, specifically, Japanese Patent Publication No. 62-36663, Japanese Patent Publication No. 61-226746, Japanese Patent Publication No. 61-226745, Japanese Patent Publication 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 2001-330953 Surfactant as described in each publication, such as No., is mentioned, A 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 Kasei Co., Ltd.), fluoride 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.), PolyFox series (made by OMNOVA Corporation) Fluorine-based surfactants such as a) or silicone-based surfactants. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Kagaku Kogyo Co., Ltd.) can also be used as a silicone type surfactant.

These surfactants may be used singly or in combination of two or more. Moreover, you may use together a fluorochemical surfactant and silicone type surfactant.

It is preferable that the addition amount of (component G) surfactant (fluorine-type surfactant, silicone type surfactant, etc.) in the photosensitive resin composition of this invention is 10 mass parts or less with respect to 100 mass parts of component A, and it is 0.01-10 mass parts more It is preferable and it is more preferable that it is 0.01-1 mass part.

(Component H) Adhesion improver

It is preferable that the photosensitive resin composition of this invention contains the (component H) adhesion improving agent.

The (component H) 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, silicon compounds, such as silicon, silicon oxide, silicon nitride, metals, such as gold, copper, aluminum, molybdenum, titanium, etc. It is a compound which improves the adhesiveness of an insulating film. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as the (component H) adhesion improving agent used in the present invention is for the purpose of modifying the interface, and a known one can be used without particular limitation.

Preferred silane coupling agents include 1,2-bis (triethoxysilyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl-4-trimethoxysilylbutane, 1,4- Bis (methyldimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5-trimethoxysilylpentane, 1,5-bis (methyldimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxysilyl) Hexane, 2,5-bis (trimethoxysilyl) hexane, 1,6-bis (methyldimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 2,5-bis (trimethoxy Silyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 2,5-bis (trimethoxysilyl) octane, 2,7-bis (tri Methoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1,10-bis (trimethoxysilyl) decane, 3,8-bis ( Rimethoxysilyl) decane, vinyltrichlorosilane, 1,3-bis (trichlorosilane) propane, 1,3-bis (tribromosilane) propane, vinyltrimethoxysilane, vinyltriethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-meta Krilloxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β -Aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrie Cysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, dimethoxy-3-mercapto Propylmethylsilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, Dimethoxymethyl-3- (3-phenoxypropylthiopropyl) silane, bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, 1,4-bis (triethoxysilyl ) Benzene, bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane, 1,2-bis (trimethoxysilyl) decane , Bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) urea, γ-chloropropyltrimethoxysilane, γ-triethoxysilylpropyl (meth) acrylate Y, γ-ureidopropyltriethoxysilane, trimethylsilanol, diphenylsilanediol, triphenylsilanol and the like.

In addition, although the compound shown below is mentioned as a preferable thing, this invention is not limited to these compounds.

In said each formula, R and R <^1> represent the partial structure chosen from the following structures, respectively. When a plurality of R and R ¹ are present in the molecule, they may be the same as or different from each other, and the synthetic phases are preferably the same.

Although the said silane coupling agent can also be suitably synthesize | combined, it is preferable to use a commercial item from a cost viewpoint, For example, Shin-Etsu Kagaku Kogyo Co., Ltd., Toray Dow Corning Co., Ltd., Momentive performance materials Since commercial items, such as a silane product marketed from Chisso Co., Ltd., etc., a silane coupling agent, correspond to this, you may select these commercial items suitably for the resin composition of this invention according to the objective.

Of these, γ-glycidoxypropyltrialkoxysilane, γ-methacryloxypropyltrialkoxysilane, bis (triethoxysilylpropyl) disulfide and bis (triethoxysililypropyl) tetrasulfide can be preferably used. have.

In addition, in this invention, an adhesion improving agent represented by Formula (H-1) is also illustrated as an adhesion improving agent.

(R ^H1 ) _{4-n '} -Si- (OR ^H2 ) _n' (H-1)

(In Formula (H-1), R ^H1 represents a substituent having no reactive group, R ^H2 represents an alkyl group, and n 'represents an integer of 1 to 3).

Examples of the adhesion improving agent represented by the formula (H-1) include the following compounds. In addition, Ph in the following compound represents a phenyl group.

These may be used alone or in combination of two or more. They are effective for improving the adhesiveness with a board | substrate and also for adjusting the taper angle with a board | substrate.

0.1-20 mass parts is preferable with respect to 100 mass parts of component A, and, as for content of the (component H) adhesion improving agent in the photosensitive resin composition of this invention, 0.5-10 mass parts is more preferable.

(Component I) Development accelerator

It is preferable that the photosensitive resin composition of this invention contains (component I) image development promoter.

(Component I) Although any compound which has image development promoting effect can be used as a development accelerator, it is preferable that it is a compound which has at least 1 sort (s) of structure chosen from the group which consists of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group, and is a carboxyl group or The compound which has a phenolic hydroxyl group is more preferable, and the compound which has a phenolic hydroxyl group is the most preferable.

Moreover, as a molecular weight of (component I) image development promoter, 100-2,000 are preferable, 150-1,500 are more preferable, 150-1,000 are the most preferable.

Examples of the development promoter include polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester and poly Butylene glycol, polyethylene glycol bisphenol A ether, polypropylene glycol bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, and the compounds described in JP-A-9-222724 have.

As a thing which has a carboxyl group, the compound of Unexamined-Japanese-Patent No. 2000-66406, Unexamined-Japanese-Patent No. 9-6001, Unexamined-Japanese-Patent No. 10-20501, Unexamined-Japanese-Patent No. 11-338150, etc. are mentioned. .

As having 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, Unexamined-Japanese-Patent No. The compound of 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, the phenol compound of 2-10 benzene rings is preferable, and the phenol compound of 2-5 benzene rings is more preferable. As a particularly preferable thing, the phenolic compound disclosed as a dissolution promoter in Unexamined-Japanese-Patent No. 10-133366 is mentioned.

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

0.1-30 mass parts is preferable, and, as for the addition amount of the (component I) image development promoter in the photosensitive resin composition of this invention, when component A is 100 mass parts from a viewpoint of a sensitivity and a residual film ratio, 0.2-20 mass parts is more preferable, It is most preferable that it is 0.5-10 mass parts.

(Component J) Antioxidant

The photosensitive resin composition of this invention may contain the (component J) antioxidant. (Component J) As antioxidant, a well-known antioxidant can be contained. (Component J) By adding antioxidant, coloring of a cured film can be prevented, the film thickness reduction by decomposition can be reduced, and there exists an advantage that it is excellent in heat transparency.

Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites and thiosulfates. And hydroxylamine derivatives. Among these, phenolic antioxidants, amide antioxidants, hydrazide antioxidants, and sulfur antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. 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-15, adecastab AO-18, adecastab AO-20, adecastab AO-23, adecastab AO-30, adecastab AO -37, Adecastab AO-40, Adecastab AO-50, Adecastab AO-51, Adecastab AO-60, Adecastab AO-70, Adecastab AO-80, Adecastab AO- 330, AdecastaB AO-412S, Adecastab AO-503, Adecastab A-611, Adecastab A-612, Adecastab A-613, Adecastab PEP-4C, Adecastab PEP-8 , Adecastab PEP-8W, Adecastab PEP-24G, Adecastab PEP-36, Adecastab PEP-36Z, Adecastab HP-10, Adecastab 2112, Adecastab 260, Adecastab 522A , Adecastab 1178, Adecastab 1500, Adecastab C, Adecastab 135A, Adecastab 3010, Adecastab TPP, Adecastab CDA-1, Adecastab CDA-6, Adecastab ZS-27, Adecastab ZS-90, Adecastab ZS-91 (above, made by ADEKA), Irganox 245FF, Irganox 1010FF, Irganox MD1024, Irganox 1035FF, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgaphos 168, Irgamod 295 (made by BASF Corporation), etc. are mentioned. Among them, Adecastab AO-60, Adecastab AO-80, Irganox 1726, Irganox 1035FF, and Irganox 1098 can be preferably used.

(Component J) It is preferable that content of antioxidant is 0.1-6 mass% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 0.2-5 mass%, It is especially preferable that it is 0.5-4 mass%. With this range, sufficient transparency of the film formed can be obtained, and sensitivity at the time of pattern formation becomes good.

Moreover, you may add various ultraviolet absorbers, metal deactivators, etc. which were described in "The development of polymer additive (Nikkan Kogyo Shimbun)" as additives other than antioxidant to the photosensitive resin composition of this invention.

(Component K) Plasticizer

The photosensitive resin composition of this invention may contain the (component K) plasticizer.

(Component K) Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl stannate, adipic acid dioctyl, triacetylglycerine, and the like.

It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of component A, and, as for content of the (component K) plasticizer in the photosensitive resin composition of this invention, it is more preferable that it is 1-10 mass parts.

(Component L) Thermal Radical Generator

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

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

The thermal radical generator is a compound that generates radicals by the energy of heat and initiates or promotes the polymerization reaction of the polymerizable compound. The cured film obtained by adding a thermal radical generating agent becomes tough more, and heat resistance and solvent resistance may improve.

Preferred 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, carbon halogens The compound which has a bond, an azo compound, a bibenzyl compound, etc. are mentioned.

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

When content of the (component L) thermal radical generating agent in the photosensitive resin composition of this invention makes component A 100 mass parts from a viewpoint of film | membrane physical property improvement, 0.01-50 mass parts is preferable, 0.1-20 mass parts is more preferable And 0.5-10 mass parts is the most preferable.

(Component M) Thermal Acid Generator

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

The thermal acid generator of the present invention is a compound in which an acid is generated by heat, and is usually a compound having a thermal decomposition point of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C, and for example, sulfonic acid and carboxylic acid by heating. It is a compound which produces low nucleophilic acid, such as a disulfonylimide.

As the generated acid, sulfonic acid having a strong pKa of 2 or less, alkyl carboxylic acid or aryl carboxylic acid substituted with an electron withdrawing group, and disulfonylimide substituted with an electron withdrawing group are likewise preferred. Examples of the electron withdrawing group include haloalkyl groups such as halogen atoms such as fluorine atoms and trifluoromethyl groups, nitro groups and cyano groups.

In the present invention, it is also preferable to use a sulfonic acid ester which does not generate an acid substantially by irradiation with exposure light and generates an acid by heat. The fact that an acid does not generate | occur | produce substantially by irradiation of exposure light can be judged that there is no change in a spectrum by IR spectrum and NMR spectrum measurement before and after exposure of a compound.

The molecular weight of the sulfonic acid ester is preferably 230 to 1,000, more preferably 230 to 800.

The sulfonic acid ester which can be used by this invention may use a commercially available thing, and may use the thing synthesize | combined by a well-known method. The sulfonic acid esters can be synthesized, for example, by reacting sulfonyl chloride or sulfonic anhydride with the corresponding polyhydric alcohol under basic conditions.

(Component M) When content of the thermal acid generator to the photosensitive resin composition makes component A 100 mass parts, 0.5-20 mass parts is preferable, and 1-15 mass parts is especially preferable.

(Component N) Acid Extender

The photosensitive resin composition of this invention can use the (component N) acid increasing agent for the purpose of a sensitivity improvement.

The acid increasing agent used in the present invention is a compound capable of further generating an acid by an acid catalyst reaction to increase the acid concentration in the reaction system, and is a compound which is stably present in a state where no acid is present. Since one or more acids are increased in one reaction, the compound accelerates as the reaction proceeds. However, since the generated acid itself is self-analyzed, the intensity of the acid generated therein is acid dissociation constant (pKa). It is preferable that it is the following, and it is especially preferable that it is 2 or less.

As a specific 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 a 47th page is mentioned.

As an acid increasing agent which can be used in the present invention, an acid having a pKa of 3 or less, such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, is decomposed by an acid generated from an acid generator. The compound to generate | occur | produce is mentioned.

It is preferable to set content of the acid increasing agent to the photosensitive resin composition as 10-1,000 mass parts with respect to 100 mass parts of (component B) photoacid generators from a viewpoint of the dissolution contrast of an exposure part and an unexposed part, and to set it as 20-500 mass parts. More preferred.

<Preparation method of the photosensitive resin composition>

The essential components of the component A-the component C and the (component D) solvent are mixed by a predetermined ratio, also by arbitrary methods, are stirred and dissolved, and the photosensitive resin composition is prepared. For example, after making the component A, the component B, or the component C into the solution which melt | dissolved in the (component D) solvent previously, respectively, these can be mixed in a predetermined ratio, and the photosensitive resin composition can also be prepared. The photosensitive resin composition thus prepared may be used for use after being filtered using a filter having a pore diameter of about 0.1 μm or the like.

(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 positive photosensitive resin composition of this invention, It is preferable to include the process of the following (1)-(5).

(1) Process of applying photosensitive resin composition of this invention on board | substrate;

(2) Process of removing solvent from applied photosensitive resin composition;

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

(4) developing the exposed photosensitive resin composition with an aqueous developer;

(5) Post-baking process to develop developed thermoset.

Each step will be described below in order.

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

<Application process and solvent removal process>

In the application process of (1), it is preferable to apply the photosensitive resin composition of this invention on a board | substrate (preferably apply | coating), and to set it as the wet film containing a solvent. It is preferable to wash | clean the board | substrate, such as alkali washing and plasma washing, before applying a photosensitive resin composition to a board | substrate, and it is more preferable to process a board | substrate surface with hexamethyldisilazane after a board | substrate washing. There exists a tendency for the adhesiveness to the board | substrate of the photosensitive resin composition to improve by performing this process. Although it does not specifically limit as a method of processing a board | substrate surface with hexamethyldisilazane, For example, the method of exposing a board | substrate to hexamethyldisilazane steam, etc. are mentioned.

As said board | substrate, an inorganic board | substrate, resin, resin composite material, etc. are mentioned.

As an inorganic substrate, the composite board | substrate which deposited molybdenum, titanium, aluminum, copper, etc. on glass, quartz, silicon, silicon nitride, and these substrates is mentioned, for example.

As the resin, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamide Mid, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, fluorine resin such as norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin And a substrate made of synthetic resin such as cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, polyaromatic ether, maleimide-olefin copolymer, cellulose and episulfide resin.

These board | substrates are rarely used as the said form, and the multilayer laminated structure like a TFT element is normally formed by the form of a final product, for example.

The application method to a board | substrate is not specifically limited, For example, methods, such as the slit coating method, the spray method, the roll coating method, the rotation coating method, the cast application method, the slit and spin method, can be used. Moreover, it is also possible to apply what is called a prewet method described in Unexamined-Japanese-Patent No. 2009-145395.

The wet film thickness at the time of application is not specifically limited, Although it can apply | coat with the film thickness according to a use, Preferably it is used in the range of 0.5-10 micrometers.

In addition, the heating conditions of the solvent removal process of (2) are the range which does not make component A in an unexposed part soluble in an alkaline developing solution, and although it changes also with the kind and compounding ratio of each component, it is for 30 to 300 second at 70-120 degreeC. It is preferable that it is about degree.

Exposure process

In the exposure process of (3), actinic light is irradiated to the board | substrate with a coating film through the mask which has a predetermined pattern. In this process, the acid generator is decomposed to generate acid. By the catalysis of the generated acid, for example, an acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.

As an exposure light source by active light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, and g line | wire (436 nm), i line | wire (365 nm), h line | wire (405 nm), etc. can be used. The actinic light which has a wavelength of 300 nm or more and 450 nm or less can be used preferably. Moreover, irradiation light can also be adjusted through spectroscopic filters, such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter, as needed.

As exposure apparatus, the exposure machine of various systems, such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a micro lens array, and laser exposure, can be used.

Post-exposure heat treatment: (hereinafter also referred to as "PEB") may be performed in order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote formation of a carboxyl group or phenolic hydroxyl group from the acid-decomposable group which component A may have, for example. 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 100 degrees C or less are especially preferable.

The acid-decomposable group which component A may have has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator upon exposure, and preferably generates a carboxyl group or a phenolic hydroxyl group. It is also possible to form a positive image.

Development Process

In the development process of (4), the copolymer which has a free carboxyl group or phenolic hydroxyl group is developed using an alkaline developing solution, for example. A positive image is formed by removing the exposure part area | region containing the resin composition which preferably has a carboxyl group or phenolic hydroxyl group which is easy to melt | dissolve in an alkaline developing solution.

It is preferable that a basic compound is contained in the developing solution used at the image development process. As a basic compound, 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; An aqueous solution of sodium silicate, sodium metasilicate or the like 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.

As a preferable developing solution, the 0.4 mass% aqueous solution, the 0.5 mass% aqueous solution, the 0.7 mass% aqueous solution, and the 2.38 mass% aqueous solution of tetraethylammonium hydroxide are mentioned.

The pH of the developing solution is preferably 10.0 to 14.0.

The developing time is preferably 30 to 500 seconds, and the developing method may be either a puddle method or a dip method. After development, flowing water washing is preferably performed for 30 to 300 seconds to form a desired pattern.

A rinse process may be performed after image development. In the rinsing step, the developer is removed and the developer residue is removed by washing the substrate after development with pure water or the like. The rinse method can use a well-known method. For example, shower rinse, deep rinse, etc. are mentioned.

<Post Baking Process (Crosslinking Process)>

In the post-baking process of (5), by heating the obtained positive image, for example, the acid-decomposable group which component A may have may be thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and crosslinked with a crosslinkable group, a crosslinking agent or the like to form a cured film. Can be. This heating is performed using a heating device such as a hot plate or an oven, heating at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes for a hot plate and 30 to 120 minutes for an oven. It is preferable to perform the treatment. By advancing a crosslinking reaction in this way, a protective film and an interlayer insulation film excellent in heat resistance, hardness, etc. can be formed. In addition, when performing heat processing, transparency can also be improved by performing in nitrogen atmosphere.

Post-baking may be performed after baking at a relatively low temperature before post-baking (addition of middle baking process). When middle baking is performed, it is preferable to post-bak at high temperature 200 degreeC or more after heating at 90-150 degreeC for 1 to 60 minutes. In addition, middle baking and post-baking can also be divided | segmented into three or more stages of a multilayer, and it can heat. The taper angle of a pattern can be adjusted by the study of such a middle baking and post-baking. These heatings can use well-known heating methods, such as a hotplate, oven, and an infrared heater.

If the degree of crosslinking is expected to be insufficient due to the characteristics of each material to be selected, it is present in the unexposed part by post-baking the whole surface by post acting on the substrate on which the pattern is formed before post-baking (post exposure). The acid can be generated from the photoacid generator to function as a catalyst for promoting the crosslinking process, and the curing reaction of the film can be promoted. As a preferable exposure amount in the case of including a post exposure process, 100-3,000mJ / cm <2> is preferable and 100-500mJ / cm <2> is especially preferable.

On the other hand, it is also possible not to perform a re-exposure process in the case of that excepting the above. In addition to improving productivity, stability in high temperature and high humidity conditions can be enhanced.

Moreover, the cured film obtained from the photosensitive resin composition of this invention can also be used as a dry etching resist. When using the cured film obtained by thermosetting by the post-baking process as a dry etching resist, dry etching processes, such as ashing, plasma etching, and ozone etching, can be performed as an etching process.

By the photosensitive resin composition of this invention, the cured film which is excellent in insulation and has high transparency even when baked at high temperature is obtained, and is useful as an interlayer insulation film. Since the interlayer insulation film formed using the photosensitive resin composition of this invention has high transparency and excellent cured film physical property, it is useful for the use of an organic electroluminescence display or a liquid crystal display device.

The organic EL display device or liquid crystal display device of the present invention is not particularly limited except for using a cured film formed by using the photosensitive resin composition of the present invention as a planarization film or an interlayer insulating film, and various known organic compounds having various structures. An EL display device and a liquid crystal display device are mentioned.

For example, amorphous silicon TFT, low temperature polysilicon TFT, oxide semiconductor TFT etc. are mentioned as a specific example of TFT (Thin-Film Transistor) with which the organic electroluminescence display and liquid crystal display of this invention are equipped. Since the cured film of this invention is excellent in an electrical property, it can be used conveniently in combination with these TFT.

The liquid crystal display device of the present invention may be a twisted nematdic (TN) method, a vertical alignment (VA) method, an in-place-switching (IPS) method, a frings field switching (FFS) method, OCB (Optical Compensated Bend) method and the like.

Moreover, the rubbing orientation method, the photo-alignment method, etc. are mentioned as a specific orientation system of the liquid crystal aligning film which the liquid crystal display device of this invention can take. Furthermore, the polymer orientation may be supported by the PSA (Polymer Sustained Alignment) technique described in JP-A-2003-149647 or JP-A-2011-257734.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows the structure of an example of the organic electroluminescent display which applied the cured film using the photosensitive resin composition of this invention as an insulating film and a planarization film.

The organic EL display device shown in FIG. 1 is a bottom emission type organic EL display device.

Of Figure 1, the insulating film 3 is TFT (1) of the bottom gate type formed on the glass substrate 6 is formed, made of a state covering the TFT (1) to the Si ₃ N ₄ is formed. After the contact holes (not shown here) are formed in the insulating film 3, a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact holes 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 flattening 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, and by forming this insulating film 8, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process is formed. You can prevent it.

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, and then a second electrode made of Al is formed on the entire surface above the substrate and sealed. It is sealed by bonding using a glass plate for glass and an ultraviolet curable epoxy resin, and an active matrix organic EL display device in which a TFT 1 for driving this is connected to each organic EL element is obtained.

It is typical sectional drawing which shows an example of the liquid crystal display device which applied the cured film using the photosensitive resin composition of this invention.

The liquid crystal display device shown in FIG. 2 is an active matrix liquid crystal display device.

In FIG. 2, the liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back side, which corresponds to all pixels disposed between two glass substrates 14 and 15 to which a polarizing film is bonded. The elements of the TFT 16 are arranged. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode through a contact hole 18 formed in the cured film 17 is wired. 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 formed.

(Example)

An Example is given to the following and this invention is demonstrated to it further more concretely. The materials, the amounts used, the ratios, the treatment contents, the treatment sequences, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below. In addition, "part" and "%" are mass references | standards unless there is particular notice.

In the following synthesis examples, the following codes | symbols represent the following compounds, respectively.

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

V-601: dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

MAEVE: Methacrylic acid 1-ethoxyethyl (synthetic product)

MATHF: methacrylate tetrahydrofuran-2-yl (synthetic product)

MATHP: methacrylate tetrahydro-2H-pyran-2-yl (manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

CHOEMA: Methacrylic acid 1- (cyclohexyloxy) ethyl (synthetic product)

StOEVE: 4- (1-ethoxyethyloxy) styrene (synthetic product)

NBMA: n-butoxymethyl acrylamide (made by Mitsubishi Rayon Co., Ltd.)

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

Oxe-30: methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Organic Kagaku Kogyo KK)

HEMA: 2-hydroxyethyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

St: Styrene (made by Wako Pure Yakugo High School)

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

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

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

AA: acrylic acid (made by Wako Pure Chemical Industries, Ltd.)

DCPM: Dicyclopentanyl methacrylate (made by Hitachi Kasei Kogyo Co., Ltd.)

HS-EDM: diethylene glycol ethyl methyl ether (Toho Kagaku Kogyo Co., Ltd., high-solve EDM)

<Mathf Synthesis>

Methacrylic acid (86 g, 1 mol) was cooled to 15 degreeC, and camphor sulfonic acid (4.6 g, 0.02 mol) was added. 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was dripped at this solution. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, and the insolubles were filtered and concentrated under reduced pressure at 40 占 폚 or lower, and the yellow oily residue was dried under reduced pressure. Distillation was carried out to obtain 125 g of methacrylic acid tetrahydrofuran-2-yl (MATHF) having a boiling point of 54 to 56 ° C / 3.5 mmHg fraction as a colorless oil (yield 80%).

<Synthesis of MAEVE>

0.5 part of phenothiazine was added to 144.2 parts (2 molar equivalents) of ethyl vinyl ether, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower, followed by stirring at room temperature (25 ° C.) for 4 hours. did. After adding 5.0 parts of p-toluenesulfonic-acid pyridium, it stirred at room temperature for 2 hours, and was left to stand overnight at room temperature. 5 parts of sodium hydrogencarbonate and 5 parts of sodium sulfate were added to the reaction solution, the mixture was stirred at room temperature for 1 hour, the insolubles were concentrated under reduced pressure to 40 ° C. or lower, and the yellow oily substance was distilled under reduced pressure to give a boiling point (b.). 134.0 parts of methacrylic acid 1-ethoxyethyl of 43-45 degreeC / 7mmHg fraction were obtained as a colorless oil.

In addition, CHOEMA and MATHF were synthesize | combined by the same method as the said methacrylic acid 1-ethoxyethyl except having changed the ethyl vinyl ether into the corresponding compound.

Synthesis of Polymer A1

66.41 parts (0.42 molar equivalent) of methacrylic acid 1-ethoxyethyl obtained, 6.89 parts (0.08 molar equivalent) of methacrylic acid, 49.75 parts (0.35 molar equivalent) of GMA, 19.52 parts (0.15 mole of 2-hydroxyethyl methacrylic acid) Equivalence) and a mixed solution of 132.5 parts of PGMEA were heated to 70 degreeC under nitrogen stream. While stirring this mixed solution, the mixed solution of radical polymerization initiator V-65 (made by Wako Pure Chemical Industries Ltd., 12.4 parts) and 100.0 parts of PGMEA was dripped over 2.5 hours. After completion of the dropwise addition, the mixture was reacted at 70 ° C for 4 hours to obtain a PGMEA solution (solid content concentration: 40%) of polymer A1. The weight average molecular weight measured by the gel permeation chromatography (GPC) of the obtained polymer A1 was 8,000.

[Synthesis of Polymers A2 to A5]

Each monomer used in the synthesis of the polymer A1 was changed to each structural unit (a1) to (a4) shown in Table 1, and the same amount as that of the synthesis of the polymer A1 except that the amount of each structural unit was changed to that shown in Table 1 Polymers A2 to A5 were synthesized, respectively. In addition, the addition amount of the radical polymerization initiator V-65 was adjusted so that it might become the molecular weight of Table 1, respectively.

Synthesis of Polymer A'1

HS-EDM (82 parts) was stirred by heating at 90 ° C. under a nitrogen stream. MATHF (43 parts (40.5 mole% equivalent)), OXE-30 (48 parts (37.5 mole% equivalent)), MAA (6 parts (9.5 mole% equivalent)), HEMA (11 parts (12.5 mole% equivalent)), Polymer A'1 by dropping a mixed solution of radical polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4.3 parts) and PGMEA (82 parts) over 2 hours, and reacting at 90 ° C for 2 hours. PGMEA solution (solid content: 40%) was obtained.

The weight average molecular weight measured by the gel permeation chromatography (GPC) of the obtained polymer A'1 was 15,000.

<Synthesis of other polymers A'2 to A'12>

Each copolymer was synthesize | combined similarly to the synthesis | combination of polymer A'1 except having changed each used monomer and its usage amount as shown in following Table 2.

In particular, the numerical value without a unit in Table 2 is based on mol%. In addition, the numerical value of an initiator is mol% when the monomer component is 100 mol%.

Solid content concentration can be computed by the following formula | equation.

Solid content concentration: Monomer mass / (monomer mass + solvent mass) * 100 (unit: mass%)

In addition, when V-601 was used as an initiator, reaction temperature was 90 degreeC, and when V-65 was used, reaction temperature was 70 degreeC.

<Examples 1-11, 66 and 67, and Comparative Examples 1-4>

(1) Preparation of photosensitive resin composition

After mixing each component shown in following Table 3 to make a uniform solution, it filtered using the polytetrafluoroethylene filter which has a pore size of 0.1 micrometer, and compares Examples 1-11, 66 and 67, and, The solution of the photosensitive resin composition of Examples 1-4 was prepared, respectively.

<Comparative Example 5: Composition described in Example 1 of Japanese Patent Laid-Open No. 10-26829>

After using a flask equipped with a reflux condenser, nitrogen was substituted in the flask, and then 200 g of a solution in which 7.0 g of 2,2'-azobisisobutylonitrile was dissolved in ethyl lactate was added to the flask as a polymerization initiator. Subsequently, 35 g of styrene, 20 g of methacrylic acid, 30 g of methacrylic acid t-butyl and 15 g of methacrylic acid-2-hydroxyethyl were added thereto, and then the temperature of the liquid was raised to 70 ° C. with slow stirring, and the temperature was increased to 7 ° C. It hold | maintained for time, copolymerized the monomer, and obtained 300g of copolymer solutions (31.6 mass% of copolymer components).

The copolymer solution obtained above was diluted with ethyl lactate such that the copolymer content was 23% by mass, and diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate was added to 100 g (23 g) of the copolymer solution. 0.69 g and surfactant BM-1000 (manufactured by BM Chemie) were dissolved and mixed. Subsequently, the photosensitive resin composition of the comparative example 5 was obtained by filtering a solution with the pore diameter filter of 0.22 micrometer of pore diameters.

<Comparative Example 6: Composition described in Example 1 of Japanese Patent Laid-Open No. 2004-264623>

7 mass parts of 2,2'- azobis (2, 4- dimethylvaleronitrile), and 200 mass parts of diethylene glycol ethyl methyl ether were thrown into the flask provided with the cooling tube and the stirrer. Subsequently, 40 parts by mass of 1- (cyclohexyloxy) ethyl methacrylate, 5 parts by mass of styrene, 45 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, and α-methylstyrene dimer After adding 3 parts by mass of nitrogen and replacing, slowly stirring was started. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer. The polystyrene reduced weight average molecular weight (Mw) of the obtained copolymer was 11,000. In addition, the solid content concentration of the polymer solution obtained here was 31.6 mass%.

Solid content concentration of the said polymer solution which is equivalent to 100 mass parts (solid content) of copolymers, and 5 mass parts of 4,7-di-n-butoxy-1- naphthyl tetrahydrothiophenium trifluoromethanesulfonate After melt | dissolving in diethylene glycol methyl ethyl ether so that it might be set to 30 mass%, it filtered by the membrane filter of 0.2 micrometer of calibers, and prepared the photosensitive resin composition of the comparative example 6.

In addition, the symbol of Table 3 is as follows.

B1: CGI-1397 (product made in Chiba Japan)

B2: PAI-101 (made in Midori Kagaku Co., Ltd.)

B3: the following compound

B4: the following compound

C1: Dulanate 17B-60PX (made by Asahi Kasei Chemicals Co., Ltd.)

In addition, C1 is a block isocyanate compound whose parent structure is a biuret structure and whose block structure is an oxime ester structure.

C3: Nikarak MW-100LM (alkoxy methylated melamine compound, Sanwa Chemical Co., Ltd. product)

C4: Dulanate D101 (made by Asahi Kasei Chemicals Co., Ltd.)

C5: Takenate D-110N (made by Mitsui Kagaku Co., Ltd.)

In addition, C4 and C5 are block isocyanate compounds whose parent structure is a biuret structure and a block structure is an oxime ester structure.

C6: VESTAGON B1065 (product made in Degusa AG company)

In addition, C6 is a block isocyanate compound which has a uretodione structure (biburet structure).

C7: JER-157S65 (multifunctional novolac type epoxy resin, crosslinking agent, Mitsubishi Kagaku Co., Ltd. product)

D1: propylene glycol monomethyl ether acetate

F1: Compound of the following structure

G1: Compound W-3 having the following structure

H1: 3-glycidoxypropyltrimethoxysilane (KBM-403 (made by Shin-Etsu Kagaku Kogyo KK))

[Synthesis of B3]

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 and reacted for 2 hours. 4NHCl aqueous solution (60 mL) was dripped at the reaction liquid under ice cooling, and ethyl acetate (50 mL) was added and liquid-separated. Potassium carbonate (19.2 g) was added to the organic layer, and the resultant was reacted at 40 ° C for 1 hour, followed by separating an aqueous solution of 2NHCl (60 mL), followed by concentration of the organic layer. It dried and the ketone compound (6.5g) was obtained.

Acetic acid (7.3g) and 50 mass% 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 B3 (2.3 g).

In addition, the ¹ H-NMR spectrum (300MHz, CDCl ₃ ) of B3 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 of B4]

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 allowed to react 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 and 48 mass% aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) were added and the mixture was allowed to react for 2 hours. . 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 crude carboxylic acid. 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, 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).

The obtained oxime (3.1 g) was sulfonated similarly to B3, and B4 (3.2 g) was obtained.

In addition, the ¹ H-NMR spectrum (300MHz, CDCl ₃ ) of B4 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).

<Examples 12-28 and Comparative Examples 7-14>

(1) Preparation of photosensitive resin composition

After mixing each component shown in following Table 4 to make a uniform solution, it filtered using the polytetrafluoroethylene filter which has a pore size of 0.1 micrometer, and the photosensitive resin of Examples 12-28 and Comparative Examples 7-14. Each solution of the composition was prepared. In addition, the unit of the addition amount in Table 4 is a mass part, and a ratio is a mass reference | standard.

In addition, the symbol of Table 4 other than a polymer and a photo-acid generator is as follows.

C'1: Dulanate 17B-60PX (made by Asahi Kasei Chemicals Co., Ltd.)

C'2: Dulanate 17B-60P (made by Asahi Kasei Chemicals Co., Ltd.)

In addition, C'1 and C'2 are block isocyanate compounds whose parent structure is a biuret structure and a block structure is an oxime ester structure.

C'6: Nikarak mw-100lm (alkoxy methylated melamine compound, manufactured by Sanwa Chemical Co., Ltd.)

C'7: Dulanate D101 (made by Asahi Kasei Chemicals Co., Ltd.)

C'8: Takenate D-110N (product made by Mitsui Kagaku Co., Ltd.)

In addition, C'7 and C'8 are nonblock isocyanate compounds, ie isocyanate compounds.

C'9: VESTAGON B1065 (product made in Degusa AG company)

In addition, C'9 is a block isocyanate compound which has a uretodione structure (biburet structure).

C'10: JER-157S65 (multifunctional novolak type epoxy resin, crosslinking agent, product of Mitsubishi Kagaku Co., Ltd.)

C'11: Denacol EX-321L (liquid aliphatic epoxy compound, Nagase Chemtex Co., Ltd. product)

C'12: Denacol EX-211L (liquid aliphatic epoxy compound, Nagase Chemtex Co., Ltd. product)

D1: the said compound (propylene glycol monomethyl ether acetate)

F1: the compound

G1: the said compound (compound W-3)

H'1: 3-glycidoxypropyltrimethoxysilane (KBM-403 (made by Shin-Etsu Kagaku Kogyo KK))

H'2: Bis (triethoxysilylpropyl) disulfide (Z-6920 (made by Toray Dow Corning))

H'3: Bis (triethoxysilylpropyl) tetrasulfide (KBE-846 (made by Shin-Etsu Kagaku Kogyo Co., Ltd.))

I'1: Irganox 1726 (antioxidant, BASF company make)

I'2: Irganox 1035FF (antioxidant, BASF company make)

I'3: Irganox 1098 (antioxidant, BASF company make)

I'4: Adecastab AO-60 (antioxidant, product made in ADEKA)

I'5: Adecastub AO-70 (antioxidant, product made in ADEKA)

The symbol of the (component B) photo-acid generator in Table 4 is as follows.

B'1: IRGACURE PAG-103 (brand name, structure shown below, product made in BASF Corporation)

B'2: PAI-101 (product name, the structure shown in the said B2, Midori Kagaku Corporation make)

B'5: Structure shown below (Synthesis example is mentioned later)

B'6: Structure shown below (Synthesis example is mentioned later)

<Synthesis of B'5>

1-1.Synthesis of Synthetic Intermediate B'5A

2-aminobenzenethiol: 31.3 g (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) under room temperature (25 ° C). Subsequently, 40.6 g of phenylacetyl chloride (made by Tokyo Kasei Kogyo Co., Ltd.) was dripped at the obtained solution, 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 was concentrated with the rotary evaporator, and the synthetic intermediate B'5A was obtained.

1-2. Synthesis of B'5

2.25 g of the synthetic intermediate B'5A obtained as described above was mixed in 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. Then, tetramethylammonium hydroxide: 4.37g (25 mass% methanol solution, the AlfaAcer company make) was dripped at the reaction liquid, and it stirred for 0.5 hour and reacted under ice bath. Moreover, isopentyl nitrite: 7.03g was dripped keeping it at internal temperature 20 degreeC or less, and after completion | finish of dripping, after heating up the reaction liquid to room temperature, it stirred for 1 hour.

Subsequently, after cooling the reaction liquid to 5 degrees C or less, p-toluenesulfonyl 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 added, it heated at 50 degreeC, stirred for 1 hour, was filtered and dried at the time, and 1.8 g of B'5 (structure mentioned above) was obtained.

The ¹ H-NMR spectrum (300 MHz, medium DMSO ((D ₃ C) ₂ S = O)) of the obtained B'5 is δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.00 (m, 1H), and 7.95 to 7.9 (m, 2H), 7.6-7.45 (m, 9H), and 2.45 (s, 3H).

It is estimated that B'5 obtained from the said ¹ H-NMR measurement result is a single geometric isomer.

<Synthesis of B'6>

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 and reacted for 2 hours. 4NHCl aqueous solution (60 mL) was dripped at the reaction liquid under ice cooling, and ethyl acetate (50 mL) was added and liquid-separated. Potassium carbonate (19.2 g) was added to the organic layer and reacted at 40 ° C for 1 hour, followed by separating an aqueous solution of 2NHCl (60 mL), separating the organic layer, and recrystallizing the crystals with diisopropyl ether (10 mL), It filtered and dried and the ketone compound (6.5g) was obtained.

Acetic acid (7.3g) and 50 mass% hydroxylamine aqueous solution (8.0g) were added and heated and refluxed to the obtained ketone compound (3.0g) and the suspension solution of methanol (30 mL). 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 2.3 g of B'6 (structure described above).

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B'6 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), and 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).

<Examples 29-65 and Comparative Example 15>

(1) Preparation of photosensitive resin composition

After mixing each component shown in following Table 5 to make a uniform solution, it filtered using the polytetrafluoroethylene filter which has a pore size of 0.1 micrometer, and the photosensitive resin composition of Examples 29-65 and the comparative example 15. The solution of was prepared respectively. In addition, the unit of the addition amount in Table 5 is a mass part, and a ratio is a mass reference | standard.

In addition, the symbol of Table 5 other than A'1-A'12 and a photo-acid generator is as follows.

A'13: ARUFON UC-3910 (product made by Toa Kosei Co., Ltd.)

A'14: Joncryl 67 (made by BASF Corporation)

C "1: Dullanate 17B-60PX (made by Asahi Kasei Chemicals Co., Ltd.)

In addition, C "1 is a block isocyanate compound whose parent structure is a biuret structure and a block structure is an oxime ester structure.

C "10: JER-157S65 (polyfunctional novolak-type epoxy resin, crosslinking agent, Mitsubishi Kagaku Corporation make)

Block isocyanate whose parent structure which has the methyl ethyl ketone oxime block structure of C "13: tolylene diisocyanate (TDI) is a biuret structure

Block isocyanate whose parent structure having the methyl ethyl ketone oxime block structure of C "14: diphenylmethane diisocyanate (MDI) is a biuret structure.

Block isocyanate whose parent structure which has the methyl ethyl ketone oxime block structure of C "15: hexamethylene diisocyanate (HDI) is a biuret structure

Block isocyanate whose parent structure having ε-caprolactam block structure of C "16: hexamethylene diisocyanate (HDI) is a biuret structure

Block isocyanate whose parent structure having a phenol block structure of C "17: hexamethylene diisocyanate (HDI) is a biuret structure

Block isocyanate whose parent structure having butanol block structure of C "18: hexamethylene diisocyanate (HDI) is biuret structure

Block isocyanate whose parent structure having the diphenylamine block structure of C "19: hexamethylene diisocyanate (HDI) is a biuret structure.

Block isocyanate whose parent structure having acetoacetic acid ethyl block structure of C "20: hexamethylene diisocyanate (HDI) is a biuret structure

Block isocyanates wherein the parent structure having a dimethylpyrazole block structure of C " 21: hexamethylene diisocyanate (HDI) is a biuret structure

Block isocyanate whose parent structure having the alkyl mercaptan block structure of C "22: hexamethylene diisocyanate (HDI) is a biuret structure

Block isocyanate whose parent structure which has the methyl ethyl ketone oxime block structure of C "23: isophorone diisocyanate (IPDI) is a biuret structure

Block isocyanates wherein the parent structure having an ε-caprolactam block structure of C ″ 24: isophorone diisocyanate (IPDI) is a biuret structure

Block isocyanates whose parent structure having a phenol block structure of C "25: isophorone diisocyanate (IPDI) is a biuret structure

Block isocyanate whose parent structure having acetoacetic acid ethyl block structure of C "26: isophorone diisocyanate (IPDI) is a biuret structure

Block isocyanates wherein the parent structure having a dimethylpyrazole block structure of C " 27: isophorone diisocyanate (IPDI) is a biuret structure.

D1: the said compound (propylene glycol monomethyl ether acetate)

E "1: DBA (9,10-dibutoxy anthracene, the Kawasaki Kasei Kogyo Co., Ltd. product)

F2: Compound having the following structure (Compound F-2)

G1: the said compound (compound W-3)

H "1: 3-glycidoxypropyltrimethoxysilane (KBM-403 (made by Shin-Etsu Kagaku Kogyo KK))

H "4: hexyl trimethoxysilane (KBM-3063 (made by Shin-Etsu Kagaku Kogyo Co., Ltd.))

I "2: Irganox 1035FF (antioxidant, product made by BASF company)

I "3: Irganox 1098 (antioxidant, BASF Corporation make)

I "4: Adecaster AO-60 (antioxidant, product made in ADEKA)

The symbol of the (component B) photo-acid generator in Table 5 is as follows.

B "6: Structure shown below (Synthesis example is mentioned later)

B "7: The compound of the following structure (it synthesize | combined according to the method of Paragraph 0108 of Unexamined-Japanese-Patent No. 2002-528451).

<Synthesis of B "6>

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 and reacted for 2 hours. 4NHCl aqueous solution (60 mL) was dripped at the reaction liquid under ice cooling, and ethyl acetate (50 mL) was added and liquid-separated. Potassium carbonate (19.2 g) was added to the organic layer and reacted at 40 ° C for 1 hour, followed by separating an aqueous solution of 2NHCl (60 mL), separating the organic layer, and recrystallizing the crystals with diisopropyl ether (10 mL), It filtered and dried and the ketone compound (6.5g) was obtained.

Acetic acid (7.3g) and 50 mass% hydroxylamine aqueous solution (8.0g) were added and heated and refluxed to the obtained ketone compound (3.0g) and the suspension solution of methanol (30 mL). 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 2.3 g of B''6 (structure described above).

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B ″ 6 shows δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), and 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 of C> 13>

Block mass isocyanate C "13 which consists of a transparent viscous liquid was obtained by putting 100 mass parts of biuret bodies of tolylene diisocyanate, and 50 mass parts of methyl ethyl ketone oxime into a reaction container, and making it react at 100 degreeC for 6 hours. As a result of IR measurement, NCO It was confirmed that there was no absorption peak of 2,250 cm ⁻¹ due to the group (C ″ 13 mainly includes a block isocyanate compound having a trifunctional block isocyanate group).

<Synthesis of C "14-C" 27>

Synthesis was carried out in the same manner as in the synthesis of C ″ 13, except that the biuret body and the block compound of the diisocyanate used in the synthesis were changed.

(2) Evaluation of the photosensitive resin composition

(Evaluation of sensitivity)

After spin-coating a solution of the photosensitive resin composition of Examples 1-67 and Comparative Examples 1-15, respectively, on the silicon wafer which has a silicon oxide film, it prebaked on a hotplate at 90 degreeC for 120 second, and the coating film of 3 micrometers in thickness Formed.

Subsequently, it exposed through the predetermined mask using the i-line stepper (FPA-3000i5 + by Canon Corporation). After leaving the substrate for 10 minutes after exposure, the substrate was developed by a puddle method at 23 ° C. for 60 seconds with 0.4% tetramethylammonium hydroxide aqueous solution, followed by rinsing with ultrapure water for 45 seconds. By these operations, the optimum exposure dose (Eopt) at the time of resolving a 10-micrometer line and space at 1: 1 was set as the sensitivity. Sensitivity can be said to be high sensitivity in the case of low exposure amount than 70mJ / cm <2>. The evaluation results are shown in Tables 6 to 8. In addition, in the column of the sensitivity of Table 6, "*" shows that pattern formation could not be carried out at 200mJ / cm <2>.

(Evaluation of heat transparency)

After spin-coating the solution of the photosensitive resin composition of Examples 1-67 and Comparative Examples 1-15 with a glass substrate (made by Eagle 2000 Corning Co., Ltd.), it prebaked on a hotplate at 90 degreeC for 120 second, and the coating film of 3 micrometers in thickness Formed. The obtained coating film was developed by a puddle method at 23 ° C. for 60 seconds with an aqueous 0.4% tetramethylammonium hydroxide solution, and further rinsed with ultrapure water for 45 seconds, followed by a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation. It exposed so that accumulated irradiation amount might be 300mJ / cm <2> (roughness: 20mW / cm <2>), Then, this board | substrate was heated at 230 degreeC in oven for 1 hour, and the cured film was obtained. After heating the obtained cured film further at 230 degreeC in oven, the light transmittance was measured with the wavelength of 400-800 nm using the spectrophotometer "150-20 type double beam (made by Hitachi, Ltd.)." Evaluation of the minimum light transmittance at that time (evaluation of heat transparency) is shown in Tables 6-8.

The evaluation criteria are as follows. In addition, the value of minimum light transmittance is converted into the value per film thickness of 2 micrometers after heating at 230 degreeC for 2 hours.

0: 92% or more

1: 87% or more but less than 92%

2: 85% or more but less than 87%

3: 82% or more and less than 85%

Less than 4: 82%

(Evaluation of chemical resistance)

After spin-coating the solution of the photosensitive resin composition of Examples 1-67 and Comparative Examples 1-15 with a glass substrate (made by Eagle 2000 Corning Co., Ltd.), it prebaked on a hotplate at 90 degreeC for 120 second, and the coating film of 3 micrometers in thickness Formed. The obtained coating film was exposed by Canon's PLA-501F exposure machine (ultra high pressure mercury lamp) so that accumulated irradiation amount might be 300 mJ / cm 2 (roughness: 20 mW / cm 2), and then the substrate was heated at 230 ° C. in an oven for 1 hour. And the cured film was obtained. The obtained cured film was immersed in N-methylpyrrolidone (NMP) for 70 degreeC for 10 minutes, and the film thickness before and behind immersion was measured. The following was defined as "swelling ratio" and the following references | standards evaluated.

Swelling rate (%) = film thickness after immersion (µm) / film thickness before immersion (µm) x 100-100

0: less than 2% of swelling ratio

1: 2% or more swelling rate less than 4%

2: 4% or more swelling rate less than 6%

3: Swelling rate 6% or more and less than 8%

4: 8% or more swelling ratio

(Evaluation of display nonuniformity in display device)

A liquid crystal display device using a thin film transistor (TFT) was produced by the following method (see FIGS. 1 and 2). In the active matrix liquid crystal display device of FIGS. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 was formed as follows as an interlayer insulating film to obtain a liquid crystal display device.

In other words, to form the glass substrate 6, the insulating film 3 made of Si ₃ N ₄ forms a bottom gate type TFT (1) on, and in a state covering the TFT (1). Subsequently, after forming a contact hole in this insulating film 3, the wiring 2 (height 1.0 micrometer in height) connected to the TFT 1 through this contact hole was formed on the insulating film 3.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization film 4 was formed on the insulating film 3 in a state of filling the unevenness by the wiring 2. Formation of the planarization film 4 on the insulating film 3 spin-coated each photosensitive resin composition of Examples 1-67 and Comparative Examples 1-15 on a board | substrate, and prebaking (90 degreeC * 2 minutes on a hotplate) After irradiating 25mJ / cm <2> (roughness 20mW / cm <2>) of i lines (365 nm) using a high pressure mercury lamp on the mask, it developed by alkaline aqueous solution, the pattern was formed, and it heat-processed at 230 degreeC for 60 minutes. 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 was not recognized 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 and the average level | step difference of the wiring 2 was 2,000 nm.

The drive voltage was applied to the obtained liquid crystal display device, the gray display when the gray test signal was input was visually observed, and the presence or absence of display nonuniformity was evaluated according to the following evaluation criteria.

0: Unevenness is not seen at all (very good)

1: unevenness is seen on the edge of the glass substrate, but there is no problem in the display part (good)

2: unevenness is seen faintly in the display part, but practical use level (usually)

3: There is irregularity in indication part (slightly bad)

4: There is strong unevenness in display part (very bad)

It can be seen from Tables 6 to 8 that all of the photosensitive resin compositions of the present invention have very high sensitivity, good thermal transparency, and excellent chemical resistance. Moreover, it turns out that there is no liquid crystal display nonuniformity and it is possible to manufacture a high quality panel.

On the other hand, as for the photosensitive resin composition of the comparative example different from the photosensitive resin composition of this invention, it turns out that a sensitivity, heat-transparency, chemical resistance, and display nonuniformity do not satisfy all the items.

<Example 68>

In the display nonuniformity evaluation of Example 43, only the following coating processes were changed and the same liquid crystal display device was obtained.

That is, after apply | coating the photosensitive resin composition of Example 43 with the slit coating method (CL1700 by Tokyo Electron Co., Ltd.), a solvent is removed by heating on a 90 degreeC / 120 second hotplate, and the photosensitive resin of 4.0 micrometers of film thicknesses is carried out. The composition layer was formed. The obtained coating film was flat and favorable surface shape without nonuniformity. Moreover, the performance as a liquid crystal display device was also favorable similarly to Example 43.

<Example 69>

In the display nonuniformity evaluation of Example 43, only the following coating processes were changed and the same liquid crystal display device was obtained.

That is, after apply | coating the photosensitive resin composition of Example 43 with the slit-and-spin method (SF-700G3 by Dainippon Screen Seijo Co., Ltd.), a solvent is removed by heating on a 90 degreeC / 120 second hotplate, and a film thickness is carried out. A 4.0 micrometers photosensitive resin composition layer was formed. The obtained coating film was flat and favorable surface shape without nonuniformity. Moreover, the performance as a liquid crystal display device was also favorable similarly to Example 43.

<Example 70>

Adhesiveness was favorable as a result of exposing the liquid crystal display device obtained in the display nonuniformity evaluation of Example 43 for one week under 120 degreeC 100% RH high temperature, high humidity conditions, and decomposing | disassembling and evaluating the base adhesiveness of a cured film.

<Example 71>

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

A glass substrate 6, the insulating film 3 made of Si ₃ N ₄ forming a TFT (1) of the bottom gate type on, and in a state covering the TFT (1) was formed. Subsequently, a contact hole (not shown here) is formed in the insulating film 3, and then a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact hole is formed on the insulating film 3. did. 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 planarization film 4 on the insulating film 3 is performed by spin-coating the photosensitive resin composition of Example 43 on a substrate, prebaking (90 ° C. × 2 minutes) on a hot plate, and then applying a high pressure mercury lamp from the mask. After irradiating i line | wire (365 nm) to 45 mJ / cm <2> (roughness 20 mW / cm <2>), it developed with alkaline aqueous solution, the pattern was formed, and the heat processing for 60 minutes was performed 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 was not recognized 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 connected to the wiring 2 through the contact hole 7, and was formed. 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. Then, the said resist pattern was stripped using the resist stripping liquid (mixed liquid 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. The insulating film 8 was formed in the insulating film by the method similar to the above using the photosensitive resin composition of Example 43. By forming this insulating film, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process can be prevented.

Further, the hole transporting layer, the organic light emitting layer, and the electron transporting layer were sequentially deposited through a desired pattern mask in a vacuum vapor deposition apparatus. Next, the 2nd electrode which consists of Al was formed in the whole surface above a board | substrate. 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 obtained by connecting the TFT 1 for driving this to each organic EL element was obtained. As a result of applying a voltage through the driving circuit, it was found that the display device exhibited good display characteristics and was a highly reliable organic EL display device.

1: TFT (thin film transistor) 2: wiring
3: insulation film 4: flattening film
5: first electrode 6: glass substrate
7: Contact hole 8: Insulation film
10: liquid crystal display device 12: backlight unit
14,15: glass substrate 16: TFT
17: Curing film 18: Contact hole
19: ITO transparent electrode 20: liquid crystal
22: color filter

Claims (18)

(Component A) resin which has an acetal structure and whose alkali solubility changes by the action of an acid,
(Component B) a photoacid generator,
(Component C) a crosslinking agent, and
(Component D) a solvent is included;
Component C comprises a block isocyanate compound,
The parent structure of the said block isocyanate compound is a biuret structure, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The isocyanate group of the block isocyanate compound is a blocking agent selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. It is blocked, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The said block isocyanate compound is a burette structure obtained by multiplying the compound selected from the group which consists of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). The photosensitive resin composition characterized by blocking the isocyanate group of the multimer which has a block agent. The method of claim 1,
Content of the said block isocyanate compound is 0.1-8 mass% with respect to the total solid amount of the said photosensitive resin composition, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
Said component A is a polymer which has a structural unit (a1) which has a residue in which a carboxyl group was protected by the acetal structure, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
Said component A is a polymer which has a structural unit (a2) which has a carboxyl group or phenolic hydroxyl group, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The said component B is an oxime sulfonate compound, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
Said component A is a polymer which has a structural unit which has (a3) crosslinkable group, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
Crosslinking group contained in the structural unit having the (a3) is a crosslinking group comprising a group represented by an epoxy group, an oxetanyl group, and a -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) Photosensitive resin composition, characterized in that at least one selected from the group. The method of claim 1,
The photosensitive resin composition which further contains antioxidant. (1) An application step of applying the photosensitive resin composition according to any one of claims 1 to 10 on a substrate,
(2) a solvent removal step of removing the solvent from the applied photosensitive resin composition,
(3) an exposure step of exposing the photosensitive resin composition from which the solvent is removed by actinic light;
(4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer; and
(5) A method of forming a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition. The method of claim 11,
And a step of exposing the entire surface of the photosensitive resin composition developed after the developing step and before the post-baking step. The method of claim 11,
A method of forming a cured film, comprising a step of exposing the entire surface of the photosensitive resin composition developed after the developing step and before the post-baking step. The method of claim 11,
(6) The method of forming a cured film, further comprising a dry etching step of performing dry etching on a substrate having a cured film obtained by thermosetting. It formed by the formation method of the cured film of Claim 11, The cured film characterized by the above-mentioned. The method of claim 15,
It is an interlayer insulation film, The cured film characterized by the above-mentioned. The cured film of Claim 15 is provided, The organic electroluminescence display characterized by the above-mentioned. The cured film of Claim 15 is provided, The liquid crystal display device characterized by the above-mentioned.

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