KR101738466B1 - Photosensitive resin composition, method for producing cured film, cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

[일반식(c-1) 중, 환(A)은 환 내에 1개의 질소원자 또는 황원자를 갖는 방향환을 나타내고, X는 수소원자, 알킬기 또는 아릴기를 나타내고, Y는 히드록시기, 카르복실기, 알킬카르보닐기, 아릴카르보닐기, 알킬옥시카르보닐기, 알콕시기, 아릴옥시기, 메르캅토기 또는 아미노기를 나타낸다. m은 1 이상의 정수를 나타내고, n은 1 이상의 정수를 나타낸다]Provided is a photosensitive resin composition which is excellent in chemical resistance in a state of being a cured film and suppresses occurrence of panel display unevenness in a state of being a cured film.
(A) a polymer having (a1) a structural unit having an acidic group and (a2) a structural unit having a crosslinkable group,
(B) a quinone diazide compound,
(C) a compound represented by the following general formula (c-1), and
(D) a solvent.

(A) represents an aromatic ring having one nitrogen atom or sulfur atom in the ring, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a hydroxyl group, a carboxyl group, an alkylcarbonyl group, An arylcarbonyl group, an alkyloxycarbonyl group, an alkoxy group, an aryloxy group, a mercapto group or an amino group. m represents an integer of 1 or more, and n represents an integer of 1 or more]

Description

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

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as "photosensitive resin composition" or "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 composition, and various image display devices using the cured film.

More specifically, the present invention relates to a planarizing film for electronic components such as a liquid crystal display, an organic EL display, an integrated circuit element, and a solid-state imaging element, a photosensitive resin composition suitable for forming a protective film or an interlayer insulating film, and a method for producing a cured film using the same.

An organic EL display device, a liquid crystal display device, or the like is provided with a patterned interlayer insulating film (cured film). In order to form the interlayer insulating film, a photosensitive resin composition is widely used (for example, Patent Documents 1 and 2) because the number of processes for obtaining a desired pattern shape is small and sufficient flatness can be obtained.

Japanese Patent Application Laid-Open No. 5-165214 Japanese Patent Application Laid-Open No. 2008-256974

Since the interlayer insulating film is exposed to the resist stripping solution used for forming the pattern of the transparent electrode film after the formation of the interlayer insulating film and NMP (N-methylpyrrolidone) used in forming the liquid crystal alignment film, Is required. Further, in the panel reliability test, an interlayer insulating film which does not cause panel display irregularity is required even if it is deviated from severe conditions such as high temperature, high humidity and high pressure.

It is an object of the present invention to solve the problems described above, and an object of the present invention is to provide a cured film which is excellent in chemical resistance in a state of being a cured film, It is an object of the present invention to provide a resin composition. It is also an object of the present invention to provide a method for producing a cured film using such a photosensitive resin composition, a cured film, an organic EL display, and a liquid crystal display.

Under these circumstances, the inventor of the present invention has made intensive investigations. As a result of intensive studies, the present inventors have found that a polymer containing a repeating unit having an acidic group and a repeating unit having a crosslinkable group in a photosensitive resin composition and containing a nitrogen atom or a sulfur atom in an aromatic ring, , It is possible to improve the chemical resistance when the photosensitive resin composition is used for an interlayer insulating film application and to prevent occurrence of panel display irregularity in the panel reliability test in a state of using a cured film And the present invention has been accomplished.

Although this mechanism is not clear, the decomposition products from the photosensitive resin composition generated under the conditions of high temperature, high humidity, and high pressure, chelate and interact with coordination sites in the ring and out of ring in the molecule of the aromatic ring compound, And it contributes to the improvement of the panel reliability. Further, it is presumed that the aromatic ring compound promotes crosslinking of the cured film, contributing to improvement of chemical resistance.

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

(A) a polymer having (a1) a structural unit having an acidic group and (a2) a structural unit having a crosslinkable group,

(B) a quinone diazide compound,

(C) a compound represented by the following general formula (c-1), and

(D) a solvent.

(A) represents an aromatic ring having one nitrogen atom or sulfur atom in the ring, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a hydroxyl group, a carboxyl group, an alkylcarbonyl group, An arylcarbonyl group, an alkyloxycarbonyl group, an alkoxy group, an aryloxy group, a mercapto group or an amino group. m represents an integer of 1 or more, and n represents an integer of 1 or more]

&Lt; 2 > A compound according to < 1 >, wherein the compound represented by the general formula (c-1) is a 5-membered aromatic heterocyclic compound, a 6-membered aromatic heterocyclic compound, a 5-membered aromatic heterocyclic structure, Wherein the photosensitive resin composition is any one of polycyclic aromatic heterocyclic compounds containing at least one of them.

<3> The compound according to <1> or <2>, wherein the ring (A) in the compound represented by the general formula (c-1) is a pyrrole ring, a thiophene ring, a pyridine ring, a benzothiophene ring, , An isoquinoline ring, an indole ring or an acridine ring.

<4> The compound according to any one of <1> to <3>, wherein Y in the compound represented by the general formula (c-1) is a hydroxyl group, A phenoxy group, a mercapto group or an amino group.

<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the structural unit (a1) is a repeating unit having a carboxyl group and / or a phenolic hydroxyl group.

(6) The positive resist composition according to any one of (1) to (5), wherein the structural unit (a2) is an epoxy group, an oxetanyl group and -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) And a structural unit represented by the following formula (1).

<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the amount of the quinone diazide compound (B) is 10 to 50 parts by mass based on 100 parts by mass of the total of the polymer component (A).

(8) A process for producing a photosensitive resin composition, comprising the steps of (1) applying the photosensitive resin composition described in any one of (1) to (7)

(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 developer, and

(5) A post-baking step of thermally curing the developed photosensitive resin composition.

<9> The method for producing a cured film according to <8>, which comprises: before the post-baking step after the developing step; and (6) entirely exposing the developed photosensitive resin composition.

<10> The method for producing a cured film according to <8> or <9>, which comprises a step of performing dry etching on a substrate having a cured film obtained by thermosetting in the post baking step.

<11> A cured film formed by the method for producing a cured film according to any one of <8> to <10>.

<12> A cured film as an interlayer insulating film according to <11>.

<13> An organic EL display device or liquid crystal display device having the cured film according to <11> or <12>.

(Effects of the Invention)

According to the present invention, it is possible to provide a photosensitive resin composition that is excellent in chemical resistance in a state of being a cured film and suppresses occurrence of panel display unevenness in a panel reliability test in a state of being a cured film.

Fig. 1 shows a configuration diagram of an example of a liquid crystal display device. 1 is a schematic sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.
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, and has a planarizing film 4.

Hereinafter, the contents of the present invention will be described in detail. The following description of the constituent elements described below is based on a representative embodiment of the present invention, but the present invention is not limited to these embodiments. In the present specification, &quot; &quot; is used to mean that the numerical values described before and after the numerical value are included as the lower limit value and the upper limit value.

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 and 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).

The composition of the present invention comprises (A) a polymer having (a1) a structural unit having an acidic group and (a2) a structural unit having a crosslinkable group as a polymer component, (B) a quinone diazide compound, and (C) (c-1), and (D) a solvent.

According to the present invention, it is possible to provide a photosensitive resin composition that is excellent in chemical resistance in a state of being a cured film and suppresses occurrence of panel display unevenness in a panel reliability test in a state of being a cured film.

Further, according to the present invention, it is possible to provide a photosensitive resin composition that is excellent in adhesion to various substrates in a state of being developed and a cured film.

<(A) Polymer Component>

The polymer component (A) used in the present invention is a polymer (hereinafter referred to as (A) polymer) comprising (a1) a structural unit having an acidic group and (a2) a structural unit having a crosslinkable group. The polymer component (A) is a main component of the component excluding the solvent of the composition of the present invention, and preferably accounts for 30% by mass or more of the total solid content.

<< (a1) Structural unit having an acidic group >>

(A1) containing a structural unit having an acidic group in the polymer component (A) is easy to dissolve in an alkaline developer, and the effect of the present invention is more effectively exhibited. The acid group is usually contained in the polymer as a structural unit having an acidic group by using a monomer capable of forming an acidic group. When such a structural unit having an acidic group is contained in the polymer, it tends to be easily dissolved in an alkaline developer.

Examples of the acidic group used in the present invention include a carboxylic acid group, a phenolic hydroxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a constituent unit derived from a sulfonylimide group, etc., and a carboxylic acid group and / or a phenolic hydroxyl group Is more preferable. In particular, the constituent unit having an acidic group (a1) used in the present invention is preferably a repeating unit having a carboxyl group and / or a phenolic hydroxyl group. For example, compounds described in paragraphs [0021] to [0023] and paragraphs [0029] to [0044] of JP-A-2012-88459 can be used.

The constituent unit having an acidic group used in the present invention is preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth) acrylic acid and / or an ester thereof. For example, compounds described in paragraphs [0021] to [0023] and paragraphs [0029] to [0044] of JP-A-2012-88459 can be used.

Among them, acrylic acid, methacrylic acid, maleic anhydride, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, From the viewpoints of solubility and ease of availability. These compounds may be used alone or in combination of two or more.

(A1) is contained in an amount of preferably from 3 to 70 mol%, more preferably from 5 to 60 mol%, even more preferably from 10 to 50 mol%, of all structural units of the polymer component (A) Do. By setting the proportion of the structural unit (a1) within the above range, the radiation-sensitive resin composition having excellent sensitivity can be obtained, while (A) optimizing the solubility of the polymer component in an aqueous alkali solution.

<< (a2) Structural unit having a crosslinkable group >>

The polymer (A) has a structural unit (a2) having a crosslinkable group. The crosslinking group is not particularly limited as long as it is a group causing a curing reaction in the heat treatment. Preferable examples of the structural unit having a crosslinkable group include a group represented by an epoxy group, an oxetanyl group, a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), and an ethylenic unsaturated group , And is preferably at least one member selected from the group consisting of an epoxy group, an oxetanyl group and -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) Do. More specifically, the following can be mentioned.

<<< (a2-1) Constituent Unit Having an Epoxy Group and / or an Oxetanyl Group >>>

The polymer (A) preferably contains a structural unit (a2-1) having an epoxy group and / or an oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicyclohexylmethyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, -Epoxy cyclohexylmethyl,? -Ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Compounds containing an alicyclic epoxy skeleton described in paragraphs [0031] to [0035] of Japanese Patent No. 4168443, and the like, and the contents thereof are included in the specification of the present invention.

Specific examples of the radically polymerizable monomers used for forming the oxetanyl group-containing structural unit include oxetanyl groups having an oxetanyl group as described in paragraphs [0011] to [0016] of JP-A No. 2001-330953 Methacrylic acid ester, and compounds described in paragraph [0027] of Japanese Patent Application Laid-Open Publication (KOKAI) No. 08-088459, the contents of which are incorporated herein by reference.

Specific examples of the radically polymerizable monomer used to form the structural unit (a2-1) having an epoxy group and / or an oxetanyl group are monomers containing a methacrylic acid ester structure and monomers containing an acrylic ester structure Do.

Of these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether (3-ethyloxetan-3-yl) methyl methacrylate (3-ethyloxetan-3-yl) methyl methacrylate, and the improvement of various properties of the cured film . These constituent units may be used singly or in combination of two or more.

Preferable specific examples of the above-mentioned structural unit (a2-1) having an epoxy group and / or an oxetanyl group include the following constitutional units. R represents a hydrogen atom or a methyl group.

<<< (a2-2) Structural unit having an ethylenic unsaturated group >>>

Examples of the structural unit (a2) having a crosslinkable group include a structural unit (a2-2) having an ethylenic unsaturated group. As the structural unit (a2-2), a structural unit having an ethylenic unsaturated group in its side chain is preferable, and a structural unit having an ethylenic unsaturated group at the terminal and having a side chain of 3 to 16 carbon atoms is more preferable.

Other preferable examples of the structural unit (a2-2) include compounds described in paragraphs [0013] to [0031] of Japanese Patent Application Laid-Open No. 2008-256974, the contents of which are incorporated herein by reference.

<<< (a2-3) Constituent unit having a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>>

As the structural unit (a2) having a crosslinking group, -NH-CH ₂ -OR is also preferred structural units (a2-3) having a group represented by (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-3), a curing reaction can be caused in a gentle heat treatment, and a cured film excellent in various characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group. The structural unit (a2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).

[In the general formula (a2-30), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms]

R ² is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group.

Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group and an n-hexyl group. Among them, an i-butyl group, an n-butyl group and a methyl group are preferable.

(A2) is preferably contained in an amount of 20 to 80 mol%, more preferably 20 to 70 mol%, and more preferably 20 to 65 mol% in the whole constituent units of the polymer component (A) Do. By setting the usage ratio of the structural unit (a2) within the above range, a cured film having various properties can be formed.

<< (a3) Other building blocks >>

In the present invention, the polymer (A) may contain, in addition to the above structural units (a1) and (a2), other structural units (a3). The monomer to be the other structural unit (a3) is not particularly limited as far as it is an unsaturated compound other than the structural units (a1) and (a2). Specific examples of the radical polymerizable monomer used for forming the structural unit (a3) include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, Unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, pyran skeletons, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, ) And other unsaturated compounds including a skeleton represented by the following formula (1). Specific examples of the radical polymerizable monomer used for forming the structural unit (a3) include compounds described in paragraphs [0046] to [0065] of JP-A No. 2012-88459, .

In the formula (4), R ²³ is a hydrogen atom or a methyl group. s is an integer of 1 or more.

Of these structural units (a3), a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, An unsaturated compound having a skeleton, an unsaturated aromatic compound, an acrylic acid cyclic alkyl ester, and acryloylmorpholine are preferable. Of these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-methacrylate, (Meth) acrylate, polyethylene glycol (n = 2-10) mono (meth) acrylate, 3- (methacryloyloxyethyl) Methacryloyloxytetrahydrofuran-2-one and acryloylmorpholine are more preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution. These (a3) compounds may be used alone or in combination of two or more.

(A3) is preferably contained in an amount of 1 to 90 mol%, more preferably 5 to 80 mol%, and more preferably 7 to 60 mol%, in the total constituent units of the polymer component (A) Do. By setting the usage ratio of the constituent unit (a3) within the above range, a cured film excellent in various properties can be formed.

<< (A) Molecular weight of polymer >>

The molecular weight of the polymer (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene reduced weight average molecular weight. Within the range of the above numerical values, various characteristics are good.

The ratio (number of dispersions) of the number average molecular weight to the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< (A) Method of producing polymer >>

Various methods are also known for the synthesis of the component (A). For example, a radical polymerization (hereinafter also referred to as a &quot; polymerization method &quot;) comprising a radical polymerizable monomer used for forming at least the structural units represented by Can be synthesized by polymerization of a monomeric monomer mixture using a radical polymerization initiator in an organic solvent. It may also be synthesized by a so-called polymer reaction.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauryl peroxide, t-butyl peroxypivalate, and 1,1-bis- (t-butylperoxy) cyclohexane, and hydrogen peroxide.

As a method for producing the polymer (A), for example, the methods described in paragraphs [0067] to [0073] of Japanese Patent Application Laid-Open No. 8-88549 can be used.

&Lt; (B) Quinone diazide compound >

As the (B) quinone diazide compound used in the composition of the present invention, for example, a 1,2-quinonediazide compound which generates a carboxylic acid upon irradiation with an actinic ray can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother nucleus") and 1,2-naphthoquinone diazidesulfonic acid halide can be used. As specific examples of these compounds, reference may be made to, for example, the description of paragraphs [0075] to [0078] of Japanese Patent Application Laid-Open No. 08-088459, the contents of which are incorporated herein by reference.

In the condensation reaction of the phenolic compound or the alcoholic compound (mother nucleus) with 1,2-naphthoquinonediazide sulfonic acid halide, the condensation reaction is preferably carried out in an amount of 30 to 85 mol%, preferably 30 to 85 mol%, based on the number of OH groups in the phenolic compound or alcohol compound 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

Examples of the 1,2-quinonediazide compounds include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus is changed to an amide bond, for example, 2,3,4-triaminobenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid amide and the like are also suitably used.

These (B) quinone diazide compounds can be used alone or in combination of two or more. The amount of the quinone diazide compound (B) in the photosensitive resin composition of the present invention is preferably 1 to 50% by mass, more preferably 10 to 40% by mass relative to the total solid content in the photosensitive resin composition , And more preferably more than 12 mass% and not more than 40 mass%.

The amount of the quinone diazide compound (B) in the photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the total amount of the polymer (A) More preferably 10 to 35 parts by mass.

When the amount of the quinone diazide compound (B) is in the above range, the difference in solubility between the irradiated portion of the actinic light ray and the unirradiated portion of the aqueous alkaline solution serving as the developer becomes large, the patterning performance becomes good, and the solvent resistance And becomes good.

&Lt; (C) Compound Represented by Formula (c-1)

The composition of the present invention contains (C) a compound represented by the general formula (c-1) (heterocyclic compound). (C) The compound represented by the general formula (c-1) contains one coordinating atom in the aromatic ring, and the aromatic ring has a substituent including a coordinating atom. By employing such a compound, the chemical resistance can be improved while maintaining the sensitivity. In addition, when the cured film formed from the composition of the present invention is used for a display device, it is possible to improve the panel display irregularity of the display device.

(A) represents an aromatic ring having one nitrogen atom or sulfur atom in the ring, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a hydroxyl group, a carboxyl group, an alkylcarbonyl group, An arylcarbonyl group, an alkyloxycarbonyl group, an alkoxy group, an aryloxy group, a mercapto group or an amino group. m represents an integer of 1 or more, and n represents an integer of 1 or more]

X represents a hydrogen atom, an alkyl group or an aryl group.

The alkyl group is preferably an alkyl group having from 1 to 10 carbon atoms, more preferably an alkyl group having from 1 to 8 carbon atoms, and still more preferably an alkyl group having from 1 to 6 carbon atoms. The alkyl group may have a substituent (T) described later, but preferably has no substituent. The alkyl group may be any of linear, branched and cyclic, but a linear alkyl group is preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, tert-butyl, pentyl, hexyl and cyclohexyl. In the present invention, a methyl group and a cyclohexyl group are particularly preferable, and a methyl group is more preferable.

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 (T) described later, but preferably has no substituent. As the aryl group, for example, a phenyl group, a naphthyl group, and an anthracenyl group are exemplified. In the present invention, a phenyl group and a naphthyl group are particularly preferable, and a phenyl group is preferable.

Among them, X is preferably a hydrogen atom, a methyl group or a phenyl group.

Y represents a hydroxy group, a carboxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkoxy group, an aryloxy group, a mercapto group or an amino group.

The alkylcarbonyl group is preferably an alkylcarbonyl group having from 2 to 10 carbon atoms, more preferably an alkylcarbonyl group having from 2 to 8 carbon atoms, still more preferably an alkylcarbonyl group having from 2 to 6 carbon atoms, more preferably an acetyl group or a propionyl group, More preferable. The alkylcarbonyl group may be any of linear, branched and cyclic, but a linear alkylcarbonyl group is preferred.

As the arylcarbonyl group, an arylcarbonyl group having 7 to 10 carbon atoms is preferable, and a benzoyl group is preferable.

The alkyloxycarbonyl group is preferably an alkyloxycarbonyl group having 2 to 30 carbon atoms, more preferably an alkyloxycarbonyl group having 2 to 10 carbon atoms, and still more preferably an alkyloxycarbonyl group having 2 to 5 carbon atoms. The alkyloxycarbonyl group may have a substituent (T) described later, but preferably has no substituent. Examples of the alkyloxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl and the like. Among them, a methoxycarbonyl group is preferable.

The alkoxy group is preferably an alkoxy group having from 1 to 10 carbon atoms, more preferably an alkoxy group having from 1 to 8 carbon atoms, and still more preferably an alkoxy group having from 1 to 6 carbon atoms. The alkoxy group may have a substituent (T) described later, but preferably has no substituent. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Among them, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, more preferably an aryloxy group having 6 to 20 carbon atoms, and even more preferably an aryloxy group having 6 to 10 carbon atoms. The aryloxy group may have a substituent (T) described later, but preferably has no substituent. Examples of the aryloxy group include phenoxy group, phenoxymethyl group and the like. Among them, a phenoxy group is preferable.

Among them, Y is preferably a hydroxyl group, a carboxyl group, an acetyl group, a benzoyl group, a methoxycarbonyl group, a methoxy group, a phenoxy group, a mercapto group or an amino group. More preferably a hydroxyl group, a carboxyl group, an acetyl group, a benzoyl group, a methoxycarbonyl group, a methoxy group or a phenoxy group. These can further improve the sensitivity. More preferably a hydroxyl group, a carboxyl group, a methyl group, or a methoxycarbonyl group.

m represents an integer of 1 or more. The number of X excluding hydrogen atoms is preferably an integer of 0 to 3, more preferably 0 or 1.

n represents an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2.

Examples of the substituent (T) which the alkyl group, aryl group and the like may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, Fluorine atom, chlorine atom, bromine atom and iodine atom). These substituents may further have a substituent.

The ring (A) represents an aromatic ring having one nitrogen atom or sulfur atom in the ring. The ring (A) is not particularly limited as long as it is an aromatic ring, but may be a polycyclic aromatic group containing at least one of a 5-membered aromatic heterocyclic compound, a 6-membered aromatic heterocyclic compound, a 5-membered aromatic heterocyclic ring structure and a 6-membered aromatic heterocyclic ring structure A recycling compound is preferred.

The polycyclic aromatic heterocyclic compound means a compound (for example, quinoline) in which one or more aromatic rings and one or more aliphatic rings and / or aromatic rings are condensed. In the present invention, as long as at least one ring constituting the aromatic ring is a 5-membered aromatic heterocyclic ring structure or a 6-membered aromatic heterocyclic ring structure, the other ring may be any ring, but the other ring is preferably selected from benzene ring and naphthalene ring. The number of rings forming a polycyclic aromatic heterocyclic compound is preferably two or three in one molecule, and more preferably two.

Examples of the 5-membered aromatic heterocyclic compound include pyrrole compounds, thiophene compounds and the like.

Examples of the pyrrole-based compound include pyrrole-2-carboxylic acid, pyrrole-3-carboxylic acid, methyl pyrrole-2-carboxylate, ethyl pyrrole- Acetyl-1-methylpyrrole, N- (2-hydroxyethyl) pyrrole, 2-propionylpyrrole, 2- (trichloroacetyl) pyrrole , Methyl 1-methyl-2-pyrrole carboxylate, 2,5-dimethylpyrrole-3-carboxylic acid, 3,5-dimethylpyrrole-2-carboxylic acid, 2,5-dimethylpyrrole- Methyl-1,5-diphenylpyrrole-3-carboxylate, ethyl 4-methylpyrrole-3-carboxylate, 4- Methylpyrrole-3-carboxylate, ethyl 3,4,5-trimethylpyrrole-2-carboxylate, methyl 4-bromo-1H- Methyl-2-pyrrole carboxylic acid, 1-benzylpyrrole-3-carboxylate, 3,5-dimethyl-2,4-pyrrole dicarboxylic acid di Ethyl and the like desirable.

Examples of the thiophene-based compound include thiophene, 2-methoxythiophene, 3-methoxythiophene, 2-acetylthiophene, 3-acetylthiophene, 3-aminothiophene, thiophene- Dicarboxylic acid, methyl thiophene-2-carboxylate, ethyl thiophene-2-carboxylate, methyl thiophene-3-carboxylate, ethyl thiophene- Acetyl-5-bromothiophene, 3-acetyl-2,5-dichlorothiophene, 2-acetyl-3-methylthiophene, 2- Methylthiophene, 2-benzoylthiophene, 3-phenoxythiophene, 2- (trifluoroacetyl) thiophene, 3,4-dimethoxythiophene, etc. .

Examples of the 6-membered aromatic heterocyclic compound include pyridine-based compounds and the like.

Examples of the pyridine compound include 2-acetylpyridine, 3-acetylpyridine, 4-acetylpyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-benzoylpyridine, 3-benzoylpyridine, , 3-diaminopyridine, 2-methoxypyridine, 4-methoxypyridine, 2-methoxypyridine, 2-methoxypyridine, 2-phenoxypyridine, 3-mercaptopyridine, 3-mercaptopyridine, 3-mercaptopyridine, 3-mercaptopyridine, 3-ethoxypyridine, 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,6-pyridine dicarboxylic acid, 2,4-phenoxypyridine, Pyridine thiol and the like are preferable.

Examples of the polycyclic aromatic heterocyclic compound include benzothiophene compounds, quinoline compounds, isoquinoline compounds, indole compounds, acridine compounds, and benzoquinoline compounds.

Examples of the benzothiophene compounds include 2-acetylbenzo [b] thiophene, benzo [b] thiophene-2-carboxylic acid, benzo [b] thiophene-3-carboxylic acid, 3- chlorobenzo [ 2-carboxylic acid, 1-benzothiophene-5-carboxylic acid, 6-tert-butyl-1-benzothiophene-3-carboxylic acid, 3-chloro- Fluoro-1-benzothiophene-2-carboxylic acid, 3-chloro-6-fluoro-1-benzothiophene- 3-chloro-6-methoxy-1-benzothiophene-2-carboxylic acid, 3-chloro-4-methyl-1-benzothiophene- Thiophene-2-carboxylic acid, 3,6-dichloro-1-benzothiophene-2-carboxylic acid, 6-methyl-1-benzothiophene- , 6,7-tetrahydro-1-benzothiophene-2-carboxylic acid, and 4,5,6,7-tetrahydro-1-benzothiophene-3-carboxylic acid.

Examples of the quinolinic compound include quinoline-2-carboxylic acid, quinoline-3-carboxylic acid, quinoline-5-carboxylic acid, quinoline-6-carboxylic acid, quinoline-8-carboxylic acid, 2-hydroxyquinoline, Hydroxyquinoline, 8-hydroxyquinoline, 2-aminoquinoline, 3-aminoquinoline, 5-aminoquinoline, 6-aminoquinoline, 8-aminoquinoline, Amino-2-methylquinoline, 8-amino-2-methylquinoline, 2-cyano-8-hydroxyquinoline, 5,7-dichloro- Fluoro-4-hydroxyquinoline, 4-hydroxy-2-methylquinoline, 6-hydroxy-4-hydroxyquinoline, Hydroxyquinoline, 6-methoxyquinoline, 6-methoxy-8-nitroquinoline, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,8-dihydroxyquinoline, 8-amino-7-methylquinoline, 6- Methoxy-2-methylquinoline, 8-hydroxy-7-propylquinoline, 5-bromo-8-hydroxyquinoline, 2-methyl-6-ethoxyquinoline, 7 4-hydroxyquinoline, 2-methyl-8-hydroxyquinoline, 2-hydroxyquinoline-4-carboxylic acid and 2-phenyl-4-quinolinecarboxylic acid.

Examples of the isoquinoline-based compound include 1-hydroxyisoquinoline, 5-hydroxyisoquinoline, 7-hydroxyisoquinoline, 4-aminoisoquinoline, 5-aminoisoquinoline, 6-aminoisoquinoline, 6,7-dimethoxy Isoquinoline-1-carboxylic acid, isoquinoline-1-carboxylic acid, isoquinoline-3-carboxylic acid, isoquinoline-5-carboxylic acid, desirable.

Examples of the indole-based compound include indole-2-carboxylic acid, indole-3-carboxylic acid, indole-4-carboxylic acid, indole-5-carboxylic acid, indole- An amino group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, 6-hydroxyindole, 4-methoxyindole, 5-methoxyindole, 6-methoxyindole, and 7-methoxyindole.

As the benzoquinoline-based compound, 10-hydroxybenzoquinoline and the like are preferable.

Among them, examples of the ring (A) include pyrrole ring, furan ring, thiophene ring, pyridine ring, benzofuran ring, benzothiophen ring, quinoline ring, isoquinoline ring, coumarin ring, chroman ring, indole ring, More preferably a pyridine ring, a quinoline ring and an isoquinoline ring, and more preferably a pyridine ring and a quinoline ring.

Examples of the compound represented by the general formula (c-1) include pyrrole-2-carboxylic acid, methyl pyrrole-2-carboxylate, 2-acetylpyrrole, 2-methoxyfuran, 2- The compound of formula (I) is preferably selected from the group consisting of acid, 2,5-furandicarboxylic acid, 3-aminothiophene, thiophene-2-thiol, 2-benzoylthiophene, 3-phenoxythiophene, Hydroxybenzofuran, 2-benzofuran-carboxylic acid, 2-acetylbenzo [b] thiophene, benzo [b] thiophene-2-carbaldehyde Hydroxyquinoline, 5-aminoisoquinoline, 5-aminoquinoline, isoquinoline-5- carboxylic acid, quinoline-2-carboxylic acid, 8-hydroxyquinoline, 2-aminoquinoline, Carboxylic acid, coumarin-3-carboxylic acid, 7-hydroxycoumarin, chromone-3-carboxylic acid, hydroxyflavone, indole-2-carboxylic acid, 5-hydroxyindole, Quinoline, 2-amino-8-quinolinol, 6-amino-8-quinolinol More preferred are 2-hydroxypyridine, 2-aminopyridine, 2-hydroxypyridine, 2-pyridinecarboxylic acid, quinoline-2-carboxylic acid, 8-hydroxyquinoline, Quinoline, 2-aminoquinoline, 2-amino-8-quinolinol and 6-amino-8-quinolinol are more preferable.

The molecular weight of the compound represented by the general formula (c-1) is preferably 1000 or less, more preferably 750 or less, still more preferably 500 or less. When the molecular weight is 1000 or less, the compound represented by the general formula (c-1) tends to move toward the substrate side, and adhesion to various substrates can be improved at the time of development and as a cured film.

The amount of the compound represented by the general formula (c-1) in the photosensitive resin composition of the present invention is preferably 0.001 to 20 parts by mass, more preferably 0.003 to 10 parts by mass, and most preferably 0.005 to 10 parts by mass, To 7 parts by mass is more preferable.

The amount of the compound represented by the general formula (c-1) in the photosensitive resin composition of the present invention is preferably 0.001 to 10 parts by mass, more preferably 0.003 to 8 parts by mass per 100 parts by mass of the total amount of the polymer component (A) More preferably 0.005 to 7.5 parts by mass.

The component (C) may be a single kind or two or more kinds. In the case of two or more types, the total is preferably in the above range.

&Lt; (D) Solvent >

The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential component of the present invention and any of the components described below are dissolved in the (D) solvent. As the solvent to be used for preparing the composition of the present invention, essential components and optional components are uniformly dissolved, and those which do not react with each component are used.

As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, di Propylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like. Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvent described in paragraphs [0174] to [0178] of JP-A No. 2011-221494, paragraph [0167] of JP- , And the contents thereof are included in the specification of the present invention.

In these solvents, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1 Solvents such as octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may also be added. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably a single solvent or a combination of two solvents, more preferably two solvents, more preferably propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and di It is more preferable to use ethylene glycol dialkyl ethers or esters in combination with butylene glycol alkyl ether acetates.

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 占 폚), propylene glycol monoethyl ether acetate (boiling point: 158 占 폚), propylene glycol methyl n-butyl ether (boiling point: 155 占 폚), propylene glycol Methyl-n-propyl ether (boiling point 131 占 폚).

As the solvent having a boiling point of 160 캜 or more, ethyl 3-ethoxypropionate (boiling point: 170 캜), diethylene glycol methyl ethyl ether (boiling point: 176 캜), propylene glycol monomethyl ether propionate (boiling point: 160 캜), dipropylene glycol methyl ether acetate (Boiling point: 213 占 폚), 3-methoxybutyl ether acetate having a boiling point of 171 占 폚, diethylene glycol diethyl ether having a boiling point of 189 占 폚, diethylene glycol dimethyl ether having a boiling point of 162 占 폚, propylene glycol diacetate having a boiling point of 190 占), Diethylene glycol monoethyl ether acetate (boiling point 220 占 폚), dipropylene glycol dimethyl ether (boiling point 175 占 폚), and 1,3-butylene glycol diacetate (boiling point 232 占 폚).

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, per 100 parts by mass of the total components in the photosensitive resin composition.

<Other ingredients>

The composition of the present invention may contain, in addition to the above components, a crosslinking agent, an antioxidant, a development accelerator, an alkoxysilane compound (silane coupling agent), a surfactant, an adhesion promoter, , A heat-sensitive acid generator, and the like. These optional components may be used alone or in combination of two or more. As these compounds, for example, compounds described in paragraphs [0201] to [0224] of Japanese Patent Application Laid-Open Publication No. 2012-88459 can be used, and these contents are included in the specification of the present invention.

Alkoxysilane compound

The photosensitive resin composition of the present invention preferably contains 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 can be used as an inorganic substance to be a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, molybdenum, Is preferable. Specifically, known silane coupling agents and the like are also effective.

As the silane coupling agent, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropyldialkoxysilane,? -Methacrylate (3,4-epoxycyclohexyl) ethyl trialkoxysilane,? -Methacryloxypropyl dialkoxysilane,? -Methacryloxypropyl dialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - And vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is even more preferable, and 3-glycidoxypropyltrimethoxy Silane is even more preferred. These may be used alone or in combination of two or more.

Further, a compound represented by the following general formula can also be preferably employed.

(R ¹ ) _4-n- Si- (OR ² ) _n

R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group; and n is an integer of 1 to 3.) In the general formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms which does not have a reactive group;

Specific examples thereof include the following compounds.

In the above, Ph is a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited to these, and known alkoxysilane compounds may be used.

The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, per 100 parts by mass of the total of the polymer components (A).

Surfactants

The photosensitive resin composition of the present invention preferably contains a surfactant. As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but 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 JP-A-2012-88459, paragraphs [0185] May be used, and these descriptions are included in the specification of the present invention.

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.), POLYFLOW No. 2, (Manufactured by Mitsubishi Materials Chemicals Co., Ltd.), MEGAFAC (manufactured by DIC Corporation), FLUORAD Novec FC-4430 (Sumitomo 3M Limited), SURFLON S-242 (manufactured by Kyoeisha Chemical Co., Ltd.) (Manufactured by Seiko Chemical Co., Ltd.), POLYFOX PF-6320 (manufactured by OMNOVA Solutions Inc.), SH-8400 (manufactured by Dow Corning Toray Co., Ltd.) and FTERGENT FTX- have.

The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass to 10 parts by mass, and most preferably 0.01 parts by mass to 5 parts by mass, relative to 100 parts by mass of the total amount of the polymer (A) More preferable. A plurality of surfactants may be used in combination, and in that case, the content is calculated by adding up all the surfactants.

Cross-linking agent

The photosensitive resin composition of the present invention may contain a crosslinking agent, if necessary. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made into a stronger film.

The crosslinking agent is not limited as long as it causes crosslinking reaction by heat (excluding the above component (A)). For example, a compound having two or more epoxy groups or oxetanyl groups in a molecule, a crosslinking agent containing an alkoxymethyl group, a compound having at least one ethylenically unsaturated double bond, a block isocyanate compound and the like can be added.

The amount of the crosslinking agent to be added in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and most preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the total amount of the polymer (A) More preferable. When added in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. The crosslinking agent may be used in combination with a plurality of the crosslinking agents, in which case the crosslinking agents are all added to calculate the content.

&Lt; Compounds having two or more epoxy groups or oxetanyl groups in the molecule &

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 and the like.

These are available as commercial products. For example, commercial products described in paragraph [0189] of JP-A No. 2011-221494 such as JER152, JER157S70, JER157S65, JER806, JER828 and JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation).

Specific examples of the compound having two or more oxetanyl groups in the molecule include Aron Oxetane OXT-121, OXT-221, OX-SQ and PNOX (manufactured by Toagosei Co., Ltd.).

Further, the compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.

&Lt; Block isocyanate compound >

In the photosensitive resin composition of the present invention, a block isocyanate compound can also be preferably employed as a crosslinking agent. The block isocyanate compound is not particularly limited as long as it is a compound having a block isocyanate group, but is preferably a compound having at least two block isocyanate groups in one molecule from the viewpoint of curability.

The block isocyanate group in the present invention is a group capable of forming an isocyanate group by heat, and for example, a group in which an isocyanate group is protected by reacting a blocking agent with an isocyanate group can be preferably exemplified.

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 forming the block structure of the block isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, . 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.

The block isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available and is commercially available, for example, from CORONATE AP Stable M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS- (Manufactured by Mitsui Chemicals, Inc.), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B- B40T, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000, E402-B80T, DURANATE 17B-60PX, TPA-B80X, TPA-B80E, (Manufactured by Asahi Kasei Chemicals Corporation), DESMODUR BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, SUMIDUR BL3175 Co., Ltd.), KARENZ MOI-BP, and KARENZ MOI-BM (manufactured by Showa Denko KK).

As the other crosslinking agent, for example, a methylated melamine resin (for example, NIKALAC MW-30HM (manufactured by Sanwa Chemical Co., Ltd.) can be used.

Antioxidant

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. The addition of an antioxidant can prevent coloration of the cured film or reduce the film thickness reduction due to decomposition and has an advantage of excellent heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, And hydroxylamine derivatives. Of these, a phenol-based antioxidant, an amide-based antioxidant, a hydrazide-based antioxidant and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used singly or in combination of two or more kinds.

Specific examples thereof include compounds described in paragraphs [0034] to [0031] of JP-A No. 2005-29515 and compounds described in paragraphs [0106] to [0116] of JP-A No. 2001-227106, The contents of which are incorporated herein by reference.

ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO- , IRGANOX 1726, IRGANOX 1035, IRGANOX 1098.

The content of the antioxidant is preferably 0.1 to 10 mass%, more preferably 0.2 to 7 mass%, and particularly preferably 0.5 to 5 mass% with respect to 100 mass parts of the total amount of the polymer (A). Within this range, sufficient transparency of the film formed can be obtained, and sensitivity at the time of pattern formation becomes good.

&Lt; Preparation method of photosensitive resin composition >

The composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, followed by stirring and dissolving. For example, it is also possible to prepare a solution in which each component is previously dissolved in the above-mentioned solvent, and then mix them in a predetermined ratio to prepare a resin composition. The composition solution thus prepared may be used after being filtered using, for example, a filter having a pore size of 0.2 mu m.

&Lt; Process for producing a cured film &

Next, a method for producing the cured film of the present invention will be described.

The method for producing the 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 onto a substrate;

(2) removing the solvent from the applied photosensitive resin composition;

(3) exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray;

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

(5) a post-baking step of thermally curing the developed photosensitive resin composition.

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 (preferably applied) to a substrate to form a wet film containing a solvent. It is preferable to clean the substrate subjected to alkali cleaning or plasma cleaning before applying the photosensitive resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after the substrate cleaning. By 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 hexamethyldisilazane vapor may 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 polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, aryldiglycol carbonate, polyamide, polyimide, Fluorine resins such as polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin and polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionomer resins , A cyanate resin, a crosslinked fumaric acid diester, a cyclic polyolefin, an aromatic ether, a maleimide olefin, a cellulose, and 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 application method to the substrate is not particularly limited. For example, a slit coating method, a spraying method, a roll coating method, a rotation coating method, a spin coating method, a slit and spin method and the like can be used.

The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but is usually in the range of 0.5 to 10 mu m.

Before applying the composition to be used in the present invention to the substrate, it is also possible to apply the so-called pre-wet method as described in JP-A-2009-145395.

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

(3), an active ray of a predetermined pattern is irradiated onto the substrate provided with the coating film.

(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. If necessary, the irradiation light may 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 micro lens array, a lens scanner, and a laser exposure can be used.

(4), a copolymer having a carboxyl group or a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposed region including a resin composition having a carboxyl group or a phenolic hydroxyl group which is liable to dissolve in an alkaline developer.

The developing solution used in the developing step preferably contains 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 and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. 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.

As a preferable developing solution, an aqueous solution of 0.2 to 2.5% of tetramethylammonium hydroxide can be mentioned.

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

The development time is preferably 30 to 500 seconds, and the developing method may be any of a 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. Examples thereof include shower rinses and deep rinses.

In the post-baking step of (5), the obtained positive image is heated to crosslink the acidic group with the crosslinkable group, the crosslinking agent or the like, thereby forming the cured film. The heating is performed at a predetermined temperature, for example, 180 to 250 캜 for a predetermined time, for example, 5 to 90 minutes for a hot plate, or 30 to 120 minutes for an oven, using a heating apparatus such as a hot plate or an oven . By carrying out such a crosslinking reaction, an excellent protective film or an interlayer insulating film can be formed by heat resistance, hardness and the like. 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 ° C or higher after heating at 90 to 150 ° C for 1 to 60 minutes. In addition, middle baking and post baking may be divided into three or more stages and heated. The taper angle of the pattern can be adjusted by such a study of the middle baking and the post baking. These heating may be performed using a known heating method such as a hot plate, an oven, or an infrared heater.

In addition, from the viewpoint of improving the transparency, it is preferable to carry out the whole re-exposure (post exposure) of the substrate on which the pattern is formed by an actinic ray before the post-baking. In the case of including the post exposure step, the preferable exposure amount is preferably 100 to 3,000 mJ / cm2, and particularly preferably 100 to 2000 mJ / cm2.

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

[Coating film]

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

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 above-described method of forming a cured film of the present invention.

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent transparency can be obtained even when the insulating resin is baked 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.

[Liquid crystal display device]

The liquid crystal display device of the present invention is characterized by including the cured film of the present invention.

As the liquid crystal display device of the present invention, there is no particular limitation but a well-known liquid crystal display device having various structures other than those having a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention.

For example, specific examples of a TFT (Thin-Film Transistor) included in the liquid crystal 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 electrical characteristics, it can be preferably used in combination with these TFTs.

As a liquid crystal driving method that can be adopted by the liquid crystal display of the present invention, twisted nematic (VA), VA (virtual alignment), IPS (in-place switching), FFS Compensated Bend) method.

In the panel construction, the cured film of the present invention can also be used in a COA (Color Filter on All) type liquid crystal display device. For example, the organic insulating film 115 of Japanese Patent Application Laid-Open No. 2005-284291, Japanese Laid-Open Patent Publication No. 2005-346054 Can be used as the organic insulating film 212. 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 Patent Application Laid-Open Nos. 2003-149647 and 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 applications and can be used for various purposes. For example, in addition to a planarizing film and an interlayer insulating film, a protective film for a color filter or a spacer for maintaining the thickness of a liquid crystal layer in a liquid crystal display device at a constant level, or a microlens provided on a color filter in a solid- Can be used.

Fig. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. Fig. This 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 has TFTs corresponding to all the pixels disposed between two glass substrates 14, (16) are disposed on the substrate. An ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17 in each element formed on the glass substrate. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of a 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), and organic ELs.

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

[Organic EL display device]

The organic EL display device of the present invention is characterized by including 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 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 preferably used in combination with these TFTs.

2 is a conceptual diagram showing an example of an 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 planarizing 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 wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3. The wiring 2 is for connecting the organic EL element formed in the TFT 1 or in a subsequent step to the TFT 1. [

The flattening layer 4 is formed on the insulating film 3 in a state in which the irregularities due to the wiring 2 are embedded in order to planarize the irregularities due to the formation of the wiring 2. [

On the planarizing film 4, a bottom-emission 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. Also, the first electrode 5 corresponds to the anode of the organic EL element.

An insulating film 8 is formed so as to cover the edge of the first electrode 5. By providing this insulating film 8, a short circuit is prevented between the first electrode 5 and the second electrode formed in the subsequent steps can do.

Although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask. Next, a second electrode made of Al is formed on the entire upper surface of the substrate, And an ultraviolet curing type epoxy resin are used to seal the organic EL element, and the TFT 1 for driving the organic EL element is connected to the active matrix type organic EL display device.

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 separating wall, do. Examples of such MEMS devices include SAW filters, BAW filters, gyro sensors, micro-shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. More specific examples are exemplified in Japanese Patent Publication No. 2007-522531, Japanese Patent Application Laid-Open No. 2008-250200, and Japanese Patent Laid-Open No. 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 Patent Laid-Open Publication No. 2011-107476, Japanese Patent Application Laid- The bank layer 221 and the third interlayer insulating film 216b shown in Fig. 10 of Japanese Patent Application Laid-Open No. 2010-27591, the Japanese Patent Laid-Open No. 2000-27591, the separating wall 12 and the planarizing 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 2009-128577 A, the planarization film 12 described in FIG. 3 of JP 2010-182638 A, The isolation insulating film 14 and the like. In addition, it can be suitably used for a spacer for maintaining the thickness of the liquid crystal layer at a constant level in a liquid crystal display device, an imaging optical system of an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state imaging element, or a microlens of an optical fiber connector .

(Example)

Hereinafter, the present invention will be described in more detail by way of examples. The materials, amounts, ratios, processing contents, processing procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

In the following Synthesis Examples, the measurement of the weight average molecular weight (Mw) of the copolymer was carried out by gel permeation chromatography (GPC) under the following conditions and conditions.

Apparatus: GPC-101 (manufactured by Showa Denko K. K.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Detector: differential refractometer

Standard material: monodisperse polystyrene

&Lt; Synthesis of (A) Polymer &

(Synthesis of P-1)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Subsequently, 12 parts by mass of methacrylic acid, 50 parts by mass of glycidyl methacrylate, 8 parts by mass of 3- (2-methacryloyloxyethyl) oxetane, 10 parts by mass of N-cyclohexylmaleimide, 15 parts by mass of tetrahydrofurfuryl oxide, 5 parts by mass of acryloylmorpholine and 2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) were purged with nitrogen, and gentle stirring was started. The temperature of the solution was raised to 70 캜, and the polymerization was started when the temperature of the reaction solution reached 70 캜. Subsequently, 3 minutes after N-cyclohexylmaleimide was added 30 minutes after the initiation of polymerization, and after 1 hour, 3 parts by mass of N-cyclohexylmaleimide was added dropwise to the reaction solution. Thereafter, the solution was kept for 3 hours to obtain an aggregate solution containing the copolymer (P-1). The copolymer P-1 had a polystyrene reduced weight average molecular weight (Mw) of 9,000 and a molecular weight distribution (Mw / Mn) of 2.0.

Other polymers were also synthesized in the same manner as P-1 using the monomers described in the following table (raw materials for the monomer components ((a1) to (a3))), polymerization initiator, molecular weight adjuster and solvent.

In the following tables, numerical values not particularly appended with units denote mass units.

&Lt; Preparation of Photosensitive Resin Composition >

The component (A), the component (B), the component (C), the alkoxysilane compound and the surfactant were dissolved and mixed in a solvent to a solid content concentration of 32 mass% so as to have a solid content ratio shown in the following table, And filtered with a filter made of tetrafluoroethylene to obtain photosensitive resin compositions of various examples and comparative examples.

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

&Lt; Component (B) >

B-1: 4,4'-l- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide -5-sulfonic acid chloride (3.0 mol)

B-2: A condensate of 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

B-3: 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol)

&Lt; Component (C) >

The following compounds (C-1) to (C-35) were used.

(Alkoxysilane compound)

E-1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Crosslinking agent)

F-1: KARENZ MOI-BM (produced by Showa Denko K. K.)

F-2: NIKALAC MW-30HM (manufactured by Sanwa Chemical Co., Ltd.)

F-3: DURANATE E402-B80T (manufactured by Asahi Kasei Chemicals Corporation)

F-4: DURANATE MF-K60X (manufactured by Asahi Kasei Chemicals Corporation)

F-5: JER 157S70 (manufactured by Mitsubishi Chemical Holdings Corporation)

F-6: ARON OXETANE OXT-221 (manufactured by Toagosei Co., Ltd.)

(Surfactants)

W-1: Silicone surfactant ("SH 8400 FLUID" manufactured by Dow Corning Toray Co., Ltd.)

W-2: Fluorine-based surfactant FTX-218 (manufactured by Neos Corporation)

The obtained composition was evaluated as follows.

&Lt; Evaluation of adhesion at the time of development &

A glass substrate (10 cm x 10 cm x 0.5 mm) on which a Mo (molybdenum) thin film was formed on a half area (10 cm x 5 cm) of one side of the substrate and a SiN x thin film was formed on the other half area (10 cm x 5 cm) (HMDS) vapor for 30 seconds. Each of the photosensitive resin composition solutions was applied to a dry film thickness of 3 mu m using a spin coater, and then pre-baked on a hot plate at 90 DEG C for 2 minutes The solvent was volatilized. Thereafter, an exposure dose of 150 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) was exposed to light through a mask capable of reproducing 10 탆 lines / 10 탆 space using an ultra high pressure mercury lamp, Methyl ammonium hydroxide aqueous solution) at 23 DEG C for 60 seconds, and then rinsed with ultrapure water for 1 minute. Obtained substrate was observed with an optical microscope, and defects and peeling of a pattern of 10 mu m line / 10 mu m space were observed for Mo part and SiNx part. The results are shown in the following table. The less the peeling, the better, and A or B is preferable.

A: There is no defect, no peeling.

B: Defects, peeling less than 30%

C: Defects, exfoliation exceeding 30% and not more than 60%

D: Defective, peeling more than 60% and less than 100%

&Lt; Cohesion of cured film: Mo>

A glass substrate (10 cm x 10 cm x 0.5 mm) on which a Mo (molybdenum) thin film was formed was exposed for 30 seconds under the steam of hexamethyldisilazane (HMDS), and then each photosensitive resin composition was applied to a spin coat, Minute hot plate to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 占 퐉. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the cumulative dose was 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line), and then the substrate was heated in an oven at 230 캜 for 30 minutes to obtain a cured film.

Subsequently, a cut portion was inserted into the cured film at intervals of 1 mm vertically and horizontally using a cutter, and a tape peeling test (100mass cross-cutting method: according to JIS 5600) was performed 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 side 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 preferable.

A: Less than 1% of transferred area

B: Transferred area is 1% or more and less than 5%

C: Transferred area is 5% or more and less than 10%

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

E: Over 50% of transferred area

&Lt; Cured film adhesion property: Ti>

A glass substrate (10 cm x 10 cm x 0.5 mm) on which a Ti (titanium) thin film was formed was exposed for 30 seconds under steam of hexamethyldisilazane (HMDS), and then each photosensitive resin composition was applied to a spin coat, Minute hot plate to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 占 퐉. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the cumulative dose would be 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line), and then the substrate was heated in an oven at 230 캜 for 30 minutes to obtain a cured film.

Subsequently, a cut portion was inserted into the cured film at intervals of 1 mm vertically and horizontally using a cutter, and a tape peeling test (100mass cross-cutting method: according to JIS 5600) was performed 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 side 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 preferable.

A: Less than 1% of transferred area

B: Transferred area is 1% or more and less than 5%

C: Transferred area is 5% or more and less than 10%

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

E: Over 50% of transferred area

&Lt; Cured film adhesion property: SiNx >

A glass substrate (10 cm x 10 cm x 0.5 mm) on which a SiNx (silicon nitride) thin film was formed was exposed for 30 seconds under steam of hexamethyldisilazane (HMDS), and then each photosensitive resin composition was coated with a spin coat, The solution was prebaked on a 2 minute hot plate to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3 m. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the cumulative dose would be 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line), and then the substrate was heated in an oven at 230 캜 for 30 minutes to obtain a cured film.

Subsequently, a cut portion was inserted into the cured film at intervals of 1 mm vertically and horizontally using a cutter, and a tape peeling test (100mass cross-cutting method: according to JIS 5600) was performed 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 side 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 preferable.

A: Less than 1% of transferred area

B: Transferred area is 1% or more and less than 5%

C: Transferred area is 5% or more and less than 10%

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

E: Over 50% of transferred area

&Lt; Evaluation of Chemical Resistance &

<< Evaluation of peeling liquid resistance >>

The glass substrate was exposed to HMDS vapor for 30 seconds. Each of the photosensitive resin compositions was spin-coated on the substrate, pre-baked on a hot plate at 90 DEG C for 120 seconds to volatilize the solvent to obtain a film thickness of 3.0 Mu m of the photosensitive resin composition layer. Then, the substrate was exposed in an oven at 230 占 폚 for 30 minutes, and then heated in an oven at 230 占 폚 for 2 hours. The substrate was then exposed to ultraviolet radiation at 300 mJ / cm2 (illuminance: 20 mW / And heated.

The film thickness (T1) of the obtained cured film was measured. Then, the substrate on which the cured film was formed was immersed in monoethanolamine of temperature controlled at 60 DEG C for 5 minutes at 80 DEG C, and then the film thickness t1 of the cured film after immersion was measured to determine the film thickness change ratio {| t1-T1 | / T1} x 100 [%]. The results are shown in the following table. A, B, and C are practically unproblematic levels.

A: less than 2%

B: 2% or more and less than 3%

C: 3% to less than 4%

D: 4% to less than 6%

E: 6% or more

<< Evaluation of NMP Resistance >>

The glass substrate was exposed to HMDS vapor for 30 seconds. Each of the photosensitive resin compositions was spin-coated on the substrate, pre-baked on a hot plate at 90 DEG C for 120 seconds to volatilize the solvent to obtain a film thickness of 3.0 Mu m of the photosensitive resin composition layer. Then, the substrate was exposed in an oven at 230 占 폚 for 30 minutes, and then heated in an oven at 230 占 폚 for 2 hours. The substrate was then exposed to ultraviolet radiation at 300 mJ / cm2 (illuminance: 20 mW / And heated.

The film thickness (T1) of the obtained cured film was measured. Subsequently, the substrate on which the cured film was formed was immersed in NMP (N-methylpyrrolidone) controlled at 80 占 폚 at 80 占 폚 for 10 minutes, and then the film thickness t1 of the cured film after immersion was measured to determine the film thickness The rate of change {| t1-T1 | / T1} x 100 [%] was calculated. The results are shown in the following table. A, B, and C are practically unproblematic levels.

A: less than 2%

B: 2% or more and less than 3%

C: 3% to less than 4%

D: 4% to less than 6%

E: 6% or more

<Evaluation of display irregularity (display irregularity of panel) in display device>

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

That is, 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. Subsequently, a contact hole was formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole was formed on the insulating film 3.

In order to planarize the irregularities formed by the formation of the wirings 2, the flattening film 4 was formed on the insulating film 3 in the state of embedding the irregularities by the wirings 2. The planarizing film 4 was formed on the insulating film 3 by spin coating each of the photosensitive resin compositions of the examples and the comparative examples on a substrate and prebaking on a hot plate (90 DEG C x 120 seconds) , An i-line (365 nm) was irradiated with 25 mJ / cm 2 (energy intensity 20 mW / cm 2) and then developed with an aqueous alkaline solution to form a pattern and subjected to a heat treatment at 230 ° C. for 30 minutes.

A driving voltage was applied to the obtained liquid crystal display device, a gray test signal was inputted, the panel was continuously lit in an environment of 60 ° C and 90%, and a gray display after lighting for 1000 hours was observed with a visual observation to check whether or not display unevenness Were evaluated according to the following evaluation criteria.

A: I can not see completely unevenness (very good)

B: The edge of the glass substrate is slightly irregular, but there is no problem in the display portion (good)

C: The display shows faint unevenness, but at a practical level (normal)

D: There is irregularity on the display part (slightly bad)

E: There is strong unevenness on the display (very bad)

As apparent from the above results, the composition of the present invention comprises (A) a polymer comprising (a1) a repeating unit having an acidic group, (a2) a polymer comprising a repeating unit having a crosslinkable group, (B) a quinone diazide compound, and Since the compound (heterocyclic compound) represented by the general formula (c-1) is contained, the resistance to peeling liquid or NMP (chemical resistance) of the resist is excellent and the occurrence of panel display irregularity Respectively. Further, it was found that the adhesion to various substrates was excellent in a state of being developed and a cured film.

In Comparative Example 1, since the component (C) is not used, the adhesion of the cured film to various substrates, adhesion to various substrates at the time of development, chemical resistance, and panel display unevenness after the panel reliability test are shown in Which is worse than the used embodiment.

In Comparative Examples 2 to 9, an aromatic heterocyclic compound containing one nitrogen atom or sulfur atom in the aromatic ring but not having X and Y (substituent) in the general formula (c-1) , The adhesion of the cured film to various substrates, adhesion to various substrates at the time of development, chemical resistance, and panel display unevenness after the panel reliability test were significantly worse than those using the above compound (c-1).

In Comparative Example 12, the polymer containing the repeating unit having a crosslinkable group (a2) was not used as the component (A), and the adhesion of the cured film to various substrates, the adhesiveness to various substrates at the time of development, Panel display irregularity after the test was poor.

In Comparative Examples 10 and 11, an aromatic heterocyclic compound containing no nitrogen atom or sulfur atom in the aromatic ring was used, so that the adhesion of the cured film to various substrates, adhesion to various substrates at the time of development, chemical resistance and panel reliability test The panel display unevenness was significantly worse than in the case of using the compound (c-1).

&Lt; Preparation of organic EL display device >

An organic EL display device using a TFT was produced by the following method (for example, 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. Subsequently, 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 . This wiring 2 is for connecting the organic EL element formed in the TFT 1 or in a subsequent step to the TFT 1. [

The planarization layer 4 was formed on the insulating film 3 in a state in which the irregularities due to the wiring 2 were embedded in order to planarize the irregularities due to the formation of the wiring 2. [ The planarizing film 4 was formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 8 on a substrate and pre-baking (90 占 폚 for 2 minutes) on a hot plate and then using a high-pressure mercury lamp i line at 100 mJ / cm &lt; 2 &gt;, and then developed with an aqueous alkaline solution to form a pattern, followed by heat treatment at 220 DEG C for 60 minutes.

Subsequently, a bottom-emission type organic EL device was formed on the obtained planarization film 4. 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, prebaked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using an ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and DMSO). The first electrode thus obtained corresponds to the anode of the organic EL element.

Then, an insulating layer 8 having a shape covering the edge of the first electrode was formed. An insulating film 8 was formed in the same manner as above using the photosensitive resin composition of Example 1 for the insulating layer. By providing this insulating layer, it was possible to prevent a short circuit between the first electrode and the second electrode formed in the subsequent step.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially evaporated through a desired pattern mask in a vacuum evaporation apparatus. Then, a second electrode made of Al was formed on the entire upper surface of the substrate. The obtained substrate was taken out 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 good display characteristics and is highly reliable when a voltage is applied through a driving circuit.

&Lt; Production of liquid crystal display device &

In the active matrix type liquid crystal display device shown in Figs. 1 and 2 of Japanese Patent No. 3321003, the photosensitive resin composition of Example 1 of the present invention is used as the interlayer insulating film 17, and the other is the liquid crystal display device .

As a result of application of a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

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

Claims (13)

(A) a polymer having (a1) a structural unit having an acidic group and (a2) a structural unit having a crosslinkable group,
(B) a quinone diazide compound,
(C) a compound represented by the following general formula (c-1), and
(D) a solvent;

In formula (c-1), ring A represents a pyrrole ring, thiophene ring, pyridine ring, benzothiophene ring, quinoline ring, isoquinoline ring, indole ring or acridine ring, An alkyl group or an aryl group, Y represents a hydroxyl group, a carboxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an alkoxy group, an aryloxyl group, a mercapto group or an amino group; m represents an integer of 1 to 3, and n represents 1. Y represents a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an alkoxy group, an aryloxy group or an amino group when the ring (A) is a pyrrole ring, a thiophene ring or a pyridine ring. The method according to claim 1,
Y in the compound represented by the general formula (c-1) represents a hydroxyl group, a carboxyl group, an acetyl group, a benzoyl group, a methoxycarbonyl group, a methoxy group, a phenoxy group, a mercapto group or an amino group, Represents a hydroxyl group, an acetyl group, a benzoyl group, a methoxycarbonyl group, a methoxy group, a phenoxy group, or an amino group, when Y is a pyrrole ring, a thiophene ring or a pyridine ring. 3. The method according to claim 1 or 2,
Wherein the structural unit (a1) is a repeating unit having at least any one of a carboxyl group and a phenolic hydroxyl group. 3. The method according to claim 1 or 2,
The structural unit (a2) is a structural unit containing at least one selected from the group consisting of groups represented by an epoxy group, an oxetanyl group and the -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) By weight based on the total weight of the photosensitive resin composition. 3. The method according to claim 1 or 2,
Wherein the amount of the quinone diazide compound (B) is from 10 to 50 parts by mass based on 100 parts by mass of the total of the polymer component (A). (1) a step of applying the photosensitive resin composition described in any one of claims 1 or 2 on 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 developer, and
(5) a post-baking step of thermally curing the developed photosensitive resin composition. The method according to claim 6,
(6) a step of exposing the developed photosensitive resin composition to the whole surface before the post-baking step after the developing step. The method according to claim 6,
And a step of performing dry etching on the substrate having the cured film obtained by thermosetting in the post-baking step. A cured film formed by the method for producing a cured film according to claim 6. 10. The method of claim 9,
Wherein the cured film is an interlayer insulating film. An organic EL display device having the cured film according to claim 9. A liquid crystal display device having the cured film according to claim 9. delete

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