KR101807630B1 - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device - Google Patents

Abstract

Provided are a photosensitive resin composition having excellent adhesion to a substrate, a high transmittance, a high heat resistance, and a high sensitivity, a method for producing a cured film, a cured film, a liquid crystal display, and an organic EL display. (A) a polybenzoxazole precursor containing a repeating unit represented by the general formula (1), (B) a photoacid generator having a pKa of the generated acid of 4 or less, (C) a solvent, and (D) A photosensitive resin composition comprising a crosslinking agent having two or more crosslinkable groups reactive with a phenolic hydroxyl group. Wherein at least one of R ¹ and R ² is an acid-decomposable group.
In general formula (1)

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a method of producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device using the photosensitive resin composition,

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as "composition of the present invention"). The present invention also relates to a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing a photosensitive resin composition, and various image display devices using the cured film.

More particularly, the present invention relates to a photosensitive resin composition suitable for forming a planarizing film, a protective film or an interlayer insulating film of an electronic part such as a liquid crystal display, an organic EL (organic electroluminescence) display, an integrated circuit element, And a method for producing the cured film.

In an organic EL display device, a liquid crystal display device, or the like, a patterned interlayer insulating film is provided. In forming the interlayer insulating film, a photosensitive resin composition is widely used in that the number of processes for obtaining a desired pattern shape is small and sufficient flatness is obtained.

The photosensitive resin composition for an interlayer insulating film or the interlayer insulating film in the above display device needs performance such as high sensitivity, high resolution, high transparency, and solvent resistance. As a representative material, attempts have been made to use an acrylic resin as a film-forming component, and for example, those described in Patent Documents 1 and 2 are known.

In recent years, attempts have been made to perform heat treatment or film formation at a higher temperature (for example, about 300 캜) than in the prior art, in order to improve manufacturing efficiency and display device performance.

Polybenzoxazole (PBO) is known as a material having higher heat resistance than acrylic resin. Attempts have been made to form photosensitive resin compositions using PBO precursors and to form various fine patterns (Patent Documents 3 to 5).

Patent Document 1: Japanese Laid-Open Patent Publication No. 2011-209681 Patent Document 2: JP-A No. 2011-221471 Patent Document 3: JP-A-2008-224970 Patent Document 4: Japanese Laid-Open Patent Publication No. 2011-512552 Patent Document 5: JP-A-2004-170611

However, the conventional photosensitive compositions such as Patent Documents 3 to 5 have a problem in that adhesion to a substrate is lowered when exposed to a chemical solution used in a subsequent step of an insulating film. In addition, the transmittance was not sufficiently high as a material for a display device.

Disclosure of the Invention The present invention has been made in order to solve the above problems and provides a photosensitive resin composition excellent in adhesion to a substrate, And an object of the present invention is to provide a device.

Under these circumstances, the present inventors have conducted intensive studies and, as a result, have found that the polybenzoxazole precursor having an acid-decomposable group, the photoacid generator having a pKa of the generated acid of 4 or less, and a predetermined crosslinking agent are contained, , A high transmittance, a high heat resistance, and a high sensitivity, thereby completing the present invention.

More specifically, according to the following solving means <1>, preferably, the above-mentioned problems are solved by <2> to <14>.

(1) A polybenzoxazole precursor comprising a repeating unit represented by the general formula (1)

(B) a photoacid generator having a pKa of the generated acid of 4 or less,

(C) a solvent, and

(D) a crosslinking agent having two or more crosslinkable groups reactive with a benzene ring and / or a phenolic hydroxyl group.

In general formula (1)

[Chemical Formula 1]

(In the general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an acid decomposable group or -CORc Rc Represents an alkyl group or an aryl group, at least one of R ¹ and R ² is an acid-decomposable group.)

<2> The photosensitive resin composition according to <1>, wherein the crosslinkable group of the crosslinking agent (D) is selected from an epoxy group, a methylol group, an alkoxymethyl group and a block isocyanate group.

<3> A photosensitive resin composition according to <1> or <2>, wherein the terminal of the polybenzoxazole precursor (A) is a group represented by the general formula (1-1).

(1-1)

(2)

(In the general formula (1-1), Z represents a single bond, a carbon atom or a sulfur atom, R ¹¹ represents a monovalent organic group, n represents 0 or 1, and when Z represents a single bond, And when Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2. When n is 0, two R ¹¹ may be bonded to each other to form a ring.

(4) The polybenzoxazole precursor as described in any one of (1) to (4) above, wherein the polybenzoxazole precursor comprises a repeating unit represented by m general formula (1-2) and a repeating unit represented by n general formula (3) n is from 0 to 1000, and m + n is from 3 to 1000. The photosensitive resin composition according to any one of < 1 >

In general formula (1-2)

(3)

In general formula (3)

[Chemical Formula 4]

(In the general formulas (1-2) and (3), Y ¹ each independently represents an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or a group represented by -CH ₂ - X ¹ represents an aromatic ring, a heterocyclic ring, an aliphatic ring, or a group formed by combining at least _{two of} R ₁ , R ₂ , R 3, R ₄ , -CH ₂ -, an oxygen atom, a sulfur _{atom, -SO 2 -, -CO-, -NHCO-} , and -C (CF _{3) 2} - represents a tetravalent made of a combination of at least one kind of, Ra and Rb R 2 and R 3 each independently represents a hydrogen atom, an acid-decomposable group, an alkyl group or -COR c, and at least one of Ra and Rb is an acid-decomposable group, Rc represents an alkyl group or an aryl group, X ² represents an arylene group, , A divalent cyclic aliphatic group or a combination of at least one of -CH ₂ -, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ - &Lt; / RTI &gt;

<5> The photosensitive resin composition according to any one of <1> to <4>, further comprising an adhesion promoter.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the (B) photoacid generator is an oxime sulfonate photo acid generator and / or an imide sulfonate photo acid generator.

<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the acid-decomposable group is a group which is cleaved by the action of an acid or -C (R ⁵ ) ₂ -COOR ⁴ . Provided that each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and R ⁴ represents a group which is eliminated by the action of an acid.

<8> The photosensitive resin composition according to <7>, wherein the group eliminated by the action of an acid is a substituent group of a vinyl ether group.

<9> The photosensitive resin composition according to <7>, wherein the group which is eliminated by the action of an acid is an alkoxycarbonyl group, an alkoxyalkyl group, an alkylsilyl group, a group constituting an acetal, or a group constituting a ketal.

(10) A method for producing a photosensitive resin composition, comprising the steps of (1) applying at least one surface of a substrate a photosensitive resin composition according to any one of (1) to (9)

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

(3) a step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray,

(4) a step of developing the exposed photosensitive resin composition by an aqueous developing solution, and

(5) Post-baking process for thermally curing the developed photosensitive resin composition

Wherein the cured film has a thickness of 100 nm or less.

(4) After the developing step, (5) before the post-baking step, the step of exposing the developed photosensitive resin composition to the entire surface.

<12> A cured film obtained by curing a photosensitive resin composition according to any one of <1> to <9>, or a cured film formed by a method according to <10> or <11>.

<13> A cured film according to <12>, which is an interlayer insulating film.

<14> A liquid crystal display device or organic EL display device having a cured film according to <12> or <13>.

According to the present invention, it becomes possible to provide a photosensitive resin composition, a method of producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device which are excellent in adhesion to a substrate, have high transmittance, high heat resistance and high sensitivity.

Fig. 1 shows a configuration diagram of an example of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device.
2 shows a configuration diagram of an example of the organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "" is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Further, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The solid content concentration in the present invention means the solid content concentration at 25 占 폚.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by using, for example, HLC-8220 (manufactured by TOSOH CORPORATION), TSKgel Super AWM- 6.0 mm ID x 15.0 cm) as the eluent was used, using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

Photosensitive resin composition

The photosensitive resin composition of the present invention comprises (A) a polybenzoxazole precursor containing a repeating unit represented by the general formula (1), (B) a photoacid generator having a pKa of the generated acid of 4 or less, (C) a solvent, and (D) a crosslinking agent having two or more crosslinkable groups which react with a benzene ring and / or a phenolic hydroxyl group.

In general formula (1)

[Chemical Formula 5]

(In the general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an acid decomposable group or -CORc Rc Represents an alkyl group or an aryl group, at least one of R ¹ and R ² is an acid-decomposable group.)

By using the composition of the present invention, the adhesion to the substrate is excellent, the transmittance is high, the heat resistance is high, and the sensitivity is high. The details of this mechanism are unclear, but by adding a crosslinking agent, it is possible to form a crosslinked structure between the polymers by reacting a benzene ring or a hydroxyl group of the polybenzoxazole precursor (A) with a crosslinkable group of the crosslinking agent, Heat resistance can be achieved. In Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2008-224970), since the ring structure of the oxetane ring is stable, although the oxetate ring is used as the bridging ring group, I never do that. In this document, it is merely that the compounds including oxetase react with each other to bind (A) the polyvinylbenzoxazole precursor.

The photosensitive resin composition of the present invention is preferably used as a chemically amplified positive photosensitive resin composition. Hereinafter, the composition of the present invention will be described in detail.

<Polybenzoxazole precursor having (A) an acid-decomposable group>

The composition of the present invention comprises (A) a polybenzoxazole precursor containing a repeating unit represented by the general formula (1) (hereinafter simply referred to as "(A) a polybenzoxazole precursor", " In some cases). The repeating unit represented by the general formula (1) is a repeating unit having an acid-decomposable group. The polybenzoxazole precursor (A) used in the present invention preferably has a crosslinkable group at the terminal. The terminal may be one terminal, more preferably both terminals have a crosslinkable group. In the present invention, the terminus of the polybenzoxazole precursor means the main chain terminal of the polybenzoxazole precursor.

<< (a-1) Repeating unit having an acid-decomposable group >>

In the present invention, the repeating unit having an acid-decomposable group (a-1) is a repeating unit represented by the general formula (1). The polybenzoxazole precursor (A) used in the present invention may contain only one kind of the repeating unit represented by the general formula (1), or may contain two or more kinds. The polybenzoxazole precursor (A) preferably contains a repeating unit represented by the general formula (1) in an amount of 70 mol% or more, more preferably 80 mol% or more, and most preferably, 90 mol% or more.

The polybenzoxazole precursor (A) preferably contains a repeating unit containing an acid-decomposable group in a proportion of 50 to 100 mol%, more preferably 10 to 50 mol%, of the total repeating units .

In general formula (1)

[Chemical Formula 6]

(In the general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an acid decomposable group or -CORc Rc Represents an alkyl group or an aryl group, at least one of R ¹ and R ² is an acid decomposable group.)

X represents a tetravalent organic group. The tetravalent organic group represented by X is not particularly limited, but preferably has at least one cyclic structure, and more preferably has 1 to 2 cyclic structures. The cyclic structure may be any of an aromatic ring, a heterocyclic ring and an aliphatic ring, preferably an aromatic ring and / or a heterocyclic ring, and more preferably an aromatic ring. By adopting such an annular structure, the effect of the present invention can be more effectively exhibited.

Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the heterocyclic ring include furan ring, thiophen ring, pyrrole ring, pyrrole ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, A thiazole ring, a pyrazoline ring, a pyrazoline ring, a pyrazolidine ring, a triazole ring, a furan ring, a tetrazole ring, a pyran ring, a thiazole ring, a pyridine ring, a piperidine ring, a oxazine ring, a morpholine ring, , Pyrimidine ring, pyrazine ring, piperazine ring, and triazin ring. Examples of the aliphatic ring include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.

In addition, when having a plurality of cyclic structures, ring-axis _{(preferably, -C (CF 3) 2 -} ) may be, -O-, -S-, a fluorine-substituted alkylene group bright, -CH ₂ -, -SO ₂ -, -NHCO-, or the like. The linking group, -O-, -S-, -C (CF 3) 2 -, -CH 2 -, -SO 2 -, or -NHCO-, and should preferably, -C (CF _{3) 2} - are more preferred Do.

In the present invention, it is preferable that the X moiety comprises a fluorine-substituted alkylene group. By including a fluorine-substituted alkylene group, the transparency of the composition of the present invention tends to be further improved.

Specific examples of X include, but are not limited to, the following. In the formulas, X ¹ represents a linking group.

(7)

It is preferred that NH and R &lt; ¹ &gt; and NH and R &lt; ² &gt; bonded to X are bonded so as to be ortho (adjacent) in the cyclic structure.

As X, (2) and (10) are preferable, and (2) is more preferable. Particularly, when X ¹ is a fluorine-substituted alkylene group (preferably -C (CF ₃ ) ₂ -), the transparency of the composition of the present invention is further improved.

R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an acid decomposable group or -CORc. At least one of R ¹ and R ² is an acid-decomposable group.

The alkyl group may or may not have a substituent.

As the alkyl group, a straight chain, branched or cyclic alkyl group is preferable. In the case of a straight chain or branched alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms desirable. The cyclic alkyl group is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having 5 to 15 carbon atoms, and more preferably an alkyl group having 5 to 10 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl. Examples of the substituent include a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

The acid-decomposable group is a group which is cleaved by the action of an acid or a group capable of leaving an alkali-soluble group such as a hydroxyl group or a carboxyl group by the action of an acid, such as -C (R ⁵ ) ₂ -COOR ⁴ .

R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a group which is eliminated by the action of an acid. Here, the acid acting on the acid generally means an acid generated from an acid generator described later.

Examples of the group capable of eliminating by the action of an acid include a vinyl ether group-containing substituent, an alkoxycarbonyl group (preferably having 2 to 5 carbon atoms), an alkoxyalkyl group (preferably having 2 to 5 carbon atoms), an alkylsilyl group To 20), or a group constituting acetal or ketal. From the viewpoint of sensitivity, an acetal group or a ketal group is preferable.

Examples of the group constituting the acetal or ketal include those having the following structures.

[Chemical Formula 8]

Wherein R ^1x and R ^2x each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ^1x and R ^2x represents an alkyl group or an aryl group, R ^3x represents an alkyl group or an aryl group, R ^1x or R ^2x and R ^3x may be connected to form a cyclic ether.)

The alkyl group represented by R ^1x and R ^2x is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. The aryl group represented by R ^1x and R ^2x is preferably an aryl group having 6 to 10 carbon atoms, more preferably a phenyl group. Each of R ^1x and R ^2x is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ^3x represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.

Specific examples of the group cleaved by the action of an acid include an alkoxycarbonyl group such as a t-butoxycarbonyl group, an alkoxyalkyl group such as methoxymethyl group and ethoxyethyl group, an alkylsilyl group such as methylsilyl group and ethylsilyl group, A tetrahydropyranyl group, an alkoxy-substituted tetrahydropyranyl group, an alkoxy-substituted tetrahydrofuranyl group, and the like are exemplified as typical examples, but are not limited thereto. The most preferred group for leaving groups by the action of an acid is an ethoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group. These may be used alone or in combination.

Represents a preferable group structure as a group which is eliminated by the action of an acid.

[Chemical Formula 9]

Rc represents an alkyl group or an aryl group, and may or may not have these air-substituent groups.

The alkyl group represented by Rc is synonymous with the alkyl group represented by R ¹ and R ² , and the preferable range is also the same.

The aryl group represented by Rc is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group and a naphthyl group. The substituent which the aryl group may have is the same as the substituent which the alkyl group may have.

Y represents a divalent organic group. The divalent organic group represented by Y is not particularly limited, but it is preferable to have at least one cyclic structure, more preferably one having 2 or more cyclic structures. The cyclic structure may be any of an arylene group, a divalent cyclic aliphatic group and a divalent heterocyclic group, and preferably contains an arylene group and / or a divalent heterocyclic ring, and more preferably an arylene group. Specifically, examples of the divalent organic group represented by Y include an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or a group having a methylene group, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO -, and -C (CF ₃ ) ₂ -.

The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 14 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group and an anthraceneylene group.

Examples of the divalent cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkenylene group. The cyclic alkylene group is preferably an alkylene group having 3 to 20 carbon atoms, more preferably a cyclic alkylene group having 3 to 18 carbon atoms, and more preferably a cyclic alkylene group having 3 to 15 carbon atoms. The cyclic alkenylene group is preferably an alkenylene group having 3 to 20 carbon atoms, more preferably a cyclic alkenylene group having 3 to 18 carbon atoms, and more preferably a cyclic alkenylene group having 3 to 15 carbon atoms. The cyclic alkenylene group is preferably a cyclic alkane-containing group having 3 to 20 carbon atoms, more preferably a cyclic alkane-containing group having 3 to 18 carbon atoms, and more preferably a cyclic alkane-containing group having 3 to 15 carbon atoms. Specific examples of the divalent cyclic aliphatic group include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, a 1,2-cyclohexylene group and an octylene group.

The divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocycle. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is more preferable. As the hetero atom constituting the heterocycle, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocyclic ring is preferably an aromatic heterocyclic ring. The aromatic heterocycle is generally an unsaturated heterocycle, and more preferably an unsaturated heterocycle having the most double bond. Specific examples of the heterocycle include furan ring, thiophen ring, pyrrole ring, pyrrole ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imida A thiazole ring, a pyrazoline ring, a pyrazolyl ring, a triazole ring, a furan ring, a tetrazole ring, a pyran ring, a thiazole ring, a pyridine ring, a piperidine ring, a oxazine ring, a morpholine ring, A pyrimidine ring, a pyrazine ring, a piperazine ring and a triazine ring.

Y represents an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or a group of the following formulas: a methylene group, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ -. Specific examples thereof include the following groups. In the formula, A represents a methylene group, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, or -C (CF ₃ ) ₂ -.

[Chemical formula 10]

Of these, Y is preferably 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group or octylene group.

The repeating unit represented by the general formula (1) is more preferably represented by the general formula (1-2).

In general formula (1-2)

(11)

(Compound (1-2) of, Y ¹ are each, independently represent an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or mixtures thereof with, -CH ₂ -, an oxygen atom, a sulfur atom, -SO ₂ - , -CO-, -NHCO-, and -C (CF _{3) 2} - at least one represents a group comprising a combination of one kind, X ¹ is an aromatic ring, a heterocyclic ring, an aliphatic ring, or mixtures thereof with, -CH ₂ - , A sulfur atom, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ -, and Ra and Rb each independently represent a hydrogen atom, At least one of Ra and Rb represents an acid-decomposable group, and Rc represents an alkyl group or an aryl group.

Y ¹ each independently represents an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or a group selected from the group consisting of a methylene group, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ -.

The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 14 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group and an anthraceneylene group.

The divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocycle. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is more preferable. As the hetero atom constituting the heterocycle, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocyclic ring is preferably an aromatic heterocyclic ring. An aromatic heterocycle is generally an unsaturated heterocycle. More preferred is an unsaturated heterocycle having the most double bond. Specific examples of the heterocycle include furan ring, thiophen ring, pyrrole ring, pyrrole ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imida A thiazole ring, a pyrazoline ring, a pyrazolyl ring, a triazole ring, a furan ring, a tetrazole ring, a pyran ring, a thiazole ring, a pyridine ring, a piperidine ring, a oxazine ring, a morpholine ring, A pyrimidine ring, a pyrazine ring, a piperazine ring and a triazine ring.

Examples of the divalent cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkenylene group. The cyclic alkylene group is preferably a cyclic alkylene group having 3 to 20 carbon atoms, more preferably a cyclic alkylene group having 3 to 18 carbon atoms, and more preferably a cyclic alkylene group having 3 to 15 carbon atoms. The cyclic alkenylene group is preferably a cyclic alkenylene group having 3 to 20 carbon atoms, more preferably a cyclic alkenylene group having 3 to 18 carbon atoms, and more preferably a cyclic alkenylene group having 3 to 15 carbon atoms. The cyclic alkenylene group is preferably a cyclic alkane-containing group having 3 to 20 carbon atoms, more preferably a cyclic alkane-containing group having 3 to 18 carbon atoms, and more preferably a cyclic alkane-containing group having 3 to 15 carbon atoms. Specific examples of the divalent cyclic aliphatic group include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, a 1,2-cyclohexylene group and an octylene group.

Y ¹ represents an alkylene group, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ -, and more preferably a group consisting of a combination of these and -C (CF ₃ ) ₂ -, and more preferably a combination of an arylene group and -C (CF ₃ ) ₂ - &Lt; / RTI &gt;

Y ¹ is preferably a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group or an octylene group, , A 2-phenylene group and an octylene group are more preferable.

[Chemical Formula 12]

X ¹ is an aromatic ring, a heterocyclic ring, an aliphatic ring, or mixtures thereof with, -CH ₂ -, an oxygen atom, a sulfur _{atom, -SO 2 -, -CO-, -NHCO-} , and -C (CF _{3) 2} - Or a combination thereof. X ¹ preferably has at least one of an aromatic ring, a heterocyclic ring and an aliphatic ring, and more preferably has 1 to 2 of any one of an aromatic ring, a heterocyclic ring and an aliphatic ring. X ¹ preferably contains an aromatic ring and / or a heterocyclic ring, and more preferably contains an aromatic ring.

Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the heterocyclic ring include furan ring, thiophen ring, pyrrole ring, pyrrole ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, A thiazole ring, a pyrazoline ring, a pyrazoline ring, a pyrazolidine ring, a triazole ring, a furan ring, a tetrazole ring, a pyran ring, a thiazole ring, a pyridine ring, a piperidine ring, a oxazine ring, a morpholine ring, , Pyrimidine ring, pyrazine ring, piperazine ring, and triazin ring. Examples of the aliphatic ring include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.

When the tetravalent group represented by X ¹ has a plurality of cyclic structures, the ring may be condensed or may be substituted with -O-, -S-, -C (CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ - Or may be bonded to a plurality of cyclic structures via a linking group such as -NHCO-. Linking group, -O-, -S-, -C (CF 3) 2 -, -CH 2 -, -SO 2 -, or -NHCO-, and should preferably, -C (CF _{3) 2} - are more preferred Do.

Ra and Rb each independently represent a hydrogen atom, an alkyl group, an acid-decomposable group or -CORc, and are synonymous with R ¹ and R ² in the general formula (1), and preferable ranges are also the same.

Specific examples of -X ¹ (ORa) (ORb) - in the repeating unit represented by the general formula (1-2) include, but are not limited to, the following. Wherein, X ¹ is a methylene group, an oxygen atom, a sulfur _{atom, -SO 2 -, -CO-, -NHCO-} , or -C (CF _{3) 2} - a indicates, -C (CF _{3) 2} - is desirable. R represents any one of Ra and Rb.

[Chemical Formula 13]

NH and ORa bonded to X, and NH and ORb are preferably bonded so as to be ortho (adjacent) in the cyclic structure.

As X, (2) and (10) are preferable, and (2) is more preferable.

<< (a-2) Other repeating units >>

The polybenzoxazole precursor having an acid-decomposable group may contain (a-1) other repeating units other than the repeating unit having an acid-decomposable group.

Examples of other repeating units include repeating units represented by the general formula (2), repeating units represented by the general formula (3), and repeating units represented by the general formula (4).

<<< Repeating unit represented by general formula (2) >>>

In general formula (2)

[Chemical Formula 14]

R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, or -CORc, Rc represents an alkyl group or an alkenyl group, An aryl group, provided that R ³ and R ⁴ are not an acid-decomposable group.

In the general formula (2), X, Y, R ³ , R ⁴ and Rc are synonymous with X, Y ¹ , Ra, Rb and Rc in the general formula (1-2), and preferable ranges are also the same.

<<< Repeating unit represented by general formula (3) >>>

In general formula (3)

[Chemical Formula 15]

(Formula (3) of the, Y ¹ are each, independently represent an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or mixtures thereof with, -CH ₂ -, an oxygen atom, a sulfur atom, -SO ₂ -, - - (CF ₃ ) ₂ -, and X ² represents an arylene group, a divalent heterocyclic group, a divalent cyclic aliphatic group, or a group formed by combining them with - Represents a group consisting of a combination of at least one of CH ₂ -, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ -

In the general formula (3), Y ¹ is the Y ¹ as agreed in the general formula (1-2), are also the same preferable range.

In the general formula (3), X ² represents an arylene group, a divalent heterocyclic group, a divalent cyclic aliphatic group, or a group selected from a methylene group, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO- , And -C (CF ₃ ) ₂ -, and these groups may contain a silicon atom.

The arylene group, divalent heterocyclic group and divalent cyclic aliphatic group represented by X ² are the same as the arylene group, divalent heterocyclic group and divalent cyclic aliphatic group represented by Y ¹ in the general formula (1-2) Do.

X ² is an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or mixtures thereof with a methylene group, an oxygen atom, a sulfur _{atom, -SO 2 -, -CO-, -NHCO-} , and -C (CF ₃ ) ₂ -. Specifically, the following groups may be mentioned. In the formula, A represents a methylene group, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, or -C (CF ₃ ) ₂ -.

[Chemical Formula 16]

<<< Repeating unit represented by the general formula (4) >>>

In general formula (4)

[Chemical Formula 17]

(Wherein Y ¹ represents an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or a group represented by -CH ₂ -, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO- , And -C (CF ₃ ) ₂ -, and X ³ represents a group containing a silicon atom.)

Here, Y ¹ agrees with Y ¹ in the general formula (1-2), and the preferable range thereof is also the same. X &lt; ³ &gt; is preferably a group shown below.

[Chemical Formula 18]

(R ⁵ and R ⁶ each independently represent a divalent organic group, and R ⁷ and R ⁸ each independently represent a monovalent organic group.)

The divalent organic group represented by R ⁵ and R ⁶ is not particularly limited, but specifically includes a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, an arylene group having 6 to 20 carbon atoms which may have a substituent, A divalent cyclic aliphatic group having 3 to 20 carbon atoms which may have a substituent, or a group formed by combining these.

As the straight chain or branched alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable. Specific examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group and a t-butylene group.

As the arylene group having 6 to 20 carbon atoms, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group and an anthraceneylene group.

The divalent cyclic aliphatic group having 3 to 20 carbon atoms is preferably a divalent cyclic aliphatic group having 3 to 10 carbon atoms, more preferably a divalent cyclic aliphatic group having 5 to 6 carbon atoms. Examples of the divalent cyclic aliphatic group include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group and a 1,2-cyclohexylene group.

These straight-chain or branched alkylene groups of 1 to 20 carbon atoms, arylene groups of 6 to 20 carbon atoms, and divalent cyclic aliphatic groups of 3 to 20 carbon atoms may have substituents. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

The group formed by combining a straight chain or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms is not particularly limited, but a divalent cyclic group having 3 to 20 carbon atoms And a group formed by combining aliphatic groups. Specific examples of the group formed by combining a straight-chain or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms include the followings. But is not limited thereto.

[Chemical Formula 19]

The monovalent organic group represented by R ⁷ and R ⁸ represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.

As the linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group.

The aryl group which may have a substituent is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group and a naphthyl group.

These straight-chain or branched alkyl groups or aryl groups having 1 to 20 carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

Specific examples of X ³ include, but are not limited to, the following.

[Chemical Formula 20]

The polybenzoxazole precursor (A) used in the present invention includes m repeating units represented by the general formula (1-2) and n repeating units represented by the general formula (3) 1000, preferably from 5 to 300, more preferably from 10 to 100. n represents 0 to 1000, preferably 0 to 300, more preferably 0 to 100. Provided that m + n represents 3 to 1000, preferably 5 to 600, more preferably 10 to 200. Here, the repeating unit represented by the general formula (1-2) and the repeating unit represented by the general formula (3) may be so-called random polymers.

The repeating unit represented by the general formula (1-2) and the repeating unit represented by the general formula (3) may each contain one kind or two or more kinds thereof. It may contain a repeating unit other than the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3). However, such another repeating unit is preferably 5 mol% or less of the total repeating units.

The polybenzoxazole precursor in the present invention may be a mode having a crosslinkable group at the terminal. By such an embodiment, film properties such as film hardness can be improved. The terminal having a crosslinkable group may have one terminal, but both terminals are preferably terminal.

The terminal of the polybenzoxazole precursor (A) is not particularly limited, but preferably includes a crosslinkable group. The crosslinkable group is preferably a group containing at least one kind selected from an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bonding group and a block isocyanate group. The terminal of the polybenzoxazole precursor (A) in the present invention is preferably a group represented by the general formula (1-1).

(1-1)

[Chemical Formula 21]

(In the general formula (1-1), Z represents a single bond, a carbon atom or a sulfur atom, R ¹¹ represents a monovalent organic group, n represents 0 or 1, and when Z represents a single bond, And when Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2. When n is 0, two R ¹¹ may be bonded to each other to form a ring.

Z represents a single bond, a carbon atom or a sulfur atom, preferably a single bond or a carbon atom.

R ¹¹ represents a monovalent organic group. The monovalent organic group represented by R &lt; ¹¹ &gt; is not particularly limited, and examples thereof include a compound having a formula (formula weight) of 20 to 500 per molecule. The atom constituting the monovalent organic group represented by R ¹¹ is preferably selected from a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom and a sulfur atom, and is preferably selected from a carbon atom, an oxygen atom, a nitrogen atom and a hydrogen atom Is more preferable.

Specifically, R ¹¹ is preferably an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms) (Preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 10 carbon atoms), an alkoxy group A carbonyl group, a sulfonyl group, an arylene group (preferably having 6 to 20 carbon atoms, and more preferably having 6 to 10 carbon atoms), a carboxyl group, a crosslinkable group, and an oxygen atom, (Preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), and an alkenylene group , An alkenyl group, an alkynyl group, an aryl group, a carbonyl group, a carboxyl group, Group, it is more preferable crosslinking group, an oxygen atom, an alkylene group, a group formed of a alkynyl group, or a combination of an arylene group.

The crosslinkable group represented by R &lt; ¹¹ &gt; is the same as the above-mentioned crosslinkable group, and the preferable range is also the same.

These groups may have a substituent. Examples of the substituent include a hydroxyl group, an alkyl group, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

Specific examples of the group represented by the general formula (1-1) include, but are not limited to, the following. In the formula, Ph represents a phenyl group.

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(A) when the terminal of the polybenzoxazole precursor is not a crosslinkable group, it may be encapsulated by a sealing group. As the sealing agent in this case, an acetyl group is exemplified.

On the other hand, in the present invention, it is also preferable that the structure of the polybenzoxazole precursor does not have a crosslinkable group at the terminal. By such an embodiment, it becomes easy to control the molecular weight of the polybenzoxazole precursor, and it becomes easy to obtain a resin having a more uniform molecular weight.

The polybenzoxazole precursor (A) preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 100,000, and most preferably 5,000 to 50,000. By setting this range, the lithography performance and physical properties of the cured film can be made excellent. Here, the weight average molecular weight is defined as the polystyrene reduced value of the gel permeation chromatography.

The polybenzoxazole precursor (A) preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 40,000, and still more preferably 3,000 to 30,000. Here, the number average molecular weight is defined as a polystyrene reduced value of gel permeation chromatography.

The polybenzoxazole precursor (A) used in the present invention may have a structure substantially not containing a crosslinkable group in addition to the terminal. Means that the repeating unit containing a crosslinkable group in the total repeating units is not more than 1 mol%.

The content of the polybenzoxazole precursor (A) in the composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or less, particularly preferably 70% by mass or more in terms of solid content. When two or more polybenzoxazole precursors are used, the total amount is in the above range.

&Lt; Production method of polybenzoxazole precursor &gt;

The polybenzoxazole precursor used in the present invention can be synthesized by referring to the description of JP-A-2008-224907. In the present invention, it is preferable to encapsulate the polybenzoxazole precursor with a group represented by the general formula (1-1). Such endblocking can be achieved by synthesizing a resin having an amino group at the terminal, Capped with an acid anhydride or an acid derivative, which is bonded through a carbonyl group or a sulfonyl group, or by mixing a monofunctional amine or acid chloride at the time of the polymerization reaction.

&Lt; (B) Photoacid generator having pKa of the generated acid of 4 or less>

The photosensitive resin composition of the present invention contains (B) a photoacid generator that generates an acid having a pKa of 4 or less. By using such an acid generator, a cured film having high transparency can be obtained. The photoacid generator used in the present invention is preferably a compound which generates an acid having a pKa of 4 or less in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but is not limited to the chemical structure thereof. In the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid in response to an actinic ray having a wavelength of 300 nm or more in combination with a sensitizer can be preferably used in combination with a sensitizer. As the photoacid generator used in the present invention, a photoacid generator that generates an acid with a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid with 2 or less is more preferable. When a strong acid having a pKa of 2 or less is used, the heat resistance is improved.

In the present invention, pKa basically indicates pKa in water at 25 占 폚. What can not be measured in water indicates that the solvent is changed to a solvent suitable for measurement. Specifically, the pKa described in the Chemical Manual can be referred to.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. . Of these, oxime sulfonate compounds or imide sulfonate compounds are preferably used from the viewpoints of sensitivity and insulation. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazine, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, imide sulfonate compounds, and diazomethane derivatives are disclosed in Japanese Patent Application Laid- -221494, and the compounds described in paragraphs 0065 to 0072 of WO11 / 087011, the contents of which are incorporated herein by reference. As the triarylsulfonium salts, triarylsulfonium salts having the following structures can be preferably used.

(28)

As the imide sulfonate compound, an imide sulfonate compound having the following structure can be preferably used. The imide sulfonate compound is preferably used together with a sensitizer described later.

[Chemical Formula 29]

(Wherein each R independently represents a hydrogen atom, a group consisting of a carbon atom and / or an oxygen atom (excluding C, H, and O), and the sum of carbon atoms and oxygen atoms is 16 or less. R ¹ represents a monovalent organic group having 16 or less carbon atoms.)

Each R independently represents a group consisting of a hydrogen atom, a carbon atom and / or an oxygen atom (excluding C, H, and O), and the sum of carbon atoms and oxygen atoms is 16 or less. R is preferably a hydrogen atom or an alkylene oxide group having 8 or less carbon atoms.

R ¹ represents a monovalent organic group having 16 or less carbon atoms. It is preferable that R ¹ does not include C, H, O, F or the like. Examples of R ¹ include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a tosyl group.

As specific examples of such compounds, the following compounds are exemplified.

(30)

In addition, specific examples of the imide sulfonate compound include compounds described in paragraphs 0065 to 0075 of WO2011 / 087011, and the following compounds.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following general formula (B1-1) can be preferably exemplified.

In general formula (B1-1)

(31)

(In the general formula (B1-1), R ²¹ is represents an alkyl group or an aryl group; and the broken line shows the binding of the other groups.)

The alkyl group in R ²¹ may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is preferably a group selected from the group consisting of a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (such as a bridged ) Alicyclic group, preferably a bicycloalkyl group or the like).

As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

It is also preferable that the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is an oxime sulfonate compound represented by the following general formula (B1-2).

In general formula (B1-2)

(32)

(In the formula (B1-2), R ⁴² represents an alkyl group or an aryl group which may be substituted, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, m4 Is 2 or 3, plural Xs may be the same or different.)

The preferable range of R &lt; ⁴² &gt; is the same as the preferable range of R &lt; ²¹ &gt;

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom.

m4 is preferably 0 or 1. In the above general formula (B1-2), and m4 are 1, X is a methyl group, the substitution position of X is the ortho above, R ⁴² is a straight chain alkyl group, 7,7-dimethyl-2 of 1 to 10 carbon atoms An oxononylmethyl group, or a p-toluyl group is particularly preferable.

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).

In general formula (B1-3)

(33)

(Formula (B1-3) of, R ⁴³ is R ⁴² and consent of the formula (B1-2), X ¹ is a halogen atom, a hydroxyl group, an alkoxy group having from 1 to 4 carbon atoms, having from 1 to 4 carbon atoms A cyano group or a nitro group, and n4 represents an integer of 0 to 5.)

Examples of R ⁴³ in the general formula (B1-3) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, Propyl group, perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.

As X ¹ , an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group is more preferable.

As n4, 0 to 2 is preferable, and 0 to 1 is particularly preferable.

As specific examples of the compound represented by the above general formula (B1-3) and specific examples of the preferable oxime sulfonate compound, reference may be made to the disclosure of Japanese Patent Application Laid-Open No. 2012-163937, paragraphs 0080 to 0082, .

As the compound containing an oxime sulfonate structure represented by the general formula (B1-1), a compound represented by the following general formula (OS-1) is also preferable.

(34)

In the general formula (OS-1), R ¹⁰¹ 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, Or a heteroaryl group. R ¹⁰² represents an alkyl group or an aryl group.

¹⁰¹ X is ^{-O-, -S-, -NH-, -NR 105} -, -CH 2 -, -CR 106 H-, or -CR ¹⁰⁵ R ¹⁰⁷ - represents a, R ¹⁰⁵ ~ R ¹⁰⁷ is an alkyl group, or Lt; / RTI &gt;

R ¹²¹ to R ¹²⁴ 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, Or an aryl group. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

As R ¹²¹ to R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, an embodiment in which all of R ¹²¹ to R ¹²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

All of the above-mentioned functional groups may further have a substituent.

The compound represented by the above general formula (OS-1) is preferably a compound represented by the general formula (OS-2) described in paragraphs 0087 to 0089 of JP-A No. 2012-163937, The contents are incorporated herein by reference.

Specific examples of the compound represented by the above general formula (OS-1) that can be suitably used in the present invention include the compounds (exemplified compounds b-1 to b-34) described in paragraphs 0128 to 0132 of Japanese Patent Application Laid- But the present invention is not limited thereto.

(OS-3), the following general formula (OS-4), or the following general formula (OS-5) is preferably used as the compound containing an oxime sulfonate structure represented by the general formula (B1-1) Is an oxime sulfonate compound represented by the following formula

(35)

(Formula (OS-3) ~ formula (OS-5) of, R ^22, R ²⁵ and R ²⁸ are each, independently, an alkyl group, an aryl group or a heteroaryl group, R ^23, R ²⁶ and R ²⁹ is Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and each of R ²⁴ , R ²⁷ and R ³⁰ independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfone represents a group, X ¹ ~ X ³ are each, independently represents an oxygen atom or a sulfur atom, n1 ~ n3 are each, independently represent 1 or 2, m1 ~ m3 are each independently an integer from 0 to 6 .

With respect to the above general formulas (OS-3) to (OS-5), for example, reference can be made to the description of paragraphs 0034 to 0071 of Japanese Laid-Open Patent Publication No. 2013-47765, the contents of which are incorporated herein by reference .

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) can be obtained by reacting a compound represented by the general formula (OS-6) to a compound represented by the general formula (OS-6) described in Japanese Patent Application Laid- (OS-11), the contents of which are incorporated herein by reference.

Preferable ranges for the above general formulas (OS-6) to (OS-11) are preferably those of (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of Japanese Patent Application Laid- Range, the contents of which are incorporated herein by reference.

Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the above general formula (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP-A No. 2011-221494, Are incorporated herein by reference. The present invention is not limited thereto.

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).

In general formula (B1-4)

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(In the general formula (B1-4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group or a heteroaryl group, R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form an alicyclic or aromatic ring, and X represents -O- or -S-, .

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having a branched structure or an alkyl group having a cyclic structure.

The number of carbon atoms in the alkyl group is preferably 3 to 10. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, Propyl group, hexyl group, 2-ethylhexyl group, cyclohexyl group, and octyl group, and is preferably isopropyl group, tert-butyl group, neopentyl group or cyclohexyl group.

The carbon number of the aryl group is preferably 6 to 12, more preferably 6 to 8, and still more preferably 6 to 7. Examples of the aryl group include a phenyl group and a naphthyl group, and preferably a phenyl group.

The alkyl group and aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chloro atom, bromine atom, iodine atom), a straight chain, branched or cyclic alkyl group (e.g., methyl group, An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyloxy group, an arylthio group, an arylthio group, an arylthio group, an arylthio group, an arylthio group, An acyloxy group, an amino group, a nitro group, a hydrazino group, and a heterocyclic group. These groups may be further substituted. Preferably, it is a halogen atom or a methyl group.

From the viewpoint of transparency, R ¹ is preferably an alkyl group, and from the viewpoint of achieving both storage stability and sensitivity, R ¹ is an alkyl group having a branched structure of 3 to 6 carbon atoms, an alkyl group having 5 to 7 carbon atoms Or a phenyl group, and more preferably an alkyl group having a branched structure of 3 to 6 carbon atoms or an alkyl group having a cyclic structure of 5 to 7 carbon atoms. By employing such a bulky group (particularly, a bulky alkyl group) as R ¹ , transparency can be further improved.

Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. As the alkyl group represented by R ² , a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, neopentyl, Is a methyl group.

The aryl group is preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group and a p-toluyl group (p-methylphenyl group), and preferably a phenyl group and a p-toluyl group.

Examples of the heteroaryl group include a pyrrolyl group, an indole group, a carbazole group, a furan group, and a thiophen group.

The alkyl group, aryl group, and heteroaryl group represented by R ² may have a substituent. The substituent is the same as the substituent which the alkyl group and the aryl group represented by R ¹ may have.

R ² is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. The substituent of the phenyl group is preferably a methyl group.

R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R ³ to R ⁶ is synonymous with the alkyl group represented by R ² , and the preferable range is also the same. The aryl group represented by R ³ to R ⁶ is synonymous with the aryl group represented by R ¹ , and the preferable range is also the same.

Among R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form a ring. The ring is preferably an alicyclic or aromatic ring, The ring is more preferable.

R ³ ~ R ⁶ is a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, a chloro atom, a bromine atom), or R ³ and R ^4, R ⁴ and R ^5, or R ⁵ and R ⁶ are bonded to benzene A methyl group, a fluorine atom, a chloro atom, a bromine atom, or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ combine to form a benzene ring, Is more preferable.

Preferred embodiments of R ³ to R ⁶ are as follows.

(Embodiment 1) At least two of them are hydrogen atoms.

(Mode 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.

(Embodiment 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ combine to form a benzene ring.

(Mode 4) An aspect that satisfies the above aspects 1 and 2, and / or an aspect that satisfies the above aspects 1 and 3.

X represents -O- or -S-.

Specific examples of the general formula (B1-4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

(37)

In the photosensitive resin composition of the present invention, the content of the photoacid generator (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the total solid components in the photosensitive resin composition. To 5 parts by mass is more preferable. The photoacid generator may be used alone or in combination of two or more. The photoacid generators may be used alone, or two or more of them may be used in combination. When two or more kinds of photoacid generators are used, the total amount is in the above range.

&Lt; (C) Solvent >

The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and any of the components described below are dissolved in a solvent. As the solvent used for the preparation of the composition of the present invention, essential components and optional components are uniformly dissolved and reacted with each component is used.

As the solvent to be used in the photosensitive resin composition of the present invention, known solvents may be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene Propylene glycol monoalkyl ether acetates such as propylene glycol monoalkyl ether, propylene glycol dialkyl ether and propylene glycol monomethyl ether acetate, and diethylene glycol ethyl methyl ether. Diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, Lactones such as lactic acid, lactic acid, lactic acid, lactic acid, lactic acid, tartaric acid, ester, ketone, amide and γ-butyrolactone. Specific examples of the solvent to be used in the photosensitive resin composition of the present invention include the solvent described in paragraphs 0174 to 0178 of Japanese Patent Laid-Open Publication No. 2011-221494, the solvent described in paragraphs 0167 to 0168 of Japanese Laid-Open Patent Publication No. 2012-194290 , The contents of which are incorporated herein by reference.

If necessary, these solvents may contain at least one solvent selected from the group consisting of benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, iso A solvent such as toluene, toluene, xylene, toluene, xylene, toluene, xylene, toluene, xylene, May be added. These solvents may be used singly or in combination of two or more kinds. The solvent which can be used in the present invention is preferably a single solvent or a combination of two or more solvents, more preferably two solvents, more preferably propylene glycol monoalkyl ether acetates or dialkyl ethers, It is more preferable to use diacetates and diethylene glycol dialkyl ethers, or ester esters and butyleneglycol alkyl ether acetates together.

The solvent is preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or more, or a mixture thereof.

Propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol monoethyl ether acetate (boiling point: 158 ° C), propylene glycolmethyl-n-butyl Ether (boiling point 155 캜), and propylene glycol methyl-n-propyl ether (boiling point 131 캜).

Examples of the solvent having a boiling point of 160 캜 or more include ethyl 3-ethoxypropionate (boiling point: 170 캜), diethylene glycol methyl ethylether (boiling point: 176 캜), propylene glycol monomethylethercaptopropionate (boiling point: , Dipropylene glycol methyl ether acetate (boiling point 213 캜), 3-methoxybutyl ether acetate (boiling point 171 캜), diethylene glycol diethyl ether (boiling point 189 캜), diethylene glycol Propylene glycol diacetate (boiling point 190 占 폚), diethylene glycol monoethyl ether acetate (boiling point 220 占 폚), dipropylene glycol dimethyl ether (boiling point 175 占 폚) (Boiling point 232 占 폚), N-methyl-2-pyrrolidone (boiling point 204 占 폚), and gamma butyrolactone (boiling point 204 占 폚).

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 98 parts by mass, more preferably 60 to 95 parts by mass, and most preferably 70 to 90 parts by mass, per 100 parts by mass of the total components in the photosensitive resin composition desirable. The solvent may be used alone, or two or more solvents may be used in combination. When two or more kinds of solvents are used, the total amount is in the above range.

&Lt; (D) Crosslinking agent >

The photosensitive resin composition of the present invention contains at least one crosslinking agent (hereinafter also referred to as "(D) crosslinking agent") having two or more crosslinkable groups composed of groups reactive with a benzene ring and / or a phenolic hydroxyl group. In the present invention, the crosslinking agent reacts with the benzene ring or the phenolic hydroxyl group contained in the polybenzoxazole precursor to form a crosslinked structure between the polybenzoxazole.

The crosslinkable group comprising a benzene ring or a group which reacts with a phenolic hydroxyl group is not particularly limited, and examples thereof include an epoxy group, a methylol group, an alkoxymethyl group and a block isocyanate group. In the present invention, when two or more such crosslinkable groups are contained in one molecule, the respective crosslinkable groups may be the same or different. Preferably, the crosslinkable groups contained in one molecule are the same.

The crosslinking agent (D) used in the present invention is preferably a crosslinking agent having two or more crosslinkable groups selected from an epoxy group, a methylol group, an alkoxymethyl group and a block isocyanate group, and those having an epoxy group and / or an alkoxymethyl group More preferable. More specifically, as the crosslinking agent (D), a compound having two or more epoxy groups in the molecule, a crosslinking agent containing two or more alkoxymethyl groups and / or methylol groups in the molecule, a crosslinking agent containing two or more block isocyanate groups May be mentioned as preferred examples. The crosslinking agent (D) can react with the phenolic hydroxyl group of the component (A) or the benzene ring to crosslink the components (A), and since the crosslinking reaction is accelerated by the acid generated from the acid generating agent, The cured film obtained by the photosensitive resin composition of the present invention can be made into a stronger film.

The molecular weight of the crosslinking agent used in the present invention is preferably from 150 to 30,000, more preferably from 200 to 10000. By setting this range, the effect of the present invention can be exerted more effectively.

The content of the crosslinking agent (D) in the photosensitive resin composition of the present invention is preferably from 1 to 50 parts by mass, more preferably from 3 to 30 parts by mass, more preferably from 5 to 5 parts by mass, relative to 100 parts by mass of the total amount of the component (A) To 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of (D) crosslinking agents may be used in combination. In that case, (D) the total amount of the crosslinking agents are added and the content is calculated.

In the photosensitive resin composition of the present invention, a crosslinking agent other than the crosslinking agent (D) may be used in combination. In that case, the proportion of the crosslinking agent (D) in the whole crosslinking agent is preferably 50% by mass or more, and more preferably 80% by mass or more.

<< Compounds having two or more epoxy groups in the molecule >>

In the photosensitive resin composition of the present invention, as the (D) crosslinking agent, a compound having two or more epoxy groups in the molecule can be used. Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin, Resins and the like.

These are available as commercial products. For example, commercially available products such as JER152, JER157S70, JER157S65, JER806, JER828 and JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and disclosed in Japanese Patent Laid-Open Publication No. 2011-221494, paragraph 0189, EX-614, EX-614, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, -321L, EX-211, EX-212, EX-810, EX-811, EX-850, EX-821, EX-821, EX-832, DLC-204, DLC-205, DLC-206, DLC-201, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX- -301, DLC-402 (manufactured by Nagase ChemteX), YH-300, YH-301, YH-302, YH-315, YH-324, YH- 2081, EHPE3150, EHPE3150CE (available from Daicel), Epicote 828 (manufactured by Yucca Shell Epoxy), and the like. These may be used alone or in combination of two or more.

Among them, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin and an aliphatic epoxy resin are more preferable, and a bisphenol A type epoxy resin is particularly preferable.

<< Crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule >>

In the photosensitive resin composition of the present invention, as the crosslinking agent (D), a crosslinking agent containing an alkoxymethyl group or a methylol group can be used. As the cross-linking agent containing two or more alkoxymethyl groups or methylol groups in the molecule, a cross-linking agent having two or more structures represented by the following general formula (1) or (2) in the molecule and either one of an alkoxymethyl group and a methylol group, Both of which are contained in a total of two or more molecules.

-CH ₂ OR ¹ (1)

(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.)

-CH ₂ OH (2)

The alkoxymethyl group or methylol group is preferably bonded to a carbon atom forming a nitrogen atom or an aromatic ring.

Examples of the crosslinking agent in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylol melamine, alkoxymethylated benzoguanamine, methylol benzoguanamine, alkoxymethylated glycoluril, methylol glycolluryl, Alkoxymethylated elements and methyloledic elements are preferred. The alkoxymethylated melamine, the alkoxymethylated benzoguanamine, the alkoxymethylated glycoluril, and the alkoxymethylated urea are methylol melamine, methylol benzoguanamine, methylol glycolluryl, or the methylol group of the methylol moiety is reacted with an alkoxymethyl group . Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of generated outgas, a methoxymethyl group is particularly preferable.

Of these crosslinking compounds, alkoxymethylated melamine, methylolmelamine, alkoxymethylated benzoguanamine, methylolbenzoanamine, alkoxymethylated glycoluril and methylol glycolluryl are preferable crosslinking compounds, and transparency , Alkoxymethylated glycoluril and methylol glycoluril are particularly preferred.

In the present invention, the alkoxymethyl group-containing crosslinking agent described in paragraph [0107] of Japanese Laid-Open Patent Publication No. 2012-8223 can be preferably used, and these contents are incorporated herein by reference.

(8-1) to (8-4), as a preferable structure of a crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule.

(38)

(8-1) to (8-4), each of R ⁷ and R 8 independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each of R ⁸ to R ¹¹ independently represents a hydrogen atom , A hydroxyl group, an alkyl group or an alkoxyl group, and X ² represents a single bond, a methylene group or an oxygen atom.

The alkyl group represented by R ⁷ and R preferably has 1 to 8 carbon atoms and more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group. The alkyl group represented by R ⁸ to R ¹¹ preferably has 1 to 8 carbon atoms and more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group. The alkoxyl group represented by R ⁸ to R ¹¹ preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methoxy group, ethoxy group and propoxy group. X ² is preferably a single bond or a methylene group. R ⁷ to R ¹¹ and X ² may be substituted with an alkyl group such as a methyl group or an ethyl group, a halogen atom or the like. The plurality of R ⁷ , R, and R ⁸ to R ¹¹ may be the same or different.

Specific examples of the compound represented by the formula (8-1) include the compounds shown below.

[Chemical Formula 39]

(40)

Specific examples of the compound represented by the formula (8-2) include N, N, N, N, N-tetramethylolglycoluril, N, N, N, N, N, N, N, N, N, N, N, N, N-tetramethylolglycol, methoxymethylated 1 to 4 methoxyl groups, N, Compounds obtained by subjecting 1 to 4 methylol groups of lycorian to n-propoxymethylation, 1 to 4 methylol groups of N, N, N, N-tetramethyloligolcoryl are isopropoxymethylated, N, N, N, N, N, N, N, N, N, N, N, N, N, N-tetramethylolglycoluril, 1 to 4 methylol groups of N, tert-butoxymethylated compounds, and the like. Of these, compounds in which 1 to 4 methylol groups of N, N, N, N-tetramethyloligoucolyl are methoxymethylated are particularly preferred.

Specific examples of the compound represented by the formula (8-3) include the compounds shown below.

(41)

Specific examples of the compound represented by the formula (8-4) include N, N, N, N, N, N-hexamethylol melamine, N, N, N, N, N, N, N, N, N-hexamethylol melamine, 1 to 6 ethoxymethylated methylol groups of the N, N, N, N, N, N, N, N-hexamethylol melamine having 1 to 6 methylol groups and 1 to 6 methylol groups of N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, Hexamethylolmelamine and 1 to 6 tert-butoxymethyl groups of methylol groups of N-hexamethylol melamine. Among these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.

Examples of the crosslinking agent in which an alkoxymethyl group or a methylol group is bonded to a carbon atom forming an aromatic ring include those represented by the following general formulas (4) to (5).

(42)

(Wherein X represents a single bond or an organic group having 1 to 4 valences, R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent organic group, n is an integer of 1 to 4, p and and q is independently an integer of 0 to 4.)

(43)

(In the formula (5), two Y's may independently be an oxygen atom or a fluorine atom with a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹³ to R ¹⁶ each independently represent a hydrogen atom Or a monovalent organic group, m and n are each independently an integer of 1 to 3, and p and q are each independently an integer of 0 to 4.)

Specific examples of the compounds represented by the general formulas (4) to (5) include the following compounds. Me represents a methyl group.

(44)

The cross-linking agent containing two or more alkoxymethyl groups or methylol groups in these molecules is also available as a commercially available product. For example, a cross-linking agent such as Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141 , 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300 (manufactured by Mitsui Cyanamide), NIKALAC MX-750, -032, -706, -40, -31, -270, -280, -290, -750LM, Nikarac MS-11, Nikarac MW-30HM, -100LM, -270 and -390 (manufactured by Sanwa Chemical Co., Can be preferably used. These may be used alone or in combination of two or more.

<< Compounds Containing Two or More Block Isocyanate Groups in Molecules >>

In the photosensitive resin composition of the present invention, as the (D) crosslinking agent, a compound containing two or more block isocyanate groups in the molecule can be used.

The block isocyanate group in the present invention is a group capable of generating an isocyanate group by heat, and includes, for example, a group in which an isocyanate group is protected by reacting a blocking agent and an isocyanate group, For example. The block isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C to 250 ° C.

The skeleton of the block isocyanate compound is not particularly limited and may be any of those having two or more isocyanate groups in one molecule, and may be any of aliphatic, alicyclic or aromatic polyisocyanates For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophoronediisocyanate, 1,6-hexamethylene diisocyanate, 1 , 3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene di Isocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl Tadashi Issaia Dienes such as diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (Cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate Pentaerythritol tetraisocyanate, p-phenylene diisocyanate, 3,3'-methyleneditholylene-4,4'-diisocyanate, 4,4'-diphenyl ether isocyanate, tetrachlorophenyl Isocyanate compounds such as benzene diisocyanate, hydrogenated 1,3-xylylene diisocyanate, and hydrogenated 1,4-xylylene diisocyanate, and these compounds Of the prepolymer type skeleton Compounds can be suitably used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophoronediisocyanate (IPDI) are particularly preferable. desirable.

Examples of the parent structure of the block isocyanate compound in the photosensitive resin composition of the present invention include a burette type, an isocyanurate type, an adduct type, and a bifunctional prepolymer type.

Examples of the block agent for forming the block structure of the block isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, And the like. Among them, a block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable.

Examples of the oxime compounds include oxime and ketoxime. Specific examples thereof include formaldehyde, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.

Examples of the lactam compound include? -Caprolactam,? -Butyrolactam, and the like.

Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

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

Examples of the amine compound include primary amines and secondary amines, and may be any of aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

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

Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole, and the like.

Examples of mercaptan compounds include alkyl mercaptans, aryl mercaptans, and the like.

The block isocyanate compound which can be used in the photosensitive resin composition of the present invention is available as a commercially available product and includes, for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, B-810N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B- B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B (trade names, manufactured by Mitsui Chemicals, Inc.), durabate 17B-60PX, 17B-60P, TPA- , SBN-70D, SBB-70P, K6000 (manufactured by Asahi Kasei Chemicals Corporation), desmodur BL1100, BL1265MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / BL4265SN, PL340, PL350, and Sumidur BL3175 (manufactured by Sumika Bayer Eleten Co., Ltd.) can be preferably used.

&Lt; Compound containing two or more methacryloyl groups and / or acryloyl groups in the molecule &gt;

In the photosensitive resin composition of the present invention, a compound containing a methacryloyl group or an acryloyl group as the crosslinking agent other than the crosslinking agent (D) may be used together with the (D) crosslinking agent. The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of an acrylate ester and a methacrylate ester. The acryloyl group and the methacryloyl group are preferably compounds having two or more, more preferably three or more functional groups in one molecule.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonene diol di (Meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene diacrylate, and the like can be used in combination with at least one selected from the group consisting of .

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

A-200, A-400, A-600, A-1000, ABE-300 and A-BPE-4 are commercially available from Nippon Kayaku KAYARAD DPHA and Shin Kagaku Kagaku Kogyo Co., , A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A-B1206PE, A HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, , IND, BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3PG, 9PG, trifunctional A- A-TMPT-3EO, A-TMPT-9EO, A-TMPT-3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, TMPT, TMPT- , ATM-4E, AD-TMP, AD-TMP-L, ATM-4P, A-TMMT and A-DPH.

&Lt; Compounds containing two or more oxetane groups in the molecule &gt;

The photosensitive resin composition of the present invention may contain a compound containing oxetane as a crosslinking agent other than the (D) crosslinking agent and the (D) crosslinking agent. It is preferable that two or more oxetane rings are present in the molecule. Examples of the compound having two or more oxetane groups in the molecule include the compounds described in paragraphs 0134 to 0145 of JP-A No. 2008-224970, the content of which is incorporated herein by reference. As specific examples, Aromaxhene OXT-121, OXT-221, OX-SQ and PNOX (manufactured by Doago Kosai Co., Ltd.) can be used.

<(E) Compound in which an acid group is protected with an acid-decomposable group>

The photosensitive resin composition of the present invention may contain a compound in which an acid group is protected with an acid-decomposable group (also referred to as "(E) compound"). A compound in which an acid group is protected with an acid-decomposable group means a compound in which an acid group is protected with an acid-decomposable group and the protecting group is cleaved by the action of an acid to increase alkali solubility. The compound (E) has a role of reducing the alkali solubility of the unexposed area and increasing the alkali solubility of the exposed area. As the acid group, a carboxy group or a phenolic hydroxyl group is preferable.

The acid decomposable group is not particularly limited as long as it is a group decomposing by the action of an acid. An acetal group, a ketal group, a silyl group and a silyl ether group, and an acetal group is preferable from the viewpoint of sensitivity. Specific examples of the protecting group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, Methylmethyl group, n-methyl group, trimethylsilyl ether group and the like. From the viewpoint of sensitivity and stability, an ethoxyethyl group and a tetrahydrofuranyl group are preferable.

The compound (E) may be a polymer (for example, more than 5000, more preferably more than 10,000) and a low molecular weight (for example, 5000 or less) Do. The molecular weight is the number average molecular weight determined by conversion to polystyrene in the case of a polymer. The lower limit of the molecular weight is preferably 150 or more, more preferably 300 or more.

The compound (E) preferably contains any one of an aromatic ring, a heterocyclic ring and an alicyclic structure from the viewpoint of improving the dissolution inhibiting ability.

From the viewpoint of improving the sensitivity, the compound (E) preferably has two or more acid groups protected in the molecule.

From the viewpoint of improvement of compatibility with the component (A), the compound (E) preferably contains an aromatic ring or a heterocyclic ring.

Preferred embodiments of the compound (E) are described below.

The compound (E) is preferably a compound represented by the following formula (E-1-1).

In general formula (E-1-1)

[Chemical Formula 45]

(Formula (E-1-1) wherein, R represents a molecular weight of from 1 to 6-valent organic group not more than 2000, R ¹ and R ² are each, independently represent a hydrogen atom, an alkyl group, or aryl, R ¹ and R one of the ^two one is an alkyl group, or an aryl group. R ³ is a monovalent alkyl, or aryl, in combination with R ¹ or R ² may form a cyclic ether. n1 represents an integer of 1-6.)

R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group.

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. The alkyl group may have a substituent. The alkyl group may be any of linear, branched and cyclic, and is preferably a linear alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl and cyclohexyl.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group, and among them, a phenyl group is preferable.

R ³ represents an alkyl group or an aryl group, and may form a cyclic ether by bonding with R ¹ or R ² . As the alkyl group, an alkyl group having 1 to 16 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl and hexyl. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group and a naphthyl group.

R ³ may be linked with R ¹ or R ² to form a cyclic ether. The cyclic ether formed by connecting with R ¹ or R ² is preferably a 3- to 6-membered cyclic ether, more preferably a 5- to 6-membered cyclic ether.

R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable that R ³ is an alkyl group having 1 to 4 carbon atoms, and R ¹ or R ² is bonded to form a tetrahydrofuranyl group.

R ¹ to R ³ may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), and these substituents may further have a substituent.

R represents a 1- to 6-valent organic group having a molecular weight of 2000 or less. The organic group represented by R is preferably a 1- to 6-valent organic group having a molecular weight of 2000 or less, preferably a 1- to 6-valent organic group having a molecular weight of 1,500 or less, and more preferably a 1- to 6-valent organic group having a molecular weight of 1000 or less. The organic group represented by R is preferably an organic group containing an aromatic ring or a heterocyclic ring and not including C, H, O or N atoms, more preferably an organic group containing a cyclic structure and / or a carbonyl group And is preferably a group formed by a combination of an aromatic group, a cyclic aliphatic group, a carbonyl group, an alkylene group, a phenylene group, and an oxygen atom.

Specifically, as R, when the acid group is a phenolic hydroxy group, the following organic groups are preferable. R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; m and n each independently represent an integer of 0 to 4; .

(46)

Specifically, when R is a carboxy group, R is preferably the following organic group. R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 8 carbon atoms), m and / or an alkyl group having 1 to 10 carbon atoms, Each n independently represents an integer of 0 to 4 (preferably 0).

(47)

Specific examples of the compound represented by formula (E-1-1) include the following compounds, but the present invention is not particularly limited thereto.

(48)

The compound (E) is preferably a compound represented by the following formula (E-1-2).

In general formula (E-1-2)

(49)

(In the general formula (E-1-2), R ¹ represents an organic group of n1 valency, Ar represents an optionally substituted aryl group, a represents an integer of 0 or more, n1 represents an integer of 2 or more, , n1-a is an integer of 1 or more.)

R ¹ represents an organic group having a valency of n1, preferably 2 to 8, and more preferably 2 to 6 organic groups. R ¹ is preferably a hydrocarbon group having 2 to 15 carbon atoms or a group having a hydrocarbon group in which one or two oxygen atoms form an ether bond in the hydrocarbon group as a main structure. Specifically, R ¹ is an aliphatic hydrocarbon structure (for example, a linear alkylene structure, a branched alkylene structure, a cycloalkylene structure, a norbornene structure, a norbornene structure, a norbornene skeleton or a norbornene skeleton An aromatic hydrocarbon structure (e.g., a benzene structure), an aralkyl structure, a structure in which a plurality of these structures are bonded, a structure in which these structures are bonded to each other through an ether bond, And a structure containing a hydrazine structure or the like. As R ¹ , an alkylene structure, an alicyclic structure, an ether structure, an aralkyl structure, or a combination thereof is particularly preferable as a basic skeleton.

Ar represents an optionally substituted aryl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group and a naphthyl group.

a represents an integer of 0 or more, preferably an integer of 0 to 3, and more preferably 0. n represents an integer of 2 or more, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and more preferably 2.

In the synthesis step of the compound represented by the general formula (E-1-2), a may be obtained as a mixture having a distribution from 0 to n, but it can be suitably used as a mixture. And n-a is an integer of 1 or more, preferably 1 to 7. Ar represents an optionally substituted aryl group, and specific examples thereof include a phenyl group and a naphthyl group, and examples of the substituent include a halogen atom such as a chlorine atom; An alkyl group such as methyl group, tert-butyl group; And an alkoxy group such as a methoxy group.

The compound represented by the general formula (E-1-2) preferably contains no C, H, O, or N atoms from the viewpoint of improving the compatibility with the component (A).

Specific examples of the compound represented by formula (E-1-2) include, but are not limited to, the following.

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Specific examples of the compound represented by the general formula (E-1-2) include the compounds described in paragraphs 0018 to O of JP-A No. 2001-83709, the contents of which are incorporated herein by reference.

The compound (E) is preferably a compound having a repeating unit represented by the following formula (E-1-3).

In general formula (E-1-3)

(51)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and either one of R ¹ and R ² is an alkyl group or an aryl group, R ³ R ⁴ represents a hydrogen atom or a methyl group, and X represents a divalent organic group.) In the formula, R ¹ represents an alkyl group or an aryl group, and may form a cyclic ether by bonding with R ¹ or R ² .

R ¹ and R ^2, and R ¹ and R ² as agreed in the formula (E-1-1), a preferred range is also the same.

R ³ is synonymous with R ³ in formula (E-1-1), and the preferred range is also the same.

X represents a divalent organic group. Examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, and a p-phenylene carbonyl group.

Specific preferred examples of the compound having a repeating unit represented by the formula (E-1-3) include polymers having any one of the following constitutional units. R ⁴ represents a hydrogen atom or a methyl group.

(52)

The weight average molecular weight of the compound having a repeating unit represented by the general formula (E-1-3) is preferably from 2,000 to 50,000, more preferably from 3,000 to 20,000. Here, the weight average molecular weight is defined as the polystyrene reduced value of the gel permeation chromatography.

When a compound having a repeating unit represented by the general formula (E-1-3) is used as the compound (E), it is preferable to copolymerize the other components from the viewpoint of compatibility with the component (A) and developability. The other components are not particularly limited as long as they can be copolymerized with a compound having a repeating unit represented by the formula (E-1-3).

The other component is preferably a compound having a repeating unit represented by the following formula (E-1-4).

In general formula (E-1-4)

(53)

(In the general formula (E-1-4), R ⁴¹ represents a hydrogen atom or a methyl group, X represents a single bond or a divalent organic group, R ⁴² represents an aryl group which may have a substituent or a hydroxyl group Lt; / RTI &gt;

X represents a single bond or a divalent organic group, and examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, a carboxyl group, and a p-phenylene carbonyl group.

R ⁴² represents an aryl group or a hydroxyl group which may have a substituent, and the aryl group which may have a substituent is synonymous with the aryl group represented by R ¹ in the formula (E-1-1) . The aryl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), and a hydroxyl group. These substituents may further have a substituent.

Specific preferred examples of the compound having a repeating unit represented by the formula (E-1-4) include polymers having any of the following constitutional units. R ⁴ represents a hydrogen atom or a methyl group.

(54)

As the compound having a repeating unit represented by the general formula (E-1-4), it is preferable to use the compounds (1) to (3) from the viewpoint of compatibility with the component (A) It is preferable to use a compound having an acid group of (5).

The ratio (mass%) of the compound having a repeating unit represented by the general formula (E-1-3) to other components is preferably 30/70 to 100/0 in the component (E-1-3) , And preferably from 40/60 to 80/20. A plurality of other components may be used.

The content of the compound (E) is preferably from 5 to 50 parts by mass, more preferably from 10 to 40 parts by mass, per 100 parts by mass of the polybenzoxazole precursor (A). When the content is 5 to 50 parts by mass, the film property and sensitivity can be improved. Two or more compounds (E) may be used, and when two or more compounds are used, the total amount thereof is in the above range.

Further, in the present invention, (A) the polybenzoxazole precursor contains an acid-decomposable group, the compound (E) may be made up to 1% by mass or less of the total solid content of the composition of the present invention.

<Other components>

To the photosensitive resin composition of the present invention, an adhesion improver (alkoxysilane compound), a sensitizer, a basic compound, a surfactant, and an antioxidant may be added, if necessary, in addition to the above components. In the photosensitive resin composition of the present invention, known additives such as an acid growth agent, a development promoter, a plasticizer, a heat radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor may be added. As these compounds, for example, compounds described in paragraphs 0201 to 0224 of Japanese Laid-Open Patent Publication No. 2012-88459 can be used, and these contents are incorporated herein by reference.

<< Adhesion improver >>

The photosensitive resin composition of the present invention may contain an alkoxysilane compound as an adhesion improver. When the alkoxysilane compound is used, the adhesion between the film formed by the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed by the photosensitive resin composition of the present invention can be adjusted. The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an alkoxysilane compound that can be used as an inorganic substance such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal compound such as gold, copper, molybdenum, It is preferable to be a compound which improves the adhesion between the metal and the insulating film. Specifically, known silane coupling agents and the like are also effective.

As the silane coupling agent, there may be mentioned, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethene Methacryloxypropyltrialkoxysilane such as? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropyldialkoxysilane, 3-methacryloxypropylmethyldimethoxysilane and the like such as methoxystyrene and? (Meth) acrylate,? -Methacryloxypropyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyl And trialkoxysilane. Of these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is more preferable, and? -Glycidoxypropyl Trimethoxysilane is even more preferred. These may be used alone or in combination of two or more.

The alkoxysilane compound is not particularly limited to these, and known ones can be used.

When the photosensitive resin composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition desirable. The alkoxysilane compound may be used singly or in combination of two or more. When two or more alkoxysilane compounds are used, the total amount is in the above range.

<< Increase / decrease >>

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator in order to accelerate the decomposition thereof. The sensitizer absorbs an actinic ray to become an electron-excited state. The sensitizer brought into the electron-excited state comes into contact with the photoacid generator to generate electron movement, energy transfer, heat generation, and the like. As a result, the photoacid generator decomposes by chemical change to generate an acid. Examples of preferred sensitizers include compounds having an absorption wavelength in an arbitrary wavelength region of the wavelength range from 350 nm to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Diethoxyxyanthracene), xanthines (e.g., fluorescein, eosine, erythrosine, rhodamine B, rose bengal), jantones (e.g., xanthones, thioguanthones, Ethylthioxanthone), a cyanide (e.g., thiacaboxane, oxacarbocyanine), a melocyanidic (e. G., Merocyanine, carbomerocyanine), a rhodacyanide, an oxo (Such as acridine orange, chloroflavin, acriflavine), acridines (e. G., Acridine, e. G. Acrydon, 10-butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaryliums (for example, Benzooxazole), coumarins (e. G., 7-diethylamino &lt; / RTI &gt; 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinoline 11-one).

Among these sensitizers, preferred are polynuclear aromatic compounds, acridones, styrenes, base styryls and coumarins, and more preferably polynuclear aromatic compounds. Of the polynuclear aromatics, anthracene derivatives are most preferred.

When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.001 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, relative to 100 parts by mass of the total solid components in the photosensitive resin composition And more preferably 0.5 to 20 parts by mass. Two or more kinds of sensitizers may be used in combination. When two or more kinds of sensitizers are used, the total amount becomes the above range.

<< Basic compound >>

The photosensitive resin composition of the present invention may contain a basic compound. As the basic compound, any of those used as a chemically amplified resist may be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraphs Nos. 0204 to 0207 of Japanese Patent Laid-Open Publication No. 2011-221494 and compounds described in paragraphs 0141 to 0145 of Japanese Laid-Open Patent Publication No. 2012-133091, do.

Specific examples of the aliphatic amine include aliphatic amines such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Amine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8 4-methylmorpholine, N-cyclohexyl-N '- [2- (4-morpholin-4-yl) -pyridine, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, Diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7-undecene, 1,8-diazabicyclo [5.4.0] -7-undecene.

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

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

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

When the photosensitive resin composition of the present invention contains a basic compound, the content of the basic compound is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 1 part by mass relative to 100 parts by mass of the total solid components in the photosensitive resin composition Do. When two or more kinds of basic compounds are used, the total amount is in the above range.

<< Surfactant >>

The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants may be used, and preferred surfactants are nonionic surfactants. Examples of the surfactant used in the composition of the present invention include those described in paragraphs 0201 to 0205 of Japanese Laid-Open Patent Publication No. 2012-88459, and those described in paragraphs 0185 to 0188 of Japanese Laid-Open Patent Publication No. 2011-215580 And these descriptions are incorporated herein by reference.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. Further, KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Manufactured by Mitsubishi Materials Gaseous Co., Ltd.), Megapack (manufactured by DIC Corporation), Fluoradovec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Surfron S-242 (manufactured by AGC Seiyaku Chemical Co., Ltd.), PolyFoxPF-6320 (manufactured by OMNOVA), SH-8400 (TORAY DOW CORNING SILICONE), FTERGENT FTX-218 and FTX-218G (manufactured by Neos).

It is preferable that the surfactant is at least one selected from the group consisting of polystyrene (hereinafter referred to as &quot; polystyrene &quot;) measured by gel permeation chromatography in which tetrahydrofuran (THF) And a weight-average molecular weight (Mw) in the range of 1,000 to 10,000 is mentioned as a preferable example.

The compound represented by the general formula (I-1-1)

(55)

(In the formula (I-1-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴⁰⁴ represents a hydrogen atom or L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages indicating polymerization ratios, p is a value of 10 mass% or more and 80 mass% or less, q represents a numerical value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.

It is preferable that L is a branched alkylene group represented by the following general formula (I-1-2). R ⁴⁰⁵ in the general formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in view of compatibility and wettability to a surface to be coated, Or 3 is more preferable. It is preferable that the sum (p + q) of p and q is p + q = 100, that is, 100 mass%.

In general formula (I-1-2)

(56)

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants may be used singly or in combination of two or more.

When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass, per 100 parts by mass of the total solid components in the photosensitive resin composition , And more preferably 0.01 to 3 parts by mass. The surfactants may be used singly or in combination of two or more. When two or more kinds of surfactants are used, the total amount is in the above range.

<< Mountain propagation agent >>

The photosensitive resin composition of the present invention can use an acid growth agent for the purpose of improving the sensitivity.

The acid-proliferating agent usable in the present invention is a compound capable of generating an acid by an acid catalytic reaction to increase the acid concentration in the reaction system, and is a compound stably present in the absence of acid.

Specific examples of such an acid-proliferating agent include the acid-proliferating agents described in paragraphs 0226 to 0228 of Japanese Laid-Open Patent Publication No. 2011-221494, the contents of which are incorporated herein by reference.

When the composition of the present invention contains an acid-proliferating agent, the content of the acid-proliferating agent in the photosensitive composition is preferably 10 to 1,000 parts by mass per 100 parts by mass of the photoacid generator, , More preferably from 20 to 500 parts by mass. The acid proliferating agent may be used singly or in combination of two or more kinds. When two or more acid-proliferating agents are used, the total amount is in the above range.

<< Development Promoter >>

The photosensitive resin composition of the present invention may contain a development accelerator.

As the development promoter, reference may be made to those described in Japanese Patent Laid-Open Publication No. 2012-042837, paragraphs 0171 to 0172, which are incorporated herein by reference.

The development accelerator may be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention contains a development accelerator, the content of the development accelerator is preferably 0 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, More preferably 20 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass. When two or more kinds of phenomenon promoting agents are used, the total amount is in the above range.

<< Antioxidants >>

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. By containing an antioxidant, coloring of the cured film can be prevented, or film thickness reduction due to decomposition by light or heat can be reduced, and furthermore, there is an advantage of excellent heat and heat transparency.

Examples of the antioxidant include phosphorus antioxidants, amides, hydrazides, sulfur-based antioxidants, phenol-based antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives . Of these, a phenol-based antioxidant, a phosphorus-based antioxidant and a sulfur-based antioxidant are preferable from the viewpoints of coloring of a cured film due to light or heat and reduction in film thickness, and phenolic antioxidants are more preferable. These may be used alone or in combination of two or more. When two or more are used in combination, there is no particular limitation, but from the viewpoint of coloring of the cured film due to light or heat and film thickness reduction, the combination of the phenol antioxidant and the sulfur antioxidant is preferable.

Preferred commercial products are adekastab AO-15, adekastab AO-18, adekastab AO-20, adekastab AO-23, adekastab AO-30, adekastab AO- 37, Adekastab AO-40, Adekastab AO-50, Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO- Adekastab AO-412S, Adekastab AO-503, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab Stab PEP-36, Adekastab PEP-36Z, Adekastab HP-10 (manufactured by ADEKA Corporation).

When the photosensitive resin composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the total solid components of the photosensitive resin composition , And particularly preferably 0.5 to 4 parts by mass. When two or more kinds of antioxidants are used, the total amount is in the above range.

As other additives, a thermal radical generator described in paragraphs 0120 to 0121 of Japanese Laid-Open Patent Publication No. 2012-8223, a nitrogen-containing compound described in WO2011 / 136074A1, and a thermal acid generation system may be used .

&Lt; Preparation method of photosensitive resin composition >

The respective components are mixed in a predetermined ratio in any manner, and dissolved by stirring to prepare a photosensitive resin composition. For example, each of the components may be previously dissolved in a solvent to prepare a solution, and then these may be mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be provided for use after filtration using a filter having a pore diameter of 0.2 m or the like.

The solid content concentration of the composition of the present invention at 25 캜 is preferably from 1 to 60 mass%, more preferably from 3 to 40 mass%, still more preferably from 5 to 30 mass%, still more preferably from 5 to 17 mass% desirable.

The viscosity of the composition of the present invention at 25 캜 is preferably from 1 to 100 mPa · s, more preferably from 2 to 60 mPa · s, most preferably from 3 to 40 mPa · s. By setting the solid content concentration and the viscosity within the above range, high-quality coating can be performed. The viscosity can be measured by, for example, using a viscosity measuring instrument RE85L (rotor: 1 ° 34 '× R24 measuring range: 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd. and adjusting the temperature to 25 ° C.

(Production method of cured film)

The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).

(1) a step of applying the photosensitive resin composition of the present invention to at least one side of a substrate,

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

(3) a step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray,

(4) a step of developing the exposed photosensitive resin composition by an aqueous developing solution, and

(5) Post-baking process for thermally curing the developed photosensitive resin composition

Wherein the cured film has a thickness of 100 nm or less.

Each step will be described below in order.

In the application step of (1), it is preferable that the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent. It is preferable to clean the substrate such as alkali washing or plasma cleaning before applying the photosensitive resin composition to the substrate, and more preferably, the substrate surface is treated with hexamethyldisilazane after the substrate cleaning. By carrying out this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and for example, a method of exposing the substrate to steam, which is hexamethyldisilazane, can be mentioned.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material.

Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and composite substrates obtained by depositing molybdenum, titanium, aluminum, copper, or the like on a substrate such as glass, quartz, silicon or silicon nitride.

Examples of the resin include polyolefin resins such as polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polystyrene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycolcarbonate, Fluorine resins such as polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin and polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, silicone A substrate made of a synthetic resin such as a resin, an ionomer resin, a cyanate resin, a crosslinked fumaric acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose or an episulfide compound.

These substrates are rarely used in the above-described form, and a multi-layered laminate structure such as a TFT element is usually formed depending on the shape of the final product.

The photosensitive resin composition can be coated on a substrate by a known coating method such as slit coating, spin coating, or inkjet coating. Among them, slit coating is preferable. Since the slit coat can be efficiently applied to a large substrate, the productivity is high. Large substrate refers to a area of the substrate of more than 300000mm ² 12000000mm ² below. When the slit is applied, the relative moving speed of the substrate and the slit die is preferably 20 to 180 mm / sec. It is also possible to combine spin application after slit application.

The coating film thickness (dry film thickness) is not particularly limited, and it can be applied in a film thickness according to the application, and it is usually used in the range of 0.5 to 10 mu m.

In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum pressure) and / or heating to form a dry film on the substrate. The heating condition of the solvent removing step is preferably about 70 to 130 DEG C for about 30 to 300 seconds. When the temperature and the time are in the above ranges, the pattern adhesion tends to be better and the residue tends to be lowered.

In the exposure step of the step (3), the substrate provided with the coating film is irradiated with an actinic ray of a predetermined pattern. In this step, the photoacid generator is decomposed to generate acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to form a carboxyl group or a phenolic hydroxyl group.

(365 nm), h-line (405 nm), g-line (436 nm), and the like can be used as the exposure light source by the actinic ray. Examples of the exposure light source include a low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, chemical lamp, LED light source, Can be preferably used as the active light ray having a wavelength of 300 nm or more and 450 nm or less. In addition, if necessary, the irradiation light can be adjusted by passing through a spectral filter such as a long wavelength cutoff filter, a short wavelength cutoff filter, or a bandpass filter. The exposure dose is preferably 1 to 500 mJ / cm ² .

As the exposure apparatus, various types of exposure apparatus such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, a laser exposure, and a liquid immersion exposure can be used.

It is also possible to perform exposure using so-called super resolution technology. Examples of the super resolution technique include multiple exposure for exposing a plurality of times, a method using a phase shift mask, and a ring zone illumination method. By using these super-resolution techniques, it is possible to form a pattern with higher definition, which is preferable.

Post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as "PEB") may be performed to accelerate the hydrolysis reaction in the region generated by the acid catalyst. PEB can promote the generation of a carboxyl group or a phenolic hydroxyl group from an acid decomposable group. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 100 占 폚.

(4), a favorable carboxyl group or a copolymer having a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed region including a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.

The developing solution used in the developing step preferably contains an aqueous solution of a basic compound. Examples of the basic compound include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and the like; Hydroxyalkyl) trialkylammonium hydroxides; Silicates such as sodium silicate and sodium metasilicate; Alkylamines such as ethylamine, propylamine, diethylamine and triethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Alicyclic amines such as 1,8-diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene can be used.

Among these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline (2-hydroxyethyltrimethylammonium hydroxide ) Is preferable.

An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

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

The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid-jet method (puddle method), a shower method, and a dipping method.

After the development, a rinsing process may be performed. In the rinsing step, the developed substrate is cleaned with pure water or the like to remove the attached developing solution and remove the developing residue. As the rinsing method, known methods can be used. For example, a shower rinse or a deep rinse.

In the post-baking step of (5), the obtained positive image is heated to pyrolyze the acid-decomposable group to generate a carboxyl group or phenolic hydroxyl group, to crosslink the crosslinkable group, the crosslinking group, etc., and / A film can be formed. The heating is carried out at a predetermined temperature, for example, 180 to 400 ° C for a predetermined time, for example, 5 to 120 minutes for a hot plate, 30 to 360 minutes for an oven, It is preferable to perform the heat treatment. By carrying out the crosslinking reaction and the cyclization reaction in this way, a protective film or an interlayer insulating film having better heat resistance and hardness can be formed. Further, when the heat treatment is performed, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

Post-baking may be performed after baking at a relatively low temperature before the post-baking (addition of the middle baking step). In the case of performing the middle baking, post baking is preferably performed at a high temperature of 200 DEG C or higher after heating at 90 to 150 DEG C for 1 to 60 minutes. In addition, middle baking and post baking can be divided into three or more stages and heated. The taper angle of the pattern can be adjusted by devising such a middle bake and post bake. For these heating, a known heating method such as a hot plate, an oven, and an infrared heater can be used.

In addition, prior to the post-baking, the substrate on which the pattern is formed is subjected to an entire surface re-exposure (post exposure) by an actinic ray and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, And the curing reaction of the film can be promoted. As a preferred exposure dose in the case of including a post-exposure step, the 100 ~ 3,000mJ / cm ² are preferred, and particularly preferred is 100 ~ 500mJ / cm ^2.

The cured film obtained from the photosensitive resin composition of the present invention may also be used as an etching resist. When the cured film obtained by thermal curing by the post-baking process is used as a dry etching resist, dry etching such as ashing, plasma etching, and ozone etching can be performed as the etching process.

(Cured film)

The cured film of the present invention is a cured film obtained by curing the above-mentioned photosensitive resin composition.

The cured film of the present invention can be suitably used as an interlayer insulating film. It is preferable that the cured film of the present invention is a cured film obtained by the aforementioned method of forming a cured film of the present invention.

By the photosensitive resin composition of the present invention, an interlayer insulating film having high transparency can be obtained even when the insulating resin is excellent in bake at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention is useful for a liquid crystal display device and an organic EL display device because it has high transparency and excellent physical properties of a cured film.

The transmittance of the cured film of the present invention at a wavelength of 400 nm is preferably 85 to 100%, more preferably 90 to 100%, and even more preferably 95 to 100%. The transmittance at a wavelength of 400 nm can be measured by, for example, a spectrophotometer (U-3000, manufactured by Hitachi, Ltd.).

(Liquid crystal display device)

The liquid crystal display device of the present invention comprises the cured film of the present invention.

The liquid crystal display of the present invention is not particularly limited, except that it has a protective film, a planarization film and an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and includes a known liquid crystal display device having various structures.

For example, specific examples of a TFT (Thin-Film Transistor) included in the liquid crystal display of the present invention include an amorphous silicon TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be suitably used in combination with these TFTs.

As a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a twisted nematic (TN) method, a VA (virtual alignment) method, an in-plane switching (IPS) method, a fringe field switching Optical Compensated Bend) method.

In the panel construction, the cured film of the present invention can also be used in a color filter on array (COA) type liquid crystal display device. For example, the organic insulating film 115 of Japanese Laid-Open Patent Publication No. 2005-284291, 2005-346054. &Lt; / RTI &gt; Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. It may also be polymer-oriented supported by the PSA (Polymer Sustained Alignment) technique described in Japanese Unexamined Patent Application Publication No. 2003-149647 or Japanese Unexamined Patent Publication No. 2011-257734.

In addition, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned use, and can be used for various purposes. For example, a protective film of a color filter, a spacer for keeping the thickness of the liquid crystal layer constant in a liquid crystal display device, a microlens provided on a color filter in a solid-state image pickup device, or the like.

1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel is a liquid crystal display panel in which all the pixels And the elements of the TFT 16 corresponding to the TFTs 16 are disposed. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are arranged is provided.

The light source of the backlight is not particularly limited and a known light source can be used. For example, white LEDs, multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), organic ELs, and the like.

The liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type. It can also be used as a flexible type, and can be used as the second interlayer insulating film 48 described in Japanese Patent Application Laid-Open No. 2011-145686 or the interlayer insulating film 520 described in Japanese Patent Application Laid-Open No. 2009-258758.

Also, in the liquid crystal display device of the static driving system, it is also possible to display a pattern having high designability by applying the present invention. For example, the present invention can be applied to an insulating film of a polymer network type liquid crystal as described in Japanese Patent Application Laid-Open No. 2001-125086.

(Organic EL display device)

The organic EL display device of the present invention comprises the cured film of the present invention.

The organic EL display device of the present invention is not particularly limited, except that it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices and liquid crystal display devices .

For example, specific examples of a TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include an amorphous silicon TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be suitably used in combination with these TFTs.

2 is a conceptual diagram of an example of the organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device and has a planarization film 4.

A bottom gate type TFT 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed in a state of covering the TFT 1. A contact hole (not shown) is formed in the insulating film 3 and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 . The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

The flattening film 4 is formed on the insulating film 3 in a state of filling the irregularities formed by the wirings 2 in order to planarize the irregularities due to the formation of the wirings 2.

On the flattening film 4, a bottom emission type organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the planarization film 4 by being connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing the insulating film 8, the distance between the first electrode 5 and the second electrode It is possible to prevent a short circuit.

Although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited by evaporation through a desired pattern mask. Then, a second electrode made of Al is formed on the entire surface above the substrate, An organic EL display device of an active matrix type in which a sealing glass plate and an ultraviolet curing type epoxy resin are used to seal each other and to which a TFT 1 for driving the organic EL element is connected is obtained.

Since the photosensitive resin composition of the present invention has excellent curability and cured film properties, it is possible to use a resist pattern formed by using the photosensitive resin composition of the present invention as a structural member of a MEMS device as a partition wall or as a part of a mechanical driving component Is used. Examples of the MEMS device include components such as a SAW filter, a BAW filter, a gyro sensor, a display micro shutter, an image sensor, an electronic paper, an ink jet head, a biochip, and a sealant. More specific examples are exemplified in JP-A-2007-522531, JP-A-2008-250200 and JP-A-2009-263544.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer 16 and the planarization film 57 shown in Fig. 2 of Japanese Laid-Open Patent Publication No. 2011-107476, Japanese Laid-Open Patent Publication No. 2010-9793 The bank layer 221 and the third interlayer insulating film 216b shown in FIG. 10 of Japanese Laid-Open Patent Publication No. 2010-27591, the barrier layer 12 and the planarization film 102 described in FIG. 4 (a) The second interlayer insulating film 125 and the third interlayer insulating film 126 shown in Fig. 4A of JP-A-128577, the planarization film 12 and the pixel isolation insulating film 14 described in Fig. 3 of JP-A- And the like. In addition, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a focusing optical system of an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state imaging element, Can also be suitably used.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise specified, "part" and "%" are based on mass.

Synthesis Example A-1: Synthesis of Resin A-1

(0.8 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Nippon Kayaku Co., Ltd.) was added to a three-necked flask equipped with a stirrer, 158.2 g (2.0 mol) of pyridine and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to -25 占 폚 with a dry ice / acetone bath. To this solution were added 73.9 g (0.364 mol) of isophthaloyl chloride (manufactured by TOKYO KASEI CO., LTD.) And 107.4 g (0.364 mol) of 4,4 ' -Oxybisbenzoyl chloride (obtained by converting 4,4'-oxybisbenzoic acid (made by Aldrich) into acid chloride by a predetermined method) and 700 g of NMP (1-methyl-2-pyrrolidone) were added dropwise. After completion of the dropwise addition, the resulting mixture was stirred at room temperature for 16 hours.

Next, the reaction solution was cooled to -5 deg. C or lower with an ice / methanol bath, and 17.0 g (0.217 mol) of acetyl chloride was added dropwise while maintaining the reaction temperature at -0 deg. After the dropwise addition was completed, the reaction mixture was further stirred for 16 hours.

The reaction solution was diluted with 2 L of acetone and charged into 20 L of deionized water stirred vigorously. The precipitated white powder was recovered by filtration and washed with deionized water and a mixture of water / methanol (50/50 by mass ratio) did. The polymer was dried under vacuum at 40 캜 for 24 hours to obtain Resin A-1.

Synthesis Examples A-2 to A-14: Synthesis of Resins A-2 to 14

Synthesis was also carried out for Resins A-2 to A-14 by the same procedure as for Resin A-1. The device used in these syntheses, the amount of the pyridine, the amount of the solvent, the method of extracting the polymer, and the like are all the same as those of Synthesis Example A-1. All of the acid dichloride was mixed and placed in the dropwise liquid side. The amount of the monomer used and the molecular weight of the obtained polymer are shown in the following table.

&Lt; Polybenzoxazole precursor in which the terminal is capped with an acetyl group >

[Table 1]

Bis-APAF represents hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, ODC represents 4,4'-oxybisbenzoyl chloride, IC represents isophthalic acid C represents adipic acid dichloride (made by ALDRICH), and CHD-C represents 1,4-cyclohexane di Carboxylic acid dichloride (Tokyo Gasee now acid-chlorinated with 1,4-cyclohexanedicarboxylic acid by a prescribed method), and AcCl represents acetyl chloride (Tokyo Gaseem).

The molecular weight (GPC) represents the value in the table 占 1000. The molecular weight is an Mw value measured by gel permeation chromatography in terms of polystyrene equivalent, and represents the value in the table 占 1000 (hereinafter the same with respect to the molecular weight of the resin).

(57)

Synthesis Example A-101a: Synthesis of Resin A-101a

150 g of the polymer (A-1) obtained in Synthesis Example A-1 and 2.4 L of propylene glycol-1-monomethylether-2-acetate (PGMEA) were added to a three-necked flask, Until it was concentrated. 17.4 g (2.25 mmol) of camphorsulfonic acid (3 mass% PGMEA solution) and 12.99 g (0.169 mol) of 2,3-dihydrofuran were added using a thermometer, a stirrer and a nitrogen inlet tube, Lt; / RTI &gt; Next, 5.68 g (5.62 mmol) of triethylamine (10 mass% PGMEA solution) was added and the reaction was terminated.

This reaction solution was diluted with 1.5 L of acetone and poured into 20 L of hexane stirred vigorously, and the precipitated white powder was recovered by filtration. The polymer was dried under vacuum at 4O &lt; 0 &gt; C for 4 hours, and 120 g of this polymer was dissolved in 2 L of acetone and poured into 10 L of vigorously stirred water and a mixture of deionized water and water / methanol (50/50 by mass) Lt; / RTI &gt; The polymer was dried under vacuum at 40 캜 for 24 hours to obtain Resin A-101a.

Synthesis Examples A-101b to A-114c: Synthesis of Resins A-101b to A-114c

Resins A-101b to A-114c were also synthesized in the same manner as Resin A-101a. The apparatus, the solvent amount, and the method of extracting the polymer used in these syntheses are all the same as those of Synthesis Example A-101a and in the same amount. The amounts of the monomers used and the molecular weights of the obtained polymers are shown in the following table.

&Lt; Polybenzoxazole precursor into which an acid-decomposable group is introduced into the main chain >

[Table 2]

In the table, DHF represents 2,3-dihydrofuran, 3% CSA represents camphorsulfonic acid (3 mass% PGMEA solution) and 10% NEt ₃ represents triethylamine (10 mass% PGMEA solution).

Synthesis Example A-201a: Synthesis of Resin A-201a

In the same manner as in Synthesis Example A-101a except that 12.99 g of 2,3-dihydrofuran in Synthesis Example A-101a was changed to 12.19 g (0.169 mol) of ethyl vinyl ether, the reaction and reprecipitation of the polymer, Drying was carried out. At this time, the obtained polymer had an OH group protection ratio of 30% and a molecular weight of 6700.

Synthesis Example A-301a: Synthesis of Resin A-301a

The procedure of Synthesis Example A-101a was repeated except that 21.9 g (0.169 mol) of cyclohexyl vinyl ether was changed to 12.99 g of 2,3-dihydrofuran in Reaction Example A- , And dried. At this time, the obtained polymer had an OH group protection ratio of 30% and a molecular weight of 6800.

&Lt; Preparation of Photosensitive Resin Composition >

Each component was weighed so as to have a solid content ratio shown in the following table and filtered with a filter made of polytetrafluoroethylene having a pore size of 0.2 m to obtain photosensitive resin compositions of various examples and comparative examples. Unless otherwise specified, the figures in the table indicate the parts by mass.

Details of the abbreviations used for the compounds used in Examples and Comparative Examples are as follows.

B. Photo acid generator

B-1: The structure shown below (PAG-103, manufactured by BASF), the pKa of the generated acid is 2 or less

(58)

B-2: Structure shown below (PAI-101, manufactured by Midori Kagaku), and Me represents a methyl group. The pKa of the generated acid is 2 or less

[Chemical Formula 59]

B-3: Structure shown below (synthesis example will be described later). The pKa of the generated acid is 2 or less

(60)

B-4: Structure shown below (synthesis example will be described later). Ts represents a tosyl group. The pKa of the generated acid is 2 or less

(61)

B-5: Structure shown below (synthesis example will be described later). The pKa of the generated acid is 2 or less

(62)

B-6: The structure shown below (synthesized according to the description in paragraph 0249 of WO11 / 087011). The pKa of the generated acid is 2 or less

(63)

B-7: Structure shown below (GSID-26-1, triarylsulfonium salt, manufactured by BASF). The pKa of the generated acid is 2 or less

&Lt; EMI ID =

NQD: The structure shown below (synthesized according to Example 2 of JP-A 2000-39714). The pKa of the acid generated is greater than 4.

(65)

C. Solvent

GBL: gamma-butyrolactone (manufactured by Mitsubishi Chemical)

PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko)

D. Cross-linking agent

D-1: Structure shown below (JER828, manufactured by Mitsubishi Chemical Holdings)

(66)

D-2: Structure shown below (JER157S65, manufactured by Mitsubishi Chemical Holdings)

(67)

D-3: The structure shown below (Denacol EX-321L, manufactured by Nagase ChemteX)

(68)

D-4: Structure shown below (Epikote 828, manufactured by Yucca Shell Epoxy Co., Ltd.)

(69)

D-5: Structure shown below

(70)

D-6: Structure shown below (NIKARAK MW-100LM, manufactured by Sanwa Chemical Co., Ltd.)

(71)

D-7: Structure shown below (NIKARAK MW-270, manufactured by Sanwa Chemical Co., Ltd.)

(72)

D-8: The structure shown below (Dyuranate 17B-60P, manufactured by Asahi Kasei Chemicals Co., Ltd.)

(73)

D-9: Structure shown below (Takenate B870N, manufactured by Mitsui Chemicals, Inc.)

&Lt; EMI ID =

D-10: The structure shown below (compound O-1 described in JP-A-2008-224970)

(75)

D-11: Structure shown below (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

[Formula 76]

Adhesion improver

E-1:? -Glycidoxypropyltrimethoxysilane

E-2:? -Glycidoxypropyltriethoxysilane

Basic compound

H-1: Compound of the following structure

[Formula 77]

H-2: 1,8-Diazabicyclo [5.4.0] -7-undecene

(Surfactants)

W-1: Compound of the following structure

(78)

W-2: Megafac F-554 (manufactured by DIC)

(Sensitizer)

DBA: 9,10-butoxyanthracene

<< Synthesis of benzooxazole precursor polymer (PBO-1) (polymer of Example 2 of JP-A No. 2000-39714) >>

(0.03 mole) of BAHF (0.03 mole) and 4.0 g (0.02 mole) of 4,4'-diaminodiphenyl ether were dissolved in 30 g of acetone and 58 g (1.0 mole) of propylene oxide in a four-necked flask under a dry nitrogen flow, And cooled to -10 ° C. A solution of 21.1 g (0.1 mole) of trimellitic anhydride chloride in 40 g of acetone was slowly added dropwise so that the temperature of the reaction solution did not exceed 0 占 폚. After completion of the dropwise addition, the reaction was carried out at -5 DEG C or lower for 1 hour, and 9.0 g (0.045 mol) of 4,4'-diaminodiphenyl ether and 0.1 g (0.045 mol) of 1,3- (0.005 mol) in 80 g of N-methylpyrrolidone (NMP) was added, and the mixture was allowed to react at 0 占 폚 for 1 hour, followed by reaction at 30 占 폚 for 4 hours.

After the reaction was completed, the solution was poured into 10 L of water to form a precipitate of polyhydroxyamide acid. This precipitate was collected by filtration, washed with water, and dried in a vacuum dryer at 50 ° C for 20 hours to obtain a polybenzoxazole precursor PBO-1 (PBO precursor having no crosslinking group) of Comparative Example.

<< Synthesis of acrylic polymer >>

66 parts of 1-ethoxyethyl methacrylate, 50 parts of GMA, 20 parts of 2-hydroxyethyl methacrylate, and 132.5 parts of PGMEA was heated to 70 占 폚 under a nitrogen stream. This mixed solution was added dropwise over 2.5 hours to a mixed solution of radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 12.4 parts) and PGMEA (100.0 parts) while stirring. After completion of the dropwise addition, the reaction was carried out at 70 DEG C for 4 hours to synthesize an acrylic polymer. And then reprecipitated according to a prescribed method to obtain a powder.

<< Synthesis of B-3 >>

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 캜 for reaction for 2 hours. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 占 폚 for 1 hour. 2N HCl aqueous solution (60 mL) was added thereto to separate the liquid. The organic layer was concentrated, and crystals were dissolved in diisopropyl ether (10 mL) Filtered, and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 mass% hydroxylamine aqueous solution (8.0 g) were added to the resulting suspension of the ketone compound (3.0 g) and methanol (30 ml), and the mixture was heated to reflux. 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 the temperature was raised to room temperature and reacted for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered and then slurry was rinsed with methanol (20 mL), followed by filtration and drying to obtain B-3 (2.3 g).

In addition, ¹ H-NMR spectrum of _{B-3 (300MHz, CDCl 3} ) is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (d, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

<< Synthesis of B-4 >>

4.0 g of 1-amino-2-naphthol hydrochloride (Tokyo Kasei) was suspended in 16 g of N-methylpyrrolidone (Wako Pure Chemical Industries, Ltd.), 3.4 g of sodium hydrogencarbonate (Wako Pure Chemical Industries, Ltd.) 4.9 g of dimethyl-3-oxovalerate (Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was heated at 120 캜 for 2 hours in a nitrogen atmosphere. After cooling, water and ethyl acetate were added to the reaction mixture to separate the layers. The organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain crude (B-1-2A). The crude B-1-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-1-2A.

B-1-2A (1.7 g) and p-xylene (6 mL) were mixed, and 0.23 g of p-toluenesulfonic acid monohydrate (Wako Pure Chemical Industries, Ltd.) was added and heated at 140 占 폚 for 2 hours. After cooling, water and ethyl acetate were added to the reaction mixture, and the mixture was separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-1-2B.

To the mixture was added THF (2 mL) and the whole amount of the crude B-1-2B, 6.0 mL of a 2M hydrochloric acid / THF solution under ice-cooling and then isopentyl nitrite (Wako Junyaku Co., Ltd.) (0.84 g) did. Water and ethyl acetate were added to the reaction mixture to separate the layers. The organic layer was washed with water, dried over magnesium sulfate, filtered, and concentrated to obtain intermediate compound B-1-2C.

The whole amount of the intermediate group B-1-2C was mixed with acetone (10 mL), and then 1.2 g of triethylamine (Wako Pure Chemical Industries, Ltd.) and 1.4 g of p-toluenesulfonyl chloride The mixture was heated to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the resulting reaction mixture, and the mixture was separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-4. The crude B-4 was slurried with cold methanol, filtered and dried to obtain B-4 (1.2 g).

Further, ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-4 was found to be 隆 = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7.6 7.5 (m, 1H), 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H).

<< Synthesis of B-5 >>

33.6 g of N-hydroxynaphthalimide sodium salt, 0.72 g of 4-dimethylaminopyridine and 300 ml of tetrahydrofuran were placed in a separable flask equipped with a stirrer and a thermometer and dissolved under stirring at room temperature of 25 ° C. Then, (+) 10-camphorsulfonyl chloride (42 g) was added and stirred for 3 hours. Then, 15 g of triethylamine was added, and the mixture was stirred at room temperature for 10 hours. Subsequently, the reaction solution was put into 300 ml of distilled water, and the precipitated precipitate was separated by filtration. This precipitation was repeated several times by reprecipitation treatment using acetone and hexane to obtain N-camphorsulfonyloxy-1,8-naphthalimide (12 g).

&Lt; Evaluation of viscosity &

The viscosity of the composition thus obtained was measured at 25 占 폚 using a viscosity measuring instrument RE85L (rotor: 1 占 34 '占 R24 measuring range 0.6 to 1200 mPa 占 퐏).

A: less than 2 mPa · s

B: 2 mPa 占 퐏 or more and less than 15 mPa 占 퐏

C: 15 mPa · s or more and less than 30 mPa · s

D: 30 mPa · s or more

[Table 3]

[Table 4]

[Table 5]

&Lt; Evaluation of reactivity of crosslinking agent &

2 parts by mass of the crosslinking agent used in each of the Examples and Comparative Examples and 2 parts by mass of Maruka Linker M (Maruzen Sekishi Chemical Co., Ltd., number average molecular weight: 1500) were dissolved in 100 parts by mass of THF.

Confirm before heating

The solution was subjected to GPC analysis to confirm that two peaks (peaks of the cross-linking agent and peaks of the phenol) were observed. In addition, we recorded retention time of Maruka linker.

Evaluation of reactivity

After the slurry was applied to the glass substrate with the dissolution liquid, the solvent was volatilized with Vacuum dry and then pre-baked on a hot plate at 90 DEG C for 120 seconds to form a resin layer having a thickness of 2.0 mu m. This glass substrate was heated in an oven at 200 DEG C for 30 minutes. 0.1 part by mass of the film after heating was cut out, and 10 parts by mass of PGMEA was added to perform GPC analysis in the same manner.

A when the polymer peak detected by this analysis deviates from the retention time of the first marukin linker M is A;

In case of A, a benzene ring or phenolic hydroxyl group of Maruka Linker M reacted with a crosslinking agent. As a result, it means that the polymer has a higher molecular weight.

B means that the benzene ring or the phenolic hydroxyl group of the Maruka Linker M did not react with the crosslinking agent.

&Lt; Evaluation of sensitivity &

The glass substrate (OA-10, manufactured by Nippon Denshikazai Co., Ltd.) was exposed for 30 seconds under the steam of hexamethyldisilazane (HMDS), each of the photosensitive resin compositions was coated with a slit, , And then pre-baked on a 120 占 폚 / 120 second hot plate to form a photosensitive resin composition layer having a thickness of 2.0 占 퐉.

Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF manufactured by Canon Inc. After the exposure, the photosensitive resin composition layer heated on a hot plate at 80 占 폚 for 60 seconds was developed with an alkaline developer (2.38% aqueous tetramethylammonium hydroxide solution) at 23 占 폚 for 80 seconds and rinsed with ultrapure water for 20 seconds. The optimum i-line exposure amount (Eopt) at the time of resolving the hole of 5 mu m by these operations was taken as the sensitivity. A and B are practical levels.

A: Less than 100 mJ / cm ²

B: 100 mJ / cm ² or more, less than 200 mJ / cm ²

C: not less than 200 mJ / cm ^{2, not} more than 400 mJ / cm ²

D: 400 mJ / cm ² or more

The composition of Example 104 was evaluated in the same manner as in the above evaluation of sensitivity except that the 80 ° C hot plate after pattern exposure was not heated for 60 seconds.

&Lt; Evaluation of transmittance &

The glass substrate (OA-10, manufactured by Nippon Denshikazai Co., Ltd.) was exposed for 30 seconds under the steam of hexamethyldisilazane (HMDS), each of the photosensitive resin compositions was coated with a slit, , And then pre-baked on a 120 占 폚 / 120 second hot plate to form a photosensitive resin composition layer having a thickness of 2.0 占 퐉. Subsequently, exposure was carried out using an ultra-high pressure mercury lamp so that the cumulative dose was 300 mJ / cm ² (energy intensity: 20 mW / cm ² ), and the substrate was heated in an oven at 300 ° C for 60 minutes in an oven. The transmittance of this cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: Hitachi, Ltd.). The unit is expressed in%. A, B, and C are practical levels.

A: 95% or more

B: 90% or more and less than 95%

C: 85% or more and less than 90%

D: Less than 85%

<Heat resistance>

The glass substrate was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds. Each of the photosensitive resin compositions was applied to a spin coat, pre-baked on a hot plate at 120 DEG C for 120 seconds, and the solvent was volatilized to form a photosensitive resin composition layer having a thickness of 2.0 mu m. Subsequently, exposure was carried out using an ultra-high pressure mercury lamp so that the cumulative irradiation amount became 300 mJ / cm ² (energy intensity: 20 mW / cm ² ). Thereafter, this substrate was heated in an oven under nitrogen atmosphere at 300 ° C / 60 min to obtain a cured film.

Next, after the cured film was cut, the temperature was raised from room temperature to 300 占 폚 at 20 占 폚 / min, and then maintained at 300 占 폚 for 60 minutes to evaluate the decrease in the thermal weight. Evaluation was carried out in a nitrogen atmosphere. The results are shown in the following table. The smaller the numerical value, the higher the heat resistance, and A or B is the practical level.

A: Weight reduction rate less than 3%

B: weight reduction rate 3% or more and less than 5%

C: weight reduction rate 5% or more and less than 10%

D: weight reduction rate 10% or more

<Adherence of Cured Film>

A glass substrate on which a Mo (molybdenum) thin film was formed was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds. Each of the photosensitive resin compositions was applied to a spin coat, pre-baked on a hot plate at 120 DEG C for 120 seconds, and the solvent was volatilized to form a photosensitive resin composition layer having a thickness of 2.0 mu m. Subsequently, exposure was carried out using an ultra-high pressure mercury lamp so that the cumulative irradiation amount became 300 mJ / cm ² (energy intensity: 20 mW / cm ² ). Thereafter, this substrate was heated in an oven under nitrogen atmosphere at 300 ° C / 60 min to obtain a cured film. The substrate on which the cured film was formed was immersed in N-methyl-2-pyrrolidone (NMP) temperature-controlled at 80 캜 for 30 minutes.

After the immersion, the cured film was cut with a cutter at intervals of 1 mm in the longitudinal and lateral directions, and subjected to a tape peeling test (100-cross cut method: JIS 5600) using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred on the back surface of the tape. The results are shown in the following table. The smaller the numerical value is, the higher the adhesion to the substrate is, and A or B is a practical level.

A: Less than 10% of transferred area

B: Transferred area is 10% or more and less than 50%

C: 50% or more of transferred area

[Table 6]

[Table 7]

[Table 8]

From the above table, it can be seen that Examples 1 to 109 using the photosensitive resin composition of the present invention are all excellent in reactivity, sensitivity, transmittance, heat resistance, and adhesion. On the other hand, in Comparative Examples 1 to 6, which did not satisfy the requirements of the present invention, it was found that either of the reactivity, the sensitivity, the transmittance, the heat resistance, and the adhesion was inferior to those in Examples. Specifically, in Comparative Example 1 which does not contain the crosslinking agent (D), it was found that the adhesiveness was remarkably poor. It was found that Comparative Examples 2 to 3 containing a crosslinking agent other than the crosslinking agent (D) were remarkably inferior in reactivity, transmittance, heat resistance and adhesion to each other. In Comparative Example 4 containing no photoacid generator, it was found that the sensitivity and adhesion were significantly lower than those in Examples. In Comparative Example 5 using a photoacid generator having a pKa of more than 4, the sensitivity, the transmittance, the heat resistance, and the adhesion were remarkably lower than those of the examples. Also, in Comparative Example 6 containing no polybenzoxazole precursor, it was found that the transmittance and the heat resistance were significantly lower than those in Examples.

(355 nm laser exposure)

The photosensitive resin compositions of Examples 1 to 109 were subjected to pattern formation in the same manner as in the evaluation of the sensitivity except that the exposure was changed as follows in the evaluation of the sensitivity. That is, a predetermined photomask was set with a gap of 150 mu m from the coating film, and a laser beam having a wavelength of 355 nm was irradiated. The laser device used was "AEGIS" (wavelength: 355 nm, pulse width: 6 nsec) manufactured by Kabushiki Kaisha V-Technology.

In any of the examples, it was found that a pattern could be formed similarly to MPA5500CF.

(UV-LED exposure)

In addition, the photosensitive resin compositions of Examples 1 to 109 were evaluated in the same manner as in the evaluation of the sensitivity (without PEB) except that the exposure was changed to a UV-LED light source exposing device. .

(Example 200)

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

A bottom gate type TFT 1 was formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ was formed in a state of covering the TFT 1. Next, after a contact hole was formed in the insulating film 3, a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole was formed on the insulating film 3.

The flattening film 4 was formed on the insulating film 3 in a state of filling the irregularities formed by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 2. The planarization film 4 was formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 2 on the substrate, pre-baking (90 占 폚 for 2 minutes) on a hot plate, The resist film was irradiated with i-line (365 nm) using a mercury lamp to measure the exposure amount of the sensitivity component measured by the sensitivity evaluation, heated on a hot plate at 80 캜 for 60 seconds, developed with an aqueous alkali solution to form a pattern, Was performed. The coating properties upon application of the photosensitive resin composition were satisfactory, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Next, a bottom emission type organic EL device was formed on the obtained flattening film 4. Then, First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, the resist was applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was performed by wet etching using ITO etchant. Thereafter, the resist pattern was peeled off at 50 占 폚 using a resist stripping solution (Remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed in the same manner as above using the photosensitive resin composition of Example 2.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially deposited through a desired pattern mask in a vacuum evaporation apparatus. Then, a second electrode made of Al was formed on the entire surface above the substrate. The obtained substrate was removed from the evaporator, and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements are connected to each organic EL element was obtained. It was found that the organic EL display device exhibits very good display characteristics when a voltage is applied through the driving circuit and is highly reliable.

(Example 201)

An organic EL display device was produced in the same manner as in Example 200 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 46. [ The obtained organic EL display device exhibited very good display characteristics and was found to be an organic EL display device with high reliability.

(Example 202)

An organic EL display device was produced in the same manner as in Example 200 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 91. [ The obtained organic EL display device exhibited good display characteristics and was found to be an organic EL display device with high reliability.

(Example 203)

An organic EL display device was produced in the same manner as in Example 200 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 97. [ The obtained organic EL display device exhibited good display characteristics and was found to be an organic EL display device with high reliability.

(Example 204)

In the active matrix type liquid crystal display device shown in Figs. 1 and 2 of Japanese Patent Publication No. 3321003, a cured film 17 as an interlayer insulating film was formed as follows to obtain a liquid crystal display device of Example 204. [

That is, the photosensitive resin composition of Example 2 was used to form a cured film 17 as an interlayer insulating film in the same manner as the method of forming the planarization film 4 of the organic EL display device in Example 200. [

It was found that the obtained liquid crystal display device exhibited very good display characteristics when a driving voltage was applied and that it was a highly reliable liquid crystal display device.

(Example 205)

A liquid crystal display device was produced in the same manner as in Example 204 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 46. [ The obtained liquid crystal display device exhibited very good display characteristics and was found to be a highly reliable liquid crystal display device.

(Example 206)

A liquid crystal display device was produced in the same manner as in Example 204 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 91. The obtained liquid crystal display device exhibited good display characteristics and was found to be a highly reliable liquid crystal display device.

(Example 207)

A liquid crystal display device was produced in the same manner as in Example 204 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 97. [ The obtained liquid crystal display device exhibited good display characteristics and was found to be a highly reliable liquid crystal display device.

1: TFT (thin film transistor)
2: Wiring
3: Insulating film
4: Planarizing film
5: First electrode
6: glass substrate
7: Contact hole
8: Insulating film
10: Liquid crystal display
12: Backlight unit
14, 15: glass substrate
16: TFT
17:
18: Contact hole
19: ITO transparent electrode
20: liquid crystal
22: Color filter

Claims (15)

A polybenzoxazole precursor containing a repeating unit represented by the general formula (1)
A photoacid generator having a pKa of the generated acid of 4 or less,
A solvent,
A crosslinking agent having at least two crosslinkable groups reactive with at least one member selected from a benzene ring and a phenolic hydroxyl group,
Wherein the crosslinkable group of the crosslinking agent is selected from an epoxy group, a methylol group, an alkoxymethyl group and a block isocyanate group.
In general formula (1)
[Chemical Formula 1]

In the general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group; R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an acid-decomposable group, or -CORc; Rc represents an alkyl group or an aryl group; At least one of R ¹ and R ² is an acid-decomposable group. delete The method according to claim 1,
Wherein the terminal of the polybenzoxazole precursor is a group represented by the general formula (1-1);
(1-1)
(2)

In the general formula (1-1), Z represents a single bond, a carbon atom or a sulfur atom, and R ¹¹ represents a monovalent organic group; n is 0 or 1, and when Z is a single bond, a is 0, and when Z is a carbon atom, a is 1 and when Z is a sulfur atom, a is 2; When n is 0, the two R &lt; ¹¹ &gt; may be bonded to each other to form a ring. The method according to claim 1,
Wherein the polybenzoxazole precursor contains repeating units represented by m general formula (1-2) and repeating units represented by n general formula (3), m represents 3 to 1000, and n represents 0 to 1000 And m + n is 3 to 1000;
In general formula (1-2)
(3)

In general formula (3)
[Chemical Formula 4]

In the general formulas (1-2) and (3), Y ¹ each independently represents an arylene group, a divalent cyclic aliphatic group, a divalent heterocyclic group, or a group represented by -CH ₂ -, an oxygen atom, SO ₂ -, -CO-, -NHCO-, and -C (CF _{3) 2} - at least one represents a group comprising a combination of one kind, X ¹ is an aromatic ring, a heterocyclic ring, an aliphatic ring, or mixtures thereof with, - Represents a tetravalent group consisting of a combination of at least one of CH ₂ -, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ - , An acid-decomposable group, an alkyl group or -CORc, and at least one of Ra and Rb is an acid-decomposable group; Rc represents an alkyl group or an aryl group; X ² represents an arylene group, a divalent heterocyclic group, a divalent cyclic aliphatic group, or a group represented by -CH ₂ -, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -NHCO-, and -C CF ₃ ) ₂ -. The method according to claim 1,
Wherein the photosensitive resin composition further contains an adhesion promoter. The method according to claim 1,
Wherein the photoacid generator is at least one selected from the group consisting of an oxime sulfonate photo acid generator and an imide sulfonate photo acid generator. The method according to claim 1,
A group in which an acid-decomposable group is eliminated by the action of an acid, or -C (R ⁵ ) ₂ -COOR ⁴ ; Provided that each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and R ⁴ represents a group which is eliminated by the action of an acid. The method of claim 7,
Wherein the group which is eliminated by the action of an acid is a substituent group of a vinyl ether group. The method of claim 7,
Wherein the group which is eliminated by the action of an acid is an alkoxycarbonyl group, an alkoxyalkyl group, an alkylsilyl group, a group constituting an acetal, or a group constituting a ketal. A step of applying the photosensitive resin composition according to claim 1 to at least one side of a substrate,
A step of removing the solvent from the applied photosensitive resin composition,
A step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray,
A step of developing the exposed photosensitive resin composition by an aqueous developing solution, and
A post-baking step of thermally curing the developed photosensitive resin composition
Wherein the cured film has a thickness of 100 nm or less. The method of claim 10,
And a step of exposing the developed photosensitive resin composition to the whole surface after the developing step and before the post-baking step. A cured film obtained by curing the photosensitive resin composition according to claim 1. The method of claim 12,
A curing film which is an interlayer insulating film. A liquid crystal display device having the cured film according to claim 12 or 13. An organic EL display device having the cured film according to claim 12 or 13.

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