KR20120120240A - Photosensitive resin composition, cured film, method for forming cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

A copolymer containing 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 structural unit (2) having at least one selected from an epoxy group and an oxetanyl group, Provided are a photosensitive resin composition containing a photoacid generator, a sensitizer, and a solvent having a specific structure having an oxime sulfonate group.

Description

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

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

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

In addition to transparency, the interlayer insulation film and planarization film patterned using the above photosensitive resin composition are required to be a highly reliable cured film which is excellent in solvent resistance.

As such a photosensitive resin composition, JP-A-5-165214 discloses, for example, (A) (a) unsaturated carboxylic acid or unsaturated carboxylic anhydride, (b) radical polymerizable compound having an epoxy group, and (c) other radicals. The photosensitive resin composition which has resin soluble in the aqueous alkali solution which is a copolymer of a polymeric compound, and (B) a radiation sensitive acid formation compound is described.

In addition, Japanese Patent Laid-Open No. 2004-264623 discloses a photosensitive resin composition capable of securing high stability (transparency, solvent resistance) of storage stability, sensitivity, and formed cured film, for example, having an acetal structure or a ketal structure ( Radiation-sensitive property containing resin which is a copolymer of a meta) acrylic acid ester compound, a radically polymerizable compound which has an epoxy group, and another radically polymerizable compound, and a compound in which pKa produces an acid below 4.0 by irradiation of radiation. Resin compositions are described.

Further, Japanese Patent Laid-Open No. 2009-98616 discloses a photoacid generator having a structural unit having a specific acid dissociable group, a resin which is a copolymer with a structural unit capable of reacting with a carboxyl group to form a covalent bond, and an oxime sulfonate group. Positive type photosensitive resin composition containing is described.

On the other hand, in an optical system material used for an imaging optical system or an optical fiber connector of an on-chip color filter such as a facsimile, an electronic copier, a solid-state imaging device, a microlens having a lens diameter of about 3 to 100 µm or a microarray in which these microlenses are regularly arranged. Lens arrays are being 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 is used as it is or by dry etching using the meltflow-lens pattern as a mask. Background Art A method of transferring a lens shape to a base is known. The photosensitive resin composition is widely used for formation of such a lens pattern (for example, refer Unexamined-Japanese-Patent No. 6-18702, and Unexamined-Japanese-Patent No. 6-136239).

The photosensitive resin composition for forming the interlayer insulating film is required to have high sensitivity and good storage stability, and high reliability (transparency, solvent resistance, etc.) is required for the cured film formed of the photosensitive composition. In addition, the formability of a favorable pattern shape is calculated | required from a viewpoint of contact hole formation etc. for an interlayer insulation film, and it is preferable that it is a pure taper as said pattern shape.

However, like the positive photosensitive resin composition described in JP-A-2004-264623 and JP-A-2009-98616, it contains a photoacid generator, such as a triazine system, an onium salt system, an oxime sulfonate system, etc. However, it is not necessarily satisfactory in view of achieving high sensitivity and achieving high sensitivity.

In addition, when performing pattern formation of an insulating film etc. using the photosensitive resin composition, heat processing (post-baking process) is normally performed after exposure of the photosensitive resin composition. However, in the conventional photosensitive resin composition, it becomes high sensitivity. Since the pattern shape after a postbaking process became close to a rectangle, the improvement of a sensitivity and the formation of a favorable pattern shape had a relationship of a trade-off. Therefore, at the present time, a photosensitive resin composition for forming an interlayer insulating film, which has both high sensitivity and storage stability, and secures high reliability (transparency and solvent resistance) of the formed cured film, and has a good pattern shape formed. I can't.

The 1st subject which this invention seeks to solve is providing the photosensitive resin composition which is excellent in storage stability and sensitivity, and can form the cured film excellent in transparency, solvent resistance, and pattern shape.

Moreover, the 2nd subject which this invention intends to solve is equipped with the cured film excellent in transparency, solvent resistance, and pattern shape formed by the positive photosensitive resin composition of this invention, the method of forming the cured film, and the said cured film as an interlayer insulation film. It is to provide an organic EL display device and a liquid crystal display device which are excellent in display characteristics and have high productivity.

An aspect of the present invention is described below.

<1> (A) A structural unit 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 structural unit having at least one selected from an epoxy group and an oxetanyl group (2) Copolymer containing, (B) represented by the following general formula (I), general formula (OS-1), general formula (OS-3), general formula (OS-4), and general formula (OS-5) A photosensitive resin composition containing at least one photoacid generator selected from the photoacid generator, (C) sensitizer, and (D) solvent.

R ^1A -C (R ^2A ) = NO-SO ₂ -R ^3A (Ⅰ)

In general formula (I), R <^1A> is a C1-C6 alkyl group, a C1-C4 halogenated alkyl group, a phenyl group, a biphenyl group, a naphthyl group, 2-furyl group, 2-thienyl group, and carbon atom number When a 1-4 alkoxy group or 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, a C1-4 alkyl group, and a C1-1 carbon atom. It may be substituted by a substituent selected from the group consisting of an alkoxy group and a nitro group of 4. 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 a phenyl group which may be substituted with W The naphthyl group which may be substituted by W or the anthranyl group, dialkylamino group, morpholino group, or cyano group which may be substituted by W is shown. R ^2A and R ^1A may be bonded to each other to form a 5- or 6-membered ring, and the 5- or 6-membered ring may be linked to a benzene ring which may have one or two arbitrary substituents. 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 a phenyl group which may be substituted with W And naphthyl group which may be substituted with W or anthranyl group which may be substituted with W. W is a halogen atom, cyano group, nitro group, alkyl group of 1 to 10 carbon atoms, alkoxy group of 1 to 10 carbon atoms, halogenated alkyl group of 1 to 5 carbon atoms or halogenated alkoxy of 1 to 5 carbon atoms 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 heteroaryl Group. R ² represents an alkyl group or an aryl group. X represents —O—, —S—, —NH—, —NR ⁵ —, —CH ₂ —, —CR ⁶ H—, or —CR ⁶ R ⁷ —, and R ^{5 to} R ⁷ each independently , An alkyl group, or an aryl group. R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group.

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 each independently represent a hydrogen atom, an alkyl group, an aryl group, or R ⁶ which represents a halogen atom, and which may be present in plural, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, X represents O or S, and n is 1 Or 2, and m represents an integer of 0 to 6;

<2> Photosensitive resin composition as described in said <1> whose said (C) sensitizer is a compound represented by the following general formula (III), general formula (IV), general formula (V), or general formula (VI).

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 represent a monovalent substituent. m and n each independently represent the integer of 0-4.

In general formula (IV), R <^5> represents a C1-C6 alkyl group or the phenyl group which may be substituted. R ⁶ and R ⁷ each independently represent 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> respectively independently represent a monovalent substituent, q, r, and s respectively independently represent the integer of 0-2. Two or more of R ⁸ , R ⁹ , and R ¹⁰ may be connected to each other to form a five-membered ring or a six-membered ring.

In General Formula (VI), R ¹¹ and R ¹² each independently represent 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 linked to each other to form a 5-membered ring or a 6-membered ring.

The photosensitive resin composition as described in said <1> or <2> whose photo-acid generator represented by <3> above-mentioned general formula (I) is a photo-acid generator represented with the following general formula (II).

In general formula (II), R <^4A> represents a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a nitro group, and l represents the integer of 0-5. 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 a phenyl group which may be substituted with W And naphthyl group which may be substituted with W or anthranyl group which may be substituted with W. W is a halogen atom, cyano group, nitro group, alkyl group of 1 to 10 carbon atoms, alkoxy group of 1 to 10 carbon atoms, halogenated alkyl group of 1 to 5 carbon atoms or halogenated alkoxy of 1 to 5 carbon atoms Group.

The photosensitive resin composition in any one of said <1>? <3> whose structural unit (2) which a <4> above-mentioned (A) copolymer has is a structural unit which has an oxetanyl group.

The photosensitive resin composition in any one of said <1>? <4> which further contains a <5> crosslinking agent.

<6> Cured film formed by providing at least one of light and heat to the photosensitive resin composition in any one of said <1>-<5>.

<7> (1) Applying the photosensitive resin composition in any one of said <1>-<5> on a board | substrate,

(2) removing a solvent from the applied photosensitive resin composition,

(3) exposing the applied photosensitive resin composition by actinic light,

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

(5) The formation method of the cured film containing thermosetting the developed photosensitive resin composition.

<8> Cured film formed by the method as described in said <7>.

The cured film as described in said <6> or <8> which is a <9> interlayer insulation film.

<10> The organic electroluminescence display provided with the cured film as described in said <6>, <8>, or <9>.

<11> The liquid crystal display device provided with the cured film as described in said <6>, <8>, or <9>.

According to 1 aspect of this invention, the photosensitive resin composition which is excellent in storage stability and sensitivity, and can form the cured film excellent in transparency, solvent resistance, and pattern shape is provided.

Moreover, according to another aspect of this invention, the cured film which was excellent in transparency, solvent resistance, and pattern shape formed by the positive photosensitive resin composition of this invention, the method of forming the cured film, and the display characteristic provided with this cured film as an interlayer insulation film. An excellent organic EL display device and a liquid crystal display device are provided.

BRIEF DESCRIPTION OF THE DRAWINGS The 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.
The figure which shows the structure which shows an example of the liquid crystal display device which applied the cured film using the photosensitive resin composition of this invention.

(Photosensitive resin composition)

Hereinafter, the photosensitive resin composition of this invention is demonstrated in detail.

In addition, in this invention, solid content of the photosensitive resin composition represents the mass remove | excluding the mass of volatile components, such as a solvent, from the gross mass of all components contained in the photosensitive resin composition.

The numerical range shown using "?" In this specification shows the range which includes the numerical value described before and after "?" As minimum value and the maximum value, respectively.

The photosensitive resin composition of this invention has (A) structural unit (1) which has at least 1 selected from the carboxyl group protected by the acid-decomposable group, and the phenolic hydroxyl group protected by the acid-decomposable group, and at least one selected from an epoxy group and an oxetanyl group. A copolymer containing the structural unit (2), (B) 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 selected from the photoacid generator represented by -5) (hereinafter, collectively referred to as hostile "photoacid generator (B)"), (C) sensitizer, and (D) solvent It is a photosensitive resin composition to contain.

R ^1A -C (R ^2A ) = NO-SO ₂ -R ^3A (Ⅰ)

In said general formula (I), R <^1A> is a C1-C6 alkyl group, a C1-C4 halogenated alkyl group, a phenyl group, a biphenyl group, a naphthyl group, 2-furyl group, 2-thienyl group, a carbon atom When a C1-4 alkoxy group or 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, a C1-C4 alkyl group, and C1-C1 It may be substituted by a substituent selected from the group consisting of an alkoxy group 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 a phenyl group which may be substituted with W The naphthyl group which may be substituted by W or the anthranyl group, dialkylamino group, morpholino group, or cyano group which may be substituted by W is shown. R ^2A and R ^1A may be bonded to each other to form a 5- or 6-membered ring, and the 5- or 6-membered ring may be linked to a benzene ring which may have one or two arbitrary substituents. 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 a phenyl group which may be substituted with W And naphthyl group which may be substituted with W or anthranyl group which may be substituted with W. W is a halogen atom, cyano group, nitro group, alkyl group of 1 to 10 carbon atoms, alkoxy group of 1 to 10 carbon atoms, halogenated alkyl group of 1 to 5 carbon atoms or halogenated alkoxy of 1 to 5 carbon atoms 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 heteroaryl Group. R ² represents an alkyl group or an aryl group. X represents —O—, —S—, —NH—, —NR ⁵ —, —CH ₂ —, —CR ⁶ H—, or —CR ⁶ R ⁷ —, and R ^{5 to} R ⁷ each independently , An alkyl group, or an aryl group. R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group.

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 each independently represent a hydrogen atom, an alkyl group, an aryl group, or R ⁶ which represents a halogen atom, and which may be present in plural, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, X represents O or S, and n is 1 Or 2, and m represents an integer of 0 to 6;

The photosensitive resin composition of this invention is a positive photosensitive resin composition.

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

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, in this invention, that "pattern shape" is excellent means that the shape of the formed pattern is a forward taper.

For this reason, the photosensitive resin composition of this invention is especially useful for formation of an interlayer insulation film, and in that case, the formation of the pattern of the pure taper shape suitable for forming a contact hole etc. becomes possible.

In addition, the "transparency" in this invention means the property which coloring is suppressed in the cured film obtained by performing heat processing (baking process) at least after exposure using the photosensitive resin composition of this invention. . In addition, below, the transparency which the cured film formed with the photosensitive resin composition of this invention shows may be called "heat-resistant transparency."

Moreover, the photosensitive resin composition of this invention is useful also for microlens formation.

This is because the photosensitive resin composition for microlens formation is excellent in sensitivity and storage stability, and the microlens (cured film) formed from the photosensitive resin composition is excellent in transparency and solvent resistance, and has good melt shape (purpose curvature). Radius), the photosensitive resin composition of this invention is excellent in sensitivity and storage stability, and the cured film formed by this has the advantage that it is excellent in transparency and solvent resistance, and also shows favorable melt shape. Because.

Hereinafter, each component contained in the photosensitive resin composition is demonstrated.

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

[(A) Contains 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 structural unit (2) having at least one selected from an epoxy group and an oxetanyl group Copolymer to do]

The photosensitive resin composition of this invention has (A) structural unit (1) which has at least 1 selected from the carboxyl group protected by the acid-decomposable group, and the phenolic hydroxyl group protected by the acid-decomposable group, and at least one selected from an epoxy group and an oxetanyl group. It contains the copolymer (henceforth called "copolymer (A)") containing the structural unit (2).

It is preferable that copolymer (A) is alkali insoluble and becomes resin which becomes alkali-soluble when the acid-decomposable group which has in a molecule | numerator decomposes.

Here, in this invention, an "acid-decomposable group" means the functional group which can produce | generate the carboxy group or phenolic hydroxyl group protected by the said acid-decomposable group by decomposing in presence of an acid.

In the present invention, the copolymer (A) is &quot; alkali soluble &quot; means that a coating film formed by applying a solution containing the copolymer (A) after decomposition of an acid-decomposable group onto a substrate and heating at 90 캜 for 2 minutes ( It means that the dissolution rate with respect to the 0.4% tetramethylammonium hydroxide aqueous solution in 23 degreeC shown by thickness 3 micrometers) is 0.01 micrometer / sec or more. The alkali solubility is more preferably 0.005 µm / second or more.

In addition, in this invention, a copolymer (A) "alkali insoluble" means that the coating film (3 micrometers in thickness) formed by apply | coating the solution containing copolymer (A) on a board | substrate, and heating at 90 degreeC for 2 minutes. This means that the dissolution rate in the 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. is less than 0.01 μm / sec. The alkali insolubility is more preferably less than 0.005 µm / sec.

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

It is preferable that a copolymer (A) is an acrylic polymer.

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

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

In addition, "the structural unit derived from (meth) acrylic acid and / or its ester" is also called "acrylic-type structural unit." In addition, (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) has a structural unit (1) (hereinafter abbreviated as "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. .

One of the preferred aspects 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 carboxyl group is protected by an acid-decomposable group, and is deprotected by an acid to generate a carboxyl group. In addition, the partial structure represented by following formula (Ib) is a partial structure in which a phenolic hydroxyl group was protected by the acid-decomposable group, and is deprotected by an acid and produces | generates phenolic hydroxyl group.

In a formula (Ia) and a formula (Ib), a broken line part shows the coupling point with another structure.

In formula (Ia) and formula (Ib), R <^1> represents an alkyl group or a cycloalkyl group each independently.

The alkyl group represented by R ¹ may be linear or branched.

As carbon number of the alkyl group represented by R <^1> , it is preferable that it is 1-20, It is more preferable that it is 1-10, It is more preferable that it is 1-7.

As carbon number of the cycloalkyl group represented by R <^1> , it is preferable that it is 3-20, It is more preferable that it is 3-10, It is more preferable that it is 5-7.

Moreover, when R <^1> has a substituent further, these carbon atom numbers also include the carbon atom number of the said substituent.

As the alkyl group represented by R ¹ , for example, 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, etc. are 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.

In addition, the alkyl group and cycloalkyl group represented by R <^1> may have a substituent. As a substituent which can be introduce | transduced into the alkyl group or cycloalkyl group represented by R <^1> , A C1-C10 alkyl group (methyl group, an ethyl group, a propyl group, a butyl group etc.), a C3-C10 cycloalkyl group, a carbon atom An aryl group having 6 to 10 atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and the like can be exemplified. The substituent may be further substituted with the above substituent.

As R ¹ , 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 is preferable, and an alkyl group having 1 to 6 carbon atoms and carbon The cycloalkyl group having 3 to 6 atoms, or the benzyl group is more preferable, more preferably an ethyl group or a cyclohexyl group, and particularly preferably an ethyl group.

In formulas (Ia) and (Ib), R ² represents an alkyl group.

The alkyl group represented by R ² may be linear or branched.

As preferable carbon number of the alkyl group represented by R <^2> , it is preferable that it is 1-20, It is more preferable that it is 1-10, It is more preferable that it is 1-7.

Moreover, when R <^2> has a substituent further, these carbon atom numbers also include the carbon atom number of the said substituent.

As an alkyl group represented by R <^2> , a C1-C6 alkyl group is preferable and a methyl group is especially preferable.

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

There is no restriction | limiting in particular as a bivalent aromatic group represented by Ar <^1> , A phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group, etc. can be illustrated, and it is a phenylene group or a substituted phenylene group. It is preferable that it is a phenylene group, and it is more preferable that it is a 1, 4- phenylene group.

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.) and the number of carbon atoms 3-10 cycloalkyl group, aryl group having 6-10 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, alkoxy group having 1-10 carbon atoms Etc. can be illustrated, and these substituents may be further substituted with the above substituents.

The structural unit which has the partial structure represented by Formula (Ia) can be introduce | transduced into a copolymer (A) using the carboxyl group-containing monomer which can form the said structural unit.

As a carboxyl group-containing monomer which can form the structural unit which has a partial structure represented by Formula (Ia), if the carboxyl group which the said monomer has is protected and can be structural unit (1), it can be used, for example, acrylic acid Monocarboxylic acids such as 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.

Moreover, as a structural unit derived from these carboxyl group-containing monomers, as a structural unit (1), the structural unit in which the carboxyl group which the said monomer has protected is mentioned as a preferable thing.

The structural unit which has the partial structure represented by Formula (Ib) can be introduce | transduced into a copolymer (A) using the phenolic hydroxyl group containing monomer which can form the said structural unit.

As a phenolic hydroxyl group containing monomer which can form the structural unit which has a partial structure represented by Formula (Ib), as long as it can become structural unit (1) by protecting the phenolic hydroxyl group which the said monomer has, it can be used. As such a phenolic hydroxyl group containing monomer, For example, hydroxy styrene, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, Paragraph [0011] of Unexamined-Japanese-Patent No. 2008-40183? ], The 4-hydroxybenzoic acid derivatives of Paragraph [0007]-[0010] of Unexamined-Japanese-Patent No. 2888454, the addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydride Addition reaction products of oxybenzoic acid and glycidyl acrylate etc. are mentioned as a preferable thing.

Among these, as a phenolic hydroxyl group containing monomer, (alpha) -methyl- p-hydroxy styrene, the compound of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2008-40183, and Paragraph 0007-0001 of Japanese Patent No. 2888454 are disclosed. More preferred are the 4-hydroxybenzoic acid derivatives described, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, and addition reactants of 4-hydroxybenzoic acid and glycidyl acrylate.

Among the structural units having the partial structure represented by the formula (Ia) or the partial structure represented by the formula (Ib), particularly preferred as the structural unit (1) is a structural unit represented by the following formula (Ic).

In formula (Ic), R ⁵ represents an alkyl group or a cycloalkyl group. The preferable aspect of R <^5> is the same as that of the preferable aspect of R <^1> in Formula (Ia) and Formula (Ib).

In addition, in formula (Ic), R <^6> represents a hydrogen atom or a methyl group.

As a preferable specific example of the radically polymerizable monomer used in order to form the structural unit represented by Formula (Ic), 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- (2-cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1- Benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate, and the like. Preferred are 1-ethoxyethyl methacrylate and 1-ethoxyethyl acrylate. These radically polymerizable monomers can be used individually by 1 type or in combination of 2 or more types.

A radically polymerizable monomer used for forming the structural unit (1) containing the partial structure represented by the formula (Ia) and the partial structure represented by the formula (Ib) may be a commercially available one, and a known method. Synthesized by For example, as long as it is a monomer represented by following structural formula (A), it can synthesize | combine by reacting (meth) acrylic acid with a vinyl ether compound in presence of an acid catalyst, as shown in following Reaction Formula.

Of the above reaction scheme, R ⁵ and R ⁶ is R ⁵ and R ⁶ with the consent of the formula (Ⅰc).

Moreover, the structural unit (1) which contains the partial structure represented by Formula (Ia) or the partial structure represented by Formula (Ib) is a structural unit (2)? (To mention later) a protected carboxyl group or phenolic hydroxyl group containing monomer. After polymerization with 5) and its precursor, it can also form by making a carboxyl group or phenolic hydroxyl group react with a vinyl ether compound. In addition, the specific example of the preferable structural unit formed in this way is the same as the structural unit derived from the preferable specific example of the said radically polymerizable monomer.

Another suitable aspect 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 formulas (IIa) and (IIb), R ³ represents a tertiary alkyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, and R ⁴ represents a tertiary alkyl group, tert-butoxycarbonyl group, 2 - represents a tetrahydropyranyl group or a 2-tetrahydrofuranyl, Ar ² represents a divalent aromatic, a broken line portion represents a bond with other portions of the structure.

As the tertiary alkyl group in R ³ and R ⁴ , one having 4 to 20 carbon atoms is preferable, one having 4 to 14 carbon atoms is more preferable, and one having 4 to 8 carbon atoms is more preferable.

A tertiary alkyl group in R ^3, 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, R ⁴ a tertiary alkyl group in, tert- butoxycarbonyl group, 2-tetrahydropyranyl group or a 2-tetra The hydrofuranyl group and the divalent aromatic group in Ar ² may have a substituent. As said substituent, a C1-C10 alkyl group (methyl group, an ethyl group, a propyl group, a butyl group etc.), a C3-C10 cycloalkyl group, a C6-C10 aryl group, a halogen atom (fluorine atom, a chlorine atom, a bromine atom) , Iodine atom), a cyano group, a nitro group, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and the like can be exemplified. These substituents may further be substituted by the said substituent.

Moreover, it is more preferable that it is at least 1 sort (s) chosen from the group which consists of group represented by Formula (a) shown below as a tertiary alkyl group in R <^3> and R <^4> .

-C (R ⁹ ) (R ¹⁰ ) (R ¹¹ ) (a)

In formula (a), R <^9> , R <^10> and R <^11> is respectively independently a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C6-C12 aryl group, or a C7-C12 aralkyl group Moreover, any two of R <^9> , R <^10>, and R <^{11> may} combine with each other, become one with the carbon atom to which they couple | bond, and may form the ring.

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, a methyl group, an ethyl group, an n-propyl group or an i-propyl group. , n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, hexyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As a C3-C12 cycloalkyl group represented by R <^9> , R <^10> or R <^11> , it is a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, norbor, for example. And a isobornyl group.

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

As a C7-12 aralkyl group represented by R <^9> , R <^10> or R <^11> , a benzyl group, the (alpha)-methyl benzyl group, a phenethyl group, a naphthyl methyl group, etc. are mentioned, for example.

In addition, R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring with one carbon atom to which they are bonded. As ring structure at the time of R <^9> and R <^10> , R <^9> and R <^11> or R <^10> and R <^11> couple | bonding, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, tetrahydro Furanyl group, adamantyl group, and tetrahydropyranyl group etc. are mentioned.

Moreover, it is preferable that R <^3> in Formula (IIa) is a C4-12 tertiary alkyl group, 2-tetrahydropyranyl group, or 2-tetrahydrofuranyl group, and a C4-8 tertiary alkyl group It is more preferable that it is a 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, It is more preferable that it is a t-butyl group or 2-tetrahydrofuranyl group, A 2-tetrahydrofuranyl group is especially preferable.

Moreover, it is preferable that R <^4> in Formula (IIb) is a C4-C12 tertiary alkyl group, tert-butoxycarbonyl group, 2-tetrahydropyranyl group, or 2-tetrahydrofuranyl group, and it is C4-C4? It is more preferable that it is a tertiary alkyl group, 2-tetrahydropyranyl group, or 2-tetrahydrofuranyl group of 8, It is more preferable that it is a t-butyl group or 2-tetrahydrofuranyl group, A 2-tetrahydrofuranyl group Particularly preferred.

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

The preferable aspect of Ar <^2> in Formula (IIb) is the same as the preferable aspect of Ar <^1> in said 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 carboxyl group, the structure represented by the formula (IIa) can be formed by protecting the carboxyl group of the monomer. Can be used. As said carboxylic acid monomer, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid, (alpha) -methyl- p- carboxy styrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Moreover, as a structural unit (1), the monomeric unit derived from the carboxylic acid in which these carboxy groups were protected is mentioned as a preferable thing.

As a monomer which has the phenolic hydroxyl group which can form the structural unit (1) which has a structure represented by said Formula (IIb) by protecting a phenolic hydroxyl group, the phenolic hydroxyl group which the said monomer has is protected, and it is Formula (IIa) It can be used as long as it can form a structure represented by, for example, hydroxy styrene, such as p-hydroxy styrene, (alpha) -methyl- p-hydroxy styrene, Paragraph of Unexamined-Japanese-Patent No. 2008-40183. The compounds described in 0011 to 0016, the 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, and 4-hydroxybenzoic acid And the addition reactant of glycidyl acrylate and the like can be cited as preferable ones.

Among these, the (alpha) -methyl-p-hydroxy styrene, the compound of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2008-40183, and the 4-hydroxybenzoic acid derivation of Paragraph 0007-0010 of Unexamined-Japanese-Patent No. 2888454 are derived. More preferred are retention, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, and addition reactants of 4-hydroxybenzoic acid and glycidyl acrylate.

Among the structural units having the partial structure represented by the formula (IIa) or the partial structure represented by the formula (IIb), particularly preferred as the structural unit (1) is a structural unit represented by the following formula (IIc).

In formula (IIc), R ⁷ represents a tertiary alkyl group, 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group, and R ⁸ represents a hydrogen atom or a methyl group.

In addition, in Formula (IIc), the preferable aspect of R <^7> is the same as that of R <^3> in Formula (IIa).

As a preferable specific example of the radically polymerizable monomer used for forming the monomeric unit represented by Formula (IIc), For example, tert- butyl methacrylate, tert- butyl acrylate, tetrahydro-2H-pyran methacrylate- 2-yl, tetrahydro-2H-pyran-2-yl acrylate, tetrahydro-2H-furan-2-yl methacrylate, tetrahydro-2H-furan-2-yl acrylate, 2-methyl-2 methacrylate -Adamantyl, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, 1-methylcyclohexyl acrylate, and the like, and in particular, tert-butyl methacrylate and tert-butyl acrylate; Preference is given to tetrahydro-2H-furan-2-yl methacrylate and tetrahydro-2H-furan-2-yl acrylate. These monomeric units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of structural unit (1), the structural unit shown to the following (a1-1)-(a1-4) and (a2-1)-(a2-6) can be illustrated.

Among these, the structural units shown to (a2-5) and (a2-6) are the most preferable from a viewpoint of the compatibility of a sensitivity and transparency.

In all the structural units which comprise a copolymer (A), 10-80 mol% is preferable, as for the content rate of a structural unit (1), 15-70 mol% is more preferable, 20-60 mol% is especially preferable.

<Structural unit (2) having at least one selected from an epoxy group and an oxetanyl group>

The copolymer (A) contains a structural unit (2) (hereinafter abbreviated as "structural unit (2)") having at least one selected from an epoxy group and an oxetanyl group.

The structural unit (2) may have at least one epoxy group or oxetanyl group in one structural unit, and at least one epoxy group and at least one oxetanyl group, two or more epoxy groups, or two or more oxetanyls Although it may have a group and is not specifically limited, It is preferable to have 1-3 epoxy groups and / or oxetanyl groups in total, It is more preferable to have 1 or 2 epoxy groups and / or oxetanyl groups in total, Epoxy group or jade It is more preferable to have one cetanyl 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 more preferably a structural unit having an oxetanyl group in view of sensitivity and storage stability.

In addition, as a combination of the structural unit (1) and the structural unit (2) in a copolymer (A), a structural unit (1) is a structural unit which has a carboxy group protected by the acid-decomposable group, and a structural unit (2) is jade The combination which is a structural unit which has a cetanyl group is preferable.

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

The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

As a specific example of the radically polymerizable monomer used for forming the structural unit which has an epoxy group, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycine (alpha)-n-propyl acrylate Cydyl, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-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, Japanese Patent No. 4168443 And compounds containing alicyclic epoxy skeletons described in paragraphs [0031] to [0035].

As an example of the radically polymerizable monomer used for forming the structural unit which has an oxetanyl group, it has the oxetanyl group as described in Paragraph [0011]-[0016] of Unexamined-Japanese-Patent No. 2001-330953, for example. ) Acrylic acid ester etc. are mentioned.

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

Among these monomers, more preferably, a compound containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and oxetanyl described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953. It is (meth) acrylic acid ester which has a group, Especially preferably, it is (meth) acrylic acid ester which has the oxetanyl group of Paragraph 0011-0001 of Unexamined-Japanese-Patent No. 2001-330953. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyl jade). Cetane-3-yl) methyl, most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of a structural unit (a3), the structural unit represented by following (a3-1)-(a3-6) can be illustrated.

In all the structural units which comprise a copolymer (A), 10-80 mol% is preferable, as for the content rate of a structural unit (2), 15-70 mol% is more preferable, 20-65 mol% is especially preferable. By having the structural unit (2) in said ratio, the physical property of the cured film obtained by the photosensitive resin composition of this invention becomes favorable.

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

<Other structural units (3)>

The copolymer (A) may have the other structural unit (3) in the range which does not prevent the effect of this invention, and as said structural unit (3), a carboxy group, a carboxylic anhydride residue, and / or a phenolic hydroxyl group The structural unit (3b) other than the structural unit (3a) which has, the said structural unit (1)-(2), (3a) is mentioned.

<Structural unit (3a) having a carboxyl group, carboxylic anhydride residue and / or phenolic hydroxyl group>

The copolymer (A) is a structural unit (3a) having a carboxyl group, a carboxylic anhydride residue, and / or a phenolic hydroxyl group in a range in which the copolymer (A) is not alkali-soluble (hereinafter, referred to as a "structural unit (3a) It is preferable to contain a structural unit having a carboxyl group and / or phenolic hydroxyl group.

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

Moreover, as a radically polymerizable monomer used for forming the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. are mentioned as a preferable thing, for example. As a radically polymerizable monomer used in order to form the structural unit which has a phenolic hydroxyl group, For example, hydroxystyrenes, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, Unexamined-Japanese-Patent No. 2008- The compounds described in paragraphs 0011 to 0016 of Publication 40183, the 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, 4-hydroxybenzoic acid and methacrylate glycidyl The addition reaction product of and the addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate etc. are mentioned as a preferable thing.

Among these, as a radically polymerizable monomer for introducing a structural unit (3a) into a copolymer (A), methacrylic acid, acrylic acid, the compound of Paragraph 0011-0008 of Unexamined-Japanese-Patent No. 2008-40183, and a Japanese patent The 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Publication No. 2888454, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, of 4-hydroxybenzoic acid and glycidyl acrylate The addition reactant is more preferable, and the compound described in paragraphs [0011] to [0016] of JP 2008-40183 A and the 4-hydroxy described in paragraphs [0007] to [0010] of JP 2888454 Especially preferred are benzoic acid derivatives, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, and addition reactants of 4-hydroxybenzoic acid and glycidyl acrylate. These structural units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of structural unit (3a), the structural unit represented by following (a4-1)-(a4-11) can be illustrated.

When a copolymer (A) has a structural unit (3a), 1-25 mol% is preferable and, as for the content rate of a structural unit (3a) in all the structural units which comprise a copolymer (A), 2-25 mol% Is more preferable, and 3-20 mol% is especially preferable. By having the structural unit 3a in said ratio, high sensitivity can be obtained and developability becomes favorable.

<Structural unit (3b) other than (1)? (2), (3a)>

Copolymer (A) is abbreviated as structural unit (3b) other than said (1)-(2), (3a) (hereafter an appropriate "structural unit (3b)" in the range which does not prevent the effect of this invention. May contain).

As a radically polymerizable monomer used in order to form structural unit (3b), the compound of Unexamined-Japanese-Patent No. 2004-264623-the paragraphs [0021]-[0024] is mentioned, for example. Except for monomers forming units (1) to (2), (3a).

Among these, as a radically polymerizable monomer for obtaining a structural unit (3b), it contains alicyclic structure containing such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate from a viewpoint of an electrical property improvement. (Meth) acrylic acid ester and styrene are preferable. In view of transparency, methyl (meth) acrylate is preferred. (Meth) acrylic acid 2-hydroxyethyl is preferable from a viewpoint of a sensitivity. Among these, 2-hydroxyethyl (meth) acrylate is more preferable.

The structural unit (3b) can be used individually by 1 type or in combination of 2 or more types.

When a copolymer (A) has a structural unit (3a), 1-50 mol% is preferable and, as for the content rate of a structural unit (3a) in all the structural units which comprise a copolymer (A), 5-40 mol % Is more preferable, and 5-30 mol% is especially preferable.

It is preferable that it is 1,000-100,000, and, as for the weight average molecular weight of a copolymer (A), it is more preferable that it is 2,000-50,000. In addition, the weight average molecular weight in this invention is polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

As a method of introducing each structural unit which a copolymer (A) has into a copolymer (A), a polymerization method may be sufficient, a polymer reaction method may be sufficient, and these 2 methods may be used together.

When using a polymerization method, after monomer previously containing a predetermined functional group is synthesize | combined, these monomers are copolymerized. That is, copolymer (A) is radically polymerizable containing structural unit (1), structural unit (2), and the radically polymerizable monomer used in order to form structural unit (3a), (3b) as needed. A monomer mixture can be synthesize | combined by superposing | polymerizing using a radical polymerization initiator in the organic solvent.

For example, an ethylenically unsaturated compound having a partial structure represented by the formula (1a) or formula (1b) and an ethylenically unsaturated compound having an epoxy group or an oxetanyl group are mixed and addition-polymerized to obtain a desired copolymer ( A) can be obtained.

When using a polymer reaction method, after performing a polymerization reaction using a predetermined kind of monomer, the necessary functional group is introduce | transduced into a structural unit using the reactive group contained in the structural unit of the obtained copolymer. The functional group to be introduced herein includes a crosslinkable group such as a protecting group, an epoxy group or an oxetanyl group, a phenolic hydroxyl group or the like for protecting the phenolic hydroxyl group or the carboxy group and decomposing them in the presence of a strong acid. An alkali-soluble group (acidic group), such as a carboxy group, etc. can be illustrated.

For example, epichlorohydrin is made to react with the copolymer which copolymerized methacrylic acid 2-hydroxyethyl, and introduction of an epoxy group can be illustrated. Thus, after copolymerizing the ethylenically unsaturated compound which has a reactive group, the partial structure and crosslink which are represented by Formula (Ia) and / or Formula (Ib) by polymer reaction are utilized by utilizing the reactive group which remains in a side chain. A functional group such as a penis group can be introduced into the side chain of the copolymer (A).

Hereinafter, although a preferable thing is illustrated as a copolymer (A) used by this invention, this invention is not limited to this.

In addition, the weight average molecular weights of the copolymer (A) illustrated below are 2,000-50,000. The composition ratio is shown in mol% in ().

1-Ethoxyethyl Methacrylic Acid / Glycidyl Glymethacrylate Copolymer (50/50)

1-Ethoxyethyl Methacrylate / Glycidyl Methacrylic Acid / Methacrylic Acid Copolymer (50/40/10)

1-Ethoxyethyl Methacrylate / Glycidyl Methacrylic Acid / Methacrylic Acid / Methacrylic Acid 2-Hydroxyethyl Copolymer (40/30/10/20)

1-Ethoxyethyl Methacrylic Acid / Tetrahydro-2H-pyran-2-yl Methacrylate / Glycidyl Methacrylic Acid / Methacrylic Acid / 2-Hydroxymethacrylate (20/20/30 ／ 10 ／ 20)

1-ethoxyethyl methacrylate / tetrahydro-2H-furan-2-yl methacrylate / glycidyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate (20/20/30 ／ 10 ／ 20)

Methacrylic acid tetrahydro-2H-furan-2-yl / methacrylate glycidyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer (40/30/10/20)

1-Ethoxyethyl Methacrylic Acid / Methacrylic Acid 3,4-Epoxycyclohexylmethyl / Methacrylic Acid Copolymer (45/40/15)

Methacrylic acid 1-ethoxyethyl / methacrylic acid 3,4- epoxycyclohexylmethyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer (40/30/10/20)

Methacrylic acid 1-ethoxyethyl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / methacrylic acid 2-hydroxy Ethyl Copolymer (40/30/10/20)

1-Ethoxyethyl Methacrylic Acid / Methacrylic Acid (3-ethyloxetan-3-yl) methyl Copolymer (50/50)

1-Ethoxyethyl Methacrylic Acid / Methacrylic Acid (3-ethyloxetan-3-yl) methyl / Methacrylic Acid Copolymer

1-Ethoxyethyl Methacrylic Acid / Methacrylic Acid (3-ethyloxetan-3-yl) methyl / Methacrylic Acid / Methacrylic Acid 2-Hydroxyethyl Copolymer (40/30/10/20)

Methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer (40/30/10 ／ 20)

Methacrylic acid tetrahydro-2H-furan-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer (40/30/10 ／ 20)

Methacrylic acid tetrahydro-2H-furan-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid / methacrylic acid 2-hydroxyethyl / styrene copolymer (40/30 / 10/10/10

1-Ethoxyethyl Methacrylic Acid / Methacrylic Acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate Copolymer (40/30/10/20)

1-Ethoxyethyl Methacrylic Acid / 1-Methyl-1 -cyclohexyl Methacrylic Acid / Methacrylic Acid (3-ethyloxetan-3-yl) Methyl / Methacrylic Acid / 2-Methacrylate 2-Hydroxyethyl Coalescing (20/20/30/10/20)

1-Ethoxyethyl Methacrylic Acid / Methacrylic Acid Tetrahydro-2H-pyran-2-yl / Methacrylic Acid (3-Ethyl Oxetan-3-yl) Methyl / 4-Hydroxybenzoic Acid (3-Methacrylo Iloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer (20/20/30/10/20)

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid glycidyl / methacrylic acid copolymer (50/35/15)

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid glycidyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer (35/30/10/25)

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid 3, 4- epoxycyclohexyl methyl / methacrylic acid copolymer (50/40/10)

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid 3,4-epoxycyclohexylmethyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer (40/30/10/20)

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid copolymer (50/40/10)

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer (40/30/10 / 20)

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / alpha -methyl- parahydroxy styrene / 2-methacrylic acid 2-hydroxyethyl copolymer (30 ／ 30 ／ 20 ／ 20)

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3 -Methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer (40/30/15/15)

1-ethoxyethyl ether / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid 2-methacrylic acid of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester Roxyethyl 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, It is more preferable that it is 40-97 mass%, 60-95 mass% Is more preferred. If content of a copolymer (A) is this range, the pattern formation property at the time of image development will become favorable.

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

[(B) Photoacid Generator]

The photosensitive resin composition of this invention is a general formula (I), general formula (OS-1), general formula (OS-3), general formula (OS-4), and general formula (OS-5) which are detailed below. It contains at least one photoacid generator (photoacid generator (B)) selected from the photoacid generator represented by.

Among the photoacid generators included in the photoacid generator (B), photoacid generation represented by General Formula (I), General Formula (OS-3), General Formula (OS-4), or General Formula (OS-5). I am more preferred.

Hereinafter, each photoacid generator contained in the photoacid generator (B) will be described in detail.

One aspect of the photoacid generator contained in the photoacid generator (B) is a photoacid generator represented by the following general formula (I).

R ^1A -C (R ^2A ) = NO-SO ₂ -R ^3A (I)

In general formula (I), R <^1A> is a C1-C6 alkyl group, a C1-C4 halogenated alkyl group, a phenyl group, a biphenyl group, a naphthyl group, 2-furyl group, 2-thienyl group, and carbon atom number When a 1-4 alkoxy group or 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, a C1-4 alkyl group, and a C1-1 carbon atom. It may be substituted by a substituent selected from the group consisting of an alkoxy group and a nitro group of 4. 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 a phenyl group which may be substituted with W The naphthyl group which may be substituted by W or the anthranyl group, dialkylamino group, morpholino group, or cyano group which may be substituted by W is shown. R ^2A and R ^1A may be bonded to each other to form a 5- or 6-membered ring, and the 5- or 6-membered ring may be linked to a benzene ring which may have one or two arbitrary substituents. 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 a phenyl group which may be substituted with W And naphthyl group which may be substituted with W or anthranyl group which may be substituted with W. W is a halogen atom, cyano group, nitro group, alkyl group of 1 to 10 carbon atoms, alkoxy group of 1 to 10 carbon atoms, halogenated alkyl group of 1 to 5 carbon atoms or halogenated alkoxy group of 1 to 5 carbon atoms Indicates.

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

As a C1-C4 halogenated alkyl group represented by R <^1A> , a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, or 2-bromopropyl group is mentioned, for example.

A methoxy group or an ethoxy group is mentioned as a C1-C4 alkoxy group represented by R <^1A> .

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, an alkyl group of 1-4 carbon atoms (for example For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group), alkoxy group having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group) and nitro group may be substituted by a substituent selected from the group consisting of.

As a specific example of the C1-C10 alkyl group represented by R <^2A> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group , n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

As a specific example of the C1-C10 alkoxy group represented by R <^2A> , a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-jade A yloxy 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, and perfluoro- n-amyl group etc. are mentioned.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group and a perfluoro-n-butoxy group And a perfluoro-n-amyloxy group.

As a specific example of the phenyl group which may be substituted by W represented by R <^2A> , o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, p- (n -Propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group , m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (n-butoxy) phenyl group, p- (i-butoxy ) Phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-amyloxy ) Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, 2,4, 6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4 , 6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group, etc. are mentioned.

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

As a specific example of the anthranyl group which may be substituted by W represented by R <^2A> , 2-methyl-1- anthranyl group, 3-methyl-1- anthranyl group, 4-methyl-1- anthranyl group, 5-methyl-1- Anthranyl group, 6-methyl-1-antranyl group, 7-methyl-1-antranyl group, 8-methyl-1-antranyl group, 9-methyl-1-antranyl group, 10-methyl-1-antranyl group, 1- Methyl-2-antranyl group, 3-methyl-2-antranyl group, 4-methyl-2-antranyl group, 5-methyl-2-antranyl group, 6-methyl-2-antranyl group, 7-methyl-2-anthra And a nil 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, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, and the like.

As a specific example of the C1-C10 alkyl group represented by R <^3A> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group , n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

As a specific example of the C1-C10 alkoxy group represented by R <^3A> , a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-jade A yloxy 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, and perfluoro- n-amyl group etc. are mentioned.

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, and a perfluoro-n-butoxy group And a perfluoro-n-amyloxy group.

As a specific example of the phenyl group which may be substituted by W represented by R <^3A> , o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, p- (n -Propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group , m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (n-butoxy) phenyl group, p- (i-butoxy ) Phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-amyloxy ) Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, 2,4, 6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4 , 6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group, etc. are mentioned.

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

As a specific example of the anthranyl group which may be substituted by W represented by R <^3A> , 2-methyl-1- anthranyl group, 3-methyl-1- anthranyl group, 4-methyl-1- anthranyl group, 5-methyl-1- Anthranyl group, 6-methyl-1-antranyl group, 7-methyl-1-antranyl group, 8-methyl-1-antranyl group, 9-methyl-1-antranyl group, 10-methyl-1-antranyl group, 1- Methyl-2-antranyl group, 3-methyl-2-antranyl group, 4-methyl-2-antranyl group, 5-methyl-2-antranyl group, 6-methyl-2-antranyl group, 7-methyl-2-anthra And a nil group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by W, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy having 1 to 5 carbon atoms include R ^2A or As a specific example of a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C5 halogenated alkyl group represented by R <^3A> , and a C1-C5 halogenated alkoxy group And the like.

R ^2A and R ^1A may be bonded to each other to form a 5- or 6-membered ring.

When R ^2A and R ^1A are bonded to each other to form a 5- or 6-membered ring, examples of the 5- or 6-membered ring include carbocyclic groups and heterocyclic vents. For example, cyclopentane, cyclohexane, cyclo Heptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring may be used. The 5- or 6-membered ring may be combined with a benzene ring which may have one or two arbitrary substituents, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chromman, fluorene, xanthene or thy. Orcanthene ring system. The 5- or 6-membered ring may contain a carbonyl group, and examples thereof include cyclohexadienone, naphthalenone, and anthrone ring systems.

One of the preferred embodiments 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} General Formula (I-1) are bonded to form a five-membered ring.

In the general formula (Ⅰ-1), R ^3A are R ^3A and copper in the formula (Ⅰ), X is an alkyl group, an alkoxy group, or a halogen atom, t represents an integer of 0? 3, t When is 2 or 3, some X may be same or different.

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

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

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

As t, 0 or 1 is preferable.

In general formula (I-1), t is 1, X is a methyl group, a substitution position of X is an ortho position, R <^3A> is a C1-C10 linear alkyl group, 7,7-dimethyl-2- Particularly preferred are compounds that are oxonorbornylmethyl groups or p-toluyl groups.

As a specific example of the oxime sulfonate compound represented by general formula (I-1), the following compound (i), a compound (ii), a compound (i), a compound (i), etc. are mentioned, These compounds are 1 You may use individually by species and can also use two or more types together. Compound (i)-(iv) can be obtained as a commercial item.

Moreover, the oxime sulfonate compound represented by general formula (I-1) can also be used in combination with another kind of photo-acid generator (B).

As one of the preferable aspects of the photo-acid generator represented by general formula (I),

R ^1A represents an alkyl group having 1 to 4 carbon atoms, trifluoromethyl group, phenyl group, chlorophenyl group, dichlorophenyl group, methoxyphenyl group, 4-biphenyl group, naphthyl group or 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 a phenyl group which may be substituted with W , Naphthyl group which may be substituted by W or an anthranyl group which may be substituted by W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms , A halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

As a photo-acid generator represented by general formula (I), it is preferable that it is a photo-acid generator represented by general formula (II).

In general formula (II), R <^4A> represents a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a nitro group, and l represents the integer of 0-5. 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 a phenyl group which may be substituted with W , Naphthyl group which may be substituted by W or an anthranyl group which may be substituted by W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms , A halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

Examples of R ^3A in General Formula (II) include 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 is preferable, and it is especially preferable that they are a methyl group, an ethyl group, n-propyl group, n-butyl group, or p-tolyl group.

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

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

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

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

As a preferable aspect of the compound contained in the photo-acid generator represented by general formula (II) among the photo-acid generator represented by general formula (I), R <^1A> is a phenyl group or 4-methoxyphenyl group in general formula (I). It is an aspect which R <^2A> represents a cyano group and R <^3A> represents a methyl group, an ethyl group, n-propyl group, n-butyl group, or 4-tolyl group.

Hereinafter, although the especially preferable example of the compound contained in the photo-acid generator represented by general formula (II) among the photo-acid generator represented by general formula (I) is shown, this invention is not limited to these.

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, R ² = -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, R ^2A = -CN group, R ^3A = 4-tolyl group)

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

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 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. R ⁶ , which may be present in plural, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, and n represents 1 or 2 M represents an integer of 0-6.

In general formula (OS-3)-(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 in total which may have a substituent.

Examples of the substituent which the alkyl group represented by R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, and the like.

As an alkyl group represented by R <^1> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-jade And a methyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group.

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

Examples of the substituent which 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, an aminocarbonyl group, a sulfonic acid group, and an aminosulfo. And an alkoxy sulfonyl group.

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

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

Examples of the substituent which the heteroaryl group represented by R 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, an aminocarbonyl group, a sulfonic acid group, and an amino group. Sulfonyl groups, alkoxysulfonyl groups and the like.

In the general formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ may contain at least one heteroaromatic ring, and for example, the heteroaromatic ring and the benzene ring may be condensed. You may do it.

The heteroaryl group represented by R ¹ includes a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzoimidazole ring, which may have a substituent. The group remove | excluding one hydrogen atom from the ring selected by the above is mentioned.

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), one or two of R ² present in the compound is preferably an alkyl group, an aryl group or a halogen atom, and one is an alkyl group, an aryl group or a halogen It is more preferable that it is an atom, It is especially preferable that one is an alkyl group and the remainder is a hydrogen atom.

In general formula (OS-3)-(OS-5), the alkyl group or aryl group represented by R <^2> may have a substituent.

As a substituent which the alkyl group or aryl group represented by R <^2> may have, the group similar to the substituent which the alkyl group or aryl group represented by said R <^1> may have can be illustrated.

As an alkyl group represented by R <^2> , it is preferable that it is a C1-C12 alkyl group which may have a substituent, and it is more preferable that it is a C1-C6 alkyl group which may have a substituent.

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, aryl group, chloromethyl group and bromo The methyl group, the methoxymethyl group, the benzyl group, etc. are mentioned, A methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, or n-hexyl group More preferably, a methyl group, an ethyl group, n-propyl group, n-butyl group, or n-hexyl group is more preferable, and a methyl group is especially preferable.

As an aryl group represented by R <^2> , it is preferable that it is a C6-C30 aryl group which may have a substituent.

Examples of the aryl group represented by R ² include a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, or p-phenoxyphenyl group.

As a halogen atom represented by R <^2> , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

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

In general formula (OS-3)? (OS-5), n represents 1 or 2, when X is O, n is preferably 1, and when X is S, n is preferably 2 Do.

In general formula (OS-3)-(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 in total which may have a substituent.

Examples of the substituent which the alkyl group represented by R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, and the like.

As an alkyl group represented by R <^6> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-jade And a methyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group.

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 in total.

Examples of the substituent which the alkyloxy group represented by R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, and the like.

Examples of the alkyloxy group represented by R ⁶ include a methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, ethoxyethyloxy group, methylthioethyloxy group, A phenylthio ethyloxy group, an ethoxy carbonyl ethyl oxy group, a phenoxy carbonyl ethyl oxy group, a dimethylamino carbonyl ethyl oxy group, etc. are mentioned.

Among these, methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, or ethoxyethyloxy group is preferable.

In the general formulas (OS-3) to (OS-5), the aminosulfonyl group represented by R ⁶ includes a methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group, aminosulfonyl group and the like. Can be mentioned.

Examples of the alkoxysulfonyl group represented by R ⁶ in General Formulas (OS-3) to (OS-5) include a methoxy sulfonyl group, an ethoxysulfonyl group, a propyloxasulfonyl group, and a butyloxasulfonyl group. Can be.

Moreover, in general formula (OS-3)-(OS-5), m represents the integer of 0-6, It is preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1, It is especially preferable that it is 0 Do.

Moreover, it is especially preferable that the photo-acid generator represented by the said general formula (OS-3) is a photo-acid generator represented with 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 a photoacid generator represented by the following general formula (OS-7), and the photoacid generator represented by the general formula (OS-5), It is especially preferable that it is a photo-acid generator represented with the following general formula (OS-8) or (OS-9).

R <^1> represents an alkyl group, an aryl group, or a heteroaryl group in general formula (OS-6)? (OS-11), R <^7> represents a hydrogen atom or a bromine atom, R <^8> represents a hydrogen atom, C1-C8 An alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ¹⁰ represents a hydrogen atom or a methyl group Indicates.

Formula (OS-6)? R ¹ has the formula in (OS-11) (OS- 3)? And R ¹ and agree in (OS-5), as a preferred aspect.

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

R ⁸ in General Formula (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 It represents a chlorophenyl group, It is preferable that it is a C1-C8 alkyl group, a halogen atom, or a phenyl group, It is more preferable that it is a C1-C8 alkyl group, It is more preferable that it is an C1-C6 alkyl group, Especially it is a methyl group desirable.

R <^9> in general formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and it is preferable that it is a hydrogen atom.

R <^10> in general formula (OS-8)-(OS-11) represents a hydrogen atom or a methyl group, and it is preferable that it is a hydrogen atom.

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

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

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

Another aspect of the photoacid generator contained 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 heteroaryl Group. R ² represents an alkyl group or an aryl group.

In General Formula (OS-1), X represents -O-, -S-, -NH-, -NR ^5- , -CH _2- , -CR ⁶ H-, or -CR ⁶ R ^7- , and R ^{5 to} R ⁷ each independently represent an alkyl group or an aryl group.

In 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 shown. Two of R ^{21 to} R ²⁴ may be bonded to each other to form a ring.

As R <^21> -R <^24> , each independently, a hydrogen atom, a halogen atom, and an alkyl group are preferable, Moreover, the aspect in which at least 2 of R <^21> -R <^24> couple | bonds with each other to form an aryl group is also mentioned preferably. Especially, the aspect whose R <^21> -R <^24> is all hydrogen atoms is preferable from a viewpoint of a sensitivity.

All of the functional groups described may further have a substituent.

As for a photo-acid generator represented by general formula (OS-1), it is more preferable that it is a photo-acid generator represented with the following general formula (OS-2).

In the general formula ^{(OS-2), R 1} , R 2, R 21? R 24 are each independently selected from the general formulas in ^{(OS-1) R 1,} R 2, R 21? R 24 and accept and Preferred examples are also the same.

Among these, are represented by the general formula (OS-1) and general formula (OS-2) R ¹ is a cyano group, or, more preferably an aryl group sun, and the general formula (OS-2) in a, R ¹ The aspect which is this cyano group, a phenyl group, or a naphthyl group is the most preferable.

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

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

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

A photoacid generator (B) can be used individually by 1 type or in combination of 2 or more types.

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

The photosensitive resin composition of this invention is a photo-acid generator sensitive to actinic light, and may contain photo-acid generators other than a photo-acid generator (B) as needed, but does not contain a 1, 2- quinonediazide compound. It is preferable. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but the quantum yield is necessarily 1 or less, and the sensitivity is low. On the other hand, since the acid generated in response to actinic light (B) acts as a catalyst for deprotection of the protected acidic group, the acid produced | generated by the action of one light proton has many deprotection. Contributing to the reaction, the quantum yield exceeds 1, for example, becomes a large value such as a power of 10, and it is estimated that high sensitivity can be obtained as a result of so-called chemical amplification.

[(C) sensitizer]

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

A sensitizer absorbs actinic light or a radiation and will be in an electronic excited state. The sensitizer which has become an electron-excited state comes into contact with the photoacid generator to generate an action such as electron transfer, energy transfer, and heat generation. As a result, photoacid generators cause chemical changes to decompose and produce acids.

As an example of a preferable sensitizer, the compound which belongs to the following compounds, and has an absorption wavelength in 350 nm-450 nm area is mentioned.

Polynuclear aromatics (e.g., 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, dimethyl thioxanthone, diethyl thioxanthone) ), Cyanines (e.g., thiacarbocyanine, oxacarbocyanine), melococyanates (e.g., melocyanine, carbomelocyanine), rhodyanine, oxonol, thiazines ( For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavin), acridones (for example, acridon, 10- Butyl-2-chloroacridone), anthraquinones (e.g., anthraquinones), squalariums (e.g., squaals), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino4-methylcoumarin, 7-hydroxy4-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 which absorbs actinic rays or radiation to become an electron excited state and has an electron transfer action to a photoacid generator is preferable, and in particular, polycyclic aromatics, acridones, styryls, base styryls, coumarins Are preferred.

Among the above-mentioned sensitizers, as a more suitable sensitizer, the sensitizer contained in the compound represented by the following general formula (III), general formula (IV), general formula (V), or general formula (VI) is mentioned. have.

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 represent a monovalent substituent. m and n each independently represent the integer of 0-4.

As an alkyl group of 1-4 carbon atoms represented by R <^1> or R <^2> , a methyl group, an ethyl group, n-propyl group, or n-butyl group is preferable.

As a monovalent substituent represented by R <^3> or R <^4> , a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a nitro group is mentioned, A methyl group, an ethyl group, n- A propyl group, a methoxy group, an ethoxy group, or n-propyloxy group is preferable.

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 a C1-C6 alkyl group or the phenyl group which may be substituted. R ⁶ and R ⁷ each independently represent a monovalent substituent. o and p each independently represent an integer of 0 to 4;

As an alkyl group of 1-6 carbon atoms represented by R <^5> , a methyl group, an ethyl group, n-propyl group, or n-butyl group is preferable. It is preferable that the phenyl group which may be substituted is unsubstituted.

As a monovalent substituent represented by R <^6> or R <^7> , a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a nitro group is mentioned, A fluorine atom, a chlorine atom, The bromine atom, methyl group, ethyl group, n-propyl group, methoxy group, ethoxy group, or n-propyloxy group is preferable.

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 general formula (V), R <^8> , R <^9> and R <^10> respectively independently represent a monovalent substituent, q, r, and s respectively independently represent the integer of 0-2. Two or more of R ⁸ , R ⁹ , and R ¹⁰ may be connected to each other to form a five-membered ring or a six-membered ring.

Examples of the monovalent substituent represented by R ⁸ , R ⁹ , or R ¹⁰ include a halogen atom, cyano group, hydroxyl group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. Acyl group, carboxylic acid ester group having 1 to 4 carbon atoms, alkylamino group having 1 to 4 carbon atoms, dialkylamino group having 1 to 4 carbon atoms, 2-benzoimidazolyl group and 2-benzothiazolyl group Or 2-benzooxazolyl group is mentioned, Cyano group, a hydroxyl group, a methyl group, an ethyl group, n-propyl group, a methoxy group, an acetyl group, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, 2-benzoimida A jolyl group or 2-benzothiazolyl group is preferable.

Moreover, as a 5- or 6-membered ring formed of R <^8> , R <^9> , and R <^10> , the benzene ring which may have arbitrary substituents, 2,3,6,7-tetrahydroquinolizin ring, a cyclopentane ring, Cyclohexane ring is mentioned.

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 represent 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, an aromatic group, or an aromatic aliphatic group. R ¹³ and R ¹⁴ may be linked to each other to form a 5-membered ring or a 6-membered ring.

As a C1-C4 alkyl group represented by R <^11> or R <^12> , a methyl group, an ethyl group, and n-propyl group are preferable.

Moreover, a halogen atom, a cyano group, or a hydroxyl group is mentioned as a substituent which can be introduce | transduced into the alkyl group or phenyl group represented by R <^11> or R <^12> .

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 and 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, etc. are preferable.

As a heterocyclic group represented by R <^13> or R <^14> , the 2-quinoline group, 2-imidazolyl group, 2-thiazolyl group, and 2-oxazolyl group which may have arbitrary substituents are preferable.

As an aromatic group represented by R <^13> or R <^14> , the phenyl group, naphthyl group, and anthranyl group which may have arbitrary substituents is preferable.

As an aromatic aliphatic group represented by R <^13> or R <^14> , the styryl group, 2-vinyl furanyl group, 2-vinyl tetrahydrofuranyl group, 2-vinyl pyranyl group, and 2-vinyl tetrahydropyranyl which may have arbitrary substituents Groups are preferred.

As a 5- or 6-membered ring which R <^13> and R <^14> connects and forms mutually, the 2-quinoline group, 2-imidazolyl group, 2-thiazolyl group, and 2-oxazolyl group which may have arbitrary substituents are preferable. .

Among the sensitizers included in the compound represented by General Formula (III), General Formula (IV), General Formula (V), or General Formula (VI), 9,10-dibutoxyanthracene, from the viewpoint of sensitivity and transparency, 9,10-dipropyloxyanthracene, 10-butyl-2-chloroacridone, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzooxazole, 2,3,6,7-tetra Hydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolizine-11-nons are preferred, and 9,10-dibutoxyanthracene, 9,10-di Propyloxyanthracene and 10-butyl-2-chloroacridone are more preferred.

A sensitizer may use a commercially available thing and may be synthesize | combined by a well-known synthetic method.

In addition, 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 and particularly preferably 30 to 200 parts by mass with respect to 100 parts by mass of the photoacid generator (B) from the viewpoint of both sensitivity and transparency.

[(D) Solvent]

The photosensitive resin composition of this invention contains a solvent.

It is preferable that the photosensitive resin composition of this invention is prepared as a solution which melt | dissolved arbitrary components, such as a copolymer (A) and a photo-acid generator (B) which are essential components, and various additives mentioned later in a solvent.

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

As a solvent used for the photosensitive resin composition of this invention, for example,

(1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

(2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;

(3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate;

(4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

(5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

(7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

(8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate;

(9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

(10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;

(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate;

(12) lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate;

(13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate;

(14) ethyl hydroxyacetate, 2-hydroxy-2-methylpropionate, 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxypropionmethyl, 3-meth Oxypropionethyl, 3-ethoxypropionmethyl, 3-ethoxypropionethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3 Other esters such as methyl-3-methoxybutylbutyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone;

Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone;

(17) Lactones, such as (gamma) -butyrolactone, etc. are mentioned.

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

Among 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.

It is preferable to use together 1 type individually or 2 types, and, as for the solvent which can be used for this invention, it is more preferable to use 2 types together, and propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers are used. It is more preferable to use together.

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

[Other components]

In the photosensitive resin composition of this invention, in addition to the said (A) component-(D) component, (E) antioxidant, (F) crosslinking agent, (G) adhesion | attachment improving agent which are described below as arbitrary components as needed, ( Known additives such as H) basic compounds, (I) surfactants, (J) plasticizers, and (K) thermal radical generators, (L) thermal acid generators, (M) acid enhancers, and (N) development accelerators Can be added.

<(E) antioxidant>

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

As antioxidant, a well-known antioxidant can be contained.

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

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

As a commercial item of a phenolic antioxidant, adecas top AO-60 (brand name, the product made by ADEKA Co., Ltd.), adecas top AO-80 (brand name, the product made by ADEKA Co., Ltd.), Irganox 1098 (chiba Japan) Ltd.) is mentioned.

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

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

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

By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of this invention can be made a stronger film.

(Compound having two or more epoxy groups or oxetanyl groups in the molecule)

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

These crosslinking agents can be obtained as a commercial item. As an example of the crosslinking agent which can be obtained as a commercial item, all are brand name, For example, as bisphenol-A epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, brand name, keyboard) Epoxy resins), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above, brand name, made by DIC Corporation), etc., are bisphenol F-type epoxy resins such as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, A brand name, product made in Japan epoxy resin, EPICLON830, EPICLON835 (above, product made in DIC Corporation), LCE-21, RE-602S (more, brand name, product made in Nihon Kayaku Co., Ltd.) are phenol novolaks As a type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, a brand name, product made in Japan epoxy resin), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, brand names, DIC Corporation) etc. are EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON as cresol novolak-type epoxy resin, etc. N-690, EPICLON N-695 (above, brand name, made by DIC Corporation), EOCN-1020 (above, brand name, made by Nihon Kayaku Co., Ltd.), etc., are aliphatic epoxy resins such as ADEKA RESIN EP-4080S, The same EP-4085S, same EP-4088S (above, brand name, product made by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEADPB 3600, Copper PB 4700 (or higher) , A brand name, Daiserugagaku Kogyo Co., Ltd., etc. are mentioned. In addition, ADEKA RESIN EP-4000S, East EP-4003S, East EP-4010S, East EP-4011S (above, brand name, product made by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000 , EPPN-501, EPPN-502 (above, a brand name, the product made by ADEKA Corporation), etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

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

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

In addition, the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an epoxy group.

As for the addition amount to the photosensitive resin composition of the compound which has two or more epoxy groups or oxetanyl group in a molecule | numerator, when the total amount of a copolymer (A) is 100 mass parts, 1-50 mass parts is preferable, and 3-30 mass parts is more desirable.

(Alkoxymethyl group-containing crosslinking agent)

As the alkoxy methyl group-containing crosslinking agent, alkoxy methylated melamine, alkoxy methylated benzoguanamine, alkoxy methylated glycoluril, alkoxy methylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea into an alkoxymethyl group, respectively. Although it does not specifically limit about the kind of this alkoxy methyl group, For example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group etc. are mentioned, Especially, from a viewpoint of the generation amount of outgas, especially 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 alkoxy methyl group containing crosslinking agents are available as a commercial item, and all are brand 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, brand name, Mitsui Cyanamid Co., Ltd.), Nikarak MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nikarak MS-11, Nikarak MW-30HM, -100LM, -390 (above, a brand name, Sanwa Chemical Co., Ltd.), etc. can be used preferably.

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

(Compound having at least one ethylenically unsaturated double bond)

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

As monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboronyl (meth) acrylate, 3-methoxybutyl (meth) acryl The rate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned.

As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, and the like.

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

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

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

<(G) adhesion improving agent>

The photosensitive resin composition of this invention may contain an adhesive improving agent.

The adhesion improving agent which can be used for the photosensitive resin composition of this invention is made of the inorganic substance used as a base material, for example, silicon compounds, such as silicon, silicon oxide, and silicon nitride, metal, such as gold, copper, aluminum, and an insulating film. It is a compound which improves adhesiveness. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned.

The silane coupling agent as an adhesion improving agent used by this invention aims at the modification of an interface, It does not specifically limit, A well-known thing can be used.

As a preferable silane coupling agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyl trialkoxysilane, (gamma)-glycidoxy propyl alkyl dialkoxysilane, (gamma), for example -Methacryloxypropyltrialkoxysilane, (gamma) -methacryloxypropylalkyl dialkoxysilane, (gamma) -chloropropyltrialkoxysilane, (gamma)-mercaptopropyltrialkoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl tree Alkoxysilane and vinyltrialkoxysilane are mentioned.

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

These adhesion modifiers can be used individually by 1 type or in combination of 2 or more types. When the addition of the adhesion improving agent is effective for improving the adhesiveness between the substrate and the cured film when the cured film is formed by the photosensitive resin composition of the present invention on the substrate, when the cured film is formed in a pattern, the substrate and the pattern It is effective also in adjusting the taper angle of the cured film of a phase.

0.1-20 mass parts is preferable with respect to 100 mass parts of copolymers (A), and, as for content of the adhesion | attachment 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 this invention may contain a basic compound.

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

Examples of the aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, and diethanolamine. , Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, etc. are mentioned.

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

As the heterocyclic amine, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8- 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, etc. are mentioned.

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

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

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

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

<(I) Surfactant>

The photosensitive resin composition of this invention may contain surfactant.

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

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

In addition, in the following trade names, KP (made by Shin-Etsu Chemical Co., Ltd.), polyflow (made by Kyoeisha Chemical Co., Ltd.), F-Top (made by JEMCO company), mega pack (made by DIC Corporation), professional Each series, such as Ride (made by Sumitomo 3M Co., Ltd.), Asahi Guard, and Supron (made by Asahi Glass Co., Ltd.) PolyFox (made by OMNOVA), is mentioned.

As surfactant, the copolymer (1) containing the repeating unit A and repeating unit B shown below is mentioned as a preferable example. The weight average molecular weight (Mw) of the said copolymer is 1000 or more and 10000 or less, and 1500 or more and 5000 or less are preferable. The weight average molecular weight is a value of polystyrene conversion 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 straight chain alkylene group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or 1 to 4 carbon atoms. An alkyl group is represented, L represents a C3-C6 alkylene group, p and q are the mass percentages which show a polymerization ratio, p represents the numerical value of 10 mass% or more and 80 mass% or less, q is 20 mass% The numerical value of 90 mass% or more is shown, r represents the integer of 1 or more and 18 or less, and n represents the integer of 1 or more and 10 or less.

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

In formula (2), R <^25> represents a C1-C4 alkyl group, A C1-C3 alkyl group is preferable at a point of compatibility and the wettability with respect to a to-be-coated surface, and C25 is a carbon number More preferred are 2 or 3 alkyl groups.

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

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

It is preferable that the addition amount of surfactant in the photosensitive resin composition of this invention is 10 mass parts or less with respect to 100 mass parts of copolymers (A), It is more preferable that it is 0.01-10 mass parts, It is 0.01-1 mass part More preferred.

<(J) plasticizer>

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

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

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

<(K) thermal radical generator>

The photosensitive resin composition of this invention may contain the thermal radical generating agent. When it contains ethylenically unsaturated compounds, such as the compound which has at least 1 ethylenically unsaturated double bond mentioned above, it is preferable to contain a thermal radical generating agent.

As a thermal radical generating agent in this invention, a well-known thermal radical generating agent can be used.

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

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

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

When the amount of the thermal radical generator in the photosensitive resin composition of the present invention is 100 parts by mass of the copolymer (A) from the viewpoint of film physical property improvement, 0.01 to 50 parts by mass is preferable, and 0.1 to 20 parts by mass is more preferred. It is preferable and it is most preferable that it is 0.5-10 mass parts.

<(L) Thermal Acid Generator>

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

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

As the generated acid, sulfonic acid or alkyl substituted with an electron withdrawing group having a strong pKa of 2 or less is preferably arylcarboxylic acid, disulfonylimide substituted with an electron withdrawing group in the same manner. As an electron withdrawing group, halogenated alkyl groups, such as halogen atoms, such as F atom, and trifluoromethyl group, nitro group, and cyano group are mentioned.

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

The fact that an acid does not generate | occur | produce substantially by irradiation of exposure light can be judged that there is no change in a spectrum by IR spectrum and NMR spectrum measurement before and behind exposure of a compound.

The molecular weight of sulfonic acid ester is generally 230-1000, Preferably it is 230-800.

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

When the addition amount of sulfonic acid ester to the photosensitive resin composition is 100 mass parts of (A) component, 0.5-20 mass parts is preferable, Especially preferably, it is 1-15 mass parts.

<(M) acid multipliers>

The acid increasing agent can be used for the photosensitive resin composition of this invention for the purpose of a sensitivity improvement. The acid propagation agent used in the present invention is a compound capable of generating an acid by an acid catalyzed reaction to further increase the acid concentration in the reaction system, and is a compound present stably in the absence of acid. Since such compounds increase one or more acids in one reaction, the reaction proceeds rapidly with the progress of the reaction, but since the generated acid itself induces self-decomposition, the strength of the acid generated here is It is preferable that it is 3 or less as an acid dissociation constant and pKa, and it is especially preferable that it is 2 or less.

As an example of an acid increasing agent, Unexamined-Japanese-Patent No. 10-1508 [0203]-[0223], Japan Unexamined-Japanese-Patent No. 10-282642, [0016]-[0055], and Japanese Unexamined-Japanese-Patent No. 9-512498. The compounds described in the twelfth line on page 39 and the second line on page 47 are mentioned.

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

It is preferable that the addition amount of an acid increasing agent to the photosensitive resin composition shall be 10-1000 mass parts with respect to 100 mass parts of photo-acid generators (B) from a viewpoint of the dissolution contrast of an exposure part and an unexposed part, and is 20-500 mass parts More preferably.

<(N) development accelerator>

The photosensitive resin composition of this invention may contain the image development promoter.

As the development accelerator, any compound having a development promoting effect can be used, but the compound having at least one structure selected from carboxyl group, phenolic hydroxyl group, and alkyleneoxy group is preferable, and is selected from carboxyl group or phenolic hydroxyl group. The compound which has at least 1 type of structure is more preferable, and the compound which has a phenolic hydroxyl group is the most preferable.

Moreover, as molecular weight of a development accelerator, 100-3000 are preferable, 100-2000 are more preferable, 150-1000 are optimal.

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

As examples of the development accelerator, Japanese Patent Application Laid-Open No. 2000-66406, Japanese Patent Application Laid-Open No. 9-6001, Japanese Patent Application Laid-Open No. 10-20501, Japanese Patent Application Laid-Open No. 11-338150 The compound described in these etc. are mentioned.

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

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

0.1-30 mass parts is preferable, and, as for the addition amount of the development promoter in the photosensitive resin composition of this invention, when making a copolymer (A) 100 mass parts, 0.2-20 mass parts is more preferable. It is most preferable that it is 0.5-10 mass parts.

[Formation of Cured Film]

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

The formation method of the cured film of this invention includes each process of the following (1)-(5).

(1) Applying the photosensitive resin composition of this invention on a board | substrate (coating process):

(2) Removing a solvent from the applied photosensitive resin composition (solvent removal step):

(3) Exposing the apply | coated photosensitive resin composition by actinic light (exposure process):

(4) Developing the exposed photosensitive resin composition with an aqueous developer (development step):

(5) Thermosetting the developed photosensitive resin composition (post-baking process).

Each step will be described below in order.

In a coating process, the photosensitive resin composition of this invention is apply | coated on a board | substrate, and the wet film containing a solvent is formed.

In the solvent removal process, a solvent is removed from a apply | coated wet film by pressure reduction (backing) and / or heating, and a dry coating film is formed on a board | substrate.

In an exposure process, actinic light of wavelength 300nm or more and 450nm or less is irradiated to the obtained dry coating film. In this step, the photoacid generator (B) decomposes and an acid is generated. By the catalysis of the generated acid, the acid-decomposable group in the structural unit (1) contained in the copolymer (A) is hydrolyzed to produce a carboxyl group and / or a phenolic hydroxyl group.

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

The acid-decomposable group in the structural unit (1) possessed by the copolymer (A) has a low activation energy for acid decomposition, easily decomposes with an acid derived from an acid generator upon exposure, and generates a carboxyl group and / or phenolic hydroxyl group. For this reason, a positive image can also be formed by image development, without necessarily performing PEB.

In addition, by performing PEB at a relatively low temperature, hydrolysis of the acid-decomposable group can be promoted without causing a crosslinking reaction.

It is preferable that the temperature at the time of PEB is 30 degreeC or more and 130 degrees C or less, 40 degreeC or more and 110 degrees C or less are more preferable, 50 degreeC or more and 80 degrees C or less are especially preferable.

In the developing step, the polymer having an advantageous carboxyl group and / or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposure part area | region containing the resin composition which has a carboxyl group and / or phenolic hydroxyl group which is easy to melt | dissolve in an alkaline developing solution.

In the post-baking process, by heating the obtained positive image, the acid-decomposable group in the structural unit (1) is thermally decomposed to form a carboxyl group and / or phenolic hydroxyl group, and crosslinked with an epoxy group and / or oxetanyl group to form a cured film. Can be. It is preferable to heat this heating to high temperature 150 degreeC or more, It is more preferable to heat to 180-250 degreeC, It is especially preferable to heat to 200-250 degreeC. Although heating time can be suitably set according to heating temperature etc., it is preferable to set it in the range of 10 to 90 minutes.

By adding a process of irradiating the active light (preferably ultraviolet rays) to the entire surface of the positive image before the postbaking process, the crosslinking reaction can be promoted by an acid generated by actinic light irradiation.

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

<Preparation of the photosensitive resin composition>

Essential components of the copolymer (A), the photoacid generator (B), the sensitizer (C), and the solvent (D) are mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. . For example, a copolymer (A), a photoacid generator (B), or a sensitizer (C) is each dissolved in a solvent (D) in advance, and then these are mixed at a predetermined ratio to prepare a resin composition. It may be. The composition solution prepared as described above may be used for use after being filtered using a filter having a pore size of 0.2 μm or the like.

<Application process and solvent removal process>

The target dry coating film can be formed by apply | coating the photosensitive resin composition to a predetermined board | substrate, and removing a solvent by pressure reduction and / or heating (prebaking).

As a board | substrate, in manufacture of a liquid crystal display element, the glass plate etc. which provided the polarizing plate, the black matrix layer, the color filter layer as needed, and provided the transparent conductive circuit layer can be illustrated, for example.

The coating method of the photosensitive resin composition to a board | substrate is not specifically limited, For example, methods, such as a slit coating method, a spray method, a roll coating method, and a spin coating method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for large substrates. Here, a large board | substrate means the board | substrate of the magnitude | size of 1 m or more in each side.

In addition, the heating conditions of a solvent removal process are the ranges in which the acid-decomposable group which the structural unit (1) in the copolymer (A) in an unexposed part has decomposes, and does not make a copolymer (A) soluble in alkaline developing solution, Although it changes also with the kind and compounding ratio of each component, Preferably it is about 30 to 120 second at 80-130 degreeC.

Exposure process

In an exposure process, actinic light of a predetermined pattern is irradiated to the board | substrate which provided the dry coating film. Irradiation of an active light may pass through a mask and may draw directly. As actinic light, actinic light which has a wavelength of 300 nm or more and 450 nm or less can be used preferably.

After an exposure process, heat processing (PEB) is performed as needed.

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

When using a mercury lamp, actinic light which has wavelength, such as g line | wire (436 nm), i line | wire (365 nm), and h line | wire (405 nm), can be used preferably. Mercury lamps are preferred in that they are suitable for exposure to large areas compared to lasers.

When using a laser, 343 nm and 355 nm are used as a solid (YAG) laser, 351 nm (XeF) is used as an excimer laser, and 375 nm and 405 nm are used as a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from a viewpoint of stability, cost, etc. A laser can be irradiated to a coating film once or dividing into multiple times.

It is preferable that the energy density per pulse of a laser is 0.1 mJ / cm <2> or more and 10000 mJ / cm <2> or less. In order to fully harden a coating film, 0.3 mJ / cm <2> or more is more preferable, 0.5 mJ / cm <2> or more is the most preferable, In order not to decompose a coating film by an ablation phenomenon, 1000 mJ / cm <2> or less is more preferable. And most preferably 100 mJ / cm 2 or less.

In addition, it is preferable that pulse width is 0.1nsec or more and 30000nsec or less. In order not to decompose a color coating film by an ablation phenomenon, 0.5 nsec or more is more preferable, 1 nsec or more is most preferable, In order to improve the alignment precision at the time of a scanning exposure, 1000 nsec or less is more preferable, and 50 nsec or less Most preferred.

Moreover, 1 Hz or more and 50000 Hz or less are preferable, and, as for the frequency of a laser, 10 Hz or more and 1000 Hz or less are more preferable.

In addition, the frequency of the laser is more preferably 10 Hz or more, more preferably 100 Hz or more, in order to shorten the exposure processing time, and more preferably 10000 Hz or less, more preferably 1000 Hz or less, in order to improve the alignment accuracy during scan exposure. Most preferred.

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

Although there is no restriction | limiting in particular as an exposure apparatus which can be used for this invention, As what is marketed, Callisto (brand name, product made by V-Technology Co., Ltd.), AEGIS (product name, product made by V-Technology Co., Ltd.) and DF2200G (brand name, Dainippon) Screen make), etc. can be used. Moreover, the apparatus of that excepting the above can also be used suitably.

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

Development Process

In the developing step, the exposed portion region is removed using a basic developer to form an image pattern.

As a basic compound contained in a basic developing solution, For example, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; Aqueous solutions, such as sodium silicate and sodium metasilicate, can be used.

Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the aqueous solution containing the said basic compound can also be used as a developing solution.

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

The developing time is usually 30 seconds to 180 seconds, and the developing method may be any of a liquid method, a dip method, and the like. After image development, flowing water washing | cleaning can be performed for 30 second-90 second, and a target pattern can be formed.

<Post Baking Process (Crosslinking Process)>

About the pattern corresponding to the unexposed area | region obtained by image development, using heating apparatuses, such as a hotplate and oven, at a predetermined | prescribed temperature, for example, 180-250 degreeC, for a predetermined time, for example, it will be 5? If it is an oven for 60 minutes, it heat-processes for 30 to 90 minutes, decomposes the acid-decomposable group in a copolymer (A), produces | generates a carboxyl group and / or phenolic hydroxyl group, and produces these epoxy groups in copolymer (A) and / or By reacting and crosslinking with a crosslinkable group which is an oxetanyl group, cured films, such as a protective film and an interlayer insulation film excellent in heat resistance and hardness, can be formed.

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

In addition, prior to heat treatment, after re-exposure to the board | substrate with which the cured film was formed in pattern shape by actinic light, it post-bakes (re-exposure / post-baking) from the photo-acid generator (B) which exists in an unexposed part. It is preferable to generate an acid and to function as a catalyst for promoting the crosslinking process.

That is, it is preferable that the formation method of the cured film of this invention includes the re-exposure process which re-exposes by actinic light between a developing process and a postbaking process.

The exposure in the re-exposure step may be performed by the same means as the above-described exposure step, but in the re-exposure step, it is preferable to perform the entire surface exposure to the side on which the film is formed by the photosensitive resin composition of the present invention on the substrate. Do. As a preferable exposure amount of a re-exposure process, it is 100-1,000mJ / cm <2>.

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

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

As the organic EL display device and the liquid crystal display device of the present invention, the cured film formed by using the photosensitive resin composition of the present invention is not particularly limited except having a flattening film or an interlayer insulating film, and various known organic ELs having various structures A display device and a liquid crystal display device are mentioned.

FIG. 1: shows the typical cross section of the board | substrate in the bottom emission type organic electroluminescence display applicable as the organic electroluminescence display of this invention.

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

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

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

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

Although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited and provided through a target pattern mask, and a second electrode made of Al is formed on the entire surface above the substrate. Active matrix type organic EL display device which is sealed by bonding using a glass plate for encapsulation and an ultraviolet curable epoxy resin, and is connected to TFTs 1 for driving them to each organic EL element. Can be obtained.

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

[Example]

Next, the present invention will be described in more detail with reference to Examples. However, this invention is not limited by these Examples. In addition, "part" and "%" are mass references | standards unless there is particular notice.

In the following synthesis examples, the following code | 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 synthesize | combined as follows.

0.5 part of phenothiazine was added to 144.2 parts (2 molar equivalents) of ethyl vinyl ether, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower, followed by 4 hours at room temperature (25 ° C.). Stirred. After adding 5.0 parts of p-toluenesulfonic acid pyridinium, it stirred at room temperature for 2 hours and left to stand overnight at room temperature. 5 parts of sodium hydrogencarbonate and 5 parts of sodium sulfate were added to the reaction solution, the mixture was stirred at room temperature for 1 hour, the insolubles were concentrated under reduced pressure at 40 ° C or lower after filtration, and the yellow oily substance was removed under reduced pressure. Distillation was carried out to obtain 134.0 parts of 1-ethoxyethyl methacrylate (MAEVE) having a boiling point (bp.) Of 43 to 45 ° C / 7 mmHg fraction 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 stream of nitrogen. While stirring this mixed solution, the mixed solution of radical polymerization initiator V-65 (brand name, the product made by Wako Pure Chemical Industries, Ltd., 4 parts) and EDM (100.0 parts) was dripped over 2.5 hours. After completion | finish of dripping, it was made to react at 70 degreeC for 4 hours, and the EDM solution (solid content concentration: 40%) of polymer A-1 was obtained.

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

<Synthesis of Polymers A-2 to A-9>

Except having changed each used monomer and its usage amount as what was shown in following Table 1, polymer A-2 -A-10 which is a copolymer (A) was synthesize | combined similarly to the synthesis of polymer A-1.

[Table 1]

The symbol of Table 1 is as follows.

MAEVE: 1-ethoxyethyl methacrylate

GMA: glycidyl methacrylate

Oxe-30: methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Yuga Chemical Co., Ltd.)

HEMA: 2-hydroxyethyl methacrylate

M100: methacrylic acid 3,4-epoxycyclohexylmethyl (made by Daiserugagaku Kogyo Co., Ltd.)

MAA: methacrylic acid

CHOEMA: 1- (cyclohexyloxy) ethyl methacrylic acid

MATHF: Methacrylic acid tetrahydro-2H-furan-2-yl

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 synthesize | combined by the method similar to the synthesis method of MAEVE in the synthesis | combination of the said polymer A-1.

<Mathf Synthesis>

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

In addition, Ph-1 (4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester) was synthesize | combined by the method shown below.

Synthesis of Ph-1

To 100 ml solution of acetonitrile of 23 g of 4-hydroxybenzoic acid (3-hydroxypropyl) ester was added 20 ml of N-methylpyrrolidone under stirring, and 16 g of methacrylate chloride was further added. After reacting with stirring at 35 ° C. for 8 hours, the reaction mixture is poured into ice water, and the precipitated crystals are filtered off and recrystallized from ethyl acetate / n-hexane to give 4-hydroxybenzoic acid (3- Methacryloyloxypropyl) ester was obtained.

P-Ph-1 was obtained by protecting Ph-1 with 1-ethoxyethyl ether. 1-ethoxyethyl ether protection of Ph-1 was performed by the method similar to the method described in the said synthesis example 1.

Example 1

Each component was melt | dissolved and mixed so that it might become the following composition A, and it filtered with the polytetrafluoroethylene filter of 0.2 micrometer of diameters, and obtained the photosensitive resin composition of Example 1.

<Composition A>

Copolymer (A): Polyethylene glycol methyl ether acetate of polymer A-1 [hereinafter abbreviated as PGMEA. (D) component] 100.0 parts by solution solids

Photoacid generator (B): 2.0 parts of B-1 shown below

? Sensitizer (C): 2.0 parts of C-1 shown below

Adhesion improver (G): 0.5 parts of G-1 shown below

Surfactant (I): 0.02 part of I-1 shown below

[Examples 2 to 49 and Comparative Example 1]

Except having changed each compound used in Example 1 into the compound of Table 2 or Table 3, it melt | dissolves and mixes with the addition amount similar to Example 1, and the photosensitive resin composition of Examples 249 and Comparative Example 1 is Prepared.

In addition, in Examples 4-14, 21-24, and 26-49 using a crosslinking agent (F), the following crosslinking agent was added with the following addition amount.

In addition, 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): 0.01 part of H-2 shown below

The detail of the symbol which shows each compound used for Examples 1-49 and the comparative example 1 is as follows.

B-1: PAI-1001 (a brand name, a structure shown below, product of Midorigaku Co., Ltd.)

B-2: PAI-1003 (a brand name, a structure shown below, product of Midorigaku Co., Ltd.)

B-3: CGI-1397 (brand name, a structure shown below, product made in Chiba specialty chemicals company)

B-4: PAI-101 (brand name, a structure shown below, product made in Chiba specialty chemicals company)

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

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

B-7: Structure shown below (Synthesis example is mentioned later)

B-8: Structure shown below (Synthesis example is mentioned later)

B-9: Structure shown below (Synthesis example is mentioned later)

B-10: Structure shown below (Synthesis example is mentioned later)

N-1: NBCA (brand name, 10-butyl- 2-chloroacridone, the structure shown below, Kuroganekasei Co., Ltd. product)

N-2: DBA (brand name, 9,10-dibutoxy anthracene, the structure shown below, Kawasaki Kasei Co., Ltd. make)

N-3: NKX-1768 (trade name, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolizine-11 -Paddy, structure shown below, Hayashibara Seibutsu Kagaku Kyukusho Co., Ltd.)

N-4: NK-1342 (brand name, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole, the structure shown below, Hayashibara Seibutsu Chemical Co., Ltd. make)

N-5: DPA (brand name, 9,10- dipropyloxy anthracene, the structure shown below, the Kawasaki Kasei Co., Ltd. product)

N-6: DEA (brand name, 9,10- diethoxy anthracene, the structure shown below, Kawasaki Kasei Co., Ltd. make)

F-1: JER157S70 (brand name, a phenol novolak type epoxy resin, Japan epoxy resin Co., Ltd. product)

G-1: KBM-403 (brand name, 3-glycidoxy propyl trimethoxysilane, the structure shown below, the Shin-Etsu Chemical Co., Ltd. make)

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

H-2: triphenylimidazole

I-1: PolyFox PF-6320 (brand name, fluorine-based surfactant, product made by OMNOVA)

I-2: Perfluoroalkyl group containing nonionic surfactant represented by the following structural formula (W-3)

<Synthesis of B-5>

The compound ((alpha)-(methylsulfonyloxyimino) -2-phenylacetonitrile) shown as B-5 was synthesize | combined as follows.

Synthesis of α- (hydroxyimino) -2-phenylacetonitrile

5.85 g of phenylacetonitrile (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is mixed with 50 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), immersed 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, followed by stirring for 30 minutes under an ice bath. Next, 7.03 g of isonitrite nitrite (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise while keeping the temperature at 20 degrees or less, and the reaction solution was allowed to react for 1 hour at room temperature after completion of dropping. The obtained reaction solution was poured into 150 mL of water in which 1 g of sodium hydroxide was dissolved, and the mixture was completed. Then, 100 ml of ethyl acetate was added thereto, followed by separating an aqueous layer, and about 180 ml of an aqueous layer having a target product was obtained. 100 ml of ethyl acetate was further added, and the aqueous layer was made acidic with pH 3 or less with concentrated hydrochloric acid, and the product was extracted and concentrated. The obtained crude crystal was washed with hexane to give 4.6 g of α- (hydroxyimino) -2-phenylacetonitrile in 63% yield.

(2) Synthesis of α- (methylsulfonyloxyimino) -2-phenylacetonitrile (Compound B-5)

11.5 g of α- (hydroxyimino) -2-phenylacetonitrile was dissolved in 100 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), soaked in an ice bath, and the reaction solution was cooled to 5 ° C or lower. Next, 9.9 g of methanesulfonyl chloride (made by Wako Pure Chemical Industries, Ltd.) was added dropwise, and 9.55 g of triethylamine (made by Wako Pure Chemical Industries, Ltd.) was added dropwise while keeping the internal temperature at 20 ° C. or lower, and under ice bath 1 The reaction was stirred for a while.

The obtained reaction liquid was dripped at 500 mL of water, and it 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) in 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>

(Alpha)-(p-toluenesulfonyloxyimino) phenylacetonitrile (Compound B-6) was synthesize | combined according to the method of Paragraph No. 00 of Unexamined-Japanese-Patent No. 2002-528451.

<Synthesis of B-7>

1-1. Synthesis of Synthetic Intermediate B-7A

2-aminobenzenethiol: 31.3 g (made by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in toluene: 100 mL (made by Wako Pure Chemical Industries, Ltd.) under room temperature (25 degreeC). Next, phenylacetyl chloride: 40.6g (made by Tokyo Chemical Industries, Ltd.) was dripped at the obtained solution, and it stirred for 1 hour and then stirred at 100 degreeC for 2 hours, and made it react at room temperature. 500 mL of water was put into the obtained reaction liquid, the precipitated salt was dissolved, the toluene fraction was extracted, the extract was concentrated with the rotary evaporator, and the synthetic intermediate B-7A was obtained.

1-2. Synthesis of B-7

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.), and then immersed in an ice bath to cool the reaction solution to 5 ° C or lower. Next, tetramethylammonium hydroxide: 4.37 g (25 weight% methanol solution, the Alfa Acer company make) was dripped at the reaction liquid, and it stirred for 0.5 hour and reacted under ice bath. In addition, isopropyl nitrite: 7.03 g was added dropwise keeping the internal temperature at 20 ° C. or lower, and after completion of the dropwise addition, the reaction solution was heated to room temperature, followed by stirring for 1 hour.

Subsequently, after cooling the reaction liquid to 5 degrees C or less, p-toluene sulfonyl chloride (1.9 g) (made by Tokyo Kasei Kogyo Co., Ltd.) was thrown in, and it stirred for 1 hour, maintaining 10 degrees C or less. Then, 80 mL of water was thrown in and it stirred at 0 degreeC for 1 hour. After filtering the obtained precipitate, 60 mL of isopropyl alcohols (IPA) were added, it heated at 50 degreeC, stirred for 1 hour, was filtered and dried at the time, and 1.8 g of B-7 (structure mentioned above) was obtained by filtering. .

The ¹ H-NMR spectrum (300 MHz, medium DMSO ((D ₃ C) ₂ S = O)) of the obtained B-7 was obtained as δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.00 (m, 1H), 7.95-7.9 (m, 2H), 7.6-7.45 (m, 9H), and 2.45 (s, 3H).

It is estimated that B-7 obtained from the above-mentioned ¹ H-NMR measurement result is one type of geometric isomer alone.

<Synthesis of B-8>

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

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

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and it heated up to room temperature and made it react for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered off, reslurried with methanol (20 mL), filtered and dried to obtain 2.3 g of B-8 (structure described above).

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-8 includes δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d. 1H), 5.6 (q, 1H), 2.4 (s, 3H) and 1.7 (d, 3H).

<Synthesis of B-9>

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

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

About the obtained oxime (3.1 g), sulfonation was performed like B-8 and 3.2 g of B-9 (structure mentioned above) were obtained.

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-9 includes 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), 1.4-1.2 (m, 8H), and 0.8 (t, 3H).

<Synthesis of B-10>

B-10 (structure mentioned above) was synthesize | combined like B-8 except having used benzenesulfonyl chloride instead of p-toluenesulfonyl chloride in B-8.

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-10 includes δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d. 1H), 5.6 (q, 1H) and 1.7 (d, 3H).

Comparative Example 2: Example Using 1,2-quinonediazide Compound

As the photosensitive resin composition of the comparative example 2, the composition described in Example 1 of Unexamined-Japanese-Patent No. 5-165214 was prepared.

Comparative Example 3: Example Using Onium Salt-Based Photoacid Generator

As the photosensitive resin composition of the comparative example 3, the composition of Example 1 of Unexamined-Japanese-Patent No. 2004-264623 was prepared as follows.

Preparation of the photosensitive resin composition of the comparative example 3

To the flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol ethylmethyl ether were added. 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 added. After nitrogen substitution, stirring was started gently. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer. The polystyrene reduced weight average molecular weight (Mw) of the obtained copolymer was 11,000. In addition, solid content concentration of the polymer solution obtained here was 31.6%.

The solution containing the copolymer synthesize | combined above is the amount equivalent to 100 parts (solid content) of a copolymer, and 4,7-di-n-butoxy-1- naphthyl tetrahydrothiophenium trifluoromethane sulfo After dissolving 5 parts of dinate in diethylene glycol methyl ethyl ether so that solid content concentration might be 30%, it filtered by the membrane filter of 0.2 micrometer of diameters, and obtained the photosensitive resin composition of the comparative example 3.

[Comparative Example 4: Example using oxime sulfonate-based photoacid generator]

As the photosensitive resin composition of the comparative example 4, the composition of Example 8 of Unexamined-Japanese-Patent No. 2009-98616 was prepared.

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

<Evaluation of liquid aging stability (liquid preservation)>

The viscosity (initial viscosity) of the photosensitive resin composition immediately after preparation, and the viscosity (time-lapse viscosity) of the photosensitive resin composition after storage at 30 degreeC for 1 week and after 2 weeks are measured with E-type viscosity meter (made by Toki Sangyo Co., Ltd.). did. As for evaluation criteria, "3" that the viscosity with time changes 10% or more as a relative evaluation with respect to an initial viscosity (100%), "2" when the change of viscosity is less than 10% and 5% or more, the change of viscosity is 5 The case of less than% was made into "1". "1" and "2" are the levels which are satisfactory practically. The results are shown in Table 2.

<Evaluation of sensitivity>

After slit-coating each photosensitive resin composition on a glass substrate (brand name: Corning 1737, 0.7 mm thickness, Corning Corporation), prebaking is carried out on a 90 degreeC / 120 second hotplate, the solvent is volatilized, and the photosensitive resin of 3.0 micrometers of film thicknesses is carried out. The composition layer was formed.

Next, the obtained photosensitive resin composition layer was exposed through the predetermined | prescribed mask using Canon PLA-501F exposure machine (brand name, ultrahigh pressure mercury lamp). And after developing the photosensitive composition layer after exposure for 23 degreeC / 60 second with alkaline developing solution (0.4 mass% tetramethylammonium hydroxide aqueous solution), it rinsed for 20 second with ultrapure water.

By these operations, the optimum i line | wire exposure amount (Eopt) when resolving a 10 micrometers line and space by 1: 1 was made into the sensitivity. In addition, evaluation criteria are as follows. "1" and "2" are the levels which are satisfactory practically. The results are shown in Tables 2 and 3.

1: less than 40mJ / ㎠

2: 40 mJ / cm 2 or more but less than 60 mJ / cm 2

3: 60 mJ / cm 2 or more Less than 80 mJ / cm 2

4: 80 mJ / ㎠ or more

<Evaluation of transparency>

After slit-coating each photosensitive resin composition on a glass substrate (brand name: Corning 1737, 0.7 mm thickness, Corning Corporation), a solvent is removed by heating on a 90 degreeC / 120 second hotplate, and the photosensitive resin of 3.0 micrometers of film thicknesses The composition layer was formed.

The obtained photosensitive resin composition layer was exposed so that accumulated irradiation amount might be 300 mJ / cm <2> (roughness: 20 mW / cm <2>, i line | wire) with Canon PLA-501F exposure machine (brand name, ultrahigh pressure mercury lamp), and this board | substrate is thereafter, Was heated at 230 degreeC by the oven for 1 hour, and the cured film was obtained.

The light transmittance of the glass substrate which has this cured film was measured with the wavelength of 400-800 nm using the spectrophotometer "150-20 type double beam (brand name, Hitachi Seisakusho Co., Ltd.). The minimum light transmittance at that time is shown in Tables 2 and 3 as evaluation of transparency.

In addition, evaluation criteria are as follows. "1" and "2" are the levels which are satisfactory practically.

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>

The cured film was formed on the glass substrate (brand name: Corning 1737, 0.7 mm thickness, Corning Corporation make) similarly to evaluation of transparency.

The film thickness (T ¹ ) of the obtained cured film was measured. Subsequently, the substrate on which the cured film was formed was immersed in dimethyl sulfoxide having a temperature controlled at 70 ° C. for 20 minutes, and then the film thickness t ^{1 of the} cured film after immersion was measured, and the film thickness change rate by immersion {| t ¹ -T ¹ | was calculated / T ^1} × 100 [%]. 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 result of reference 1-3 is obtained), the solvent resistance of a cured film can be said to be favorable.

1: less than 1%

2: 1% or more but less than 2%

3: 2% or more and less than 3%

4: 3% or more

<Evaluation of Pattern Shape>

After slit-coating each photosensitive resin composition on a glass substrate (brand name: Corning 1737, 0.7 mm thickness, Corning Corporation), a solvent is removed on a 90 degreeC / 120 second hotplate, and the photosensitive resin composition layer with a film thickness of 3.0 micrometers is formed. did.

Subsequently, using the obtained photosensitive resin composition layer as a developing solution with 0.4% tetramethylammonium hydroxide aqueous solution, the exposure amount (roughness: 20mW / cm <2>, which can obtain a contact hole pattern of 10 micrometers angle | corner after 60 second development at 23 degreeC) i line), and it exposed through the mask which has a pattern opening part of 10 micrometers angle.

The board | substrate after exposure used the 0.4% tetramethylammonium hydroxide aqueous solution as a developing solution, and the paddle development of 60 second was performed at 23 degreeC.

The patterned photosensitive resin composition layer was exposed to a cumulative irradiation amount of 300 mJ / cm 2 (roughness: 20 mW / cm 2, i-line) with a PLA-501F exposure machine (trade name, ultra-high pressure mercury lamp) manufactured by Canon Corporation. The board | substrate was heated at 230 degreeC by oven for 1 hour, and the cured film was obtained.

The obtained glass substrate with a cured film was cut, the cross-sectional shape of the patterned contact hole was observed with the field emission scanning electron microscope S-4800 (brand name, the product made by HITACHI), and evaluation was performed.

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 reference 1 is obtained), it can be said that a pattern shape is favorable.

1: Range of taper angles greater than 10 degrees and less than 50 degrees (net taper)

2: range of taper angle of 50 degrees or more and less than 90 degrees (rectangular)

3: range of taper angle over 90 degrees (inverse taper)

[Table 2]

[Table 3]

As shown in Table 2 and Table 3, it can be seen that the photosensitive resin composition of each Example obtained excellent results with respect to any evaluation of liquid storage, transparency, solvent resistance, and pattern shape in comparison with each comparative example. have.

[Example 50]

In Example 50, using the photosensitive resin composition of Example 1, the photosensitive property of Example 1 except having changed the board | substrate into a 6-inch silicon wafer from the glass substrate (brand name: Corning1737, 0.7 mm thickness, Corning Corporation). 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 resin composition.

The results are shown in Table 4.

[Example 51]

In Example 51, using the photosensitive resin composition of Example 1, the exposure machine was changed from Canon PLA-501F exposure machine (brand name) to Nikon Corporation FX-803M (brand name, gh-Line stepper). Except having changed, the sensitivity and pattern shape were evaluated similarly to the evaluation of the sensitivity and pattern shape which were performed with respect to the photosensitive resin composition of Example 1.

The results are shown in Table 4.

[Example 52]

In Example 26, using the photosensitive resin composition of Example 1, except changing the exposure machine from Canon PLA-501F exposure machine (brand name) to the 355 nm laser exposure machine, and performing 355 nm laser exposure, 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 of Example 1.

In addition, as a 355 nm laser exposure machine, "AEGIS" made from VTech Corporation was used (wavelength 355 nm, pulse width 6 nsec), and exposure amount was measured using "PE10B-V2" by OPHIR company.

The results are shown in Table 4.

[Example 53]

In Example 53, using the photosensitive resin composition of Example 1, the photosensitive property of Example 1 except having changed the exposure machine into the UV-LED light source exposure machine from Canon PLA-501F exposure machine (brand name). 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 resin composition.

The results are shown in Table 4.

[Table 4]

As shown in Table 4, the photosensitive resin composition of an Example shows the outstanding sensitivity irrespective of a board | substrate and an exposure machine, and it turns out that it is excellent also 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).

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

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization film 4 was formed on the insulating film 3 in a state of filling the unevenness by the wiring 2. Formation of the planarization film 4 on the insulating film 3 is carried out by spin-coating the photosensitive resin composition of Example 4 on a substrate, prebaking (90 占 폚 x 2 minutes) on a hot plate, and then applying a high-pressure mercury lamp from the mask. After irradiating i line | wire (365 nm) to 45mJ / cm <2> (roughness 20mW / cm <2>), it developed with alkaline aqueous solution, the pattern was formed, and heat-process for 60 minutes was performed at 230 degreeC.

The applicability | paintability at the time of apply | coating the photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle and a crack were not seen in the cured film obtained after exposure, image development, and baking. In addition, the film thickness of the planarization film 4 which produced 500 nm of average level | step differences of the wiring 2 was 2,000 nm.

Next, the bottom emission type organic EL element was formed on the obtained planarization film 4. First, on the planarization film 4, the 1st electrode 5 which consists of ITO was connected to the wiring 2 through the contact hole 7, and was formed. Then, the resist was apply | coated and prebaked, and it exposed and developed through the mask of the target pattern. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Then, the resist pattern was peeled at 50 degreeC using the resist stripping liquid (Remover 100, the product made from AZ Electronic Materials). The 1st electrode 5 obtained in this way is corresponded to the anode of organic electroluminescent element.

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

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

As described above, an active matrix organic EL display device obtained by connecting the TFT 1 for driving the organic EL element to each organic EL element was obtained. When voltage was applied through the driving circuit, good display characteristics were shown, indicating that the display was a highly reliable organic EL display device.

[Example 55]

In the active matrix liquid crystal display device of FIG. 1 of JP-A-3321003, the cured film 17 was formed as an interlayer insulation film as follows, and the 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 insulation film by the method similar to the formation method of the planarization film 4 of the organic electroluminescence display in Example 54.

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

The disclosures of Japanese applications 2010-009333, 2010-075549, and 2010-281954 are incorporated herein by reference. All documents, patent applications, and technical specifications described in this specification are incorporated by reference in this specification to the same extent as if the individual documents, patent applications, and technical specifications were specifically and individually recorded. Is introduced.

Claims (11)

(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 structural unit (2) having at least one selected from an epoxy group and an oxetanyl group Copolymer, (B) Photoacid generation represented by the following general formula (I), general formula (OS-1), general formula (OS-3), general formula (OS-4), and general formula (OS-5) The photosensitive resin composition containing the at least 1 sort (s) of photo-acid generator chosen from the agent, (C) sensitizer, and (D) solvent.
R ^1A -C (R ^2A ) = NO-SO ₂ -R ^3A (I)
[In General Formula (I), R <^1A> is a C1-C6 alkyl group, a C1-C4 halogenated alkyl group, a phenyl group, a biphenyl group, a naphthyl group, 2-furyl group, 2-thienyl group, a carbon atom. When a C1-4 alkoxy group or 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, a C1-C4 alkyl group, and C1-C1 It may be substituted by a substituent selected from the group consisting of an alkoxy group 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 a phenyl group which may be substituted with W The naphthyl group which may be substituted by W or the anthranyl group, dialkylamino group, morpholino group, or cyano group which may be substituted by W is shown. R ^2A and R ^1A may be bonded to each other to form a 5- or 6-membered ring, and the 5- or 6-membered ring may be linked to a benzene ring which may have one or two arbitrary substituents. 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 a phenyl group which may be substituted with W And naphthyl group which may be substituted with W or anthranyl group which may be substituted with W. W is a halogen atom, cyano group, nitro group, alkyl group of 1 to 10 carbon atoms, alkoxy group of 1 to 10 carbon atoms, halogenated alkyl group of 1 to 5 carbon atoms or halogenated alkoxy group of 1 to 5 carbon atoms Is displayed.]

[In General Formula (OS-1), R <^1> is 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. An aryl group is shown. R ² represents an alkyl group or an aryl group. X represents —O—, —S—, —NH—, —NR ⁵ —, —CH ₂ —, —CR ⁶ H—, or —CR ⁶ R ⁷ —, and R ^{5 to} R ⁷ each independently , An alkyl group, or an aryl group. R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. ]

[In general formula (OS-3)-In general formula (OS-5), R <^1> represents an alkyl group, an aryl group, or heteroaryl group, and two or more R <^2> respectively independently represents a hydrogen atom, 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, X represents O or S, and n Represents 1 or 2, and m represents an integer of 0-6.] The method of claim 1,
The photosensitive resin composition whose said (C) sensitizer is a compound represented by the following general formula (III), general formula (IV), general formula (V), or general formula (VI).

[In General Formula (III), R <^1> and R <^2> represents a C1-C4 alkyl group, and R <^1> and R <^2> are the same. R ³ and R ⁴ each independently represent a monovalent substituent. m and n each independently represent an integer of 0 to 4;

[In General Formula (IV), R <^5> represents the C1-C6 alkyl group or the phenyl group which may be substituted. R ⁶ and R ⁷ each independently represent 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> represent a monovalent substituent each independently, q, r, and s respectively independently represent the integer of 0-2. Two or more of R ⁸ , R ⁹ , and R ¹⁰ may be connected to each other to form a 5- or 6-membered ring.]

[In General Formula (VI), R <^11> and R <^12> respectively independently represents a substituted or unsubstituted C1-C4 alkyl group or 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 linked to each other to form a 5- or 6-membered ring.] The method according to claim 1 or 2,
The photosensitive resin composition whose photo-acid generator represented by the said General formula (I) is a photo-acid generator represented with the following general formula (II).

[In General Formula (II), R <^4A> represents a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a nitro group, and l represents the integer of 0-5. 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 a phenyl group which may be substituted with W And naphthyl group which may be substituted with W or anthranyl group which may be substituted with W. W is a halogen atom, cyano group, nitro group, alkyl group of 1 to 10 carbon atoms, alkoxy group of 1 to 10 carbon atoms, halogenated alkyl group of 1 to 5 carbon atoms or halogenated alkoxy group of 1 to 5 carbon atoms Is displayed.] 4. The method according to any one of claims 1 to 3,
The photosensitive resin composition whose structural unit (2) which the said (A) copolymer has is a structural unit which has an oxetanyl group. 5. The method according to any one of claims 1 to 4,
The photosensitive resin composition containing a crosslinking agent further. The cured film formed by giving at least one of light and a heat | fever to the photosensitive resin composition of any one of Claims 1-5. (1) Applying the photosensitive resin composition of any one of Claims 1-5 on a board | substrate,
(2) removing a solvent from the applied photosensitive resin composition,
(3) exposing the applied photosensitive resin composition by actinic light,
(4) developing the exposed photosensitive resin composition with an aqueous developer, and
(5) thermosetting the developed photosensitive resin composition
Formation method of the cured film containing a. The cured film formed by the formation method of the cured film of Claim 7. 9. The method according to claim 6 or 8,
Cured film which is an interlayer insulation film. The organic electroluminescence display provided with the cured film of Claim 6, 8 or 9. The liquid crystal display device provided with the cured film of Claim 6, 8 or 9.

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