JP5524037B2 - Photosensitive resin composition, cured film, method for forming cured film, organic EL display device, and liquid crystal display device - Google Patents

Description

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

  An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

  The interlayer insulating film and the planarizing film patterned using the photosensitive resin composition as described above are required to be a highly reliable cured film having excellent solvent resistance in addition to transparency. It is done.

  As such a photosensitive resin composition, for example, Patent Document 1 includes (A) (a) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) a radical polymerizable compound having an epoxy group, and ( c) A photosensitive resin composition having a resin soluble in an alkaline aqueous solution, which is a copolymer of other radical polymerizable compounds, and (B) a radiation-sensitive acid generating compound is described.

  Patent Document 2 discloses, for example, an acetal structure or a ketal structure as a photosensitive resin composition that can ensure storage stability, sensitivity, and high reliability (transparency, solvent resistance) of a formed cured film. (Meth) acrylic acid ester compound having an epoxy group, a radical polymerizable compound having an epoxy group, and a resin that is a copolymer of another radical polymerizable compound, and a compound that generates an acid having a pKa of 4.0 or less upon irradiation with radiation And a radiation sensitive resin composition containing the same.

  Patent Document 3 discloses a resin having a specific acid dissociable group, a resin that is a copolymer with a structural unit capable of reacting with a carboxyl group to form a covalent bond, and a light having an oxime sulfonate group. A positive photosensitive resin composition containing an acid generator is described.

On the other hand, as an optical system material used for an imaging optical system of an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state image sensor, or an optical fiber connector, a microlens having a lens diameter of about 3 to 100 μm or a microlens thereof The microlens array which arranged regularly is used.
To form a microlens or a microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as a lens as it is, or by using the melt-flowed lens pattern as a mask. A method of transferring a lens shape to a base by etching is known. For forming such a lens pattern, a photosensitive resin composition is widely used (see, for example, Patent Document 4 and Patent Document 5).

JP-A-5-165214 JP 2004-264623 A JP 2009-98616 A JP-A-6-18702 JP-A-6-136239

  The photosensitive resin composition for forming the interlayer insulating film is required to have high sensitivity and good storage stability, and the cured film formed from the photosensitive composition has a high value. Reliability (transparency, solvent resistance, etc.) is required. Furthermore, the interlayer insulating film is required to have a good pattern shape from the viewpoint of contact hole formation and the like, and the pattern shape is preferably a forward taper.

However, as in the positive photosensitive resin compositions described in Patent Documents 2-3, those containing a photoacid generator such as a triazine, onium salt, or oxime sulfonate have poor photoacid generation efficiency. From the viewpoint of achieving high sensitivity, it is not always satisfactory.
In the case of forming a pattern such as an insulating film using a photosensitive resin composition, a heat treatment (post-baking step) is usually performed after exposure of the photosensitive resin composition. In the composition, as the sensitivity is increased, the pattern shape after the post-baking process approaches a rectangular shape, and thus there is a trade-off between improved sensitivity and good pattern shape formation. Therefore, at present, the formed pattern shape is good while having both high sensitivity and storage stability, and ensuring high reliability (transparency, solvent resistance) of the formed cured film. No photosensitive resin composition for forming an interlayer insulating film has been obtained.

The first problem to be solved by the present invention is to provide a photosensitive resin composition that is excellent in storage stability and sensitivity, and can form a cured film excellent in transparency, solvent resistance, and pattern shape. It is.
In addition, the second problem to be solved by the present invention is to form a cured film excellent in transparency, solvent resistance and pattern shape and formed from the positive photosensitive resin composition of the present invention. It is an object to provide an organic EL display device and a liquid crystal display device which are excellent in display characteristics and have high productivity, comprising the cured film as an interlayer insulating film.

The above problem is solved by the following means.
<1> (A) From a structural unit (1) having at least one selected from a carboxy group protected with an acid-decomposable group and a phenolic hydroxyl group protected with an acid-decomposable group, an epoxy group and an oxetanyl group A copolymer containing at least one selected structural unit (2), (B) the following general formula (I), general formula (OS-1), general formula (OS-3), general formula (OS-4) and at least one photoacid generator selected from photoacid generators represented by formula (OS-5), (C) a sensitizer, and (D) a solvent. Photosensitive resin composition.

^{R 1A -C (R 2A) =} N-O-SO 2 -R 3A (I)

In general formula (I), R ^1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or 2-thienyl. Group, an alkoxy group having 1 to 4 carbon atoms or a cyano group, and when R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, a carbon atom It may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and a nitro group. R ^2A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, an anthranyl group which may be substituted with W, a dialkylamino group, a morpholino group or a cyano group. R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be linked to a benzene ring. R ^3A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

In General 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 hetero Represents an aryl group. R ² represents an alkyl group or an aryl group. X is, -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or, ^-CR 6 ^{R 7} - ^represents, R 5 to R ⁷ are each Independently, it represents an alkyl group or an aryl group. R ^{21 to} R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or an aryl group is represented.

In General Formula (OS-3) to General Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^{2 s} independently represent a hydrogen atom or an alkyl group. , An aryl group, or a halogen atom, and 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, and X represents O Or represents S, n represents 1 or 2, m represents the integer of 0-6.

  <2> The above-described <1>, wherein the (C) sensitizer is a compound represented by the following general formula (III), general formula (IV), general formula (V), or general formula (VI). Photosensitive resin composition.

In general formula (III), R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are the same. R ³ and R ⁴ each independently represents a monovalent substituent. m and n each independently represents an integer of 0 to 4.

In general formula (IV), R ⁵ represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. R ⁶ and R ⁷ each independently represents a monovalent substituent. o and p each independently represent an integer of 0 to 4.

In the general formula (V), R ⁸ , R ⁹ and R ¹⁰ each independently represent a monovalent substituent, and q, r and s each independently represent an integer of 0 to 2. Two or more of R ⁸ , R ⁹ and R ¹⁰ may be connected to each other to form a 5-membered ring or a 6-membered ring.

In general formula (VI), R ¹¹ and R ¹² each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms, a heterocyclic group, or an aromatic group. R ¹³ and R ¹⁴ may be connected to each other to form a 5-membered ring or a 6-membered ring.

  <3> The photosensitive resin composition according to <1> or <2>, wherein the photoacid generator represented by the general formula (I) is a photoacid generator represented by the following general formula (II). object.

In general formula (II), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and l represents an integer of 0 to 5. Represent. R ^3A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the structural unit (2) of the (A) copolymer is a structural unit having an oxetanyl group.
<5> The photosensitive resin composition according to any one of <1> to <4>, further including a crosslinking agent.

  <6> A cured film formed by applying at least one of light and heat to the photosensitive resin composition according to any one of <1> to <5>.

<7> (1) A coating step of coating the photosensitive resin composition according to any one of <1> to <5> 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 coated photosensitive resin composition with actinic rays,
(4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.

<8> A cured film formed by the method according to <7>.
<9> The cured film according to <6> or <8>, which is an interlayer insulating film.
<10> An organic EL display device comprising the cured film according to <6>, <8>, or <9>.
<11> A liquid crystal display device comprising the cured film according to <6>, <8>, or <9>.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form the cured film excellent in storage stability and sensitivity, and excellent in transparency, solvent resistance, and pattern shape can be provided.
Further, according to the present invention, a cured film excellent in transparency, solvent resistance and pattern shape formed by the positive photosensitive resin composition of the present invention, a method of forming the cured film, and the cured film between the layers It is possible to provide an organic EL display device and a liquid crystal display device which are provided as an insulating film and have excellent display characteristics and high productivity.

It is a figure which shows the structure of an example of the organic electroluminescence display which applied the cured film using the photosensitive resin composition of this invention as an insulating film and a planarization film. It is a figure which shows the structure which shows an example of the liquid crystal display device to which the cured film using the photosensitive resin composition of this invention is applied.

(Photosensitive resin composition)
Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
In addition, in this invention, the solid content amount of the photosensitive resin composition represents the mass remove | excluding the mass of volatile components, such as a solvent, from the total mass of all the components contained in the photosensitive resin composition.

  The photosensitive resin composition of the present invention comprises (A) a structural unit (1) having at least one selected from a carboxyl group protected with an acid-decomposable group and a phenolic hydroxyl group protected with an acid-decomposable group; , A structural unit (2) having at least one selected from an epoxy group and an oxetanyl group, (B) the following general formula (I), the general formula (OS-1), the general formula ( OS-3), at least one photoacid generator selected from photoacid generators represented by general formula (OS-4) and general formula (OS-5) (hereinafter referred to as “photoacid generator”). (B) "is a generic name.), (C) a sensitizer, and (D) a photosensitive resin composition containing a solvent.

^{R 1A -C (R 2A) =} N-O-SO 2 -R 3A (I)
In the above general formula (I), in general formula (I), R ^1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, When a 2-furyl group, a 2-thienyl group, an alkoxy group having 1 to 4 carbon atoms or a cyano group is represented and R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are , A halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a substituent selected from the group consisting of nitro groups. R ^2A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, an anthranyl group which may be substituted with W, a dialkylamino group, a morpholino group or a cyano group. R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be linked to a benzene ring. R ^3A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

In General 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 hetero Represents an aryl group. R ² represents an alkyl group or an aryl group. X is, -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or, ^-CR 6 ^{R 7} - ^represents, R 5 to R ⁷ are each Independently, it represents an alkyl group or an aryl group. R ^{21 to} R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or an aryl group is represented.

In General Formula (OS-3) to General Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^{2 s} independently represent a hydrogen atom or an alkyl group. , An aryl group, or a halogen atom, and 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, and X represents O Or represents S, n represents 1 or 2, m represents the integer of 0-6.

The photosensitive resin composition of the present invention is a positive photosensitive resin composition.
The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

  The photosensitive resin composition of this invention becomes excellent in storage stability and a sensitivity by containing each component of said (A)-(D).

Moreover, the photosensitive resin composition of this invention can form the cured film excellent in transparency, solvent resistance, and pattern shape.
Here, “excellent in pattern shape” in the present invention means that the shape of the formed pattern is a forward taper.
Therefore, the photosensitive resin composition of the present invention is particularly useful for forming an interlayer insulating film. In this case, a forward tapered pattern suitable for forming a contact hole can be formed.

  Further, “transparency” in the present invention means that coloring is suppressed in a cured film obtained by performing heat treatment (baking treatment) after exposure using the photosensitive resin composition of the present invention. Means nature. Hereinafter, the transparency exhibited by the cured film formed from the photosensitive resin composition of the present invention may be referred to as “heat-resistant transparency”.

Furthermore, the photosensitive resin composition of the present invention is also useful for forming a microlens.
This is because the photosensitive resin composition for forming a microlens is excellent in sensitivity and storage stability, and the microlens (cured film) formed from the photosensitive resin composition has transparency and solvent resistance. In addition to excellent properties, the photosensitive resin composition of the present invention is excellent in sensitivity and storage stability, and is required to exhibit a good melt shape (desired radius of curvature). This is because the cured film has the advantages of being excellent in transparency and solvent resistance and exhibiting a good melt shape.

Hereinafter, each component contained in the photosensitive resin composition will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[(A) selected from a structural unit (1) having at least one selected from a carboxy group protected with an acid-decomposable group and a phenolic hydroxyl group protected with an acid-decomposable group, and an epoxy group and an oxetanyl group. Containing at least one structural unit (2)]
The photosensitive resin composition of the present invention comprises (A) a structural unit (1) having at least one selected from a carboxyl group protected with an acid-decomposable group and a phenolic hydroxyl group protected with an acid-decomposable group; And a copolymer (hereinafter referred to as “copolymer (A)” as appropriate) containing a structural unit (2) having at least one selected from an epoxy group and an oxetanyl group.

  The copolymer (A) is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group in the molecule is decomposed.

  Here, in the present invention, the “acid-decomposable group” means a functional group capable of generating a carboxy group or a phenolic hydroxyl group protected by the acid-decomposable group by decomposing in the presence of an acid. means.

  In the present invention, the copolymer (A) is “alkali-soluble” means that a solution containing the copolymer (A) after the acid-decomposable group has been decomposed is applied on a substrate, and 2% at 90 ° C. It means that the dissolution rate with respect to a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. indicated by a coating film (thickness 3 μm) formed by heating for minutes is 0.01 μm / second or more. The alkali solubility is more preferably 0.005 μm / second or more.

  Further, in the present invention, the copolymer (A) is “alkali insoluble” is formed by applying a solution containing the copolymer (A) on a substrate and heating at 90 ° C. for 2 minutes. It means that the dissolution rate with respect to a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. indicated by the coating film (thickness: 3 μm) is less than 0.01 μm / second. The alkali insolubility is more preferably less than 0.005 μm / second.

  As long as the copolymer (A) is kept insoluble in alkali as a whole, introduction of acidic groups is not excluded. As an example in case an acidic group is introduce | transduced into a copolymer (A), the case where it has the structural unit (3a) etc. which are mentioned later is mentioned, for example.

The copolymer (A) is preferably an acrylic polymer.
The “acrylic polymer” in the present invention is an addition polymerization type resin, and is a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. ) You may have structural units other than the structural unit derived from acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.

In the copolymer (A), the structural unit derived from (meth) acrylic acid and / or its ester is preferably 50 mol% or more, more preferably 80 mol% or more based on the total structural units in the polymer. It is more preferable that the polymer be composed of only structural units derived from (meth) acrylic acid and / or its ester.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. Moreover, (meth) acrylic acid shall mean methacrylic acid and / or acrylic acid.

  Hereinafter, the structural unit which comprises a copolymer (A) is demonstrated in detail.

<Structural unit (1)>
The copolymer (A) is a structural unit (1) having at least one selected from a carboxy group protected with an acid-decomposable group and a phenolic hydroxyl group protected with an acid-decomposable group (hereinafter referred to as “structure”). Abbreviated as “unit (1)”).

One of the preferred embodiments of the structural unit (1) is a structural unit having at least one selected from a partial structure represented by the following formula (Ia) and a partial structure represented by the following formula (Ib). .
The partial structure represented by the following formula (Ia) is a structure in which a carboxy group is protected by an acid-decomposable group, and is deprotected by an acid to generate a carboxy group. The partial structure represented by the following formula (Ib) is a partial structure in which a phenolic hydroxyl group is protected by an acid-decomposable group, and is deprotected by an acid to generate a phenolic hydroxyl group.

In the formula (Ia) and the formula (Ib), the wavy line portion represents a coupling point with another structure.
In formula (Ia) and formula (Ib), R ¹ each independently represents an alkyl group or a cycloalkyl group.
The alkyl group represented by R ¹ may be linear or branched.
The number of carbon atoms of the alkyl group represented by R ¹ is preferably 1-20, more preferably 1-10, and even more preferably 1-7.
The number of carbon atoms of the cycloalkyl group represented by R ¹ is preferably 3 to 20, more preferably 3 to 10, and still more preferably 5 to 7.
The number of carbon atoms includes the number of carbon atoms of the substituent when R ¹ further has a substituent.

Examples of the alkyl group represented by R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n -Pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like can be mentioned.
Examples of the cycloalkyl group represented by R ¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

Moreover, the alkyl group and cycloalkyl group represented by R ¹ may have a substituent. Examples of the substituent that can be introduced into the alkyl group or cycloalkyl group represented by R ¹ include an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), 3 to 3 carbon atoms. 10 cycloalkyl groups, aryl groups having 6 to 10 carbon atoms, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, hydroxy groups, alkoxy groups having 1 to 10 carbon atoms Etc., and these substituents may be further substituted with the above substituents.

R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms, and having 1 to 1 carbon atoms. More preferred is an alkyl group having 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a benzyl group, more preferably an ethyl group or a cyclohexyl group, and particularly preferably an ethyl group.

In formula (Ia) and formula (Ib), R ² represents an alkyl group.
The alkyl group represented by R ² may be linear or branched.
The number of carbon atoms of the alkyl group represented by R ² is preferably 1-20, more preferably 1-10, and even more preferably 1-7.
The number of carbon atoms includes the number of carbon atoms of the substituent when R ² further has a substituent.

As the alkyl group represented by R ² , an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.

In formula (Ib), Ar ¹ represents a divalent aromatic group and has —OCH (OR ¹ ) (R ² ) on the aromatic ring.

The divalent aromatic group represented by Ar ¹ is not particularly limited, and examples thereof include a phenylene group, a substituted phenylene group, a naphthylene group, and a substituted naphthylene group, and are a phenylene group or a substituted phenylene group. It is preferably a phenylene group, more preferably a 1,4-phenylene group.

In addition, the divalent aromatic group represented by Ar ¹ may further have a substituent on the aromatic ring, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (methyl group, Ethyl group, propyl group, butyl group, etc.), cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group , A nitro group, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and the like, and these substituents may be further substituted with the above substituents.

The structural unit having a partial structure represented by the formula (Ia) can be introduced into the copolymer (A) by using a carboxy group-containing monomer capable of forming the structural unit.
As the carboxy group-containing monomer capable of forming the structural unit having the partial structure represented by the formula (Ia), any monomer that can become the structural unit (1) by protecting the carboxy group of the monomer is used. Examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and α-methyl-p-carboxystyrene; and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. it can.
Moreover, as the structural unit (1), a structural unit derived from these carboxy group-containing monomers, and a structural unit in which the carboxy group of the monomer is protected can be mentioned as a preferable example.

The structural unit having a partial structure represented by the formula (Ib) can be introduced into the copolymer (A) using a phenolic hydroxyl group-containing monomer capable of forming the structural unit.
As the phenolic hydroxyl group-containing monomer capable of forming the structural unit having the partial structure represented by the formula (Ib), any monomer can be used as long as the structural unit (1) can be obtained by protecting the phenolic hydroxyl group of the monomer. Can be used. Examples of such phenolic hydroxyl group-containing monomers include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, and paragraphs [0011] to [0016] of JP-A-2008-40183. Compounds, 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid and acrylic An addition reaction product with glycidyl acid can be mentioned as a preferable one.
Among these, as the phenolic hydroxyl group-containing monomer, α-methyl-p-hydroxystyrene, a compound described in paragraphs 0011 to 0016 of JP2008-40183A, and described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 4-hydroxybenzoic acid derivatives, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, and addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

  Among the structural units having the partial structure represented by the formula (Ia) or the partial structure represented by the formula (Ib), those particularly preferable as the structural unit (1) are represented by the following formula (Ic). A structural unit.

In formula (Ic), R ⁵ represents an alkyl group or a cycloalkyl group. Preferred embodiments of R ⁵ are the same as the preferred embodiments of R ¹ in formula (Ia) and formula (Ib).
In formula (Ic), R ⁶ represents a hydrogen atom or a methyl group.

  Preferable specific examples of the radical polymerizable monomer used for forming the structural unit represented by the formula (Ic) include, 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-isobutoxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1- ( 2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- Examples include 2-cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate, and the like. Particularly preferred is 1-ethoxyethyl methacrylate. And 1-ethoxyethyl acrylate. These radically polymerizable monomers can be used singly or in combination of two or more.

  As the radically polymerizable monomer used for forming the structural unit (1) including the partial structure represented by the formula (Ia) and the partial structure represented by the formula (Ib), a commercially available one may be used. Those synthesized by a known method may be used. For example, a monomer represented by the following structural formula (A) can be synthesized by reacting (meth) acrylic acid with a vinyl ether compound in the presence of an acid catalyst as shown in the following reaction formula. .

In the above reaction formula, R ⁵ and R ⁶ have the same meanings as R ⁵ and R ⁶ in formula (Ic).

  Moreover, the structural unit (1) containing the partial structure represented by the formula (Ia) or the partial structure represented by the formula (Ib) is a structural unit (2) described below for the protected carboxy group or phenolic hydroxyl group-containing monomer. ) To (5) or a precursor thereof, and then polymerized with a vinyl ether compound to react with a carboxy group or a phenolic hydroxyl group. 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 radical polymerizable monomer.

  Another preferred embodiment of the structural unit (1) is a structural unit having at least one selected from a partial structure represented by the following formula (IIa) and a partial structure represented by the following formula (IIb).

In the formula (IIa) and the formula (IIb), R ³ represents a tertiary alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, R ⁴ represents a tertiary alkyl group, a tert-butoxycarbonyl group, It represents a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, Ar ² represents a divalent aromatic group, and a wavy line represents a bonding site with another structure.

The tertiary alkyl group for R ³ and R ⁴ preferably has 4 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and still more preferably 4 to 8 carbon atoms.
Tertiary alkyl group in R ³ , 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, Tertiary alkyl group in R ⁴ , tert-butoxycarbonyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, The divalent aromatic group in Ar ² may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a halogen atom. (Fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, alkoxy group having 1 to 10 carbon atoms and the like can be exemplified. These substituents may be further substituted with the above substituents.

The tertiary alkyl group for R ³ and R ⁴ is more preferably at least one selected from the group consisting of groups represented by the following formula (a).
^{-C (R 9) (R 10} ) (R 11) (a)
In formula (a), R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a carbon number. It represents 7 to 12 aralkyl groups, and any two of R ⁹ , R ¹⁰ and R ¹¹ may be bonded together to form a ring together with the carbon atoms to which they are bonded.

In the formula (a), the alkyl group having 1 to 12 carbon atoms represented by R ⁹ , R ¹⁰ or R ¹¹ may be linear or branched, for example, methyl group, ethyl group N-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group (2,3 -Dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.

Examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R ⁹ , R ¹⁰ or R ¹¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, An isobornyl group etc. can be mentioned.

As a C6-C12 aryl group represented by R < ⁹ >, R < ¹⁰ > or R < ¹¹ >, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group etc. can be mentioned, for example.

Examples of the aralkyl group having 7 to 12 carbon atoms represented by R ⁹ , R ¹⁰ or R ¹¹ include a benzyl group, an α-methylbenzyl group, a phenethyl group and a naphthylmethyl group.

R ⁹ , R ¹⁰ and R ¹¹ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and an adamantyl group. And a tetrahydropyranyl group.

R ³ in formula (IIa) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, and a tertiary alkyl group having 4 to 8 carbon atoms. It is more preferably an alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, further preferably a t-butyl group or a 2-tetrahydrofuranyl group, and particularly preferably a 2-tetrahydrofuranyl group.
R ⁴ in formula (IIb) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a tert-butoxycarbonyl group, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, and has 4 carbon atoms. More preferably a tertiary alkyl group of ˜8, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, more preferably a t-butyl group or a 2-tetrahydrofuranyl group, and a 2-tetrahydrofuranyl group. Is particularly preferred.

In formula (IIb), Ar ² represents a divalent aromatic group and has OCH (OR ¹ ) (R ² ) on the aromatic ring.
The preferred embodiment of Ar ² in formula (IIb) is the same as the preferred embodiment of Ar ¹ in formula (IIa).

  As the carboxylic acid monomer capable of forming the structural unit (1) having the structure represented by the formula (IIa) by protecting the carboxy group, the carboxy group possessed by the monomer is protected. Any structure that can form the structure represented by (IIa) can be used. Examples of the carboxylic acid monomer include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and α-methyl-p-carboxystyrene; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Can be mentioned. Moreover, as a structural unit (1), the monomer unit derived from carboxylic acid in which these carboxy groups are protected can be mentioned as a preferable one.

As the monomer having a phenolic hydroxyl group capable of forming the structural unit (1) having the structure represented by the formula (IIb) by protecting the phenolic hydroxyl group, the phenolic hydroxyl group of the monomer is protected. Can be used as long as the structure represented by the formula (IIa) can be formed. Examples thereof include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene; Compound described in paragraphs 0011 to 0016 of 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate Preferable addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate It can be cited as the correct ones.
Among these, α-methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, and 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 An addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

  Among the structural units having the partial structure represented by the formula (IIa) or the partial structure represented by the formula (IIb), those particularly preferable as the structural unit (1) are represented by the following formula (IIc). A structural unit.

In formula (IIc), R ⁷ represents a tertiary alkyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, and R ⁸ represents a hydrogen atom or a methyl group.
In Formula (IIc), a preferred embodiment of R ^{7 is the same as} the preferred embodiment of R ³ in Formula (IIa).

  Preferable specific examples of the radical polymerizable monomer used for forming the monomer unit represented by the formula (IIc) include, for example, tert-butyl methacrylate, tert-butyl acrylate, tetrahydro-2H-methacrylate. Pyran-2-yl, tetrahydro-2H-pyran-2-yl acrylate, tetrahydro-2H-furan-2-yl methacrylate, tetrahydro-2H-furan-2-yl acrylate, 2-methyl-2-methacrylate Examples thereof include adamantyl, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, 1-methylcyclohexyl acrylate, etc., particularly tert-butyl methacrylate, tert-butyl acrylate, tetrahydro-2H methacrylate -Furan-2-yl, acrylic acid Torahidoro -2H- furan-2-yl is preferable. These monomer units can be used singly or in combination of two or more.

  Preferable specific examples of the structural unit (1) include structural units represented by the following (a1-1) to (a1-4) and (a2-1) to (a2-6).

  Among these, the structural units shown in (a2-5) and (a2-6) are most preferable from the viewpoints of both sensitivity and transparency.

  In all the structural units constituting the copolymer (A), the content of the structural unit (1) is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, particularly preferably 20 to 60 mol%.

<Structural unit (2) having at least one selected from epoxy group and oxetanyl group>
The copolymer (A) contains a structural unit (2) having at least one selected from an epoxy group and an oxetanyl group (hereinafter abbreviated as “structural unit (2)” as appropriate).

  The structural unit (2) may have at least one epoxy group or oxetanyl group in one structural unit, one or more epoxy groups and one or more oxetanyl groups, two or more epoxy groups, or Although it may have two or more oxetanyl groups and is not particularly limited, it preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of 1 or 2 epoxy groups and / or oxetanyl groups It is more preferable to have one epoxy group or oxetanyl group.

The structural unit (2) is preferably a structural unit having at least one selected from an alicyclic epoxy group and an oxetanyl group, and is a structural unit having an oxetanyl group from the viewpoint of sensitivity and storage stability. Is more preferable.
Moreover, as a combination of the structural unit (1) and the structural unit (2) in the copolymer (A), the structural unit (1) is a structural unit having a carboxy group protected with an acid-decomposable group, and has a structure. A combination in which the unit (2) is a structural unit having an oxetanyl group is preferable.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring. Specifically, for example, 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3 -An epoxy cyclopentyl group etc. are mentioned preferably.
The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.

  Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraphs [0031] to [0035] of Japanese Patent No. 4168443 Compounds containing alicyclic epoxy skeletons And the like.

  Examples of the radical polymerizable monomer used to form a structural unit having an oxetanyl group include, for example, an oxetanyl group described in paragraphs [0011] to [0016] of JP-A No. 2001-330953 ( And (meth) acrylic acid esters.

  Examples of the radical polymerizable monomer used to form a structural unit having an epoxy group and / or an oxetanyl group may be a monomer containing a methacrylate structure or a monomer containing an acrylate structure. preferable.

  Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs 0011 to 0016 of JP 2001-330953 A. (Meth) acrylic acid esters having an oxetanyl group, particularly preferred are (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid (3-ethyloxetane). -3-yl) methyl, most preferred are acrylic acid (3-ethyloxetane-3-yl) methyl and methacrylic acid (3-ethyloxetane-3-yl) methyl. These structural units can be used singly or in combination of two or more.

  Preferable specific examples of the structural unit (a3) include structural units represented by the following (a3-1) to (a3-6).

  In all the structural units constituting the copolymer (A), the content of the structural unit (2) is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, particularly preferably 20 to 65 mol%. By having the structural unit (2) at the above ratio, the physical properties of the cured film obtained from the photosensitive resin composition of the present invention are improved.

  The content ratio of the structural unit (1) to the structural unit (2) in the copolymer (A) is a molar ratio, and is structural unit (1): structural unit (2) = 100: (10 to 200). Is more preferable, 100: (10 to 150) is more preferable, and 100: (50 to 150) is still more preferable.

<Other structural units (3)>
The copolymer (A) may have other structural units (3) as long as the effects of the present invention are not hindered. Examples of the structural units (3) include a carboxy group and a carboxylic acid anhydride residue. The structural unit (3b) other than the structural unit (3a) having a group and / or a phenolic hydroxyl group and the structural units (1) to (2) and (3a) may be mentioned.

<Structural unit (3a) having carboxy group, carboxylic acid anhydride residue and / or phenolic hydroxyl group>
The copolymer (A) is a structural unit (3a) having a carboxy group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group (hereinafter referred to as “appropriately” as long as the copolymer (A) is not alkali-soluble. It is preferable to contain a structural unit having a carboxy group and / or a phenolic hydroxyl group.

Examples of the radical polymerizable monomer used to form the structural unit having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Preferred examples include dicarboxylic acids such as itaconic acid.
Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. can be mentioned as a preferable thing, for example. Examples of the radical polymerizable monomer used to form a structural unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, and JP2008-40183A. The compounds described in paragraphs 0011 to 0016 of the publication, the 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, and the addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate An addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate can be mentioned as a preferable example.

  Among these, as a radically polymerizable monomer for introducing the structural unit (3a) into the copolymer (A), methacrylic acid, acrylic acid, described in paragraphs 0011 to 0016 of JP-A-2008-40183 Compounds, 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid and acrylic An addition reaction product with glycidyl acid is more preferable, and compounds described in paragraphs [0011] to [0016] of JP-A-2008-40183 and 4 described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454 are disclosed. -Hydroxybenzoic acid derivatives, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4- Addition reaction product of an Dorokishi benzoic acid and glycidyl acrylate are especially preferred. These structural units can be used singly or in combination of two or more.

  Preferable specific examples of the structural unit (3a) include structural units represented by the following (a4-1) to (a4-11).

  When the copolymer (A) has the structural unit (3a), the content of the structural unit (3a) in all the structural units constituting the copolymer (A) is preferably 1 to 25 mol%, 25 mol% is still more preferable, and 3-20 mol% is especially preferable. By having the structural unit (3a) at the above ratio, high sensitivity can be obtained, and developability is also improved.

<Structural unit (3b) other than (1) to (2), (3a)>
The copolymer (A) is a structural unit (3b) other than the above (1) to (2) and (3a) (hereinafter, appropriately abbreviated as “structural unit (3b)” as long as the effects of the present invention are not hindered. May be included.
Examples of the radical polymerizable monomer used for forming the structural unit (3b) include compounds described in paragraphs [0021] to [0024] of JP-A No. 2004-264623 (provided that And the monomers forming the structural units (1) to (2) and (3a) are excluded.
Among these, as the radical polymerizable monomer for obtaining the structural unit (3b), dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid from the viewpoint of improving electrical characteristics. (Meth) acrylic acid esters containing alicyclic structures such as cyclohexyl and styrenes are preferred. From the viewpoint of transparency, methyl (meth) acrylate is preferred. From the viewpoint of sensitivity, 2-hydroxyethyl (meth) acrylate is preferred. Among these, 2-hydroxyethyl (meth) acrylate is more preferable.

  As the structural unit (3b), one type may be used alone, or two or more types may be combined.

  When the copolymer (A) has the structural unit (3a), the total content of the structural unit (3a in the structural unit (3a) constituting the copolymer (A) is preferably 1 to 50 mol%, and 5 to 40 More preferred is mol%, and particularly preferred is 5 to 30 mol%.

  The weight average molecular weight of the copolymer (A) is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. In addition, the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

  The method for introducing each structural unit of the copolymer (A) into the copolymer (A) may be a polymerization method, a polymer reaction method, or a combination of these two methods. .

In the case of using a polymerization method, monomers containing predetermined functional groups are synthesized in advance, and then these monomers are copolymerized. That is, the copolymer (A) comprises a radically polymerizable monomer used to form the structural unit (1), the structural unit (2), and, if necessary, the structural units (3a) and (3b). It can synthesize | combine by superposing | polymerizing the radically polymerizable monomer mixture containing in an organic solvent using a radical polymerization initiator.
For example, an ethylenically unsaturated compound having a partial structure represented by the formula (1a) or the formula (1b) and an ethylenically unsaturated compound having an epoxy group or an oxetanyl group are mixed and subjected to addition polymerization. The copolymer (A) to be obtained can be obtained.

In the case of using a polymer reaction method, after performing a polymerization reaction using a predetermined type of monomer, a necessary functional group is obtained using a reactive group contained in the structural unit of the obtained copolymer. Is introduced into the structural unit. Here, as a functional group to be introduced, a phenolic hydroxyl group or a carboxy group is protected, and at the same time, a protecting group for decomposing and releasing them in the presence of a strong acid, a crosslinkable group such as an epoxy group or an oxetanyl group, a phenolic group Examples include alkali-soluble groups (acidic groups) such as hydroxyl groups and carboxy groups.
For example, an epoxy group can be introduced by reacting epichlorohydrin with a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate. Thus, after copolymerizing the ethylenically unsaturated compound having a reactive group, the reactive group remaining in the side chain is utilized to express the polymer by the polymer reaction by the formula (Ia) and / or the formula (Ib). A functional group such as a partial structure or a crosslinkable group can be introduced into the side chain of the copolymer (A).

Hereinafter, preferable examples of the copolymer (A) used in the present invention are illustrated, but the present invention is not limited thereto.
In addition, the copolymer (A) illustrated below has a weight average molecular weight of 2,000 to 50,000. The composition ratio is shown in mol% in ().

1-ethoxyethyl methacrylate / glycidyl methacrylate copolymer (50/50)
1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid copolymer (50/40/10)
1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40/30/10/20)
1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / glycidyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (20/20/30/10/20)
1-ethoxyethyl methacrylate / tetrahydro-2H-furan-2-yl methacrylate / glycidyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (20/20/30/10/20)
Tetrahydro-2H-furan-2-yl methacrylate / glycidyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40/30/10/20)
1-ethoxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / methacrylic acid copolymer (45/40/15)
1-ethoxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40/30/10/20)
1-ethoxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 2-hydroxyethyl methacrylate copolymer (40/30/10 / 20)
1-ethoxyethyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl copolymer (50/50)
1-ethoxyethyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid copolymer (50/40/10)

1-ethoxyethyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40/30/10/20)
Tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40/30/10/20)
Tetrahydro-2H-furan-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40/30/10/20)
Tetrahydro-2H-furan-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / 2-hydroxyethyl methacrylate / styrene copolymer (40/30/10/10/10 )
1-ethoxyethyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate copolymer (40/30/10 / 20)
1-ethoxyethyl methacrylate / 1-methyl-1-cyclohexyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / 2-hydroxyethyl methacrylate copolymer copolymer (20/20 / 30/10/20)
1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2 -Hydroxyethyl copolymer (20/20/30/10/20)
1- (cyclohexyloxy) ethyl methacrylate / glycidyl methacrylate / methacrylic acid copolymer (50/35/15)
1- (cyclohexyloxy) ethyl methacrylate / glycidyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (35/30/10/25)
1- (Cyclohexyloxy) ethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / methacrylic acid copolymer (50/40/10)
1- (Cyclohexyloxy) ethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40/30/10/20)

1- (Cyclohexyloxy) ethyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid copolymer (50/40/10)
1- (Cyclohexyloxy) ethyl methacrylate / (3-ethyloxetane-3-yl) methyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (40/30/10/20)
1- (Cyclohexyloxy) ethyl methacrylate / (3-ethyloxetane-3-yl) methyl methacrylate / α-methyl-parahydroxystyrene / 2-hydroxyethyl methacrylate copolymer (30/30/20/20)
1- (cyclohexyloxy) ethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate copolymer (40/30/15/15)
4-Hydroxybenzoic acid (3-methacryloyloxypropyl) ester 1-ethoxyethyl ether / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer (40/30 / 10/20)

  The photosensitive resin composition of this invention can contain a copolymer (A) individually by 1 type or in combination of 2 or more types.

  It is preferable that content of the copolymer (A) in the photosensitive resin composition of this invention is 20-99 mass% with respect to the total solid of the photosensitive resin composition, 40-97 mass% It is more preferable that it is 60-95 mass%. When the content of the copolymer (A) is within this range, the pattern formability upon development is good.

  In addition, the photosensitive resin composition of this invention may use resin other than a copolymer (A) together in the range which does not inhibit the effect of this invention. However, the content of the resin other than the copolymer (A) is preferably smaller than the content of the copolymer (A) from the viewpoint of developability.

[(B) Photoacid generator]
The photosensitive resin composition of the present invention has the following general formula (I), general formula (OS-1), general formula (OS-3), general formula (OS-4), and general formula (OS). At least one photoacid generator (photoacid generator (B)) selected from photoacid generators represented by OS-5).
Among the photoacid generators included in the photoacid generator (B), in general formula (I), general formula (OS-3), general formula (OS-4), or general formula (OS-5) The photoacid generator represented is more preferred.
Hereinafter, each photoacid generator included in the photoacid generator (B) will be described in detail.

One embodiment of the photoacid generator included in the photoacid generator (B) is a photoacid generator represented by the following general formula (I).
^{R 1A -C (R 2A) =} N-O-SO 2 -R 3A (I)

In general formula (I), R ^1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or 2-thienyl. Group, an alkoxy group having 1 to 4 carbon atoms or a cyano group, and when R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, a carbon atom It may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and a nitro group. R ^2A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, an anthranyl group which may be substituted with W, a dialkylamino group, a morpholino group or a cyano group. R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be linked to a benzene ring. R ^3A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

The alkyl group having 1 to 6 carbon atoms represented by R ^1A may be a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- A butyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, or a 2-ethylbutyl group is exemplified.

Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ^1A include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^1A include a methoxy group or an ethoxy group.

When R ^1A represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, a carbon atom number of 1 to 4 alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group), alkoxy groups having 1 to 4 carbon atoms (for example, methoxy group, An ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group) and a nitro group may be substituted.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^2A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^2A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, and n-octyl. An oxy group, n-decyloxy group, etc. are mentioned.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^2A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^2A include trifluoromethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoro-n-butoxy group, perfluoro group. Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted by W represented by R ^2A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-
Methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (N-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (I-amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromo Phenyl group, 2,4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl Nyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group and the like can be mentioned.

Specific examples of the naphthyl group optionally substituted by W represented by R ^2A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted by W represented by R ^2A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.
^Examples of the dialkylamino group represented by R ^2A include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^3A include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an n-amyloxy group, and an n-octyl group. An oxy group, n-decyloxy group, etc. are mentioned.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^3A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, a perfluoro group, Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted with W represented by R ^3A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-
Methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (N-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (I-amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromo Phenyl group, 2,4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl Nyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group and the like can be mentioned.

Specific examples of the naphthyl group optionally substituted by W represented by R ^3A include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, a 4-methyl-1-naphthyl group, and 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted by W represented by R ^3A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

Specific examples of 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, and a halogenated alkoxy having 1 to 5 carbon atoms represented by W Examples include an alkyl group having 1 to 10 carbon atoms represented by R ^2A or R ^3A , an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and 1 carbon atom. The thing similar to what was mentioned as a specific example of the halogenated alkoxy group of -5 is mentioned.

R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring.
When R ^2A and R ^1A are bonded to each other to form a 5-membered ring or a 6-membered ring, examples of the 5-membered ring or 6-membered ring include carbocyclic groups and heterocyclic ring groups. It may be a cyclopentane, cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered ring or 6-membered ring may be bonded to a benzene ring which may have one or two optional substituents, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman , Fluorene, xanthene or thioxanthene ring systems. The 5-membered or 6-membered ring may contain a carbonyl group, examples of which include cyclohexadienone, naphthalenone and anthrone ring systems.

One preferred embodiment of the photoacid generator (B) is an oxime sulfonate compound represented by the following general formula (I-1). The oxime sulfonate compound is a compound in which R ^2A and R ^1A in formula (I-1) are bonded to form a 5-membered ring.

In General Formula (I-1), R ^3A has the same meaning as R ^3A in General Formula (I), X represents an alkyl group, an alkoxy group, or a halogen atom, and t represents an integer of 0 to 3. And when t is 2 or 3, the plurality of X may be the same or different.

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.
t is preferably 0 or 1.

In general formula (I-1), t is 1, X is a methyl group, the substitution position of X is an ortho position, R ^3A is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the general formula (I-1) include the following compound (i), compound (ii), compound (iii), compound (iv) and the like. One kind may be used alone, or two or more kinds may be used in combination. Compounds (i) to (iv) can be obtained as commercial products.
Moreover, the oxime sulfonate compound represented by general formula (I-1) can also be used in combination with other types of photoacid generators (B).

As one of the preferable embodiments of the photoacid generator represented by the general formula (I),
R ^1A represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group, or an anthranyl group;
R ^2A represents a cyano group;
R ^3A is 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, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, 1 to 1 carbon atoms It represents a 10 alkyl group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

  The photoacid generator represented by the general formula (I) is preferably a photoacid generator represented by the general formula (II).

In general formula (II), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and l represents an integer of 0 to 5. Represent. R ^3A is 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, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, 1 to 1 carbon atoms It represents a 10 alkyl group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ^3A in the general formula (II) is methyl group, 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 A methyl group, an ethyl group, an n-propyl group, an n-butyl group or a p-tolyl group is particularly preferable.
The halogen atom represented by R ^4A is preferably fluorine, chlorine or bromine.
The alkyl group having 1 to 4 carbon atoms represented by R ^4A is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by R ^4A is preferably a methoxy group or an ethoxy group.
As l, 0-2 are preferable and 0-1 are particularly preferable.

Among the photoacid generators represented by the general formula (I), preferred embodiments of the compounds included in the photoacid generator represented by the general formula (II) include R ^1A in the general formula (I). Represents a phenyl group or a 4-methoxyphenyl group, R ^2A represents a cyano group, and R ^3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 4-tolyl group.

  Hereinafter, among the photoacid generators represented by the general formula (I), particularly preferred examples of the compounds included in the photoacid generator represented by the general formula (II) are shown, but the present invention is limited to these. Is not to be done.

α- (methylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = methyl group)
α- (Ethylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = ethyl group)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R2 = -CN group, R ^3A = n-propyl group)
α- (n-butylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = n-butyl group)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = -CN group, R ^3A = 4-tolyl group)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = methyl group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = ethyl group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-propyl group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = -CN group, R ^3A = n-butyl group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R2 = -CN group, R ^3A = 4-tolyl group)

  Another embodiment of the photoacid generator included in the photoacid generator (B) is represented by the following general formula (OS-3), general formula (OS-4), or general formula (OS-5). It is a photoacid generator.

In General Formula (OS-3) to General Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ² are each independently a hydrogen atom, an alkyl group, R ⁶ represents an aryl group or a halogen atom, and each R ⁶ independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and X represents O or S. N represents 1 or 2, and m represents an integer of 0 to 6.

In general formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group represented by R ¹ may have a substituent.
In general formulas (OS-3) to (OS-5), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that 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 and the like.

Examples of the alkyl group represented by R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group and the like.

In general formulas (OS-3) to (OS-5), the aryl group represented by R ¹ is preferably an aryl group having 6 to 30 carbon atoms in total which may have a substituent.
Examples of the substituent that the aryl group represented by R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples thereof include an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

Examples of the aryl group represented by R ¹ include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group. .

In the general formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the heteroaryl group represented by R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. , An aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

In the general formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ may be one containing at least one heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be It may be condensed.
As the heteroaryl group represented by R ¹ , an optionally substituted thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring, and benzimidazole ring And a group obtained by removing one hydrogen atom from a ring selected from the group consisting of.

In general 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 general formulas (OS-3) to (OS-5), it is preferable that one or two of R ² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
In general formulas (OS-3) to (OS-5), the alkyl group or aryl group represented by R ² may have a substituent.
Examples of the substituent that the alkyl group or aryl group represented by R ² may have include the same groups as the substituent that the alkyl group or aryl group represented by R ¹ may have. it can.

The alkyl group represented by R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl having 1 to 6 carbon atoms which may have a substituent. More preferably, it is a group.
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, A chloromethyl group, a bromomethyl group, a methoxymethyl group, a benzyl group, and the like, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, Alternatively, an n-hexyl group is more preferable, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an n-hexyl group is further preferable, and a methyl group is particularly preferable.

The aryl group represented by R ² is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Examples of the aryl group represented by R ² include a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group.
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 or a bromine atom is preferable.

In general formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.
In general formulas (OS-3) to (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
In the general 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 2 is preferable.

In general formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.
In general formulas (OS-3) to (OS-5), the alkyl group represented by R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that 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 and the like.

Examples of the alkyl group represented by R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group and the like.

In general formulas (OS-3) to (OS-5), the alkyloxy group represented by R ⁶ is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. .
Examples of the substituent that 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 amino group. A carbonyl group etc. are mentioned.

Examples of the alkyloxy group represented by R ⁶ include methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, ethoxyethyloxy group, methylthioethyloxy group, phenylthioethyloxy group Group, ethoxycarbonylethyloxy group, phenoxycarbonylethyloxy group, dimethylaminocarbonylethyloxy group and the like.
Among these, a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
In the general formulas (OS-3) to (OS-5), examples of the aminosulfonyl group represented by R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an amino group. A sulfonyl group etc. are mentioned.
In the general formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

  In general formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.

  The photoacid generator represented by the general formula (OS-3) is a photoacid generator represented by the following general formula (OS-6), (OS-10), or (OS-11). It is particularly preferable that the photoacid generator represented by the general formula (OS-4) is particularly preferably a photoacid generator represented by the following general formula (OS-7). The photoacid generator represented by OS-5) is particularly preferably a photoacid generator represented by the following general formula (OS-8) or (OS-9).

In the general formulas (OS-6) to (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 represents a hydrogen atom, Represents 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 chlorophenyl group, and R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group. R ¹⁰ represents a hydrogen atom or a methyl group.

R ¹ in the general formulas (OS-6) to (OS-11) has the same meaning as R ¹ in the general formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
R ⁷ in the general formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ⁸ in the general 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 chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable, and a methyl group is particularly preferable.
R ⁹ in 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 the general formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.

  Among the compounds represented by the general formulas (OS-6) to (OS-11), (OS-6) is more preferable from the viewpoints of liquid storage stability, sensitivity, and transparency.

  Specific examples of the photoacid generator represented by the general formula (OS-3) to the general formula (OS-5) include the following exemplary compounds, but the present invention is not limited to these. .

  Another embodiment of the photoacid generator included in the photoacid generator (B) is a photoacid generator represented by the following general formula (OS-1).

In General 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 hetero Represents an aryl group. R ² represents an alkyl group or an aryl group.

In the general formula (OS-1), X is, -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or ^-CR 6 ^{R 7} - represents, R ^{5 to} R ⁷ each independently represents an alkyl group or an aryl group.
In the general formula (OS-1), 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 is represented. Two of R ^{21 to} R ²⁴ may be bonded to each other to form a ring.
R ^{21 to} R ²⁴ are each independently preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R ^{21 to} R ²⁴ are bonded to each other to form an aryl group is also possible. Preferably mentioned. Among these, an embodiment in which R ^{21 to} R ²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The photoacid generator represented by the general formula (OS-1) is more preferably a photoacid generator represented by the following general formula (OS-2).

In general formula (OS-2), R < ¹ >, R < ² >, R < ²¹ > -R < ²⁴ > is respectively independently synonymous with R < ¹ >, R < ² >, R < ²¹ > -R < ²⁴ > in said general formula (OS-1). The preferred examples are also the same.
Among these, the aspect in which R ¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and the R ¹ is represented by the general formula (OS-2). The embodiment in which is a cyano group, a phenyl group or a naphthyl group is most preferred.

  In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

  Specific examples (exemplary compounds b-1 to b-34) of the photoacid generator represented by the general formula (OS-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. . In specific examples, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

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

A photo-acid generator (B) can be used individually by 1 type or in combination of 2 or more types.
In the photosensitive resin composition of the present invention, the photoacid generator (B) is preferably contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A). More preferably, 10 parts by mass is contained.

  The photosensitive resin composition of the present invention may contain a photoacid generator other than the photoacid generator (B), if necessary, as a photoacid generator sensitive to actinic rays. -It is preferable not to contain a quinonediazide compound. The reason is that the 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less and its sensitivity is low. On the other hand, the photoacid generator (B) was generated by the action of one photon because the acid generated in response to actinic light acts as a catalyst for the deprotection of the protected acidic group. The acid contributes to a number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as a power of 10, and it is assumed that high sensitivity is obtained as a result of so-called chemical amplification. .

[(C) Sensitizer]
The photosensitive resin composition of this invention contains a sensitizer in order to promote the decomposition | disassembly in combination with a photo-acid generator (B).

  The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.

  Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10
-Dibutoxyanthracene, 9,10-dibutoxy, 3,7-dimethoxyanthracene,
9,10-dipropyloxyanthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, Thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin) , Acriflavine), acridones (for example, acridone, 10-butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squalium ( For example, squalium), styryls, base styryls (eg 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (eg 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolizine-11-non).

  Among these sensitizers, a sensitizer that absorbs actinic rays or radiation to be in an electronically excited state and has an electron transfer action to a photoacid generator is preferable, and in particular, polycyclic aromatics, acridones, and styryls. Base styryls and coumarins are preferred.

  Among the sensitizers described above, more preferable sensitizers are included in the compounds represented by the following general formula (III), general formula (IV), general formula (V), or general formula (VI). Sensitizers.

In general formula (III), R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are the same. R ³ and R ⁴ each independently represents a monovalent substituent. m and n each independently represents an integer of 0 to 4.

As a C1-C4 alkyl group represented by R < ¹ > or R < ² >, a methyl group, an ethyl group, n-propyl group, or n-butyl group is preferable.
Examples of the monovalent substituent represented by R ³ or R ⁴ include a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group. Group, ethyl group, n-propyl group, methoxy group, ethoxy group, or n-propyloxy group is preferred.
As m, 0-2 are preferable and 0-1 are more preferable.
As n, 0-2 are preferable and 0-1 are more preferable.

In general formula (IV), R ⁵ represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. R ⁶ and R ⁷ each independently represents a monovalent substituent. o and p each independently represent an integer of 0 to 4.

The alkyl group having 1 to 6 carbon atoms represented by R ⁵ is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. The phenyl group which may be substituted is preferably unsubstituted.
Examples of the monovalent substituent represented by R ⁶ or R ⁷ include a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group. An atom, chlorine atom, bromine atom, methyl group, ethyl group, n-propyl group, methoxy group, ethoxy group, or n-propyloxy group is preferred.
As o, 0-2 are preferable and 0-1 are more preferable.
As p, 0-2 are preferable and 0-1 are more preferable.

In the general formula (V), R ⁸ , R ⁹ and R ¹⁰ each independently represent a monovalent substituent, and q, r and s each independently represent an integer of 0 to 2. Two or more of R ⁸ , R ⁹ and R ¹⁰ may be connected to each other to form a 5-membered ring or a 6-membered ring.

Examples of the monovalent substituent represented by R ⁸ , R ⁹ , or R ¹⁰ include a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, carbon An acyl group having 1 to 4 atoms, a carboxylic acid ester group having 1 to 4 carbon atoms, an alkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms, a 2-benzimidazolyl group, 2- Examples include benzothiazolyl group or 2-benzoxazolyl group, cyano group, hydroxyl group, methyl group, ethyl group, n-propyl group, methoxy group, acetyl group, methylamino group, ethylamino group, dimethylamino group, diethylamino group Group, 2-benzimidazolyl group, or 2-benzothiazolyl group is preferable.
The 5-membered or 6-membered ring formed by R ⁸ , R ⁹ , and R ¹⁰ is a benzene ring, 2, 3, 6, 7-tetrahydroquinolidine ring that may have any substituent. , Cyclopentane ring, and cyclohexane ring.
As q, 0-3 are preferable and 0-2 are more preferable.
As r, 0-2 are preferable and 0-1 are more preferable.
As s, 0-3 are preferable and 0-2 are more preferable.

In general formula (VI), R ¹¹ and R ¹² each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group. R ¹³ and R ¹⁴ each independently represents a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms, a heterocyclic group, an aromatic group, or an araliphatic group. R ¹³ and R ¹⁴ may be connected to each other to form a 5-membered ring or a 6-membered ring.

The R ¹¹ or an alkyl group having 1 to 4 carbon atoms represented by ^{R 12,} a methyl group, an ethyl group, n- propyl group are preferred.
Further, examples of the substituent capable of being introduced into the alkyl group or a phenyl group represented by R ¹¹ or R ^12, a halogen atom, a cyano group, or a hydroxyl group.

Examples of the aliphatic group having 1 to 20 carbon atoms represented by R ¹³ or R ¹⁴ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s- Butyl group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, methoxy group Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyloxy group, n-decyloxy group and the like are preferable.

The heterocyclic group represented by R ¹³ or R ¹⁴ is preferably a 2-quinoline group, 2-imidazolyl group, 2-thiazolyl group, or 2-oxazolyl group which may have an arbitrary substituent.
The aromatic group represented by R ¹³ or R ¹⁴ is preferably a phenyl group, a naphthyl group, or an anthranyl group that may have an arbitrary substituent.

As the araliphatic group represented by R ¹³ or R ¹⁴ , a styryl group, 2-vinylfuranyl group, 2-vinyltetrahydrofuranyl group, 2-vinylpyranyl group, 2-vinyltetrahydro group which may have an arbitrary substituent. A pyranyl group is preferred.

As the 5-membered ring or 6-membered ring formed by connecting R ¹³ and R ¹⁴ to each other, an optionally substituted 2-quinoline group, 2-imidazolyl group, 2-thiazolyl group, 2-oxazolyl Groups are preferred.

Among the sensitizers included in the compounds represented by the general formula (III), the general formula (IV), the general formula (V), or the general formula (VI), 9,10 is used from the viewpoint of sensitivity and transparency. -Dibutoxyanthracene, 9,10-dipropyloxyanthracene, 10-butyl-2-chloroacridone, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,
8-ij] quinolizine-11-non is preferred, 9,10-dibutoxyanthracene, 9,
10-dipropyloxyanthracene and 10-butyl-2-chloroacridone are more preferred.

A commercially available sensitizer may be used, or it may be synthesized by a known synthesis method.
Moreover, a sensitizer can be used individually by 1 type or in combination of 2 or more types.

  The sensitizer is preferably 20 to 300 parts by mass, particularly preferably 30 to 200 parts by mass with respect to 100 parts by mass of the photoacid generator (B) from the viewpoint of achieving both sensitivity and transparency.

[(D) solvent]
The photosensitive resin composition of the present invention contains a solvent.
The photosensitive resin composition of the present invention is prepared as a solution in which optional components such as copolymer (A) and photoacid generator (B), which are essential components, and various additives described below, are dissolved in a solvent. It is preferable.

  As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as 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 Examples include acetates, esters, ketones, amides, lactones and the like.

As the solvent used in the photosensitive resin composition of the present invention, for example,
(1) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;
(3) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
(4) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(5) Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, 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, propylene glycol monobutyl ether acetate;
(7) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 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, diethylene glycol monobutyl ether acetate;
(9) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
(10) Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, 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, 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, isoamyl lactate;
(13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, propionate Aliphatic carboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropion methyl, 3-ethoxypropion ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, aceto Other esters such as methyl acetate, ethyl acetoacetate, methyl pyruvate, 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, cyclohexanone;
(16) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(17) Examples include lactones such as γ-butyrolactone.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. Solvents such as benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added.
Of the above-mentioned solvents, diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate are particularly preferable.

A solvent can be used individually by 1 type or in mixture of 2 or more types.
The solvent that can be used in the present invention is a single type or a combination of two types, preferably a combination of two types, and a combination of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. More preferably.

  The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by mass and 100 to 2,000 parts by mass per 100 parts by mass of the copolymer (A). More preferably, it is 150-1500 mass parts.

[Other ingredients]
In addition to the components (A) to (D), the photosensitive resin composition of the present invention includes, as necessary, optional components described below, (E) an antioxidant, and (F) a crosslinking agent. , (G) adhesion improver, (H) basic compound, (I) surfactant, (J) plasticizer, (K) thermal radical generator, (L) thermal acid generator, (M) acid Known additives such as a proliferation agent and (N) development accelerator can be added.

<(E) Antioxidant>
The photosensitive resin composition of the present invention preferably contains an antioxidant.
As an antioxidant, a well-known antioxidant can be contained.
By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.

  Examples of commercially available phenolic antioxidants include ADK STAB AO-60 (trade name, manufactured by ADEKA), ADK STAB AO-80 (trade name, manufactured by ADEKA), and Irganox 1098 (Ciba Japan ( Co., Ltd.).

The content of the antioxidant is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

[(F) Crosslinking agent]
It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed from a viewpoint of a sensitivity and storage stability.
As a crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond are added. be able to.
By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made stronger.

(Compound having 2 or more epoxy groups or oxetanyl groups in the molecule)
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.

  These crosslinking agents are available as commercial products. Examples of commercially available cross-linking agents are all trade names. For example, as bisphenol A type epoxy resins, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (or more, Japan Epoxy Resin Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation) and the like are bisphenol F type epoxy resins, such as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (above, DIC Corporation), L E-21, RE-602S (above, Nippon Kayaku Co., Ltd.), etc. are phenol novolac type epoxy resins such as JER152, JER154, JER157S70, JER157S65 (above, Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation) and the like are cresol novolac type epoxy resins such as EPICLON N-660, EPICLON N-665, EPICLON N -670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above made by DIC Corporation), EOCN-1020 (above made by Nippon Kayaku Co., Ltd.), etc. Tribe As the xy-resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, 4700 (manufactured by Daicel Chemical Industries, Ltd.) and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation) and the like can be mentioned. These can be used alone or in combination of two or more.

  Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin. In particular, bisphenol A type epoxy resin and phenol novolac type epoxy resin are preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (all manufactured by Toagosei Co., Ltd., all trade names) are used. be able to.
Moreover, the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an epoxy group.

  The addition amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to the photosensitive resin composition is preferably 1 to 50 parts by mass when the total amount of the copolymer (A) is 100 parts by mass. 3 to 30 parts by mass is more preferable.

(Alkoxymethyl group-containing crosslinking agent)
As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of outgas generated, A methoxymethyl group is preferred.
Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.

  These alkoxymethyl group-containing crosslinking agents are available as commercial products, all of which are trade names, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak MX-750, -032, -706, -708, -40, -31, -270,- 280, -290, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

  When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the alkoxymethyl group-containing crosslinking agent is 0.05 to 50 parts by mass with respect to 100 parts by mass of the copolymer (A). It is preferable that it is 0.5-10 mass parts. By adding the alkoxymethyl group-containing crosslinking agent in this range, preferable alkali solubility during development and excellent solvent resistance of the cured film can be obtained.

(Compound having at least one ethylenically unsaturated double bond)
As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. be able to.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.

  Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.

  Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.
The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by mass or less with respect to 100 parts by mass of the component (A), 30 It is more preferable that the amount is not more than part by mass. By containing at least one compound having an ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the cured film obtained from the photosensitive resin composition of the present invention can be improved. it can. When adding a compound having at least one ethylenically unsaturated double bond, it is preferable to add a thermal radical generator (K) described later.

<(G) Adhesion improver>
The photosensitive resin composition of the present invention may contain an adhesion improving agent.
The adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds.
The silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.

Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

  These adhesion improving agents can be used singly or in combination of two or more. The addition of the adhesion improver is effective for improving the adhesion between the substrate and the cured film when the cured film is formed on the substrate with the photosensitive resin composition of the present invention, and the cured film is formed in a pattern. In this case, it is also effective for adjusting the taper angle between the substrate and the patterned cured film.

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

<(H) Basic compound>
The photosensitive resin composition of the present invention may contain a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

  Examples of the heterocyclic amine include 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, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.

  Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

  Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.

  It is preferable that content of the basic compound in the photosensitive resin composition of this invention is 0.001-1 mass part with respect to 100 mass parts of copolymers (A), 0.005-0.2. More preferably, it is part by mass.

<(I) Surfactant>
The photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

  As the surfactant, a copolymer (1) containing the repeating unit A and the repeating unit B shown below can be given as a preferred example. The weight average molecular weight (Mw) of the copolymer is 1000 or more and 10,000 or less, and preferably 1500 or more and 5000 or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.

In the copolymer (1), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a linear alkylene group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

  L in the repeating unit B is preferably an alkylene group represented by the following formula (2).

In the formula (2), R ²⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3.

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

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

  The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 0.01 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A). Is more preferable, and it is still more preferable that it is 0.01-1 mass part.

<(J) Plasticizer>
The photosensitive resin composition of the present invention may contain a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The addition amount of the plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and 1 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A). Is more preferable.

<(K) Thermal radical generator>
The photosensitive resin composition of the present invention may contain a thermal radical generator. When an ethylenically unsaturated compound such as the aforementioned compound having at least one ethylenically unsaturated double bond is contained, it is preferable 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 heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.

A thermal radical generator may be used individually by 1 type, and it is also possible to use 2 or more types together.
The addition amount of the thermal radical generator in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass when the copolymer (A) is 100 parts by mass from the viewpoint of improving film properties. 0.1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.

<(L) Thermal acid generator>
In the present invention, a thermal acid generator may be used in order to improve film physical properties and the like at low temperature curing.
In the present invention, the thermal acid generator is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. It is a compound that generates a low nucleophilic acid such as sulfonic acid, carboxylic acid, disulfonylimide and the like.

  As the generated acid, pKa is as strong as 2 or less, sulfonic acid or alkyl substituted with an electron withdrawing group is preferably arylcarboxylic acid, disulfonylimide substituted with an electron withdrawing group, or the like. Examples of the electron withdrawing group include a halogen atom such as an F atom, a halogenated alkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by exposure to exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by measuring IR spectrum and NMR spectrum before and after exposure of the compound.
The molecular weight of the sulfonate ester is generally 230 to 1000, preferably 230 to 800.

As the sulfonic acid ester usable in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
The addition amount of the sulfonic acid ester to the photosensitive resin composition is preferably 0.5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass when the component (A) is 100 parts by mass.

<(M) Acid Proliferator>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity. The acid proliferating agent used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include JP-A-10-1508 [0203] to [0223], JP-A-10-282642 [0016] to [0055] and JP-A-9-512498, page 39. The compounds described on the 12th line to the 47th line on the 2nd line can be mentioned.

  Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.

  The amount of the acid proliferating agent added to the photosensitive resin composition is 10 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator (B). To 20 to 500 parts by mass.

<(N) Development accelerator>
The photosensitive resin composition of the present invention may contain a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used. However, the development accelerator is preferably a compound having at least one structure selected from a carboxy group, a phenolic hydroxyl group, and an alkyleneoxy group. More preferred is a compound having at least one structure selected from polar hydroxyl groups, and most preferred is a compound having a phenolic hydroxyl group.
The molecular weight of the development accelerator is preferably 100 to 3000, more preferably 100 to 2000, and most preferably 150 to 1000.

  Examples of development accelerators having an alkyleneoxy group include polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, polybutylene glycol, Examples thereof include polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and compounds described in JP-A-9-222724.

Examples of development accelerators having a carboxy group include those described in JP-A 2000-66406, JP-A 9-6001, JP-A 10-20501, JP-A 11-338150, and the like. A compound can be mentioned.
As examples of development accelerators, those having a phenolic hydroxyl group include JP-A-2005-346024, JP-A-10-133366, JP-A-9-194415, JP-A-9-222724, Examples thereof include compounds described in JP-A-11-171810, JP-A-2007-121766, JP-A-9-297396, JP-A-2003-43679, and the like. Among these, a phenol compound having 2 to 10 benzene rings is preferable, and a phenol compound having 2 to 5 benzene rings is more preferable. Particularly preferred is a phenolic compound disclosed as a dissolution accelerator in JP-A-10-133366.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass when the copolymer (A) is 100 parts by mass from the viewpoints of sensitivity and residual film ratio. 0.2-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.

[Method of forming cured film]
Next, the formation method of the cured film of this invention is demonstrated.
The method for forming a cured film of the present invention includes the following steps (1) to (5).
(1) Application step of applying the photosensitive resin composition of the present invention onto a substrate (2) Solvent removal step of removing the solvent from the applied photosensitive resin composition (3) Applying the applied photosensitive resin composition An exposure step of exposing with an actinic ray (4) A development step of developing the exposed photosensitive resin composition with an aqueous developer (5) A post-baking step of thermosetting the developed photosensitive resin composition These will be described in order.

In the coating step, the photosensitive resin composition of the present invention is coated on a substrate to form a wet film containing a solvent.
In the solvent removal step, the solvent is removed from the applied wet film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.

  In the exposure step, the obtained dried coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, the photoacid generator (B) is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group in the structural unit (1) contained in the copolymer (A) is hydrolyzed to produce a carboxy group and / or a phenolic hydroxyl group.

  In the region where the acid catalyst is generated, post exposure bake (hereinafter also referred to as “PEB”) can be performed as necessary in order to accelerate the hydrolysis reaction. By PEB, the production | generation of the carboxy group and / or phenolic hydroxyl group from an acid-decomposable group can be accelerated | stimulated.

The acid-decomposable group in the structural unit (1) of the copolymer (A) has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from an acid generator upon exposure to a carboxy group and / or phenol. Since a positive hydroxyl group is generated, a positive image can be formed by development without necessarily performing PEB.
In addition, by performing PEB at a relatively low temperature, hydrolysis of an acid-decomposable group can be promoted without causing a crosslinking reaction.
The temperature at which PEB is performed is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower.

  In the development step, a polymer having a liberated carboxy group and / or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxy group and / or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.

  In the post-baking step, the obtained positive image is heated to thermally decompose the acid-decomposable group in the structural unit (1) to produce a carboxy group and / or a phenolic hydroxyl group, thereby producing an epoxy group and / or oxetanyl. A cured film can be formed by crosslinking with a group. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.

If a step of irradiating active light (preferably ultraviolet rays) with actinic rays (preferably ultraviolet rays) before the post-baking step is added, the crosslinking reaction can be promoted by the acid generated by the irradiation of actinic rays.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Preparation of photosensitive resin composition>
The essential components of the copolymer (A), the photoacid generator (B), the sensitizer (C), and the solvent (D) are mixed in a predetermined ratio and in an arbitrary method, and stirred to dissolve to be photosensitive. A resin composition is prepared. For example, a copolymer (A), a photoacid generator (B), or a sensitizer (C) is prepared by dissolving each in advance in a solvent (D), and then mixed at a predetermined ratio to obtain a resin. Compositions can also be prepared. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Coating process and solvent removal process>
A desired dry coating film can be formed by applying the photosensitive resin resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking).
As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as necessary, and a transparent conductive circuit layer can be exemplified.
The method for applying the photosensitive resin resin composition to the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, or the like can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  Moreover, the heating conditions of the solvent removal step are such that the acid-decomposable group of the structural unit (1) in the copolymer (A) in the unexposed area is decomposed and the copolymer (A) is soluble in an alkali developer. However, it is preferably about 80 to 130 [deg.] C. for about 30 to 120 seconds, although it varies depending on the type and mixing ratio of each component.

<Exposure process>
In the exposure step, the substrate provided with the dry coating film is irradiated with an actinic ray having a predetermined pattern. Irradiation with actinic rays may be performed through a mask or may be directly drawn. As the actinic ray, actinic rays having a wavelength of 300 nm to 450 nm can be preferably used.
After the exposure step, heat treatment (PEB) is performed as necessary.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, a laser generator, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.

In the case of using a laser, 343 nm and 355 nm are used for a solid (YAG) laser, 351 nm (XeF) is used for an excimer laser, and 37 for a semiconductor laser.
5 nm and 405 nm are used. Among these, 355 nm and 405 nm are more preferable from the viewpoint of stability and cost. The coating can be irradiated with the laser once or a plurality of times.

The energy density per pulse of the laser is preferably 0.1 mJ / cm ² or more and 10,000 mJ / cm ² or less. To fully cure the coating, more preferably 0.3 mJ / cm ² or more, and most preferably from 0.5 mJ / cm ² or more, in so as not to degrade the coating film by ablation phenomenon, 1000 mJ / cm ² The following is more preferable, and 100 mJ / cm ² or less is most preferable.

  The pulse width is preferably 0.1 nsec or more and 30000 nsec or less. In order to prevent the color coating film from being decomposed due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable. Is most preferred.

  Furthermore, the frequency of the laser is preferably 1 Hz or more and 50000 Hz or less, and more preferably 10 Hz or more and 1000 Hz or less.

  Furthermore, the frequency of the laser is more preferably 10 Hz or more, most preferably 100 Hz or more for shortening the exposure processing time, and more preferably 10,000 Hz or less, and 1000 Hz or less for improving the alignment accuracy during the scan exposure. Most preferred.

  Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.

  There are no particular restrictions on the exposure apparatus that can be used in the present invention. Commercially available exposure apparatuses include Callisto (buoy technology), AEGIS (buoy technology), and DF2200G (Dainippon Screen). Products other than those described above are also preferably used.

  In the exposure step, the irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter, if necessary.

<Development process>
In the development step, the exposed area is removed using a basic developer to form an image pattern.
Examples of the basic compound contained in the basic developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; bicarbonate Alkali metal bicarbonates such as sodium and potassium bicarbonate; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. .
Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution containing the above basic compound can also be used as a developing solution.

The pH of the developer is preferably 10.0 to 14.0.
The development time is usually from 30 seconds to 180 seconds, and the development method may be either a liquid piling method or a dipping method. After the development, washing with running water is performed for 30 seconds to 90 seconds, and a desired pattern can be formed.

<Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 180 to 250 ° C., for a predetermined time, for example, 5-60 minutes on the hot plate, In the case of an oven, the acid-decomposable group in the copolymer (A) is decomposed by heat treatment for 30 to 90 minutes to generate a carboxy group and / or a phenolic hydroxyl group. ) And a cross-linkable group which is an oxetanyl group, and a cured film such as a protective film and an interlayer insulating film excellent in heat resistance and hardness can be formed.

  Moreover, when performing heat processing, transparency of a cured film can also be improved by performing in nitrogen atmosphere.

  Prior to the heat treatment, the photoacid generator (B) present in the unexposed portion by post-baking (re-exposure / post-bake) after re-exposure to the substrate on which the cured film is formed in a pattern by actinic rays. It is preferable to function as a catalyst for generating an acid from the catalyst and promoting the crosslinking step.

That is, the method for forming a cured film of the present invention preferably includes a re-exposure step in which re-exposure is performed with actinic rays between the development step and the post-bake step.
The exposure in the re-exposure process may be performed by the same means as in the exposure process. In the re-exposure process, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable. A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

With the photosensitive resin composition of the present invention, a cured film having excellent insulating properties and high transparency even when baked at high temperatures is obtained, and the cured film is useful as an interlayer insulating film. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to a planarizing film, a protective layer, and an interlayer insulating film, it is suitably used for a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, be able to.

  The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that the cured film formed using the photosensitive resin composition of the present invention has a planarizing film or an interlayer insulating film, and various Examples include various known organic EL display devices and liquid crystal display devices having a structure.

FIG. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device applicable as the organic EL display device of the present invention.
In FIG. 1, a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

  FIG. 2 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device applicable as the liquid crystal display device of the present invention. In FIG. 2, the liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back side, and the liquid crystal panel is all disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. Elements of the TFT 16 corresponding to these pixels are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile)
GMA: Glycidyl methacrylate MAA: Methacrylic acid HEMA: 2-Hydroxyethyl methacrylate EDM: Diethylene glycol ethyl methyl ether

<Synthesis of Polymer A-1>
Polymer A-1 which is a copolymer (A) was synthesized as follows.
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower, and the yellow oily residue was distilled under reduced pressure to obtain a boiling point (bp .) 134.0 parts of 1-ethoxyethyl methacrylate (MAEVE) fraction of 43-45 ° C./7 mmHg was obtained as a colorless oil.

Obtained 1-ethoxyethyl methacrylate (63.28 parts (0.4 molar equivalent)), GMA (42.65 parts (0.3 molar equivalent)), MAA (8.61 parts (0.1 molar equivalent) )), HEMA (26.03 parts (0.2 molar equivalent)) and EDM (110.8 parts) were heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4 parts) and EDM (100.0 parts) was added dropwise over 2.5 hours. did. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 4 hours to obtain an EDM solution of polymer A-1 (solid content concentration: 40%).
The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained polymer A-1 was 15,000.

<Synthesis of Polymers A-2 to A-9>
Polymers A-2 to A, which are copolymers (A), in the same manner as the synthesis of polymer A-1, except that each monomer used and the amount used thereof are changed to those shown in Table 1 below. -10 was synthesized respectively.

Abbreviations in Table 1 are as follows.
MAEVE: 1-ethoxyethyl methacrylate GMA: glycidyl methacrylate OXE-30: methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
HEMA: 2-hydroxyethyl methacrylate M100: 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries)
MAA: methacrylic acid CHOEMA: 1- (cyclohexyloxy) ethyl methacrylate MATHH: tetrahydro-2H-furan-2-yl methacrylate Ph-1: 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester P-Ph-1 : 1-ethoxyethyl ether of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester St: Styrene PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis of CHOEMA>
CHOEMA was synthesized in the same manner as MAEVE in the synthesis of polymer A-1.

<Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

  Ph-1 (4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester) was synthesized by the method shown below.

<Synthesis of Ph-1>
To a solution of 23 g of 4-hydroxybenzoic acid (3-hydroxypropyl) ester in 100 ml of acetonitrile, 20 ml of N-methylpyrrolidone was added with stirring, and 16 g of methacrylic acid chloride was further added. After reacting with stirring at 35 ° C. for 8 hours, the reaction mixture was poured into ice water, and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to give 4-hydroxybenzoic acid (3-methacryloyl). Oxypropyl) ester was obtained.

  P-Ph-1 was obtained by protecting Ph-1 with 1-ethoxyethyl ether. The protection of Ph-1 with 1-ethoxyethyl ether was carried out in the same manner as described in Synthesis Example 1.

[Example 1]
Each component was dissolved and mixed so that it might become the following composition A, and it filtered with the filter made from a polytetrafluoroethylene with a diameter of 0.2 micrometer, and obtained the photosensitive resin composition of Example 1. FIG.
<Composition A>
Copolymer (A): Polyethylene glycol methyl ether acetate of polymer A-1 [hereinafter abbreviated as PGMEA. (D) component] Solution 100.0 parts by solid content / photoacid generator (B): 2.0 parts B-1 shown below / sensitizer (C): 2.0 parts C-1 shown below -Adhesion improver (G): 0.5 part of G-1 shown below-Surfactant (I): 0.02 part of I-1 shown below

[Examples 2-49, Comparative Example 1]
Except having changed each compound used in Example 1 into the compound of Table 2 or Table 3, it melt-mixed by the same addition amount as Example 1, and photosensitive of Examples 2-49 and Comparative Example 1 A functional resin composition was prepared.
In Examples 4 to 14, 21 to 24, and 26 to 49 using the crosslinking agent (F), the following crosslinking agents were added in the following addition amounts.
Moreover, in Examples 24-49 using a basic compound (H), the following basic compound was added with the following addition amount.
-Crosslinking agent (F): 2.0 parts of F-1 shown below-Basic compound (H): 0.1 part of H-1 shown below-Basic compound (H): H-20 shown below .01 parts

The details of the abbreviations indicating the compounds used in Examples 1 to 49 and Comparative Example 1 are as follows.
B-1: PAI-1001 (trade name, structure shown below, manufactured by Midori Chemical Co., Ltd.)
B-2: PAI-1003 (trade name, structure shown below, manufactured by Midori Chemical Co., Ltd.)
B-3: CGI-1397 (trade name, structure shown below, manufactured by Ciba Specialty Chemicals)
B-4: PAI-101 (trade name, structure shown below, manufactured by Ciba Specialty Chemicals)
B-5: Structure shown below (synthesis examples will be described later)
B-6: Structure shown below (synthesis example will be described later)
B-7: Structure shown below (Synthesis examples will be described later)
B-8: Structure shown below (synthesis examples will be described later)
B-9: Structure shown below (synthesis examples will be described later)
B-10: Structure shown below (synthesis examples will be described later)
N-1: NBCA (trade name, 10-butyl-2-chloroacridone, structure shown below, manufactured by Kurokin Kasei Co., Ltd.)
N-2: DBA (trade name, 9,10-dibutoxyanthracene, structure shown below, manufactured by Kawasaki Chemical Industries)
N-3: NKX-1768 (trade name, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolidine-11-non, The structure shown in the figure, manufactured by Hayashibara Biochemical Laboratories Co., Ltd.)
N-4: NK-1342 (trade name, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole, structure shown below, manufactured by Hayashibara Biochemical Laboratories)
N-5: DPA (trade name, 9,10-dipropyloxyanthracene, structure shown below, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
N-6: DEA (trade name, 9,10-diethoxyanthracene, structure shown below, manufactured by Kawasaki Chemical Industries)
F-1: JER157S70 (trade name, phenol novolac type epoxy resin, manufactured by Japan Epoxy Resins Co., Ltd.)
G-1: KBM-403 (trade name, 3-glycidoxypropyltrimethoxysilane, structure shown below, manufactured by Shin-Etsu Chemical Co., Ltd.)
H-1: 1,5-diazabicyclo [4.3.0] -5-nonene H-2: triphenylimidazole I-1: PolyFox PF-6320 (trade name, fluorine-based surfactant, manufactured by OMNOVA)
I-2: Nonionic surfactant containing a perfluoroalkyl group represented by the following structural formula (W-3)

<Synthesis of B-5>
The compound (α- (methylsulfonyloxyimino) -2-phenylacetonitrile) shown as B-5 was synthesized as follows.
Synthesis of α- (hydroxyimino) -2-phenylacetonitrile 5.85 g of phenylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) is mixed with 50 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), placed in an ice bath, and the reaction solution is cooled to 5 ° C. or lower. did. Next, 11.6 g of SM-28 (sodium methoxide 28% methanol solution, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was allowed to react with stirring for 30 minutes in an ice bath. Next, 7.03 g of isopentyl nitrite (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining the internal temperature at 20 ° C. or less, and the reaction solution was reacted at room temperature for 1 hour after the completion of the addition. The obtained reaction solution was poured into 150 mL of water in which 1 g of sodium hydroxide was dissolved to completely dissolve it, and then 100 ml of ethyl acetate was added and separated to obtain about 180 ml of an aqueous layer having a target product. Further, 100 ml of ethyl acetate was added again, the aqueous layer was acidified with concentrated hydrochloric acid to pH 3 or lower, and the product was extracted and concentrated. The obtained crude crystals were washed with hexane to obtain 4.6 g of α- (hydroxyimino) -2-phenylacetonitrile with a yield of 63%.

(2) Synthesis of α- (methylsulfonyloxyimino) -2-phenylacetonitrile (Compound B-5) 11.5 g of α- (hydroxyimino) -2-phenylacetonitrile was added to 100 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.). The reaction solution was dissolved in an ice bath and cooled to 5 ° C. or lower. Next, 9.9 g of methanesulfonyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, then 9.55 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise while maintaining the internal temperature at 20 ° C. or lower, and the mixture was stirred for 1 hour in an ice bath. Reacted.
The obtained reaction solution was dropped into 500 mL of water and stirred at room temperature for 1 hour. The obtained powdery precipitate was filtered and dried to obtain 16 g of α- (methylsulfonyloxyimino) -2-phenylacetonitrile (Compound B-5) with a yield of 90%. The H-NMR spectrum of this compound showed that the product was a mixture of oxime structural isomers (syn / anti), and the abundance ratio was syn: anti = 25/75.

<Synthesis of B-6>
Α- (p-toluenesulfonyloxyimino) phenylacetonitrile (Compound B-6) was synthesized according to the method described in paragraph No. [0108] of JP-T-2002-528451.

<Synthesis of B-7>
1-1. Synthesis of Synthesis Intermediate B-7A 2-aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C.). . Next, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour and then at 100 ° C. for 2 hours to cause a reaction. 500 mL of water was added to the resulting reaction solution to dissolve the precipitated salt, toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B-7A.

1-2. Synthesis of B-7 After 2.25 g of the synthetic intermediate B-7A obtained as described above was mixed with 10 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), the reaction solution was placed in an ice bath and the reaction solution was kept at 5 ° C. Cooled to: Next, tetramethylammonium hydroxide: 4.37 g (25 wt% methanol solution, manufactured by Alfa Acer) was added dropwise to the reaction solution, and the mixture was stirred for 0.5 hour in an ice bath to be reacted. Furthermore, 7.03 g of isopentyl nitrite: was dropped while maintaining the internal temperature at 20 ° C. or lower, and after completion of the dropping, the reaction solution was warmed to room temperature and stirred for 1 hour.
Subsequently, after cooling the reaction liquid to 5 ° C. or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred for 1 hour while maintaining 10 ° C. or lower. Thereafter, 80 mL of water was added and stirred at 0 ° C. for 1 hour. After filtration of the resulting precipitate, 60 mL of isopropyl alcohol (IPA) was added, heated to 50 ° C., stirred for 1 hour, filtered while hot, and dried to obtain B-7 (the aforementioned structure). 8 g was obtained.
¹ H-NMR spectrum of the obtained B-7 (300 MHz, heavy DMSO ((D ₃ C) ₂ S =
O)), δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.00 (m, 1H), 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).
From the above ¹ H-NMR measurement results, it is estimated that the obtained B-7 is a single geometric isomer.

<Synthesis of B-8>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated. The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, 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 the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered and dried to obtain 2.3 g of B-8 (the above-mentioned structure).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-8 has 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), 1.7 (d, 3H).

<Synthesis of B-9>
2-Naphthol (20 g) is dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) are added and reacted at 100 ° C. for 2 hours. It was. To the reaction solution are added water (300 mL) and ethyl acetate (200 mL), and the mixture is separated. The organic layer is concentrated, and then 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) are added. The reaction was performed 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, and 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), and ethyl acetate (300 mL) was added for liquid separation, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).
Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the resulting ketone compound (10.0 g) and methanol (100 mL) for 24 hours. Heated to reflux. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and 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). Got.
The obtained oxime (3.1 g) was sulfonated in the same manner as B-8 to obtain 3.2 g of B-9 (the above-mentioned structure).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-9 has 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), 0.8 (t, 3H) there were.

<Synthesis of B-10>
B-10 (the aforementioned structure) was synthesized in the same manner as B-8, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B-8.
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-10 is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (D, 3H).

[Comparative Example 2: Example using 1,2-quinonediazide compound]
As the photosensitive resin composition of Comparative Example 2, a composition described in Example 1 of JP-A-5-165214 was prepared.

[Comparative Example 3: Example using onium salt photoacid generator]
As the photosensitive resin composition of Comparative Example 3, the composition described in Example 1 of JP-A-2004-264623 was prepared as follows.

-Preparation of photosensitive resin composition of Comparative Example 3-
A flask equipped with a condenser and a stirrer was charged with 7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol ethyl methyl ether. Subsequently, 40 parts of 1- (cyclohexyloxy) ethyl methacrylate, 5 parts of styrene, 45 parts of glycidyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate and 3 parts of α-methylstyrene dimer were charged with nitrogen, and then gently stirred. . 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 resulting copolymer had a polystyrene equivalent weight average molecular weight (Mw) of 11,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.6%.
The solution containing the copolymer synthesized above was added in an amount corresponding to 100 parts (solid content) of the copolymer and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate 5 Part was dissolved in diethylene glycol methyl ethyl ether so that the solid content concentration was 30%, and then filtered through a membrane filter having a diameter of 0.2 μm to obtain a photosensitive resin composition of Comparative Example 3.

[Comparative Example 4: Example using oxime sulfonate photoacid generator]
As the photosensitive resin composition of Comparative Example 4, the composition described in Example 8 of JP2009-98616A was prepared.

  Each evaluation shown below was performed about the photosensitive resin composition of Examples 1-49 obtained by the above, and Comparative Examples 1-4.

<Evaluation of liquid aging stability (liquid storage stability)>
The viscosity (initial viscosity) of the photosensitive resin composition immediately after preparation and the viscosity (viscosity with time) of the photosensitive resin composition after storage for 1 week and 2 weeks at 30 ° C. (Manufactured by KK). The evaluation criteria are “3” when the viscosity with time changes by 10% or more as a relative evaluation with respect to the initial viscosity (100%), “2” when the change in viscosity is less than 10% and 5% or more. The case where the change was less than 5% was defined as “1”. “1” and “2” are levels that have no practical problem. The results are shown in Table 2.

<Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then prebaked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The photosensitive composition layer after the exposure was developed with an alkali developer (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity. The evaluation criteria are as follows. “1” and “2” are levels that have no practical problem. The results are shown in Tables 2 and 3.
1: Less than 40 mJ / cm ² 2: 40 mJ / cm ² or more and less than 60 mJ / cm ² 3: 60 mJ / cm ² or more and less than 80 mJ / cm ² 4: 80 mJ / cm ² or more

<Evaluation of transparency>
After each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 3 A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
The obtained photosensitive resin composition layer is subjected to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.

The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. The minimum light transmittance at that time is shown in Table 2 and Table 3 as evaluation of transparency.
The evaluation criteria are as follows. “1” and “2” are levels that have no practical problem.
1: 92% or more 2: 90% or more and less than 92% 3: 88% or more and less than 90% 4: less than 88%

<Evaluation of solvent resistance>
A cured film was formed on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) in the same manner as the evaluation of transparency.
The film thickness (T ¹ ) of the obtained cured film was measured. Then, the substrate on which this cured film is formed is 7
After immersing in dimethyl sulfoxide whose temperature is controlled at 0 ° C. for 20 minutes, the thickness (t ¹ ) of the cured film after the immersion is measured, and the rate of change in film thickness by immersion {| t ¹ −T ¹ | / T ¹ } × 100 [%] was calculated. The results are shown in Tables 2 and 3.
When the value of the film thickness change rate is less than 3% (that is, when the results of criteria 1 to 3 are obtained), it can be said that the cured film has good solvent resistance.
Less than 1: 1% 2: 1% or more but less than 2% 3: 2% or more but less than 3% 4: 3% or more

<Evaluation of pattern shape>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), and then the solvent was removed on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 3.0 μm. The photosensitive resin composition layer was formed.
Subsequently, an exposure amount (illuminance: illuminance :) obtained by developing the obtained photosensitive resin composition layer with a 0.4% tetramethylammonium hydroxide aqueous solution as a developing solution at 60 ° C. for 60 seconds. 20 mW / cm ² , i line), and exposure was performed through a mask having a 10 μm square pattern opening.
The exposed substrate was subjected to paddle development for 60 seconds at 23 ° C. using a 0.4% tetramethylammonium hydroxide aqueous solution as a developer.
The patterned photosensitive resin composition layer is subjected to an integrated irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
The obtained glass substrate with a cured film was cut, and the cross-sectional shape of the patterned contact hole was observed with a field emission scanning electron microscope S-4800 (manufactured by HITACHI) for evaluation.
The evaluation criteria are as follows. The results are shown in Tables 2 and 3.
When the taper angle of the obtained contact hole is less than 50 degrees (that is, when the result of standard 1 is obtained), it can be said that the pattern shape is good.
1: Range of taper angle of 10 to less than 50 degrees (forward taper)
2: The taper angle is in the range of 50 to less than 90 degrees (rectangular)
3: Range in which taper angle is 90 degrees or more (reverse taper)

  As shown in Tables 2 and 3, the photosensitive resin composition of each example was evaluated for any of the storage stability, transparency, solvent resistance, and pattern shape in comparison with each comparative example. It can be seen that excellent results were obtained.

[Example 50]
In Example 50, the photosensitive resin composition of Example 1 was used, and the substrate was changed from a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) to a 6 inch silicon wafer. The sensitivity and the pattern shape were evaluated in the same manner as the evaluation of the sensitivity and the pattern shape performed on the photosensitive resin composition.
The results are shown in Table 4.

[Example 51]
In Example 51, the photosensitive resin composition of Example 1 was used, and the exposure machine was changed from a Canon-made PLA-501F exposure machine to a Nikon-made FX-803M (gh-Line stepper). Except for the above, the sensitivity and pattern shape were evaluated in the same manner as the sensitivity and pattern shape evaluation performed on the photosensitive resin composition of Example 1.
The results are shown in Table 4.

[Example 52]
In Example 26, the photosensitive resin composition of Example 1 was used, and the exposure machine was changed from a Canon-made PLA-501F exposure machine to a 355 nm laser exposure machine, and 355 nm laser exposure was performed. The sensitivity and pattern shape were evaluated in the same manner as the sensitivity and pattern shape evaluation performed on the photosensitive resin composition of Example 1.
In addition, as a 355 nm laser exposure machine, "AEGIS" by a buoy technology company was used (wavelength 355nm, pulse width 6nsec), and the exposure amount was measured using "PE10B-V2" by OPHIR.
The results are shown in Table 4.

[Example 53]
In Example 53, the photosensitive resin composition of Example 1 was used, and the exposure machine was changed from a Canon-made PLA-501F exposure machine to a UV-LED light source exposure machine. The sensitivity and pattern shape were evaluated in the same manner as the sensitivity and pattern shape evaluation performed on the photosensitive resin composition.
The results are shown in Table 4.

  As shown in Table 4, it can be seen that the photosensitive resin compositions of the examples show excellent sensitivity regardless of the substrate and the exposure machine, and are excellent in the shape of the formed pattern. .

[Example 54]
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 4 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating i-line (365 nm) with 45 mJ / cm ² (illuminance 20 mW / cm ² ) using a mercury lamp, a pattern is formed by developing with an alkaline aqueous solution,
Heat treatment was performed at 230 ° C. for 60 minutes.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed by using the photosensitive resin composition of Example 7 by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

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

[Example 55]
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 55 was obtained.
That is, using the photosensitive resin composition of Example 7, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 54.

  When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (11)

(A) The structural unit (1) having at least one selected from a carboxy group protected with an acid-decomposable group and a phenolic hydroxyl group protected with an acid-decomposable group, and an epoxy group and an oxetanyl group A copolymer containing at least one structural unit (2), (B) the following general formula (I), general formula (OS-1), general formula (OS-3), general formula (OS- 4) and at least one photoacid generator selected from photoacid generators represented by formula (OS-5), (C) a sensitizer, and (D) a solvent. Resin composition.

^{R 1A -C (R 2A) =} N-O-SO 2 -R 3A (I)

[In General Formula (I), R ^1A represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, 2- A thienyl group, an alkoxy group having 1 to 4 carbon atoms or a cyano group, and when R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, a carbon It may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 atoms, an alkoxy group having 1 to 4 carbon atoms, and a nitro group. R ^2A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, an anthranyl group which may be substituted with W, a dialkylamino group, a morpholino group or a cyano group. R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be linked to a benzene ring. R ^3A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group. ]

[In General 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 Represents a heteroaryl group. R ² represents an alkyl group or an aryl group. X is, -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or, ^-CR 6 ^{R 7} - ^represents, R 5 to R ⁷ are each Independently, it represents an alkyl group or an aryl group. R ^{21 to} R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or an aryl group is represented. ]


[In General Formula (OS-3) to General Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^{2 s} independently represent a hydrogen atom or an alkyl group. R ⁶ represents a group, an aryl group, or a halogen atom, and each R ⁶ independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, and X represents O or S is represented, n represents 1 or 2, and m represents an integer of 0 to 6. ] The photosensitive resin according to claim 1, wherein the (C) sensitizer is a compound represented by the following general formula (III), general formula (IV), general formula (V), or general formula (VI). Composition.

[In General Formula (III), R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are the same. R ³ and R ⁴ each independently represents a monovalent substituent. m and n each independently represents an integer of 0 to 4. ]

[In General Formula (IV), R ⁵ represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. R ⁶ and R ⁷ each independently represents a monovalent substituent. o and p each independently represent an integer of 0 to 4. ]

[In General Formula (V), R ⁸ , R ⁹ , and R ¹⁰ each independently represents a monovalent substituent, q
, R and s each independently represents an integer of 0 to 2. Two or more of R ⁸ , R ⁹ and R ¹⁰ may be connected to each other to form a 5-membered ring or a 6-membered ring. ]

[In General Formula (VI), R ¹¹ and R ¹² each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an aliphatic group having 1 to 20 carbon atoms, a heterocyclic group, or an aromatic group. R ¹³ and R ¹⁴ may be connected to each other to form a 5-membered ring or a 6-membered ring. ] The photosensitive resin composition according to claim 1, wherein the photoacid generator represented by the general formula (I) is a photoacid generator represented by the following general formula (II).

[In General Formula (II), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and l is an integer of 0 to 5 Represents. R ^3A is 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, or W It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group. ]   The photosensitive resin composition according to any one of claims 1 to 3, wherein the structural unit (2) of the copolymer (A) is a structural unit having an oxetanyl group.   The photosensitive resin composition of any one of Claims 1-4 which further contains a crosslinking agent.   The cured film formed by providing at least one of light and heat to the photosensitive resin composition of any one of Claims 1-5. (1) The application | coating process which apply | coats the photosensitive resin composition of any one of Claims 1-5 on a board | substrate,
(2) a solvent removal step of removing the solvent from the applied photosensitive resin composition;
(3) An exposure step of exposing the coated photosensitive resin composition with actinic rays,
(4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.   A cured film formed by the method according to claim 7.   The cured film according to claim 6 or 8, which is an interlayer insulating film.   An organic EL display device comprising the cured film according to claim 6, 8 or 9.   A liquid crystal display device comprising the cured film according to claim 6, 8 or 9.