KR101754841B1 - Positive-type photosensitive resin composition, and method for formation of cured film using the same - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition excellent in sensitivity, residual film ratio and storage stability and a cured film forming method using the positive photosensitive resin composition and a positive photosensitive resin composition capable of obtaining a cured film excellent in heat resistance, adhesiveness and transmittance by curing, The present invention also provides a method for providing a method of controlling a display device.
(Solution) A resin that contains a specific styrenic constituent unit that generates a carboxyl group upon dissociation of a dissociable group and is alkali-insoluble or alkali-insoluble and becomes alkali-soluble when the acid-dissociable group is dissociated, an epoxy- , A compound having two or more epoxy groups in the molecule (excluding the above-mentioned resin containing a constitutional unit comprising an epoxy group-containing radically polymerizable compound), a resin containing a structural unit derived from an active ray having a wavelength of 300 nm or more A positive photosensitive resin composition comprising a compound capable of generating an acid upon irradiation, and a method for forming a cured film using the positive photosensitive resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive photosensitive resin composition and a method for forming a cured film using the positive photosensitive resin composition.

The present invention relates to a positive photosensitive resin composition and a cured film forming method using the positive photosensitive resin composition. More specifically, the present invention relates to a positive-type photosensitive resin composition suitable for forming a planarizing film, a protective film or an interlayer insulating film of an electronic component such as a liquid crystal display element, an integrated circuit element, a solid- .

Description of the Related Art Conventionally, in electronic parts such as liquid crystal display elements, integrated circuit elements, solid-state image pickup elements, and organic EL elements, a planarizing film for imparting flatness to the surface of electronic components, a protective film for preventing deterioration or damage of electronic components, A photosensitive resin composition is used to form an interlayer insulating film for maintaining the interlayer insulating film. For example, in a TFT type liquid crystal display element, a polarizing plate is provided on a glass substrate, a transparent conductive circuit layer such as ITO and a thin film transistor (TFT) are formed and covered with an interlayer insulating film to form a back plate, A pattern of a black matrix layer and a color filter layer is formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed in this order to form a top plate, and the back plate and the top plate are connected via a spacer And the liquid crystal is sealed between the positive and negative plates. Among them, the photosensitive resin composition used for forming the interlayer insulating film is required to have excellent sensitivity, residual film ratio, heat resistance, adhesion, and transparency. Further, the above photosensitive resin composition is further required to have excellent stability over time at the time of storage.

As a photosensitive resin composition, for example, Patent Document 1 discloses a composition comprising (A) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) a radically polymerizable compound having an epoxy group and (c) a polymer of another radically polymerizable compound A photosensitive resin composition containing (B) a radiation-sensitive acid-generating compound and a resin soluble in a phosphorus-containing aqueous alkali solution, Patent Document 2 discloses a photosensitive resin composition containing an alkali- soluble acrylic polymer binder, a quinone diazide group- Based on the total weight of the photosensitive resin composition. However, all of them are unsatisfactory in sensitivity, unfiltered film remaining ratio, resolution and stability over time, so that they are not satisfactory for producing high quality liquid crystal display devices. In Patent Document 3, the crosslinking agent, the acid generator and the compound itself are insoluble or hardly soluble in an aqueous alkali solution but have a protecting group that can be cleaved by the action of an acid, and after the protecting group is cleared, A positive type chemically amplified resist composition characterized by containing a resin is proposed. However, the adhesion and the transmittance are not sufficient, so that it is not satisfactory for producing a liquid crystal display element of high quality. Patent Document 4 proposes a radiation-sensitive resin composition comprising a resin containing an acetal structure and / or a ketal structure and an epoxy group, and an acid generator, but the sensitivity and the transmittance are low and can not be satisfied. Patent Document 5 proposes a radiation-sensitive resin composition which comprises a hydroxystyrene resin protected by acetal or ketal, a compound which generates an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more, and a crosslinking agent The transmittance was low and could not be satisfied.

Japanese Patent Application Laid-Open No. 5-165214 Japanese Patent Application Laid-Open No. 10-153854 Japanese Patent Application Laid-Open No. 2004-4669 Japanese Patent Application Laid-Open No. 2004-264623 Japanese Patent Application Laid-Open No. 2008-304902

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photosensitive resin composition which is excellent in sensitivity, residual film ratio and storage stability and a method for forming a cured film using the positive photosensitive resin composition and a positive photosensitive resin composition which can obtain a cured film excellent in heat resistance, And a method of forming a cured film.

Further, it is intended to provide a cured film obtained by using the cured film forming method, and a liquid crystal display element, an integrated circuit element, a solid-state image pickup element or an organic EL element having the cured film.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.

The present invention is as follows.

(A1) A resin which contains a constitutional unit represented by the following general formula (1), is alkali-insoluble or alkali-insoluble and is alkali-soluble when the acid-dissociable group is dissociated, (A2) A polymer or copolymer having a constituent unit derived from a radically polymerizable monomer containing a functional group capable of forming a bond, and (B) a compound capable of generating an acid upon irradiation with an actinic ray, Resin composition.

[In the general formula (1)

R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group.

R ² and R ³ each independently represent a hydrogen atom, a linear or branched alkyl group. Provided that R < ² > and R < ³ > are hydrogen atoms at the same time.

R ⁴ represents a linear, branched or cyclic alkyl or aralkyl group which may be substituted.

R ² or R ³ and R ⁴ may be connected to form a cyclic ether.]

[2] The positive photosensitive resin composition according to [1], further comprising (C) a compound having two or more epoxy groups in the molecule (excluding the above A2).

[3] The positive photosensitive resin composition according to [1] or [2], wherein the component (B) contains a compound capable of generating an acid upon irradiation with actinic rays having a wavelength of 300 nm or more.

[4] The positive photosensitive resin composition according to any one of [1] to [3], wherein the component (B) comprises a compound containing an oxime sulfonate group represented by the following general formula (2) .

[In the general formula (2)

R ⁵ represents a linear, branched, cyclic alkyl group which may be substituted or an aryl group which may be substituted.]

[5] The positive photosensitive resin composition according to [4], wherein the compound containing an oxime sulfonate group represented by the general formula (2) is a compound represented by the following general formula (2-1).

[In the general formula (2-1)

R ⁵ is the same as R ⁵ in the formula (2).

X represents a linear or branched alkyl group, an alkoxy group or a halogen atom.

m represents an integer of 0 to 3; When m is 2 or 3, plural Xs may be the same or different.]

[6] The positive photosensitive resin composition according to [4], wherein the compound containing an oxime sulfonate group represented by the general formula (2) is a compound represented by the following general formula (2-2).

[In the general formula (2-2)

R ⁵ is the same as R ⁵ in the formula (2).

R ⁶ represents a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cyano group or a nitro group.

and l represents an integer of 0 to 5. When l is 2 or more, plural R ^{6 s} may be the same or different.]

[7] The positive photosensitive resin composition according to any one of [1] to [6], wherein the functional group capable of reacting with the carboxyl group to form a covalent bond is an epoxy group.

[8] The radically polymerizable monomer containing a functional group capable of reacting with the carboxyl group to form a covalent bond according to [7], is a radically polymerizable monomer represented by any one of the following general formulas (3) to (5) Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

[In the general formulas (3) to (5)

R ⁷ represents a hydrogen atom, a methyl group or a halogen atom.

Each of R ⁸ to R ¹⁵ independently represents a hydrogen atom or an alkyl group.

X represents a divalent linking group.

and n is an integer of 1 to 10.]

[9] The positive photosensitive resin composition according to any one of [1] to [6], wherein the functional group capable of reacting with the carboxyl group to form a covalent bond is an oxetanyl group.

[10] The positive resist composition according to [9], wherein the radical polymerizable monomer containing a functional group capable of reacting with the carboxyl group to form a covalent bond is a radical polymerizable monomer represented by the following formula (6) Sensitive resin composition.

[Wherein,

R ⁷ represents a hydrogen atom, a methyl group or a halogen atom.

R ⁸ to R ¹² each independently represent a hydrogen atom or an alkyl group.

X represents a divalent linking group.

and n is an integer of 1 to 10.]

[11] The positive photosensitive resin composition according to any one of [1] to [10], further comprising (D) an adhesion aid.

[12] The positive resist composition according to any one of [1] to [11], wherein the component (A2) is a copolymer comprising a constituent unit derived from a radically polymerizable monomer containing a functional group capable of reacting with a carboxyl group to form a covalent bond, 1). ≪ / RTI >

[13] A process for producing a positive photosensitive resin composition according to any one of [1] to [12], wherein the positive photosensitive resin composition is applied onto a substrate and dried to form a coating film, And a step of heat-treating the pattern thus obtained.

[14] The method for forming a cured film according to [13], further comprising a step of performing a front exposure before the step of heat treatment of the obtained pattern after the step of forming a pattern by development using an alkaline developer.

[15] A cured film formed by the cured film forming method according to [13] or [14].

[16] A liquid crystal display element having the cured film according to [15].

[17] An integrated circuit device having the cured film according to [15].

[18] A solid-state imaging device having the cured film according to [15].

[19] An organic EL device having the cured film according to [15].

Hereinafter, preferred embodiments of the present invention will be described.

[20] The positive photosensitive resin composition according to any one of [1] to [12], which contains 0.1 to 10 parts by mass of the component (B) based on 100 parts by mass of the total amount of the components (A1) Resin composition.

[21] The positive resist composition according to any one of [1] to [12] and [20], wherein component (C) is contained in an amount of 1 to 50 parts by mass based on 100 parts by mass of the total amount of the components (A1) Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

[22] The positive resist composition according to any one of [11] to [12], wherein the component (D) is contained in an amount of 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of the components (A1) By weight based on the total weight of the positive photosensitive resin composition.

(Effects of the Invention)

A positive photosensitive resin composition excellent in sensitivity, residual film ratio and storage stability by the present invention and a cured film forming method using the positive photosensitive resin composition are excellent in sensitivity, It has become possible to provide a method of forming a semiconductor device.

Hereinafter, the present invention will be described in detail.

The notation in which the substituent and the non-substituent are not described in the notation of the group (atomic group) in the present specification includes not only a substituent but also 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).

(A) a resin component

The resin component (A) contained in the positive photosensitive resin composition of the present invention contains a constituent unit represented by the general formula (1) and is alkali-insoluble or alkali-insoluble, and becomes alkali-soluble when the acid- (Also referred to as "component (A1)") and a polymer or copolymer containing a constituent unit derived from an epoxy group-containing radical polymerizable monomer (also referred to as "component (A2)") May further contain a resin. Here, the acid-dissociable group means a functional group which can be dissociated in the presence of an acid.

However, the polymer or copolymer (A2) containing a structural unit derived from an epoxy group-containing radical polymerizable monomer may further contain a structural unit containing a structural unit represented by the general formula (1) Is considered to be the component (A2).

(A1) Component

The component (A1) is a resin that contains a constitutional unit represented by the general formula (1), is alkali-insoluble or alkali-insoluble and becomes alkali-soluble when the acid-dissociable group is dissociated.

In the general formula (1)

R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group.

R ² and R ³ each independently represent a hydrogen atom, a linear or branched alkyl group. Provided that R < ² > and R < ³ > are hydrogen atoms at the same time.

R ⁴ represents a linear, branched or cyclic alkyl or aralkyl group which may be substituted.

R ² or R ³ and R ⁴ may be connected to form a cyclic ether.

R ¹ in the general formula (1) is preferably a hydrogen atom or a methyl group.

R ² and R ³ are preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

R ⁴ is preferably a straight, branched or cyclic alkyl group of 1 to 10 carbon atoms which may be substituted. Here, the substituent is preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom.

The aralkyl group as R ⁴ is preferably an aralkyl group having 7 to 10 carbon atoms.

When R ² or R ³ and R ⁴ are connected to form a cyclic ether, it is preferable that R ² or R ³ and R ⁴ are connected to form an alkylene chain having 2 to 5 carbon atoms.

Examples of the radical polymerizable monomer used for forming the constituent unit represented by the general formula (1) include ortho - (1-alkoxyalkyloxycarbonyl) styrene, meta - (1-alkoxyalkyloxycarbonyl) styrene (1-alkyl-1-alkoxyalkyloxycarbonyl) styrene, para- (1-alkoxyalkyloxycarbonyl) styrene, (1-alkoxyalkyloxycarbonyl) styrene, ortho- (1-alkoxyalkyloxycarbonyl) -? - methylstyrene, meta- (1-alkoxyalkyloxycarbonyl) Styrene, meta- [1- (aralkyloxy) alkyloxycarbonyl] -a- methylstyrene, ortho- [1- (aralkyloxy) alkyloxycarbonyl] (2-oxacycloalkyloxycarbonyl) styrene, meta- (2-oxacycloalkyloxycarbonyl) styrene, para- [1- (aralkyloxy) Carbonyl) styrene, para-, and the like (2-oxa-bicyclo alkyloxycarbonyl) styrene. Among these, styrenes such as metha- (1-alkoxyalkyloxycarbonyl) styrene, para- (1-alkoxyalkyloxycarbonyl) styrene, meta- (2-oxacycloalkyloxycarbonyl) styrene, para- Oxycarbonyl) styrene are preferable, and para- (1-alkoxyalkyloxycarbonyl) styrene and para- (2-oxacycloalkyloxycarbonyl) styrene are particularly preferable.

Specific examples of the radical polymerizable monomer used for forming the constituent unit represented by the general formula (1) include ortho - (1-methoxyethoxycarbonyl) styrene, meta- (1-methoxyethoxy Styrene, para- (1-methoxyethoxycarbonyl) styrene, ortho- (1-ethoxyethoxycarbonyl) styrene, (1-n-propoxyethoxycarbonyl) styrene, ortho- (1-n-propoxyethoxycarbonyl) styrene, Styrene, para- (1-n-butoxyethoxycarbonyl) styrene, para- (1-n-butoxyethoxycarbonyl) styrene, Styrene, para- (1-n-butoxyethoxycarbonyl) styrene, para- (1-isobutoxyethoxycarbonyl) styrene, ortho- (1-benzylethoxycarbonyl) - (1-benzyl (2-oxacyclohexyloxycarbonyl) styrene, meta- (2-oxacyclohexyloxycarbonyl) styrene, para- (1-benzylethoxycarbonyl) styrene, - (2-oxacyclohexyloxycarbonyl) styrene, para- (2-oxacyclopentyloxycarbonyl) styrene, meta- (1-ethoxyethoxycarbonyl) Styrene, para- (1-methyl-1-ethoxyethoxycarbonyl) styrene, and the like can be used. And may be used singly or in combination of two or more.

The radically polymerizable monomer used for forming the constituent unit represented by the general formula (1) may be a commercially available one, or a compound synthesized by a known method may be used. For example, as shown below, it can be synthesized by reacting vinyl benzoic acid with vinyl ether in the presence of an acid catalyst.

Here, R ^1, R ³ and R ⁴ is a general formula ⁽¹⁾ R 1, R ³ and R ⁴ corresponding to R ¹³ and R ¹⁴ is ^{-CH (R 13) (R 14} ) a in the general Corresponds to R < ² > in the formula (1).

In the component (A1), a monomer having a constituent unit other than the monomer for forming the constituent unit represented by the general formula (1) may be copolymerized, if necessary.

Examples of the structural unit other than the structural unit represented by the general formula (1) include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene,? -Methyl-acetoxystyrene, methoxystyrene Methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl methacrylate, Isopropyl acrylate, isopropyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Examples thereof include structural units derived from hydroxypropyl, benzyl acrylate, benzyl methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, acrylonitrile and the like, It may be used in combination of two or more.

The content of the structural unit represented by the general formula (1) in the repeating units constituting the component (A1) is preferably 10 to 100 mol%, more preferably 20 to 90 mol%, and particularly preferably 30 to 80 mol% Do.

The molecular weight of the component (A1) 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.

The component (A1) may be a mixture of two or more kinds of resins containing different structural units, or a mixture of two or more kinds of resins composed of the same structural units and having different compositions.

Further, although various methods are known for the synthesis of the component (A1), for example, a radically polymerizable monomer mixture containing a radically polymerizable monomer used for forming a constitutional unit at least represented by the general formula (1) Can be synthesized by polymerization using a radical polymerization initiator in an organic solvent.

(A2) Component

The component (A2) is a polymer or copolymer containing a constituent unit derived from a functional radical-containing radical polymerizable monomer capable of reacting with a carboxyl group to form a covalent bond. The functional group capable of reacting with the carboxyl group to form a covalent bond is preferably an epoxy group or an oxetanyl group.

As the functional radical-containing radical polymerizable monomer capable of reacting with the carboxyl group to form a covalent bond, the radical polymerizable monomer represented by any one of the following general formulas (3) to (5) is preferable in one form, Can be used in combination. The molecular weight of the radical polymerizable monomer represented by the general formulas (3) to (5) is preferably 100 to 500, more preferably 120 to 200.

In the general formulas (3) to (5), X represents a divalent linking group, and examples thereof include organic groups such as -O-, -S-, -COO-, and -OCH ₂ COO-. X is preferably -COO-.

R ⁷ represents a hydrogen atom, a methyl group or a halogen atom, preferably a hydrogen atom or a methyl group.

R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , And each R ¹⁵ independently represents a hydrogen atom or an alkyl group. Preferably a hydrogen atom or a methyl group.

n is an integer of 1 to 10, preferably an integer of 1 to 3.

Specific examples of the functional group-containing radical polymerizable monomer capable of reacting with a carboxyl group to form a covalent bond include those having an epoxy group such as glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, methacryl Epoxy pentyl acrylate, 4,5-epoxy pentyl methacrylate, 6,7-epoxyhexyl acrylate, 6,7-epoxy heptyl methacrylate, 3,4-epoxycyclohexyl acrylate, (Meth) acrylates such as hexyl methyl acrylate and 3,4-epoxycyclohexyl methyl methacrylate; o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -methyl-o-vinyl benzyl glycidyl ether,? -methyl- Vinyl benzyl glycidyl ethers such as diester,? -Methyl-p-vinylbenzyl glycidyl ether; and vinylphenyl glycidyl ethers such as o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether and p-vinylphenyl glycidyl ether. Of these, glycidyl acrylate, glycidyl methacrylate, p-vinylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate are preferable, and acrylic acid Glycidyl, and glycidyl methacrylate are particularly preferable.

As the functional group-containing radical polymerizable monomer capable of reacting with the carboxyl group to form a covalent bond, the radical polymerizable monomer represented by the following general formula (6) or (7) in the other form is preferable, Can be used. The molecular weight of the radically polymerizable monomer represented by the general formula (6) or (7) is preferably 100 to 500, more preferably 120 to 200.

In the general formulas (6) and (7), X represents a divalent linking group, and examples thereof include organic groups such as -O-, -S-, -COO-, and -OCH ₂ COO-. X is preferably -COO-.

R ⁷ represents a hydrogen atom, a methyl group or a halogen atom, preferably a hydrogen atom or a methyl group.

R ⁸ to R ¹⁵ each independently represent a hydrogen atom or an alkyl group. Preferably a hydrogen atom or a methyl group.

n is an integer of 1 to 10, preferably an integer of 1 to 3.

Examples of the radically polymerizable monomer used for forming the oxetanyl group-containing structural unit include compounds in which the epoxy group is substituted with an oxetanyl group in the above specific examples of the radically polymerizable monomer containing an epoxy group, (Meth) acrylic acid esters having an oxetanyl group as described in paragraphs 0011 to 0016 of JP-A-2001-330953.

Preferable specific examples of the structural unit having a functional group capable of reacting with a carboxyl group to form a covalent bond include the following structural units.

The functional group-containing radical polymerizable monomer capable of reacting with the carboxyl group to form a covalent bond may be commercially available or may be synthesized by a known method.

A monomer having a constituent unit other than a functional group-containing radical polymerizable monomer capable of reacting with a carboxyl group to form a covalent bond in the component (A2) can be copolymerized.

Examples of these structural units include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene,? -Methyl-acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate , Ethyl vinyl benzoate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate , Isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, acrylonitrile, and the like. The term "a structural unit represented by the general formula (1) Monomer capable of forming "can be copolymerized.

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

The content of the constituent unit derived from the functional radical-polymerizable monomer capable of reacting with the carboxyl group to form a covalent bond among the repeating units constituting the component (A2) is preferably from 5 to 90 mol%, more preferably from 10 to 80 mol% , Still more preferably from 15 to 70 mol%.

The content of the structural unit represented by the general formula (1) in the repeating units constituting the component (A2) is preferably 0 to 70 mol%, more preferably 5 to 50 mol%.

The molecular weight of the component (A2) 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.

The component (A2) may be a mixture of two or more kinds of resins containing different structural units, or a mixture of two or more kinds of resins composed of the same structural units and having different compositions.

Although various methods are known for the synthesis of the component (A2), for example, a radical polymerization initiator mixture containing at least an epoxy group-containing radically polymerizable monomer can be synthesized by polymerization using a radical polymerization initiator in an organic solvent .

The mass ratio of the component (A1) to the component (A2) is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.

The composition of the present invention may contain a resin other than the component (A1) and the component (A2), and the content of the resin other than the component (A1) Is preferably 50 parts by mass or less based on 100 parts by mass of the total amount.

The content of the structural unit represented by the general formula (1) in the total repeating units of the whole resin constituting the component (A) is preferably from 10 to 90 mol%, more preferably from 20 to 50 mol%.

The content of the constituent unit derived from an epoxy group-containing radical polymerizable monomer is preferably from 5 to 50 mol%, more preferably from 10 to 40 mol%.

The content ratio of the constitutional units other than the constitutional unit derived from the constituent unit represented by the formula (1) and the radical-polymerizable monomer containing the epoxy group is 85 mol% or less in the total repeating units of the whole resin constituting the component (A) , And more preferably 70 mol% or less.

(B) a compound which generates an acid upon irradiation with an actinic ray or radiation

Examples of the compound (also referred to as a "component (B)" or "photo-acid generator") that generates an acid upon irradiation with an actinic ray or radiation used in the present invention include sulfonium salts, iodonium salts, diazomethane compounds, An imidosulfonate compound, and an oxime sulfonate compound. These compounds may be used alone or in combination of two or more.

The component (B) is preferably a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, more preferably a compound containing an oxime sulfonate group represented by the general formula (2).

In the general formula (2)

R ⁵ represents a linear, branched, cyclic alkyl group which may be substituted or an aryl group which may be substituted.

As the alkyl group for R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R < ⁵ > is preferably an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (preferably a bridged alicyclic group such as a 7,7-dimethyl- A bicycloalkyl group or the like).

The aryl group represented by R ⁵ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ⁵ may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a halogen atom.

The photoacid generator containing an oxime sulfonate group represented by the general formula (2) is more preferably an oxime sulfonate compound represented by the following general formula (2-1) in one form.

In the general formula (2-1)

R ⁵ is the same as R ⁵ in the formula (2).

X represents a linear or branched alkyl group, an alkoxy group or a halogen atom.

m represents an integer of 0 to 3; When m is 2 or 3, plural Xs may be the same or different.

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

The halogen atom as X is preferably a chlorine atom or a fluorine atom.

m is preferably 0 or 1.

Particularly, in the general formula (2-1), a compound wherein m is 1, X is a methyl group and X is a substituted position is ortho, and R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl Oxonoboronylmethyl group or a p-tolyl group is particularly preferable.

Specific examples of the oxime sulfonate compound include the following compounds (i), (ii), (iii), (iv) and (v) Can be used. Further, it may be used in combination with another kind of component (B).

The compounds (i) to (v) are commercially available.

The photoacid generator containing an oxime sulfonate group represented by the general formula (2) is more preferably a compound represented by the following general formula (2-2) in another form.

In the general formula (2-2)

R ⁵ is the same as R ⁵ in the formula (2).

R ⁶ represents a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cyano group or a nitro group.

and l represents an integer of 0 to 5. When l is 2 or more, plural R ^{6 s} may be the same or different.

The general formula (2-2) will be described in more detail.

R ⁵ is preferably an alkyl group of 1 to 10 carbon atoms, a halogenated alkyl group of 1 to 5 carbon atoms, a halogenated alkoxy group of 1 to 5 carbon atoms, a phenyl group which may be substituted by W, A naphthyl group which may be present or an anthranyl group which may be substituted by W can be exemplified. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, Or a halogenated alkoxy group.

Examples of R ⁵ in the general formula (2-2) include methyl, ethyl, n-propyl, n-butyl, n-octyl, , A perfluoro-n-butyl group, a benzyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and a methyl group, Tolyl group is particularly preferable.

The halogen atom represented by R ⁶ is preferably a fluorine atom, a chlorine atom or a bromine atom.

As the alkyl group represented by R ⁶ , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable.

As the alkoxy group represented by R ⁶ , an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is particularly preferable.

l is preferably 0 to 2, and 0 or 1 is particularly preferable.

R ⁵ is preferred aspect of the compounds included in the photo-acid generator represented by formula (2-2), a methyl group, an ethyl group, n- propyl group, an n- butyl group, or represents a 4-tolyl, R ⁶ is a hydrogen atom or Methoxy group, and l is 0 or 1.

Hereinafter, particularly preferred examples of the compound included in the photoacid generator represented by the general formula (2-2) are shown, but the present invention is not limited thereto.

? - (methylsulfonyloxyimino) benzyl cyanide (R ^3A = methyl group, R ^4A = hydrogen atom)

? - (ethylsulfonyloxyimino) benzyl cyanide (R ^3A = ethyl group, R ^4A = hydrogen atom)

? - (n-propylsulfonyloxyimino) benzyl cyanide (R ^3A = n-propyl group, R ^4A = hydrogen atom)

? - (n-butylsulfonyloxyimino) benzyl cyanide (R ^3A = n-butyl group, R ^4A = hydrogen atom)

? - (4-toluenesulfonyloxyimino) benzyl cyanide (R ^3A = 4-tolyl group, R ^4A = hydrogen atom)

? - (benzenesulfonyloxyimino) benzyl cyanide (R ^3A = phenyl group, R ^4A = hydrogen atom)

? - [(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = methyl group, R ^4A = methoxy group)

? - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = ethyl group, R ^4A = methoxy group)

(R ^{3 A} = n-propyl group, R ^{4 A} = methoxy group)

? - [(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-butyl group, R ^4A =

? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = 4-tolyl group, R ^4A = methoxy group).

? - [(benzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = phenyl group, R ^4A = methoxy group).

In the photosensitive resin composition of the present invention, the photoacid generator (B) is preferably contained in an amount of 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total amount of the components (A1) and desirable.

The photosensitive resin composition of the present invention may contain a photoacid generator other than the photoacid generator containing an oxime sulfonate group represented by the general formula (2), if necessary, as a photoacid generator which is sensitive to an actinic ray.

(C) a compound having two or more epoxy groups in the molecule

Specific examples of the compound having two or more epoxy groups in the molecule (also referred to as " component (C) ") include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, Resins and the like.

These are available as commercial products. Examples of the bisphenol A epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 { (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 {or the like) as the bisphenol F type epoxy resin, and JER 806, JER 807, JER 4004, JER 4005, JER 4007, JER152, JER154, JER157S70 (trade name, manufactured by Nippon Kayaku Co., Ltd.) as the phenol novolak type epoxy resin, (Manufactured by Dainippon Ink and Chemicals, Inc.), EPICLON N-740, EPICLON N-740, EPICLON N-770 and EPICLON N-775 EPICLON N-660, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N- -1020 (trade name, manufactured by Nippon Kayaku Co., Ltd.), and examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S Side 2081, celloxide 2083, celloxide 2085, EHPE 3150, EPOLEAD PB 3600, PB 4700 (manufactured by Daicel Chemical Industries, Ltd.) and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- 501, EPPN-502 (manufactured by ADEKA CO., LTD.), Etc. These may be used singly or in combination of two or more.

Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin. Particularly, a bisphenol A type epoxy resin is preferable.

The content of the epoxy resin (C) is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the total amount of the components (A1) and (A2).

The component (C) is effective for improving adhesion with metal layers such as chromium, molybdenum, aluminum, tantalum, titanium, copper, cobalt, tungsten and nickel. When these metal layers are produced by the sputtering method, the effect is remarkable.

(D) Adhesion preparation

The positive photosensitive resin composition of the present invention may further contain (D) an adhesion aid.

Examples of the adhesion aid (D) used in the present invention include inorganic compounds such as silicon compounds, silicon compounds such as silicon oxide and silicon nitride, and compounds which improve the adhesion between metals such as gold, copper and aluminum and insulating films. Specific examples thereof include silane coupling agents and thiol compounds.

The silane coupling agent as the adhesion promoter used in the present invention is not specifically limited and any known one may be used for the purpose of modifying the interface.

Preferred examples of the silane coupling agent include? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Methacryloxypropylalkyldialkoxysilane ,? -chloropropyltrialkoxysilane,? -mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane.

more preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, and even more preferably γ-glycidoxypropyltrialkoxysilane.

These may be used alone or in combination of two or more. These are effective in improving the adhesion with the substrate and also in adjusting the taper angle with the substrate.

The mixing ratio of the component (A), the component (B), the component (C) and the component (D) in the positive photosensitive resin composition of the present invention is (B ) Is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass.

The component (C) is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, as described above. The amount of the component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass.

<Other ingredients>

In addition to the component (A), the component (B), the component (C), and the component (D), the positive photosensitive resin composition of the present invention may further contain a basic compound, a surfactant, an ultraviolet absorbent, a sensitizer, a plasticizer, An organic solvent, an adhesion promoter, an organic or inorganic precipitation inhibitor, and the like.

&Lt; Basic compound >

As the basic compound, any of those used in the chemically amplified resist may be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic quaternary ammonium salts and the like.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amines include aniline, benzylamine, N, N-dimethylaniline, diphenylamine, and the like.

Examples of the heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy Quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] , 1,8-diazabicyclo [5,3,0] -7 undecene, and the like.

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

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

The compounding ratio of the basic compound is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.2 part by mass per 100 parts by mass of the total amount of the components (A1) and (A2).

<Surfactant>

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants. Examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Kagaku Co., Ltd.), F-top (manufactured by JEMCO), Megapack (Dainippon Ink & ), Asahi Guard, Surfron (Asahi Glass Co.), PolyFox (OMNOVA), Futazent (Neos), and the like.

The weight ratio of the surfactant in terms of polystyrene measured by gel permeation chromatography when the surfactant contains the constituent unit A and the constituent unit B represented by the following formula (I) and tetrahydrofuran (THF) A preferred example is a copolymer having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

In formula (I), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms P is an integer of not less than 10 mass% and not more than 80 mass%, q is a mass of not less than 20 mass% and not more than 90 mass%, L is an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing mass ratios, % Or less, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less.

It is preferable that L is a branched alkylene group represented by the following general formula (II). R ⁵ in the general formula (II) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, and an alkyl group having 2 or 3 carbon atoms is preferable desirable. The sum (p + q) of p and q is preferably p + q = 100, that is, 100 mass%.

The weight average molecular weight (Mw) of the copolymer is preferably 1000 or more and 10,000 or less, and more preferably 1,500 or more and 5,000 or less, in terms of polystyrene measured by gel permeation chromatography using THF as a solvent.

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

The compounding ratio of the surfactant is usually 10 parts by mass or less, preferably 0.01 to 10 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total amount of the components (A1) and (A2).

<Plasticizer>

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartrate, dioctyl adipate, triacetyl glycerin and the like.

The blending ratio of the plasticizer is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the total amount of the components (A1) and (A2).

<Increase / decrease>

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator (B) in order to promote its decomposition.

The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator to generate electron movement, energy transfer, heat generation, and the like. As a result, the photoacid generator causes a chemical change to decompose to generate an acid.

Examples of preferred sensitizers include compounds having an absorption wavelength in any one of the following 350 nm to 450 nm regions, belonging to the following compounds.

Polycyclic aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Anthracene, xanthone, xanthone, dimethylthioxanthone, diethylthioxanthone, etc.), xanthone (e.g., fluorene, eosin, erythrosine, rhodamine B, Tonnes), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), rhodacyanines, (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, acridine, acridine), acridine (for example, thionine, methylene blue, toluidine blue) Butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaryliums (for example, squalium), styryls, (E.g., 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolizine-11-pne).

Of these sensitizers, polycyclic aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polycyclic aromatic compounds are more preferable. Of the polycyclic aromatics, anthracene derivatives are most preferred.

<Solvent>

The positive photosensitive composition of the present invention is used as a solution by dissolving the above components in a solvent. As the solvent used in the positive photosensitive composition of the present invention, for example,

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

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

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

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

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

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

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

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

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

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

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

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

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

(n) is selected from the group consisting of ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxypropionate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate;

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

(p) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;

(q) lactones such as? -butyrolactone, and the like.

If necessary, these solvents may further contain one or more of benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, A solvent such as norbornene, 1-nonyl, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may be further added.

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

The blending ratio of the solvent is usually 50 to 3,000 parts by mass, preferably 100 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass, per 100 parts by mass of the total amount of the components (A1) and (A2).

According to the present invention, it is possible to provide a positive photosensitive resin composition which is excellent in sensitivity, residual film ratio and long-term stability, and which can be cured to obtain a cured film excellent in heat resistance, adhesion, transparency and the like.

&Lt; Method of forming a cured film &

Next, a method of forming a cured film using the positive photosensitive resin composition of the present invention will be described.

The positive photosensitive resin composition according to the present invention is coated on a substrate and heated to form a coating film on the substrate.

By irradiating the coating film with an actinic ray, the component (B) is decomposed to generate an acid. The acid-dissociable group in the constituent unit represented by the general formula (1) contained in the component (A1) is dissociated by the hydrolysis reaction by the catalytic action of the generated acid to produce a carboxyl group. Subsequently, a positive image is formed by removing an exposed portion containing a resin having a carboxyl group, which is liable to be dissolved in an alkaline developing solution, by using an alkali developing solution.

The reaction formula of this hydrolysis reaction is shown below.

In order to accelerate the hydrolysis reaction, Post Exposure Bake (hereinafter referred to as PEB) can be performed as needed. However, since the carboxyl group generated when the heating temperature becomes high causes a crosslinking reaction with the epoxy group, the development can not be performed.

In fact, when p-tert-butoxycarbonylstyrene is used instead of the repeating unit represented by the general formula (1), the activation energy of the acid dissociation reaction is high, so it is necessary to PEB at high temperature to dissociate the acid dissociable group, And no image is obtained.

On the other hand, the acid-cleavable group represented by the general formula (1) of the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group, , A positive image can be formed by the development.

Further, PEB may be performed at a relatively low temperature to accelerate the decomposition of the acid-dissociable group without causing a crosslinking reaction.

The PEB temperature is preferably 130 占 폚 or lower, more preferably 110 占 폚 or lower, and particularly preferably 80 占 폚 or lower.

Next, the obtained positive image is heated to pyrolyze the acid-dissociable group in the general formula (1) to produce a carboxyl group, and the cured film can be formed by crosslinking with an epoxy group. This heating is preferably heated at a high temperature of 150 ° C or higher, more preferably 180 to 250 ° C, particularly preferably 200 to 250 ° C.

The heating time can be appropriately set according to the heating temperature and the like, but is generally 10 to 90 minutes.

Addition of a step of irradiating the active ray before the heating process can accelerate the crosslinking reaction by the acid generated by irradiation of the active ray.

Next, a method of forming a cured film using the positive photosensitive resin composition of the present invention will be described in detail.

Method for preparing composition solution: The composition solution is prepared by mixing the components (A), (B), (C) and other compounding agents in a predetermined ratio and by any method, and dissolving with stirring. For example, the composition solution may be prepared by dissolving each component in advance in a solvent to prepare a solution, and then mixing them at a predetermined ratio. The composition solution prepared as described above may be used after being filtered using a filter having a pore diameter of 0.2 mu m or the like.

&Lt; Preparation method of coating film &

A desired coating film can be formed by applying a composition solution to a predetermined substrate and removing the solvent by heating (hereinafter referred to as prebaking). Examples of the substrate include a polarizing plate in the production of a liquid crystal display device, and a glass plate in which a black matrix layer and a color filter layer are formed as required and a transparent conductive circuit layer is further formed. The coating method on the substrate is not particularly limited, and for example, a spraying method, a roll coating method, a rotary coating method, a slit coating method and the like can be used.

The heating conditions at the time of prebaking are a range in which the acid-dissociable group in the repeating unit represented by the formula (1) in the component (A) in the unexposed portion dissociates and the component (A) is not soluble in the alkali developer , And it is preferably about 80 to 130 占 폚 for about 30 to 120 seconds though it depends on the kind of each component and blending ratio.

&Lt; Pattern formation method >

After irradiating the substrate on which the coating film is formed with actinic rays through a mask of a predetermined pattern, the substrate is subjected to heat treatment (PEB) if necessary, and then the exposed portion is removed using a developer to form an image pattern.

A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, or an excimer laser generator may be used for the radiation of the active ray, but an active ray having a wavelength of 300 nm or more such as g line, i line and h line is preferable. If necessary, irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

Examples of the developing solution include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide and the like; 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.

The pH of the developing solution is preferably 10.0 or more.

The developing time is usually from 30 to 180 seconds, and the developing method may be either the puddle method or the dipping method. After the development, washing with water for 30 to 90 seconds is carried out to form a desired pattern.

&Lt; Crosslinking step &

For example, from 180 to 250 DEG C for a predetermined time, for example, from 5 to 30 minutes on a hot plate, by using a heating apparatus such as a hot plate or an oven for the pattern having unexposed portions obtained by the development, , The reaction is carried out for 30 to 90 minutes to remove the acid-dissociable group in the component (A1) to generate a carboxyl group, and a reaction or crosslinking reaction with the epoxy group in the component (A2) Can be formed. Further, when the heat treatment is performed, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

In addition, it is preferable that an acid is generated from the component (B) present in the unexposed portion by irradiating an actinic ray to the substrate on which the pattern is formed before the heat treatment.

(Example)

EXAMPLES Next, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples.

[Synthesis Example 1: Synthesis of A1-1]

(0.136 mol) of para- (1-n-butoxyethoxycarbonyl) styrene, 21.1 g (0.12 mol) of benzyl methacrylate, 17.8 g (0.12 mol) of parabinyl benzoic acid and 300 ml of methyl isobutyl ketone , And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A1-1 (para- (1-n-butoxyethoxycarbonyl ) Styrene / benzyl methacrylate / parabinyl benzoic acid) as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 7,000 and a molecular weight distribution (Mw / Mn) of 1.8.

[Synthesis Example 2: Synthesis of A1-2]

(0.48 mol) of para- (1-benzyloxyethoxycarbonyl) styrene, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate, 5.2 g (0.06 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone Necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A1-2 (para- (1-benzyloxyethoxycarbonyl) styrene / Methacrylic acid 2-hydroxyethyl / methacrylic acid) was obtained as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 6,000 and a molecular weight distribution (Mw / Mn) of 1.7.

 [Synthesis Example 3: Synthesis of A1-3]

(0.42 mole) of para- (1-ethoxyethoxycarbonyl) styrene, 21.1 g (0.12 mole) of benzyl methacrylate, 7.8 g (0.06 mole) of 2-hydroxyethyl methacrylate, 300 ml were introduced into a 500-ml three-necked flask, and 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto as a radical polymerization initiator and polymerized at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A1-3 (para- (1-ethoxyethoxycarbonyl) styrene / Benzyl methacrylate / 2-hydroxyethyl methacrylate) was obtained as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 7,000 and a molecular weight distribution (Mw / Mn) of 1.8.

[Synthesis Example 4: Synthesis of A1-4]

(0.36 mol) of para- (1-ethoxyethoxycarbonyl)? -Methylstyrene, 21.1 g (0.12 mol) of benzyl methacrylate, 15.6 g (0.12 mol) of 2-hydroxyethyl methacrylate, 300 ml of isobutyl ketone was poured into a 500 ml three-necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was added thereto as a radical polymerization initiator, followed by polymerization at 80 ° C for 6 hours under a nitrogen stream . The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A1-4 (para- (1-ethoxyethoxycarbonyl) alpha -Methylstyrene / benzyl methacrylate / 2-hydroxyethyl methacrylate) as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 4,000 and a molecular weight distribution (Mw / Mn) of 1.6.

[Synthesis Example 5: Synthesis of A1-5]

(0.18 mol) of metha- (1-ethoxyethoxycarbonyl) styrene, 52.9 g (0.30 mol) of benzyl methacrylate, 10.3 g (0.12 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone were dissolved in 500 ml of 3 Necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A1-5 (meta- (1-ethoxyethoxycarbonyl) styrene / Benzyl methacrylate / methacrylic acid) was obtained as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 11,000 and a molecular weight distribution (Mw / Mn) of 1.8.

[Synthesis Example 6: synthesis of A1-6]

82.3 g (0.30 mol) of para- (1-cyclohexyloxyethoxycarbonyl) styrene, 40.3 g (0.30 mol) of p-methoxystyrene and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, A catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator, and polymerization was carried out at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A1-6 (para- (1-cyclohexyloxyethoxycarbonyl) Styrene / p-methoxystyrene) as a diethylene glycol ethyl methyl ether solution.

The molecular weight and the molecular weight distribution of the obtained polymer were measured by GPC using polystyrene as a standard, and as a result, the weight average molecular weight was about 7,000 and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 7: Synthesis of A1-7]

(0.42 mol) of para- (2-oxacyclohexyl) oxycarbonylstyrene, 19.5 g (0.12 mol) of p-acetoxystyrene, 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate, 300 ml of ketone was poured into a 500 ml three-necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was added thereto as a radical polymerization initiator, followed by polymerization for 6 hours at 80 ° C in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A1-7 (para- (2-oxacyclohexyl) oxycarbonylstyrene / p-acetoxystyrene / 2-hydroxyethyl methacrylate) as a diethylene glycol ethyl methyl ether solution.

The molecular weight and the molecular weight distribution of the obtained polymer were measured by GPC using polystyrene as a standard, and as a result, the weight average molecular weight was about 9,000 and the molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis of A1-8 to A1-11]

Polymers A1-8 to A1-11 shown in the later publication were obtained by the same method as the above-mentioned production method.

[Synthesis Example 8: Synthesis of A2-1]

51.3 g (0.36 mol) of glycidyl methacrylate, 42.3 g (0.24 mol) of benzyl methacrylate and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask. To this, a catalytic amount of 2,2 '-Azobis (methyl 2-methylpropionate) was added, and the mixture was polymerized at 80 ° C for 6 hours in a stream of nitrogen. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A2-1 (glycidyl methacrylate / benzyl methacrylate) Diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 8,000 and a molecular weight distribution (Mw / Mn) of 1.7.

[Synthesis Example 9: Synthesis of A2-2]

(0.36 mol) of glycidyl acrylate, 15.6 g (0.12 mol) of 2-hydroxyethyl methacrylate, 19.5 g (0.12 mol) of p-acetoxystyrene and 300 ml of methyl isobutyl ketone were placed in a 500 ml three-necked flask And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A2-2 (glycidyl acrylate / 2-hydroxyethyl methacrylate / p-acetoxystyrene) was obtained as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 5,000 and a molecular weight distribution (Mw / Mn) of 1.6.

[Synthesis Example 10: Synthesis of A2-3]

58.9 g (0.30 mol) of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100, manufactured by Daicel Chemical Industries, Ltd.), 31.7 g (0.18 mol) of benzyl methacrylate, 10.3 g (0.12 mol) 300 ml of butyl ketone was poured into a 500 ml three-necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was added thereto as a radical polymerization initiator, followed by polymerization at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A2-3 (3,4-epoxycyclohexylmethyl methacrylate / meta Benzyl acrylate / methacrylic acid) as a diethylene glycol ethyl methyl ether solution.

The molecular weight and the molecular weight distribution of the obtained polymer were measured by GPC using polystyrene as a standard, and as a result, the weight average molecular weight was about 7,000 and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 11: Synthesis of A2-4]

(0.12 mol) of p-vinylphenylglycidyl ether, 19.0 g (0.12 mol) of 1-ethoxyethyl methacrylate, 29.2 g (0.18 mol) of p-acetoxystyrene and 300 ml of methyl isobutyl ketone Necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization for 6 hours at 80 ° C in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A2-4 (p-vinylphenyl glycidyl ether / methacrylic acid 1 -Ethoxyethyl / p-acetoxystyrene) as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 4,000 and a molecular weight distribution (Mw / Mn) of 1.6.

[Synthesis Example 12: Synthesis of A2-5]

(0.24 mole) of glycidyl methacrylate, 38.0 g (0.24 mole) of 1-ethoxyethyl methacrylate, 15.6 g (0.12 mole) of 2-hydroxyethyl methacrylate, and 300 ml of methyl isobutyl ketone , And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, dissolved in diethylene glycol ethyl methyl ether, and the heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A2-5 (glycidyl methacrylate / methacrylic acid 1- Ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate) as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 9,000 and a molecular weight distribution (Mw / Mn) of 1.7.

[Synthesis Example 13: Synthesis of A2-6]

(0.24 mole) of glycidyl methacrylate, 28.5 g (0.18 mole) of 1-ethoxyethyl methacrylate, 7.8 g (0.06 mole) of 2-hydroxyethyl methacrylate, and 21.1 g of benzyl methacrylate 0.12 mole) and methyl isobutyl ketone (300 ml) were introduced into a 500 ml three-necked flask, and a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was added thereto as a radical polymerization initiator. For 6 hours. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration, and then dissolved in diethylene glycol ethyl methyl ether. Heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A2-6 (glycidyl methacrylate / methacrylic acid 1- Ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / benzyl methacrylate) as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 8,000 and a molecular weight distribution (Mw / Mn) of 1.7.

[Synthesis Example 14: Synthesis of A2-7]

51.2 g (0.36 mol) of glycidyl methacrylate, 21.1 g (0.12 mol) of benzyl methacrylate, 10.3 g (0.12 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask, Azobis (methyl 2-methylpropionate) was added as a radical polymerization initiator in a catalytic amount, and polymerization was carried out at 80 DEG C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration and dissolved in diethylene glycol ethyl methyl ether. The heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A2-7 (glycidyl methacrylate / benzyl methacrylate / meta Acrylic acid) as a diethylene glycol ethyl methyl ether solution.

As a result of GPC measurement using polystyrene as a standard, the molecular weight and molecular weight distribution of the obtained polymer were found to have a weight average molecular weight of about 4,000 and a molecular weight distribution (Mw / Mn) of 1.6.

[Synthesis of A2-8 to A2-11]

Polymers A2-8 to A2-11 shown in the later publication were obtained by the same method as the above-mentioned production method.

[Synthetic Comparative Example 1: Synthesis of A'1-12]

(0.36 mol) of p-tert-butoxycarbonyl styrene, 21.1 g (0.12 mol) of benzyl methacrylate, 10.3 g (0.12 mol) of methacrylic acid and 300 ml of methyl isobutyl ketone were charged into a 500 ml three-necked flask , And a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) as a radical polymerization initiator was added thereto, followed by polymerization at 80 ° C for 6 hours in a nitrogen stream. The reaction solution was cooled and poured into a large amount of heptane to precipitate a polymer. The crystals were collected by filtration and dissolved in diethylene glycol ethyl methyl ether. The heptane and methyl isobutyl ketone contained in the solution were distilled off under reduced pressure to obtain polymer A'1-12 (p-tert-butoxycarbonylstyrene / meta Benzyl acrylate / methacrylic acid) as a diethylene glycol ethyl methyl ether solution.

The molecular weight and the molecular weight distribution of the obtained polymer were measured by GPC using polystyrene as a standard, and as a result, the weight average molecular weight was about 7,000 and the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Comparative Example 2: Synthesis of A'1-13]

72.1 g of poly-4-hydroxystyrene (VP-8000 manufactured by Nippon Soda Co., Ltd.), 16.4 g of ethyl vinyl ether and 300 ml of ethyl acetate were placed in a 500 ml three-necked flask, and a catalytic amount of para- toluenesulfonic acid was added thereto, And the mixture was allowed to react at room temperature under a nitrogen stream for 3 hours. After adding a small amount of triethylamine, it is washed with pure water. Diethyleneglycol ethyl methyl ether was added to the ethyl acetate layer and the ethyl acetate was distilled off under reduced pressure to obtain a polymer A'1-13 (p-1-ethoxyethoxystyrene / p-hydroxystyrene) in diethylene glycol ethyl methyl Ether solution.

The composition ratio of the p-1-ethoxyethoxystyrene unit and the p-hydroxystyrene unit in the obtained polymer was about 35:65 from the NMR measurement. As a result of GPC measurement using polystyrene as a standard, the weight average molecular weight was about 9,000 and the molecular weight distribution (Mw / Mn) was 1.2.

[Synthesis Comparative Example 3: Synthesis of A'-14]

Synthesis of A'-14 was carried out according to Synthesis Example 1 described in JP-A-2004-264623.

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were poured into a three-neck flask, and then 1- (cyclohexyloxy) ethyl methacrylate 40 parts by mass of styrene, 5 parts by mass of styrene, 45 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethylmethacrylate and 3 parts by mass of? -Methylstyrene dimer were poured into the autoclave and purged with nitrogen, it started. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A'-14). As a result of GPC measurement using polystyrene as a standard, the molecular weight of the obtained polymer was found to have a weight average molecular weight of about 11,000 and a molecular weight distribution (Mw / Mn) of 1.9.

[Examples 1 to 17 and Comparative Examples 1 to 6]

(1) Preparation of positive-working photosensitive resin composition solution

Each component shown in Table 1 below was mixed to prepare a homogeneous solution, which was then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 mu m to prepare a positive photosensitive resin composition solution.

(2) Evaluation of storage stability

The viscosity of the positive photosensitive resin composition solution at 23 캜 was measured using an E-type clay system manufactured by Toki Sangyo K.K. After the composition was stored in a thermostatic chamber at 23 占 폚 for one month, the viscosity of the composition was measured. A viscosity increase after storage for 1 month at room temperature was evaluated as &amp; cir &amp; and a viscosity increase of less than 5% was rated &amp; cir &amp; The results are shown in Table 2 below.

(3) Evaluation of the sensitivity and the residual film ratio at the time of development

A positive photosensitive resin composition solution was spin coated on a silicon wafer having a silicon oxide film and then baked on a hot plate at 100 캜 for 60 seconds to form a coating film having a film thickness of 3 탆.

Then, an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) was used to expose through a predetermined mask. After baking at 50 DEG C for 60 seconds, the resist film was developed for 60 seconds at 23 DEG C with the alkali developer (2.38 mass% or 0.4 mass% tetramethylammonium hydroxide aqueous solution) shown in Table 2 for 60 seconds, Rinse. With these operations, the optimum exposure amount (Eopt) at the time of resolving a line-and-space of 5 mu m at a ratio of 1: 1 was taken as sensitivity.

After the development, the film thickness of the unexposed portion was measured and the ratio to the film thickness after coating (unexposed film thickness after development divided by film thickness after coating 100 (%)) was evaluated to evaluate the retention rate at the time of development.

The evaluation results of the sensitivity and the residual film ratio at the time of development are shown in Table 2.

(4) Heat resistance

A coating film was formed in the same manner as in the above (3) except that a transparent substrate (Corning 1737 produced by Corning Incorporated) was used instead of the silicon wafer having the silicon oxide film in the above (3), and a proximity photolithography apparatus (UX-1000S manufactured by Usuio Denki Co., Ltd.) Then, a predetermined mask was closely contacted, and exposure was performed using ultraviolet light having a light intensity of 36 mW / cm 2 at 365 nm. Subsequently, the resist film was developed with an alkali developing solution (2.38 mass% or 0.4 mass% tetramethylammonium hydroxide aqueous solution) shown in Table 2 at 23 占 폚 for 60 seconds and rinsed with ultrapure water for 10 seconds. By these operations, a pattern in which a line-and-space of 10 mu m was 1: 1 was produced. The obtained pattern was subjected to front exposure for 100 seconds again and heated at 220 占 폚 for 1 hour in an oven to form a heat cured film on the glass substrate.

The heat resistance was evaluated by measuring the rate of change of the bottom dimension before and after the heat curing (1 - bottom dimension of the heat cured film / bottom dimension after development) x 100 (%).

The evaluation results of the heat resistance are shown in Table 2.

(5) Transmittance and adhesion

A coating film was formed in the same manner as in the above (4), and developed at 23 DEG C for 60 seconds using the alkali developer (2.38 mass% or 0.4 mass% of tetramethylammonium hydroxide aqueous solution) described in Table 2 without exposure, And rinsed with ultrapure water for 10 seconds. Subsequently, the entire surface was exposed for 100 seconds using UV light having a light intensity at 365 nm of 18 mW / cm &lt; 2 &gt; using a proximity photolithography apparatus (UX-1000SM manufactured by Ushio Inc.). Subsequently, the heated cured film was formed on the glass substrate by heating in an oven at 240 캜 for 1 hour.

The transmittance of the obtained thermally cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer (U-3000: Hitachi, Ltd.).

The thermosetting film was cut at intervals of 1 mm vertically and horizontally using a cutter, and a tape peeling test was conducted 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. A case where the area was less than 1% was rated as?, A case where the area was less than 1 to 5% was evaluated as?, And a case where the area was not less than 5% was evaluated as X.

[Example 18]

Using the composition of Example 10, a pattern was formed as follows.

A photosensitive resin composition was coated on a glass substrate having a size of 2,160 x 2,460 mm by a slit and prebaked on a hot plate at 90 캜 for 90 seconds to remove the solvent to form a coating film having a thickness of 3 탆. Subsequently, using an FX-85S (manufactured by Nikon Corporation), an optimum exposure dose was exposed through a mask having a contact hole pattern having a diameter of 15 mu m. After exposure, the substrate was subjected to shower development at 23 DEG C for 60 seconds with a tetramethylammonium hydroxide aqueous solution of 0.4% by mass, and then rinsed with ultrapure water for 1 minute. A pattern was obtained by these operations. The pattern obtained again was exposed to the whole surface and heated at 220 캜 for 1 hour in an oven to form a heat cured film on the glass substrate. As a result of observation with an electron microscope, it was a tapered contact hole pattern having a bottom diameter of 15 mu m.

[Example 19]

A contact hole pattern was produced in the same manner as in Example 18 except that the exposure was changed to a laser having a wavelength of 355 nm. A clean contact hole pattern was obtained in the same manner as in Example 20. The laser device used was "AEGIS" manufactured by Boi Technology Co., Ltd.

The evaluation results of the transmittance and the adhesiveness are shown in Table 2.

The component (A), the component (B), the component (C), the component (D), the basic compound, the solvent and the surfactant described in Table 1 are as follows.

(A) Component

The numerical value on the right side of the structural unit represents the molar ratio of the structural unit.

Component (B)

(C) Component

C1: JER1001 (manufactured by Japan Epoxy Resin Co., Ltd.)

C2: JER834 (manufactured by Japan Epoxy Resin Co., Ltd.)

C3: JER157S70 {manufactured by Japan Epoxy Resin Co., Ltd.}

C4: JER154 (manufactured by Japan Epoxy Resins Co., Ltd.).

(D) Component

D1: gamma -glycidoxypropyltrimethoxysilane

D2:? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane

D3:? -Methacryloxypropyltrimethoxysilane.

[Basic compound]

E1: 4-Dimethylaminopyridine

E2: 1,5-Diazabicyclo [4,3,0] -5-nonene.

〔Surfactants〕

F1: Florad F-430 (manufactured by 3M)

F2: Megapack R-08 (Dainippon Ink Kagakuko Company)

F3: PolyFox PF-6320 (manufactured by OMNOVA)

W-3:

[Sensitizer]

DBA: 9,10-dibutoxyanthracene

From Table 2, it is clear that the positive photosensitive resin composition of the present invention is excellent in sensitivity, residual film ratio and storage stability, and can be cured to form a cured film excellent in heat resistance, adhesiveness and transmittance.

Claims (19)

(A1) a resin which contains a constitutional unit represented by the following general formula (1), is alkali-insoluble or alkali-insoluble and becomes alkali-soluble when the acid-dissociable group is dissociated, (A2) a resin which reacts with a carboxyl group to form a covalent bond A polymer or copolymer having a constituent unit derived from a radically polymerizable monomer containing a functional group capable of reacting with a carboxyl group and (B) a compound generating an acid upon irradiation with an actinic ray, and reacting with the carboxyl group to form a covalent bond Wherein the functional group is an epoxy group or an oxetanyl group.

[In the general formula (1)
R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group.
R ² and R ³ each independently represent a hydrogen atom, a linear or branched alkyl group. Provided that R &lt; ² &gt; and R &lt; ³ &gt; are hydrogen atoms at the same time.
R ⁴ represents a linear, branched or cyclic alkyl or aralkyl group which may be substituted.
R ² or R ³ and R ⁴ may be connected to form a cyclic ether.] The method according to claim 1,
(C) a compound having two or more epoxy groups in a molecule (excluding the above-mentioned A2). delete 3. The method according to claim 1 or 2,
Wherein the component (B) contains a compound containing an oxime sulfonate group represented by the following general formula (2).

[In the general formula (2)
R ⁵ represents a linear, branched, cyclic alkyl group which may be substituted or an aryl group which may be substituted.] 5. The method of claim 4,
Wherein the compound containing an oxime sulfonate group represented by the general formula (2) is a compound represented by the following general formula (2-1).

[In the general formula (2-1)
R ⁵ is the same as R ⁵ in the general formula (2).
X represents a linear or branched alkyl group, an alkoxy group or a halogen atom.
m represents an integer of 0 to 3; When m is 2 or 3, plural Xs may be the same or different.] 5. The method of claim 4,
Wherein the compound containing an oxime sulfonate group represented by the general formula (2) is a compound represented by the following general formula (2-2).

[In the general formula (2-2)
R ⁵ is the same as R ⁵ in the general formula (2).
R ⁶ represents a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cyano group or a nitro group.
and l represents an integer of 0 to 5. When l is 2 or more, plural R ^{6 s} may be the same or different.] 3. The method according to claim 1 or 2,
Wherein the functional group capable of reacting with the carboxyl group to form a covalent bond is an epoxy group. 8. The method of claim 7,
Wherein the radical polymerizable monomer containing a functional group capable of reacting with the carboxyl group to form a covalent bond is a radically polymerizable monomer represented by any one of the following general formulas (3) to (5) .

[In the general formulas (3) to (5)
R ⁷ represents a hydrogen atom, a methyl group or a halogen atom.
Each of R ⁸ to R ¹⁵ independently represents a hydrogen atom or an alkyl group.
X represents a divalent linking group.
and n is an integer of 1 to 10.] 3. The method according to claim 1 or 2,
Wherein the functional group capable of reacting with the carboxyl group to form a covalent bond is an oxetanyl group. 10. The method of claim 9,
Wherein the radical polymerizable monomer containing a functional group capable of reacting with the carboxyl group to form a covalent bond is a radically polymerizable monomer represented by the following general formula (6).

[Wherein,
R ⁷ represents a hydrogen atom, a methyl group or a halogen atom.
R ⁸ to R ¹² each independently represent a hydrogen atom or an alkyl group.
X represents a divalent linking group.
and n is an integer of 1 to 10.] 3. The method according to claim 1 or 2,
(D) an adhesion-promoting agent. 3. The method according to claim 1 or 2,
The component (A2) is a copolymer containing a constituent unit derived from a radically polymerizable monomer containing a functional group capable of reacting with a carboxyl group to form a covalent bond, and a constituent unit represented by the above general formula (1) Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. A positive photosensitive resin composition according to any one of claims 1 to 3, which is applied onto a substrate and dried to form a coating film, a step of exposing the film to an actinic ray through a mask, a step of developing with an alkali developer to form a pattern And a step of heat-treating the obtained pattern. 14. The method of claim 13,
Further comprising the step of performing a front exposure before the step of heat-treating the obtained pattern after the step of forming the pattern by the development using the alkali developing solution. A cured film formed by the cured film forming method according to claim 13. A liquid crystal display element having the cured film according to claim 15. An integrated circuit device having the cured film according to claim 15. A solid-state imaging device having the cured film according to claim 15. An organic EL device having the cured film according to claim 15.