KR101945752B1 - Positive type photosensitive resin composition, method for forming cured film, cured film, liquid crystal display device, and organic el display device - Google Patents

Abstract

The positive photosensitive resin composition of the present invention is a positive photosensitive resin composition which comprises (Component A) a copolymer having at least (a1) a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group, (Component B) (B1) a structural unit having an acid group and (b2) a structural unit having a crosslinkable group, (C) a photoacid generator, and (component D) a solvent.

Description

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

The present invention relates to a positive photosensitive resin composition, a method of forming a cured film, a cured film, a liquid crystal display, and an organic EL display. More particularly, 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, an organic EL display, an integrated circuit element, And a method for forming a cured film.

BACKGROUND ART Electronic components such as thin film transistors (hereinafter referred to as " TFTs ") type liquid crystal display elements, magnetic head elements, integrated circuit elements, solid state image pickup elements, An interlayer insulating film is provided. As the material for forming the interlayer insulating film, it is preferable that the number of steps for obtaining a necessary pattern shape is small and further it is desired to have a flatness, and thus a photosensitive resin composition is widely used (see Patent Documents 1 and 2).

Among the above electronic components, for example, in a TFT type liquid crystal display device, a transparent electrode film (ITO) is formed on the interlayer insulating film and a wiring made of a metal such as molybdenum (Mo) or titanium (Ti) And the liquid crystal alignment film is formed. Therefore, the interlayer insulating film can be exposed to high-temperature conditions in the process of forming the transparent electrode film, or can be removed in the form of a stripping liquid of a resist used for pattern formation of an electrode, And is exposed to the NMP (N-methylpyrrolidone) used, so that sufficient resistance to these is required.

In addition, when the interlayer insulating film has poor adhesion to the transparent electrode film or the wiring (metal) formed thereon, the display of the panel tends to be defective, and adhesion with the transparent electrode film or wiring is also required. Since the interlayer insulating film may be subjected to a dry etching process, sufficient resistance to dry etching is required (see Patent Document 2 and Patent Document 3).

As a high sensitive photosensitive resin composition for an interlayer insulating film, for example, Patent Document 4 discloses a resin composition containing (A1) a resin containing a structural unit having an acid-dissociable group, (A3) a resin containing a structural unit having an epoxy group or an oxetane group, (A1) a resin containing a structural unit having an acid-dissociable group, (A2) a resin containing a structural unit having an acid-dissociable group, and (A2) a resin containing an acid- ), A resin containing a structural unit having an epoxy group or an oxetane group, and (B) a compound which generates an acid upon irradiation with an actinic ray or radiation.

Patent Document 5 discloses a resin composition comprising (A1) a resin containing a structural unit having an acid-dissociable group, (A2) a polymer or copolymer having a structural unit derived from an epoxy group-containing radical polymerizable monomer, (B) A compound having an epoxy group and (C) a compound capable of generating an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more.

In Patent Document 6, (A) a norbornene compound having an acetal structure or a ketal structure, (meth) acrylic ester compound having an acetal or ketal structure, (a2) a structural unit having a specific crosslinking group, And (a3) a copolymer comprising an olefinically unsaturated compound other than (a1) and (a2), (B) a radiation sensitive resin composition for forming an interlayer insulating film containing a compound capable of generating an acid having a pKa of 4.0 or less by irradiation with radiation A resin composition has been proposed.

Japanese Patent Application Laid-Open No. 2001-354822 Japanese Patent Application Laid-Open No. 2000-241832 Japanese Patent Application Laid-Open No. 2005-345757 Japanese Patent No. 4637221 Japanese Patent No. 4676542 Japanese Patent No. 4207604

However, in the photosensitive resin compositions proposed in Patent Documents 4 to 6, there is a problem that resistance to a resist remover or N-methyl pyrrolidone (NMP) used after formation of an interlayer insulating film is not high, The adhesion to metal is poor, and the resistance to dry etching is not high. Therefore, defective display in a liquid crystal display device tends to occur, and improvement has been demanded.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to solve the following problems.

That is, a problem to be solved by the present invention is to provide a high sensitivity, high resistance to a peeling liquid or NMP, good adhesion to a transparent electrode film or metal, and excellent dry etching resistance, A cured film obtained by curing the photosensitive resin composition, a method for forming the cured photosensitive resin composition, and an organic EL display device and a liquid crystal display device provided with the cured film.

The above object of the present invention has been solved by the means described in the following <1>, <12>, <15>, <17> or <18>. <2> to <11>, <13>, <14> and <16> which are preferred embodiments are described below.

&Lt; 1 > (Component A) a copolymer having at least (a1) a structural unit having a residue protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group, (Component B) (Component B) having a structural unit having (b1) an acid group and (b2) a structural unit having a crosslinkable group, (C) a photoacid generator, and A positive photosensitive resin composition,

<2> The positive photosensitive resin composition according to <2>, wherein the structural unit (a1) is a structural unit having a carboxyl group in a form of acetal or ketal protected moiety,

<3> The positive photosensitive resin composition according to <1> or <2>, wherein the structural unit (a1) is a structural unit represented by formula (a1-1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, R ² and R ³ may be connected to form a ring.)

<4> The positive photosensitive resin composition according to any one of <1> to <3>, wherein the structural unit (a2) is a structural unit having an epoxy group and / or an oxetanyl group,

<5> The positive photosensitive resin composition according to any one of <1> to <5>, wherein the acid group of the structural unit (b1) is a carboxyl group or a phenolic hydroxyl group.

<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein the structural unit (b2) is a structural unit having an epoxy group and / or an oxetanyl group.

<7> The positive photosensitive resin composition according to any one of <1> to <6>, wherein the component B further comprises a structural unit represented by the formula (b3)

(Wherein R ⁴ represents a hydrogen atom or a methyl group).

<8> The positive-electrode active material according to any one of <1> to <7>, wherein the weight ratio of the content W _A of the component A to the content W _B of the component B is W _A / W _B = 98/2 to 20/80. Photosensitive resin composition,

<9> The positive photosensitive resin composition according to any one of <1> to <8>, wherein the component C is the oxime sulfonate photoacid generator represented by the formula (c1)

(In the formula (c1), R ⁵ and R ⁶ each independently represent a monovalent organic group, R ⁵ and R ⁶ may be connected to form a ring, and R ⁷ represents an alkyl group, a cycloalkyl group or an aryl group. )

<10> The compound according to any one of <1> to <9>, wherein the component C is a compound represented by the formula (OS-3), formula (OS-4), formula (OS- The positive-working photosensitive resin composition,

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ² each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ¹ represents an alkyl group, an aryl group or a heteroaryl group, ⁶ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents 0 to 6 Represents an integer.)

(Wherein R ^B1 represents an alkyl group, an alkoxy group or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.)

<11> The positive photosensitive resin composition according to any one of <1> to <10>, further containing a photosensitizer,

(1) a layer forming step of forming a film-like layer on a substrate by using the positive photosensitive resin composition according to any one of (1) to (11); (2) A solvent removing step of removing the solvent from the composition, (3) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray, (4) a developing step of developing the exposed photosensitive resin composition by an aqueous developer, and 5) a method of forming a cured film including a post-baking step of thermally curing the developed photosensitive resin composition,

<13> The method for forming a cured film according to <12> above, which comprises a step of exposing the developed photosensitive resin composition to the whole surface after the development step and before the post-baking step,

<6> A method for forming a cured film according to <12> or <13>, further comprising a dry etching step of performing dry etching on a substrate having a cured film obtained by thermosetting,

<15> A cured film formed by the method according to any one of <12> to <14>

<16> The cured film according to <15>, which is an interlayer insulating film,

<17> An organic EL display device comprising the cured film according to <15> or <16>

<18> A liquid crystal display device comprising the cured film according to <15> or <16>.

According to the present invention, it is possible to obtain a cured film having high sensitivity, high resistance to peeling liquid and NMP, good adhesiveness to transparent electrode film and metal, excellent dry etching resistance, A cured film obtained by curing the photosensitive resin composition, a method for forming the cured film, and an organic EL display device and a liquid crystal display device provided with the cured film.

Fig. 1 shows a configuration diagram of 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 planarization film 4.
2 is a conceptual diagram showing an example of the configuration of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.

Hereinafter, the present invention will be described in detail.

In the specification, the description of "lower limit to upper limit" indicates "lower limit and higher limit," and the description of "upper limit to lower limit" indicates "upper limit or lower limit. That is, a numerical range including an upper limit and a lower limit.

A "copolymer having (a1) a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group" is referred to simply as "component A" (a1) a structural unit in which the acid group has a residue protected by an acid-decomposable group "and the like are simply referred to as" structural unit (a1) ".

Further, the term "(meth) acrylate" refers to both "acrylate" and "methacrylate", and "(meth) acrylate" , Respectively.

(Positive photosensitive resin composition)

The positive photosensitive resin composition of the present invention (hereinafter also simply referred to as &quot; photosensitive resin composition &quot;) is a composition comprising (Component A) at least (a1) a structural unit having an acid group protected with an acid- decomposable group and (a2) (B) a copolymer having at least (a1) a constituent unit having an acidic group (b1) and a constituent unit having a crosslinkable group (b2) without a constituent unit having an acid- , (Component C) a photoacid generator, and (Component D) a solvent.

The photosensitive resin composition of the present invention is excellent in sensitivity because it contains two specific resin components (component A and component B) and a photoacid generator. In addition, the photosensitive resin composition of the present invention contains a specific resin component and a photoacid generator, so that it has high resistance to a peeling liquid, especially a peeling liquid containing monoethanolamine or NMP, It is possible to form a cured film which is excellent in adhesion and is also excellent in dry etching resistance and which hardly causes defective display even in a display device.

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

Further, the photosensitive resin composition of the present invention can be suitably used as a positive photosensitive resin composition for a dry etching resist.

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

The method of introducing the constituent unit contained in the copolymer such as the component A or the component B used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. In the polymer reaction method, a necessary functional group is introduced into the constituent unit by using a reactive group contained in the constituent unit of the obtained copolymer after the polymerization reaction. Examples of the functional group include a protecting group for protecting an acidic group such as a carboxyl group or a phenolic hydroxyl group and decomposing in the presence of strong acid to liberate them, a crosslinkable group such as an epoxy group or an oxetanyl group, And an alkali-soluble group (acid group) such as a carboxyl group.

(Component A) A composition comprising at least (a1) a copolymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group

The positive photosensitive resin composition of the present invention comprises (A) a copolymer having at least (a1) a structural unit having an acid group-protected residue with an acid-decomposable group and (a2) a structural unit having a crosslinkable group.

The constituent unit (a1) and the constituent unit (a2) may be the same constituent unit, but are preferably different constituent units.

Component A is preferably an alkali-insoluble resin that becomes alkali-soluble when the acid-decomposable group decomposes. Here, the "acid-decomposable group" means a functional group decomposable in the presence of an acid. "Alkali solubility" means that a coating solution (thickness: 3 μm) formed by applying a solution of a compound (resin) on a substrate and heating at 90 ° C. for 2 minutes is coated with 0.4 wt% tetramethylammonium hydroxide Means that the dissolution rate in an aqueous solution is 0.01 m / sec or more. On the other hand, "alkali insoluble" means that the dissolution rate is less than 0.01 μm / sec. It is more preferable that the alkali dissolution rate of the component A is less than 0.005 탆 / sec.

The component A is preferably an addition polymerization type resin, more preferably a polymer containing a (meth) acrylic acid and / or a structural unit derived from the ester thereof. Component A may also contain structural units other than the structural units derived from (meth) acrylic acid and / or esters thereof, for example, structural units derived from styrene or vinyl compounds.

The component A preferably contains 50 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more of monomer units derived from (meth) acrylic acid and / Or more, and particularly preferably 100 mol% or less.

The method of introducing the constituent unit contained in the component A may be a polymerization method, a polymer reaction method, or a combination of these two methods.

In the polymerization method, for example, an ethylenically unsaturated compound having an acid group-protected residue with an acid-decomposable group and an ethylenically unsaturated compound having a crosslinking group, an ethylenically unsaturated compound having a carboxyl group and / or a phenolic hydroxyl group, To obtain a desired copolymer.

In the polymer reaction method, epichlorohydrin may be reacted with a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate to introduce an epoxy group. As described above, after the ethylenically unsaturated compound having a reactive group is copolymerized, a reactive group remaining in the side chain is utilized to form a functional group such as a residue protected with an acid-decomposable group by a phenolic hydroxyl group or a carboxyl group and / Can be introduced into the side chain.

&Lt; Structural unit (a1) >

Component A has at least (a1) a constituent unit having a residue whose acid group is protected with an acid-decomposable group. By having the constituent unit (a1) in the component A, a photosensitive resin composition with extremely high sensitivity can be obtained.

The "residue in which an acid group is protected with an acid-decomposable group" in the present invention means a residue in which a carboxyl group is protected in the form of an acetal, a residue in which an acid group is protected in a ketal form, a residue in which an acid group is protected with a tertiary alkyl group, And the acid group is a residue protected with a tertiary alkylcarbonate group.

As the acid group, a carboxyl group and a phenolic hydroxyl group are preferably exemplified.

Specific examples of the residue of the acid group protected with an acid-decomposable group include esters of a group represented by the formula (A1) described below, acetal such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group Or a tertiary alkyl-based functional group such as a ketal-based functional group, a t-butyl ester group, and a t-butylcarbonate group.

(a1-1) a structural unit having a carboxyl group protected with an acid-decomposable group

The constituent unit in which the carboxyl group has a moiety protected by an acid-decomposable group is preferably a moiety in which the carboxyl group contained in the constituent unit described in (a1-1-1) or (a1-1-2) described later is protected by an acid- .

As the acid decomposable group, known ones can be used as the acid decomposable group in the positive resist for KrF and the positive resist for ArF, and there is no particular limitation. Examples of the acid decomposable group include groups which are relatively easily decomposable by an acid (for example, acetal functional groups such as tetrahydropyranyl group and ethoxyethyl group) and groups which are relatively difficult to decompose by an acid (for example, t-butyl ester group , t-butyl-based functional groups such as t-butyl carbonate groups) are known. As the structural unit (a1-1), a structural unit in which a carboxyl group is protected in the form of an acetal or a residue in which a carboxyl group is protected in the form of a ketal is preferable from the viewpoint of sensitivity, pattern shape, and formability of a contact hole.

Among the acid decomposable groups, from the viewpoint of sensitivity, the carboxyl group is a protected residue in the form of an acetal or ketal represented by the formula (A1). When the carboxy group is a protected residue in the form of an acetal or ketal represented by the formula (A1), the moiety has a structure of -C (= O) -O-CR ¹ R ² (OR ³ ) .

Wherein at least one of R ¹ and R ² is an alkyl group or an aryl group and R ³ is an alkyl group or an aryl group, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group, or an aryl group, , Or an aryl group, and R ¹ or R ² and R ³ may be connected to form a cyclic ether. The broken line portion in the formula (A1) represents a bonding position with another structure .)

In the formula (A1), the alkyl group in R ¹ , R ² and R ³ may be any of linear, branched or cyclic.

The straight chain or branched chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec- Butyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group. Among them, a methyl group and an ethyl group are preferable.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group. Among them, a monocyclic one is preferable, and a cyclohexyl group is more preferable.

The alkyl group may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an aryl group having 6 to 20 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. When R ¹ , R ² and R ³ are a haloalkyl group, and when they have an aryl group as a substituent, R ¹ , R ² and R ³ are an aralkyl group when they have a halogen atom as a substituent. As the aralkyl group, a benzyl group is preferable.

In the formula (A1), the aryl group in R ¹ , R ² and R ³ preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms can be preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned, and a phenyl group is preferable.

In formula (A1), R ¹ , R ² and R ³ may bond to each other to form a ring by being bonded to the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, and a tetrahydropyranyl group.

In formula (A1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.

As the radically polymerizable monomer used for forming the constituent unit having a moiety represented by the formula (A1), commercially available ones may be used, and for example, a method described in paragraphs 0025 to 0026 of JP 2009-098616 A , Etc., may be used.

As the structural unit (a1-1) having a carboxyl group protected by an acid-decomposable group, the structural unit represented by the formula (A2) is more preferable.

(In the formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ is an alkyl group or an aryl group , R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

In the formula (A2), R ¹ to R ³ are the same as R ¹ to R ³ in the formula (A1), and the preferable range is also the same.

In formula (A2), R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. R ³ is preferably a straight chain, branched chain or cyclic alkyl group having 6 or less carbon atoms or an aralkyl group having 7 to 10 carbon atoms, more preferably an ethyl group, a cyclohexyl group or a benzyl group. The cyclic ether to which R ¹ or R ² and R ³ are connected is preferably a tetrahydropyranyl group or a tetrahydrofuranyl group. R ⁴ is preferably a methyl group. X is preferably a single bond or a phenylene group.

Specific preferred examples of the structural unit (a1-1) include the following structural units. R represents a hydrogen atom or a methyl group.

As the structural unit (a1-1), the carboxyl group may be a structural unit having a residue protected by a tertiary alkyl group represented by the formula (A3). Compared with the protected residue in the form of acetal or ketal, the sensitivity is lower, but it is preferable from the viewpoint of excellent storage stability. Further, when the carboxy group is a residue protected by a tertiary alkyl group represented by the formula (A3), the whole of the moiety is a structure of -C (= O) -O-CR ¹ R ² R ³ .

In formula (A3), R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring. The broken line part in the formula (A3) represents a bonding position with another structure. Specific examples of the alkyl group and the aryl group in R ¹ to R ³ in the formula (A3) are the same as the specific examples of the alkyl group and the aryl group in the formula (A1).

In formula (A3), preferred examples include a combination of R ¹ = R ² = R ³ = methyl group, a combination of R ¹ = R ² = methyl group and R ³ = benzyl group.

(a1-2) a structural unit having a phenolic hydroxyl group protected with an acid-decomposable group

(a1-2) As the constituent unit in which the phenolic hydroxyl group has a moiety protected by an acid-decomposable group, the phenolic hydroxyl group of the constituent unit having a phenolic hydroxyl group (a1-2-1) A constituent unit is preferable.

(a1-2-1) a structural unit having a phenolic hydroxyl group

Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolak-based resin. Among these structural units, a structural unit derived from -methylhydroxystyrene is preferable from the viewpoint of transparency desirable. Among the constituent units having a phenolic hydroxyl group, the constituent unit represented by the formula (A4) is preferable from the viewpoints of transparency and sensitivity.

(In the formula (A4), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² independently represents a halogen atom or an alkyl group, a represents an integer of 1 to 5, , B represents an integer of 0 to 4, and a + b is 5 or less.

R ²⁰ is preferably a methyl group.

Examples of the divalent linking group of R ²¹ include an ester bond (-COO-) in which a carbon atom is bonded to a main chain (main chain), and an alkylene group. As the alkylene group, an alkylene group having 1 to 6 carbon atoms having a straight chain or a branch is preferable. -COO-, it is preferable since the sensitivity can be improved and the transparency of the cured film can be improved. Among them, R ²¹ is preferably a single bond or an ester bond. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

A represents an integer of 1 to 5, but a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of easy production.

It is preferable that the bonding position of the hydroxyl group in the benzene ring is bonded to the 4-position when the carbon atom bonded to R ²¹ is the reference (1 position).

R ²² is a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, it is preferably a chlorine atom, a bromine atom, a methyl group or an ethyl group because of easy production.

(a1-2) a structural unit having a phenolic hydroxyl group protected with an acid-decomposable group

The constituent unit in which the phenolic hydroxyl group has a moiety protected by an acid-decomposable group is a constituent unit in which the phenolic hydroxyl group of the constituent unit having a phenolic hydroxyl group (a1-2-1) has a moiety protected by an acid-decomposable group.

As the acid decomposable group, known ones can be used as described above, and there is no particular limitation.

Among the residues in which the phenolic hydroxyl group is protected by an acid-decomposable group, the phenolic hydroxyl group is a structural unit having a protected moiety in the form of an acetal or a ketal. The basic properties of the resist, particularly the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, And is preferable from the viewpoint of hole forming ability. Among the residues in which the phenolic hydroxyl group is protected by an acid-decomposable group, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected residue in the form of an acetal or ketal represented by the formula (A1). In this case, the whole of the moiety has a structure of -Ar-O-CR ¹ R ² (OR ³ ). Ar represents an arylene group.

As preferred examples of the acetal ester structure of the phenolic hydroxyl group, a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group and R ³ = benzyl group can be exemplified.

Examples of the radically polymerizable monomer used for forming a monomer unit having a phenolic hydroxyl group in the form of an acetal or ketal protected moiety include a 1-alkoxyalkyl protected product of hydroxystyrene, a tetra A tetrahydrofuranyl protecting agent of? -Methylhydroxystyrene, a tetrahydrofuranyl protecting agent of? -Methylhydroxystyrene, a tetrahydrofuranyl protecting agent of? -Methylhydroxystyrene, a tetrahydrofuranyl protecting agent of? Hydroxyphenyl methacrylate, a tetrahydrofuranyl protected derivative of 4-hydroxyphenyl methacrylate, a tetrahydrofuranyl protected derivative of 4-hydroxyphenyl methacrylate, etc., . Among these, a 1-alkoxyalkyl protected product of? -Methylhydroxystyrene or a tetrahydrofuranyl protected product of? -Methylhydroxystyrene is preferable.

Specific examples of the acetal protecting group and ketal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, , 1-cyclohexyloxyethyl group, 1- (2-cyclohexyloxy) ethyl group, 1- (2-ethylhexyloxy) , A 1-benzyloxyethyl group, a tetrahydropyranyl group, and a tetrahydrofuranyl group, and among them, a 1-ethoxyethyl group or a tetrahydrofuranyl group is preferable. These may be used alone or in combination of two or more.

The radically polymerizable monomer used for forming the structural unit (a1-2) may be a commercially available one, or a compound synthesized by a known method may be used. For example, by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The above-mentioned synthesis may be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with another monomer, and then reacting with a vinyl ether in the presence of an acid catalyst.

Specific preferred examples of the structural unit (a1-2) include the following structural units, but the present invention is not limited thereto. R represents a hydrogen atom or a methyl group.

A constituent unit in which a carboxyl group has a moiety protected with an acid-decomposable group has a faster phenomenon than a constituent unit in which the phenolic hydroxyl group has a moiety protected with an acid-decomposable group. Therefore, when a rapid development is desired, a constitutional unit in which the carboxyl group has a residue protected by an acid-decomposable group is preferable. Conversely, when it is desired to slow the development, it is preferable to use a constitutional unit having a phenolic hydroxyl group having a residue protected by an acid-decomposable group.

Among them, the structural unit (a1) is preferably a structural unit represented by the following formula (a1-1) from the viewpoint of sensitivity.

(In the formula (a1-1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms , And R ² and R ³ may be connected to form a ring.)

In the formula (a1-1), it is preferable that R ¹ is a methyl group.

In formula (a1-1), R ² is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

In formula (a1-1), R ³ is preferably an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, more preferably an ethyl group or a cyclohexyl group.

In the formula (a1-1), when R ² and R ³ are connected to form a ring, the group to which R ² and R ³ are connected is preferably an alkylene group having 3 to 6 carbon atoms, and the 1,3- Or a 1,4-butylene group.

The content of the monomer unit constituting the constituent unit (a1) is preferably 10 to 80 mol%, more preferably 10 to 70 mol%, and particularly preferably 20 to 70 mol%, in all the monomer units constituting the component A, desirable. By containing the structural unit (a1) in the above ratio, a highly sensitive photosensitive resin composition can be obtained.

&Lt; Structural unit (a2) >

Component A has at least (a2) a structural unit having a crosslinkable group.

As the crosslinkable group, any of those which form a covalent bond by reacting with the above-mentioned acid group, and those which form a covalent bond by the action of heat or light between the crosslinkable groups. It is particularly desirable to form covalent bonds with heat.

As the structural unit (a2) having a crosslinkable group which reacts with an acid group to form a covalent bond, a structural unit having a group having an epoxy group, an oxetanyl group or an N-alkoxymethyl group is preferable, and the crosslinkable groups are shared by heat or light Ethylenically unsaturated bonds are preferred as forming bonds. Among these crosslinkable groups, it is preferable to react with an acid group to form a covalent bond.

The crosslinkable group is preferably a structural unit having an epoxy group or an oxetanyl group, and is preferably contained in the component A. As the structural unit (a2), both groups of an epoxy group and an oxetanyl group may be contained, and three kinds of groups such as an epoxy group, an oxetanyl group and an ethylenic unsaturated bond may be contained.

The structural unit having an epoxy group or an oxetanyl group is preferably a structural unit having an alicyclic epoxy group or an oxetanyl group, more preferably a structural unit having an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring. Specific examples thereof include 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3-epoxycyclopentyl group and the like Can be preferably used.

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

The structural unit having an epoxy group or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, may contain at least one epoxy group and at least one oxetanyl group, and may contain two or more epoxy groups, Or may have two or more oxetanyl groups, and it is not particularly limited, but it is preferable that a total of 1 to 3 epoxy groups and oxetanyl groups are present, more preferably 1 or 2 epoxy groups and oxetanyl groups in total , And more preferably one epoxy group and oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicumyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, Heptyl,? -Ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- vinylbenzyl glycidyl ether, paragraphs of Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton described in Nos. 0031 to 0035, and the like.

Examples of the radical polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meta) acrylic acid esters having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953 .

Examples of the radically polymerizable monomer used for forming the constituent unit having an epoxy group or an oxetanyl group are preferably a monomer containing a methacrylic acid ester structure or a monomer containing an acrylic ester structure.

Of these radically polymerizable monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953 (Meth) acrylic acid ester having an oxetanyl group, and particularly preferred is a (meth) acrylic acid ester having an oxetanyl group as described in paragraphs 0011 to 001 of Japanese Patent Application Laid-Open No. 2001-330953. Among these, preferred are acrylic esters such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethacrylate, acrylic acid (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These constituent units may be used singly or in combination of two or more.

As the crosslinkable group, an N-alkoxymethyl group is preferable, and an N-alkoxymethylamide group is more preferable. As the constituent unit having an N-alkoxymethyl group, a constituent unit represented by the following formula (a2-1) is preferable.

(Wherein R ^a1 represents a hydrogen atom or a methyl group, R ^a2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ^a3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms , Or an aryl group having 6 to 20 carbon atoms.

R ^a1 in the formula (a2-1) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

In the formula (a2-1), R ^a2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group may be substituted. Examples of the substituent include a halogen atom, a hydroxyl group, , And cyano group. R ^a2 is more preferably a methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, s-butyl group, cyclohexyl group or n-hexyl group, an i-butyl group, a cyclohexyl group or an n-hexyl group is more preferable, and a methyl group, an n-butyl group or an i-butyl group is particularly preferable.

In the formula (a2-1), R ^a3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl or aryl group may be substituted. Examples of the substituent include a halogen atom, , A nitro group, a cyano group, and an alkoxy group having 1 to 20 carbon atoms. R ^a3 is more preferably a hydrogen atom or an alkoxymethyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

Examples of the radical polymerizable monomer used for forming the structural unit represented by the formula (a2-1) include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Nn- Butoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide are preferable, and Nn-butoxymethyl (meth) acrylamide and Ni- Particularly preferred is methoxymethylacrylamide.

As specific preferred examples of the structural unit (a2), the following structural units can be exemplified.

From the viewpoint of sensitivity, the content ratio of the monomer unit constituting the constituent unit (a2) in the component A is preferably from 10 to 70 mol%, more preferably from 15 to 65 mol%, based on all the monomer units constituting the component A. [ , And more preferably 20 to 60 mol%.

The content ratio of the monomer unit forming the constituent unit (a2) in the component A is preferably from 10 to 70 mol% based on all the monomer units constituting the component A from the viewpoints of adhesion, resistance to resist stripping solution and NMP, , More preferably from 10 to 60 mol%, further preferably from 10 to 50 mol%.

&Lt; Other structural unit (a3) >

The component A may further contain another structural unit (a3) within the range not hindering the effect of the present invention.

Examples of the radical polymerizable monomer used for forming the structural unit (a3) include the compounds described in paragraphs 0021 to 0024 of JP 2004-264623 A (however, the structural unit (a1) And (a2) are excluded).

From the viewpoint of sensitivity, it is preferable that the component A further has a structural unit having an acid group as the structural unit (a3).

As the acid group, a structural unit having a carboxyl group and / or a phenolic hydroxyl group is more preferable, and a structural unit having a carboxyl group is more preferable.

The structural unit (a3) is preferably a structural unit derived from at least one member selected from the group consisting of acrylic acid, methacrylic acid, p-hydroxystyrene, and -methyl-p-hydroxystyrene, More preferably a structural unit derived from methacrylic acid, and particularly preferably a structural unit derived from methacrylic acid.

Preferable examples of the structural unit (a3) include a structure derived from at least one member selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, N-substituted maleimide, and (meth) And the like.

Among these, from the viewpoint of improvement of the electrical characteristics, it is preferable to use (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylic acid esters containing an alicyclic structure such as methyl (meth) acrylate, isopropyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-methylcyclohexyl Monomers are preferred.

From the viewpoint of sensitivity, 2-hydroxyethyl (meth) acrylate and N-substituted maleimide are preferable. Of these, (meth) acrylic acid esters having an alicyclic structure are more preferable. From the viewpoint of etching resistance, styrenes such as styrene and? -Methylstyrene are preferable.

These structural units (a3) may be used alone or in combination of two or more.

The content of the monomer unit forming the constituent unit (a3) in the case of containing the constituent unit (a3) among all the monomer units constituting the component A is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol% , And particularly preferably from 5 to 30 mol%.

The weight average molecular weight of component A in the present invention is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, even more preferably 4,000 to 30,000, and particularly preferably 10,000 to 16,000. The weight average molecular weight in the present invention is preferably a polystyrene reduced weight average molecular weight determined by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

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

The content of the component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, more preferably 30 to 95% by weight, more preferably 30 to 70% by weight based on the total solid content of the photosensitive resin composition. Is more preferable. When the content is within this range, the pattern forming property upon development becomes good. The solid content of the photosensitive resin composition means an amount excluding a volatile component such as a solvent.

(Component B) A copolymer having an acid group having no structural unit having a residue protected by an acid-decomposable group and at least a structural unit having (b1) an acid group and (b2) a structural unit having a crosslinkable group

The positive photosensitive resin composition of the present invention is characterized in that, in addition to the component A, (B) the acid group does not have a structural unit having a residue protected by an acid-decomposable group and the structural unit having at least (b1) an acid group and (b2) And a structural unit having a structural unit represented by the following general formula (1).

Component B has no structural unit having an acid-decomposable group-protected residue, which is the structural unit (a1) in Component A,

The constituent unit (b1) and the constituent unit (b2) may be the same constituent unit, but are preferably different constituent units.

Component B is preferably alkali-soluble.

Component B is preferably an addition polymerization type resin, more preferably a polymer containing a constituent unit derived from (meth) acrylic acid and / or an ester thereof. Component A may also contain structural units other than the structural units derived from (meth) acrylic acid and / or esters thereof, for example, structural units derived from styrene or vinyl compounds.

The component B preferably contains 50 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more of monomer units derived from (meth) acrylic acid and / Or more, and particularly preferably 100 mol% or less.

The method of introducing the constituent unit contained in the component B may be either a polymerization method like the component A, a polymer reaction method, or a combination of these two methods.

&Lt; Construction unit (b1) >

Component B has at least (b1) a structural unit having an acid group.

As the constituent unit (b1), a constituent unit having a carboxyl group and / or a phenolic hydroxyl group is more preferable, and a constituent unit having a carboxyl group is more preferable.

Examples of the radically polymerizable monomers used for forming the constituent unit having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; And unsaturated carboxylic acids such as dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid.

As the radical polymerizable monomer used for forming the constituent unit having a carboxylic acid anhydride moiety, for example, maleic anhydride, itaconic anhydride and the like are preferably used.

Examples of the radical polymerizable monomer used for forming the constituent unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and? -Methyl-p-hydroxystyrene, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4 - addition reaction product of hydroxybenzoic acid and glycidyl acrylate, and the like.

Of these, methacrylic acid, acrylic acid, compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, 4- Addition reaction products of hydroxybenzoic acid and glycidyl methacrylate, and addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate are more preferred, and compounds described in paragraphs 0011 to 001 of Japanese Patent Application Laid-Open No. 2008-40183, Hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Patent Publication No. 2888454, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate More preferably a structural unit derived from at least one member selected from the group consisting of acrylic acid, methacrylic acid, p-hydroxystyrene, and? -Methyl-p-hydroxystyrene, And that the constituent unit derived from acrylic acid or methacrylic acid, more preferably, it is a structural unit derived from methacrylic acid are particularly preferred. These constituent units may be used singly or in combination of two or more.

As specific preferred examples of the structural unit (b1), the following structural units can be exemplified.

Among them, the structural unit (b1) is preferably (b1-1), (b1-2), (b1-11) or (b1-12) , More preferably (b1-1).

&Lt; Construction unit (b2) >

Component B has at least (b2) a structural unit having a crosslinkable group.

As the crosslinkable group, any of those which form a covalent bond by reacting with the above-mentioned acid group, and those which form a covalent bond by the action of heat or light between the crosslinkable groups.

The constituent unit (b2) in the component B is synonymous with the constituent unit (a2) in the constituent A, and the preferred embodiment is also the same.

From the viewpoint of sensitivity, the content ratio of the monomer unit constituting the constituent unit (b1) in the component B is preferably from 5 to 50 mol%, more preferably from 5 to 45 mol%, based on all monomer units constituting the component B, , And more preferably 5 to 40 mol%.

The content ratio of the monomer unit forming the constituent unit (b2) in the component B is preferably from 10 to 90 mol% based on the total monomer units constituting the component B from the viewpoints of adhesion, resistance to resist stripping solution and NMP, , More preferably from 15 to 85 mol%, still more preferably from 20 to 80 mol%.

&Lt; Other structural unit (b3) >

The component B may further contain another structural unit (b3) within the range not hindering the effect of the present invention.

Examples of the radical polymerizable monomer used for forming the constituent unit (b3) include the compounds described in paragraphs 0021 to 0024 of JP 2004-264623 A (however, the above-mentioned constituent unit (b1) And (b2), and structural units having an acid-decomposable group-protected residue).

The above-mentioned radically polymerizable monomer may be used as the structural unit (a3) in the component A.

As the radical polymerizable monomer used for forming the structural unit (b3), styrene such as styrene or? -Methylstyrene is preferable, and styrene or? -Methylstyrene is more preferable from the viewpoint of etching resistance.

Further, from the viewpoint of the etching resistance, the component B preferably further comprises a structural unit represented by the following formula (b3). R ⁴ is preferably a hydrogen atom.

(Wherein R ⁴ represents a hydrogen atom or a methyl group).

Examples of the structural unit (b3) include structural units derived from at least one member selected from the group consisting of (meth) acrylic acid esters, styrenes, and N-substituted maleimides, and (meth) acrylic acid And a structural unit derived from at least one member selected from the group consisting of esters, styrenes, and the like.

Among them, examples of the radically polymerizable monomer used for forming the structural unit (b3) include (meth) acrylic esters having an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl acrylate (Meth) acrylate, 2-hydroxyethyl (meth) acrylate and styrene, and more preferably methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and styrene And methyl (meth) acrylate can be more preferably exemplified, and methyl methacrylate is particularly preferably exemplified.

The structural unit (b3) may be used alone or in combination of two or more.

The content of the monomer unit constituting the constituent unit (b3) in the case where the constituent unit (b3) is contained among all the monomer units constituting the component B is from 1 to 60 mol% , More preferably 3 to 55 mol%, and still more preferably 5 to 50 mol%.

The weight average molecular weight of Component B in the present invention is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, even more preferably 4,000 to 30,000, and particularly preferably 10,000 to 16,000. The weight average molecular weight in the present invention is preferably a polystyrene reduced weight average molecular weight determined by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

Component B may be used alone or in combination of two or more.

The content of the component B in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, more preferably 30 to 95% by weight, more preferably 30 to 70% by weight based on the total solid content of the photosensitive resin composition. Is more preferable. When the content is within this range, the pattern forming property upon development becomes good.

The content ratio of the component A and the component B in the photosensitive resin composition of the present invention is preferably 0.5 to 2 (content of component A) / (content of component B), more preferably 0.8 to 1.2 And more preferably 0.9 to 1.1. Within the above range, the effect of the present invention can be exerted more.

In the photosensitive resin composition of the present invention, resins other than the component A and the component B may be used in combination within a range not hindering the effect of the present invention. It is preferable that the content of the resin other than the component A and the component B is smaller than the content of the component A and the content of the component B from the viewpoint of developability.

As the resin other than the component A and the component B, a resin having a carboxyl group in the side chain is preferable. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Laid-Open No. 59-53836, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc. described in the respective publications of JP-A No. 59-71048, An acidic cellulose derivative having a carboxyl group, an acid anhydride added to a polymer having a hydroxyl group, and the like, and a polymer having a (meth) acryloyl group in its side chain is also preferable.

In addition to the above, there may be mentioned 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxy Propyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydro Hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

In addition, Japanese Patent Application Laid-Open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224 A publicly known polymer compound described in JP-A-2000-56118, JP-A-2003-233179, JP-A-2009-52020, etc. can be used.

In addition to the above, the resin other than the component A and the component B may be a resin having a part of the constituent units (a1), (a2), (a3), (b1), (b2) and (b3). These resins include, for example, a resin comprising only the constituent unit (a1) and a resin comprising only the constituent unit (a3).

These resins other than the component A and the component B may contain only one kind or two or more kinds of resins.

(Component C)

The photosensitive resin composition of the present invention contains (Component C) photoacid generator.

The component C is preferably a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but is not limited to the chemical structure thereof. Also, in the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer can be preferably used in combination with a sensitizer have.

As the component C, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, and a photoacid generator that generates an acid with a pKa of 3 or less is more preferable.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds . Of these, oxime sulfonate compounds are preferably used from the viewpoint of high sensitivity. These photoacid generators may be used alone or in combination of two or more.

Specific examples thereof include the following.

As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan- (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methylphenyl) ethenyl] -bis Naphthyl) -bis (4,6-trichloromethyl) -s-triazine and the like.

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyl iodonium trifluoromethane sulfonate, 4-methoxy (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, phenyl 4- (2'-hydroxy-1'- -Tetradecaoxy) phenyl iodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-tetradecaoxy) phenyl iodonium p-toluenesulfonate.

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

Examples of the quaternary ammonium salts include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) (P-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, and the like can be used. .

Diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like.

As the imide sulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-ene-dicarboxyimide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate , N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidopropane sulfonate, and the like.

The photosensitive resin composition of the present invention preferably contains, as the (C) photoacid generator, an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following formula (c0). In addition, the broken line indicates the bonding position with other chemical structures.

The oxime sulfonate compound having at least one of the oxime sulfonate moieties represented by the formula (c0) is preferably a compound represented by the following formula (c1).

(In the formula (c1), R ⁵ and R ⁶ each independently represent a monovalent organic group, R ⁵ and R ⁶ may be connected to form a ring, and R ⁷ represents an alkyl group, a cycloalkyl group or an aryl group. )

In formula (c1), R ⁵ represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, a 2-thienyl group, Or an alkoxy group or a cyano group. When R ⁵ is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be substituted with a substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Or the like.

In formula (c1), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, W , An anthranyl group, a dialkylamino group, a morpholino group, or a cyano group which may be substituted with W or a naphthyl group which may be substituted with W; R ⁶ and R ⁵ may combine with each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or the 6-membered ring may be bonded to a benzene ring which may have 1 or 2 arbitrary substituents.

In formula (c1), R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, W A naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms Lt; / RTI &gt;

The alkyl group having 1 to 6 carbon atoms represented by R ⁵ may be a linear or branched alkyl group and includes, for example, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- , n-pentyl group, isoamyl group, n-hexyl group, or 2-ethylbutyl group.

Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ⁵ include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁵ include a methoxy group and an ethoxy group.

When R ⁵ represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be substituted with a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom and the like), a hydroxyl group, an alkyl group having 1 to 4 carbon atoms Butyl group, a tert-butyl group), an alkoxy group having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, n-propyl group, An isopropoxy group, a n-butoxy group), and a nitro group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a n-decyl group and the like.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁶ include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, A n-decyloxy group, and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁶ include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, - Amyl group.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁶ include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ⁶ include o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i- butyl) phenyl group, (o-amyl) phenyl group, o- methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (T-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-butoxy) phenyl group, Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, Trichlorophenyl group, 2,4,6-tribromophenyl group, 2 , 4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, and p-biphenyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ⁶ include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

Specific examples of the anthranyl group which may be substituted with W represented by R ⁶ include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl- Methyl-1-anthranyl, 7-methyl-1-anthranyl, 8-methyl-1-anthranyl, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group and 10-methyl-2-anthranyl group.

Examples of the dialkylamino group represented by R ⁶ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group and a diphenylamino group.

In the formula (c1), R ⁷ represents an alkyl group, a cycloalkyl group or an aryl group, and represents an alkyl group, a cycloalkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A halogenated alkyl group having 1 to 5 carbon atoms, a halogenated cycloalkyl group having 3 to 10 carbon atoms, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W are preferable. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms Lt; / RTI &gt;

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a n-decyl group and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁷ include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, a perfluoro-n - Amyl group.

Specific examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷ include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group and an isobornyl group.

Specific examples of the halogenated cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷ include a perfluorocyclopentyl group, a perfluorocyclohexyl group, and a perfluorocycloheptyl group.

Specific examples of the phenyl group which may be substituted with W represented by R ⁷ include o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i- butyl) phenyl group, (o-amyl) phenyl group, o- methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (T-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-butoxy) phenyl group, Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, Trichlorophenyl group, 2,4,6-tribromophenyl group, 2 , 4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, and p-biphenyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ⁷ include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

Specific examples of the anthranyl group which may be substituted with W represented by R ⁷ include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl- Methyl-1-anthranyl, 7-methyl-1-anthranyl, 8-methyl-1-anthranyl, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group and 10-methyl-2-anthranyl group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by W, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the alkoxy halide having 1 to 5 carbon atoms include R ⁶ or R ^The same as those exemplified as the specific examples of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy group having 1 to 5 carbon atoms, &Lt; / RTI &gt;

R ⁵ and R ⁶ may combine with each other to form a 5-membered or 6-membered ring.

When R ⁵ and R ⁶ are bonded to each other to form a 5-membered or 6-membered ring, examples of the 5-membered or 6-membered ring include a carbocyclic group and a heterocyclic group, and examples thereof include cyclopentane, cyclohexane, cycloheptane , Pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered or 6-membered ring may be bonded to a benzene ring which may have an arbitrary substituent. Examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thioxanthene ring systems. . The 5-membered or 6-membered ring may contain a carbonyl group, and examples thereof include cyclohexadieneone, naphthalenone and anthrone ring systems.

One of the favorable aspects of the compound represented by the formula (c1) is a compound represented by the following formula (c1-1). The compound represented by the formula (c1-1) is a compound in which R ⁵ and R ⁶ in the formula (c1) combine to form a 5-membered ring.

(Wherein (c1-1), R ⁷ is R ⁷ and the consent of the formula (c1), X is an alkyl group, an alkoxy group or a halogen atom, t represents an integer of 0~3, t is 2 Or 3, the plurality of X's may be the same or different.)

As the alkyl group represented by X, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable.

As the alkoxy group represented by X, a straight chain or branched chain alkoxy group having 1 to 4 carbon atoms is preferable.

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

As t, 0 or 1 is preferable.

In the formula (c1-1), t is 1, X is a methyl group, X is a substituted position in an ortho position, R ⁷ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A norbornylmethyl group, or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (c1-1) include the following compounds (i), (ii), (iii) and (iv) Or two or more of them may be used in combination. The compounds (i) to (iv) are commercially available.

It may also be used in combination with other types of photoacid generators.

As a preferred embodiment of the compound represented by the formula (c1)

R ⁵ represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group or an anthranyl group;

R ⁶ represents a cyano group;

R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W , A naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms A halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

The compound represented by the formula (c1) is also preferably a compound represented by the following formula (c1-2).

In formula (c1-2), R ⁸ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group, and L represents an integer of 0 to 5. R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W , A naphthyl group which may be substituted with W or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms , A halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

Examples of R ⁷ in the formula (c1-2) include a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, , A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a p- .

As the halogen atom represented by R ⁸ , a fluorine atom, a chlorine atom or a bromine atom is preferable.

The alkyl group having 1 to 4 carbon atoms represented by R ⁸ is preferably a methyl group or an ethyl group.

As the alkoxy group having 1 to 4 carbon atoms represented by R ⁸ , a methoxy group or an ethoxy group is preferable.

L is preferably 0 to 2, and particularly preferably 0 to 1.

Among the compounds represented by the formula (c1), preferable examples of the compound included in the compound represented by the formula (c1-2) include a compound wherein R ⁵ represents a phenyl group or a 4-methoxyphenyl group, R ⁶ And R ⁷ represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tolyl group.

Hereinafter, among the compounds represented by formula (c1), particularly preferred examples of the compounds included in the compound represented by formula (c1-2) are shown, but the present invention is not limited thereto.

? - (methylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = methyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group), and an α- (n-butylsulfonyloxyimino) benzyl cyanide

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = 4-tolyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = methyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = ethyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = n-propyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = n-butyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = 4-tolyl group)

Examples of the compound having at least one oxime sulfonate residue represented by the formula (c0) include oximesulfosuccinimide represented by the following formula (OS-3), formula (OS-4) It is preferably a compound of the formula (I).

(In the formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and the plurality of R ^{2 s} present may be each independently a hydrogen atom, an alkyl group, R ⁶ represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, and n represents 1 or 2, And m represents an integer of 0 to 6.)

In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group represented by R ¹ may have a substituent.

In the above formulas (OS-3) to (OS-5), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

In the above formulas (OS-3) to (OS-5), the aryl group represented by R ¹ is preferably an aryl group having a total of 6 to 30 carbon atoms and may have a substituent.

In the above formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having a total of 4 to 30 carbon atoms which may have a substituent, and at least one heteroaryl ring Aromatic ring), and for example, a heterocyclic aromatic ring and a benzene ring may be condensed.

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

Of the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of these formulas (OS-3) to (OS-5), one or two of R ² present in two or more of the compounds are preferably an alkyl group, an aryl group or a halogen atom, and one of R ² is preferably an alkyl group, More preferably an atom, and it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

In the above formulas (OS-3) to (OS-5), the alkyl group or aryl group represented by R ² may have a substituent.

Examples of the substituent which the alkyl group or aryl group represented by R ² may have include the same group as the substituent that the alkyl group or aryl group in R ¹ may have.

In the above formulas (OS-3) to (OS-5), the alkyl group represented by R ² is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent, More preferably an alkyl group.

As the alkyl group represented by R ² , a methyl group, ethyl group, n-propyl group, n-butyl group and n-hexyl group are preferable, and a methyl group is more preferable.

In the above formulas (OS-3) to (OS-5), the aryl group represented by R ² is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

As the aryl group represented by R ² , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group or p-phenoxyphenyl group is preferable.

Of the above formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.

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

In the above formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1. When X is S, n is preferably 2 Do.

In the above formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.

In the above formulas (OS-3) to (OS-5), the alkyl group represented by R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

The alkyloxy group represented by R ⁶ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group.

Examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group and an aminosulfonyl group.

Examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group and a butyloxysulfonyl group.

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

In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, Do.

The compound represented by the formula (OS-3) is particularly preferably a compound represented by the following formula (OS-6), formula (OS-10) or formula (OS-11) 4) is particularly preferably a compound represented by the following formula (OS-7), and the compound represented by the formula (OS-5) -9) is particularly preferable.

In the formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, , A halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom or a methyl group .

The expression (OS-6) ~ R ¹ in (OS-11) is, and R ¹ and agreed in the formula (OS-3) ~ (OS -5), as a preferred aspect.

R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom and is preferably a hydrogen atom.

R ⁸ in the formulas (OS-6) to (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, More preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group, and particularly preferably an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, Do.

R ⁹ in the formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R ¹⁰ in formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

In the oxime sulfonate compound, any of the three-dimensional structures (E, Z) of oxime may be a mixture or a mixture thereof.

Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

Another favorable embodiment of the oxime sulfonate compound having at least one oxime sulfonate moiety represented by the formula (c0) includes a compound represented by the following formula (OS-1).

In the formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Lt; / RTI &gt; R ² represents an alkyl group or an aryl group.

X is ^{-O-, -S-, -NH-, -NR 5} -, -CH 2 -, -CR 6 H-, or, -CR ⁶ R ⁷ - represents a, R ⁵ ~R ⁷ is an alkyl group, or Lt; / RTI &gt;

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

As R ²¹ to R ²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and at least two of R ²¹ to R ²⁴ are bonded to each other to form an aryl group. Among them, the case where all of R ²¹ to R ²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

Each of the substituents described above may further have a substituent.

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

The expression (OS-2) of, ^{R 1, R 2, R 21} ~R 24 are each of the formula and ^{R 1, R 2, R 21} ~R 24 and agree in (OS-1), preferred examples It is also the same.

Of these, it appears as expression (OS-1), and expression (OS-2) R ¹ is a cyano group, or an aryl group sun, and more preferably, the expression (OS-2) in, and R ¹ is a cyano group, Most preferred are the sun or the naphthyl group.

In the oxime sulfonate compound, the stereostructure (E, Z, etc.) of oxime or benzothiazole ring may be either or both of them.

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

Among these compounds, b-9, b-16, b-31 and b-33 are preferable from the viewpoint of compatibility between sensitivity and stability.

It is preferable that the photosensitive resin composition of the present invention does not contain a 1,2-quinonediazide compound as a photoacid generator (component C) sensitive to an actinic ray. The reason is that the 1,2-quinonediazide compound generates a carboxy group by sequential fluorescent chemistry, but its quantum yield is 1 or less, and the sensitivity is lower than that of the oxime sulfonate compound.

On the other hand, the oxime sulfonate compound acts as a catalyst against deprotection of an acidic group protected by an acid generated by the action of an actinic ray, so that an acid generated by the action of one photon contributes to a number of deprotection reactions, The yield is greater than 1, for example, a large value such as a power of 10, and it is presumed that a high sensitivity can be obtained as a result of so-called chemical amplification.

The content of the photoacid generator (component C) in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the total content of the component A and the component B desirable.

(Component D) Solvent

The photosensitive resin composition of the present invention contains (Component D) a solvent.

The photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving or dispersing the essential components of component A, component B and component C, and optional components of various additives described below, which are preferable components, in (solvent D) solvent .

As the solvent (component 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 There may be mentioned ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers , Dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

Examples of the solvent (component D) used in the photosensitive resin composition of the present invention include (1) ethylene glycol monomethyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Alkyl ethers; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and ethylene glycol monobutyl ether acetate; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; (5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; (7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; (8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate; (9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; (10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate; (12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, isobutyl lactate, isobutyl lactate, n-amyl lactate, and lactic acid / (13) A process for producing a compound represented by the following formula (1), wherein n is 1, Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate; (14) A process for producing a compound represented by the above formula (1), which comprises dissolving at least one compound selected from the group consisting of ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methoxypropionyl acetate, 3-methoxypropionyl acetate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; (16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; (17) lactones such as? -Butylolactone, and the like.

If necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1- It is also possible to add a solvent such as octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate.

Of these solvents, diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferred.

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

The solvent which can be used in the present invention is preferably a single solvent or a combination of two solvents, more preferably two solvents, more preferably propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers It is more preferable to use them in combination.

The content of the solvent (component D) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and most preferably 150 to 3,000 parts by weight, per 100 parts by weight of the total content of component A and component B. To 1,500 parts by weight.

&Lt; Other components >

The photosensitive resin composition of the present invention may contain other components.

As the other components, the photosensitive resin composition of the present invention preferably contains a photosensitizer in view of sensitivity, and preferably contains a basic compound from the viewpoint of liquid storage stability, and from the viewpoint of film properties, It is preferable to contain a cross-linking agent. From the viewpoint of substrate adhesion, it is preferable to contain an adhesion improver, and from the viewpoint of coatability, a surfactant is preferably contained.

If necessary, the photosensitive resin composition of the present invention may further contain additives such as a development accelerator, an antioxidant, a plasticizer, a heat radical generator, a thermal acid generator, an acid proliferator, an ultraviolet absorber, a thickener, A known additive may be added.

Hereinafter, other components that can be contained in the photosensitive resin composition of the present invention will be described.

[Photosensitizer]

The photosensitive resin composition of the present invention preferably contains a photosensitizer.

By containing a photosensitizer, it is effective for improving exposure sensitivity, and is particularly effective when the exposure light source is a g- and h-line mixed line.

As the photosensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, basestyryl derivatives, and distyrylbenzene derivatives are preferable.

Examples of the anthracene derivative include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene 9-bromoanthracene, 9,10-dibromoanthracene, 2-ethyl anthracene, and 9,10-dimethoxy anthracene are preferable.

As the acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.

As thioxanthone derivatives, thioxanthone, diethylthioxanthone, 1-chloro-4-propanedioxanthone and 2-chlorothioxanthone are preferable.

As coumarin derivatives, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.

Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole and 2- (4-dimethylaminostyryl) naphthothiazole. have.

Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene and di (3,4,5-trimethoxystyryl) benzene.

Of these, anthracene derivatives are preferable, and 9,10-dialkoxyanthracene (having 1 to 6 carbon atoms in the alkoxy group) is more preferable.

Specific examples of the photosensitizer include the following. In the following description, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

The content of the photosensitizer in the photosensitive resin composition of the present invention is preferably from 0.1 to 10 parts by weight, more preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the total content of the component A and the component B. When the content of the photosensitizer is 0.1 parts by weight or more, desired sensitivity is easily obtained, and when it is 10 parts by weight or less, transparency of the coating film is easily ensured.

[Basic compound]

The photosensitive resin composition of the present invention preferably contains a basic compound from the viewpoint of liquid storage stability.

As the basic compound, any of those used as a chemical amplification resistor may be selected and used. For example, aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

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

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

Examples of the heterocyclic amine 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 Pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N '- [2- (4-morpholinyl) Ethyl] thiourea (urea), 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-undecene.

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

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

The basic compounds which can be used in the present invention may be used singly or in combination of two or more kinds. However, two or more kinds of basic compounds are preferably used together, and more preferably two kinds of basic compounds are used. It is more preferable to use them in combination.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.002 to 0.2 part by weight based on 100 parts by weight of the total content of component A and component B.

[Crosslinking agent]

The photosensitive resin composition of the present invention preferably contains 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.

As the crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, or a block isocyanate crosslinking agent .

Of these crosslinking agents, compounds having two or more epoxy groups or oxetanyl groups in the molecule are preferable, and epoxy resins are particularly preferable.

The amount of the crosslinking agent to be added in the photosensitive resin composition of the present invention is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 44 parts by weight, more preferably 3 to 40 parts by weight, relative to the total solid content of the photosensitive resin composition Do. When added in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.

- a compound 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 and aliphatic epoxy resin.

These are available as commercial products. Examples of the bisphenol A type 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 JER4005, JER4007, and JER4010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation), and the like can be used as the bisphenol F type epoxy resin. JER152, JER154, JER157S70, and JER157S65 (manufactured by Japan Epoxy Resins Co., Ltd.) as the phenol novolak type epoxy resin, EPICLON N-760, EPICLON N-770, EPICLON N-770 and EPICLON N-775 (manufactured by DIC Corporation) EPICLON N-670, EPICLON N-670, EPICLON N-670, EPICLON N-680, EPICLON N-690 and EPICLON N-695 (manufactured by DIC Corporation) As the aliphatic epoxy resin, ADEKA RESIN EP -4080S, copper EP-4085S, copper EP-4088S (manufactured by ADEKA Corporation), seroxid 2021P, seroxide 2081, seroxide 2083, seroxide 2085, EHPE 3150, EPOLEAD PB 3600, copper PB 4700 (Manufactured by Daicel Chemical Industries, Ltd.). 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 Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX- EX-821, EX-810, EX-810, EX-810, EX- DLC-201, DLC-203, EX-820, EX-841, EX-911, EX-941, EX-920, EX- YH-300, YH-301, YH-302, YH-315, YH-324, DLC-204, DLC-205, DLC-206, DLC-301 and DLC- YH-325 (manufactured by Shinnitetsu Kagaku Co., Ltd.).

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

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

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aromoxetane OXT-121, OXT-221, OX-SQ and PNOX (manufactured by Dowa Kasei Co., Ltd.) can be used.

The oxetanyl group-containing compound is preferably used alone or in combination with a compound containing an epoxy group.

The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule added to the photosensitive resin composition of the present invention is preferably 1 to 50 parts by weight, more preferably 3 to 50 parts by weight, based on 100 parts by weight of the total content of the component A and the component B. [ More preferably 30 parts by weight.

- crosslinking agent containing an alkoxymethyl group -

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These can be obtained by converting methylol melamine, methylol benzoguanamine, methylol glycoluril, or methylol group of methylol group into alkoxymethyl group, respectively. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of generated outgas, in particular, a methoxymethyl group desirable.

Among these alkoxymethyl group-containing crosslinking agents, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable crosslinking agents. From the viewpoint of transparency, alkoxymethylated glycoluril is particularly preferable.

These alkoxymethyl group-containing crosslinking agents are commercially available, for example, from Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300 (manufactured by Mitsui Cyanamid Co.), NIKARAK MX-750, -032, -706, -708, -40, -31, -270, -280, -290, NIKARAK MS-11, NIKARAK MW-30HM, -100 LM, -390 (manufactured by SANWA CHEMICAL CO., LTD.) And the like can be preferably used.

When an alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the amount of the alkoxymethyl group-containing crosslinking agent to be added is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the total content of the components A and B It is more desirable to be negative. When added in this range, it is possible to obtain favorable alkali solubility at the time of development and excellent solvent resistance of the film after curing.

- a compound having at least one ethylenically unsaturated double bond -

As the compound having at least one ethylenic unsaturated double bond, a (meth) acrylate compound such as monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or higher functional (meth) have.

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

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

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

These compounds having at least one ethylenic unsaturated double bond among them may be used singly or in combination of two or more kinds.

The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less based on 100 parts by weight of the total content of the component A and the component B, Or less. By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the cured film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, it is preferable to add a thermal radical generator described later.

- Block isocyanate cross-linking agent -

The block isocyanate cross-linking agent is not particularly limited as long as it is a compound having a block isocyanate group (block isocyanate compound), but from the viewpoint of curability, it is preferably a compound having two or more block isocyanate groups in one molecule.

In addition, the block isocyanate group in the present invention is a group capable of generating an isocyanate group by heat, and for example, a group in which an isocyanate group is protected by reacting a block agent with an isocyanate group can be preferably exemplified. The block isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 250 캜.

The skeleton of the block isocyanate-based crosslinking agent is not particularly limited, and a skeleton of a hexamethylene diisocyanate (HDI) skeleton, an isophorone diisocyanate (IPDI) skeleton and a prepolymer skeleton derived from HDI or IPDI Can be used.

The blocking agent of the isocyanate group in the block isocyanate group is not particularly limited, and active hydrogen compounds such as active methylene compounds, oxime compounds, lactam compounds and amine compounds such as diester compounds can be preferably used. Of these, active methylene compounds are particularly preferable from the viewpoint of reactivity.

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

Examples of the oxime compounds include cyclohexanone oxime, benzophenone oxime, and acetoxime.

Examples of the lactam compound include ε-caprolactam, γ-butyrolactam, and the like.

Examples of the amine compound include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

Further, the active hydrogen compound reacts with an isocyanate group to form a block isocyanate group as shown in the following formula.

R-NCO + H-R '? R-NH-C (= O)

(Wherein H - R 'represents an active hydrogen compound, H in H - R' represents an active hydrogen atom, R represents a part other than the isocyanate group in the isocyanate compound, and R ' Represents a part other than the active hydrogen atom in the hydrogen compound.)

These block isocyanate-based cross-linking agents are available as commercial products, for example, DURANATE MF-K60X, MF-K60B, MF-B60X, 17B-60P, TPA-B80E, E402-B80B, SBN- (Manufactured by Asahi Kasei Chemical Co., Ltd.), Desmodule BL3272, BL3575 / 1, BL3475, BL3370, BL4265, BL5375, VPLS2376 / 1, VPLS2257, VPLS2078 / 1, VPLS2352 / ), Urea Hyper PUR-1804 (manufactured by DIC Corporation), and the like can be preferably used. Of these, the durenate MF-K60X, MF-K60B, SBN-70D and K6000 are particularly preferable.

When the block-isocyanate-based crosslinking agent is used in the photosensitive resin composition of the present invention, the amount of the block isocyanate-based crosslinking agent to be added is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, By weight to 15 parts by weight. When added in this range, high sensitivity and favorable alkali solubility at the time of development can be obtained.

[Adhesion improver]

The photosensitive resin composition of the present invention preferably contains an adhesion improver from the viewpoint of substrate adhesion.

The adhesion improver that can be used in the photosensitive resin composition of the present invention may be an inorganic compound such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as molybdenum, titanium, indium tin oxide, gold, And the adhesion of the insulating film. Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent used as the adhesion improver for use in the present invention is not specifically limited and any known silane coupling agent may be used for the purpose of modifying the interface.

Among them, a silane coupling agent can be preferably exemplified.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? - Silane, and vinyltrialkoxysilane.

Of these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is more preferable.

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

The content of the adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total content of Component A and Component B.

〔Surfactants〕

The photosensitive resin composition of the present invention preferably contains a surfactant from the viewpoint of coatability.

As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants may be used, but a preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine series, and silicone surfactants.

It is more preferable that the photosensitive resin composition of the present invention contains a fluorine-based surfactant and / or a silicon-based surfactant as a surfactant.

Examples of these fluorine-based surfactants and silicone-based surfactants include those described in Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Laid-Open Patent Application No. 9-54432, Japanese Laid-Open Patent Application No. 9-5988, A surfactant described in each publication, and a commercially available surfactant may be used.

(Commercially available from Shin-A KITAKA SEI Co., Ltd.), Prolide FC 430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, and others available as commercially available surfactants, F173, F176, F189 and R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., Ltd.), PolyFox series (OMNOVA And fluorinated surfactants such as fluorinated surfactants and silicone surfactants. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

The surfactant may further contain, as a surfactant, the structural unit A and the structural unit B represented by the following formula (1) and having a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography when tetrahydrofuran (THF) (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

(Wherein R ¹ and R ³ are each independently a hydrogen atom or a methyl group, R ² is a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ is a hydrogen atom or a C1- P represents an alkylene group having 3 to 6 carbon atoms, p and q each represent a weight percentage representing a polymerization ratio, p represents a value of 10 wt% or more and 80 wt% or less, q represents a weight % Or more and 90% or less by weight, 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 formula (2). R ⁵ in the formula (2) 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 coated surface, More preferably an alkyl group having 2 or 3 carbon atoms.

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

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

The amount of the surfactant to be added in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the total content of Component A and Component B More preferably by weight.

[Development promoter]

The photosensitive resin composition of the present invention preferably contains a development accelerator.

As the development accelerator, any compound having a phenomenon of promoting development may be used, but it is preferably a compound having at least one kind of group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group and an alkyleneoxy group, and a carboxyl group or a phenolic hydroxyl group Is more preferable, and a compound having a phenolic hydroxyl group is most preferable.

The molecular weight of the development promoter is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

As examples of the development accelerator, those having an alkyleneoxy group include polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester , Polybutylene glycol, polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, and compounds described in Japanese Patent Application Laid-Open No. 9-222724 .

Examples of compounds having a carboxyl group include compounds described in JP 2000-66406 A, JP 9-6001 B, JP 10-20501 A, JP 11-338150 A, and the like have.

Examples of those having a phenolic hydroxyl group include those disclosed in JP-A-2005-346024, JP-A-10-133366, JP-A-9-194415, JP-A-9-222724, The compounds described in JP-A-11-171810, JP-A-2007-121766, JP-A-9-297396, JP-A-2003-43679, etc. Among these, phenol compounds having 2 to 10 benzene ring numbers are preferred, and phenol compounds having 2 to 5 benzene ring numbers are more favorable. Particularly preferred examples include phenolic compounds disclosed as dissolution accelerators in JP-A-10-133366.

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

The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by weight, more preferably from 0.2 to 20 parts by weight, based on 100 parts by weight of the total content of the component A and the component B from the viewpoints of sensitivity and residual film ratio More preferably 0.5 to 10 parts by weight.

[Antioxidant]

The photosensitive resin composition of the present invention may contain an antioxidant.

As the antioxidant, a known antioxidant may be contained. Addition of an antioxidant has the advantage of being able to prevent the cured film from being colored or to reduce the film thickness reduction due to decomposition and also to have excellent heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite salts, sulfites, thiosulfates, hydroxyl Amine derivatives and the like. Among them, a phenol-based antioxidant is particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used alone or in combination of two or more.

Examples of commercially available products of phenolic antioxidants include adecastab AO-20, adecastab AO-30, adecastab AO-40, adecastab AO-50, adecastab AO- SumilizerGS, sumilizerMDP-S, sumilizerBBM-S, sumilizerWX-R, sumilizer GA-80, Adekastab AO-80, Adekastab AO- IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425WL, IRGANOX1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295 manufactured by Ciba Japan KK, Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 and the like.

Among them, adecastab AO-60, adecastab AO-80 (manufactured by ADEKA), and Irganox 1098 (manufactured by Ciba Japan) are preferably used.

The content of the antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, and particularly preferably 0.5 to 4% by weight based on the total solid content of the photosensitive resin composition. Within this range, sufficient transparency of the formed film can be obtained, and sensitivity at the time of pattern formation is also improved.

As the additives other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in &quot; New developments of the polymer additive &quot; (Ilgan Kogyo Shimbun) may be added to the photosensitive resin composition of the present invention.

[Plasticizer]

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

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

The content of the plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total content of Component A and Component B.

[Heat radical generator]

The photosensitive resin composition of the present invention may contain a thermal radical generator and may contain an ethylenically unsaturated compound such as a compound having at least one ethylenically unsaturated double bond as described above and may contain a thermal radical generator desirable.

As the thermal radical generator in the present invention, a known thermal radical generator may be used.

The thermal radical generator is a compound that generates radicals by heat energy to initiate or promote the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the resulting cured film becomes stronger, and heat resistance and solvent resistance may be improved.

Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, A compound having a bond, an azo-based compound, and a non-benzyl compound.

One kind of thermal radical generator may be used alone, or two or more kinds of thermal radical generators may be used in combination.

The content of the heat radical generator in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total content of the component A and the component B, More preferably from 0.5 to 10 parts by weight.

[Thermal acid generator]

In the present invention, a thermal acid generator may be used in order to improve physical properties of the film in low-temperature curing.

The thermal acid generator which can be used in the present invention is a compound which generates acid by heat and is preferably a compound having a thermal decomposition point in the range of 130 to 250 캜, more preferably 150 to 220 캜, And is a compound which generates a low nucleophilic acid such as sulfonic acid, carboxylic acid, and disulfonylimide.

Examples of the acid generated by the thermal acid generator include an alkyl or aryl carboxylic acid substituted with a sulfonic acid or an electron-withdrawing group having a strong pKa of 2 or less, disulfonylimide similarly substituted with an electron-withdrawing group, and the like desirable. Examples of the electron-withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester which generates an acid by heat without generating an acid substantially by irradiation with exposure light.

It can be determined that there is no change in the spectrum by IR spectroscopy or NMR spectrum measurement before and after exposure of the compound, in which substantially no acid is generated by irradiation of the exposure light.

The molecular weight of the sulfonic acid ester is preferably from 230 to 1,000, more preferably from 230 to 800.

The sulfonic acid ester which can be used in the present invention may be a commercially available one or a synthesized one synthesized by a known method. Sulfonic acid esters can be synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.

The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the total content of the component A and the component B. [

[Acid growth agent]

In the photosensitive resin composition of the present invention, an acid propagating agent may be used for the purpose of improving the sensitivity.

The acid-proliferating agent which can be used in the present invention is a compound capable of generating an acid by further acid catalysis reaction to increase the acid concentration in the reaction system, and is a compound stably present in the absence of acid. In such a compound, since at least one acid increases in one reaction, the reaction accelerates progressing with the progress of the reaction, but since the generated acid itself induces (induces) self-decomposition, The strength of the acid is preferably 3 or less, more preferably 2 or less, as the acid dissociation constant, pKa.

Specific examples of the acid proliferating agent include those described in paragraphs 0203 to 023 of Japanese Patent Application Laid-Open No. 10-1508, paragraphs 0016 to 555 of Japanese Patent Application Laid-Open No. 10-282642, and Japanese Patent Publication No. 9-512498 12th line to 47th page 2nd line.

Specifically, the following compounds and the like can be mentioned.

Examples of the acidic proliferative agent that can be used in the present invention include acids decomposed by acids generated from an acid generator and decomposed with pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and phenylphosphonic acid And compounds capable of generating an acid of 3 or less.

The content of the acid proliferating agent in the photosensitive resin composition is preferably from 10 to 1,000 parts by weight based on 100 parts by weight of the photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion and is preferably from 20 to 500 parts by weight More preferable.

(Method of forming a cured film)

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

The method of forming the cured film of the present invention is not particularly limited but is preferably the following steps (1) to (5), except that the positive photosensitive resin composition of the present invention is used.

(1) a layer forming step of forming a film-like layer on a substrate by using the positive photosensitive resin composition of the present invention

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

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

(4) a developing step of developing the exposed photosensitive resin composition with an aqueous developing solution

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

In the method for forming a cured film of the present invention, after the exposure in the above exposure step, the above-described developing step (4) may be performed without performing the heat treatment.

Further, before the post-baking step, the step of exposing the developed photosensitive resin composition may further include the step of:

Further, the method for forming a cured film of the present invention preferably further includes (6) a dry etching step for performing dry etching on the substrate having the cured film obtained by thermal curing.

Each step will be described below in order.

In the layer forming step of (1), it is preferable to form a film layer on the substrate using the positive photosensitive resin composition of the present invention to form a wet film containing a solvent.

In the solvent removing step (2), the solvent is removed from the applied film. In the solvent removing step, it is preferable to remove the solvent by, for example, decompression (baking) and / or heating to form a dried coating film on the substrate.

In the exposure step of (3), it is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm or more and 450 nm or less. In this step, a specific acid generator decomposes and an acid is generated. By the catalytic action of the generated acid, the acid-decomposable group in the constituent unit (a1) contained in the component A is decomposed to generate an acid group.

In the region where the acid catalyst is generated, Post Exposure Bake (hereinafter also referred to as &quot; PEB &quot;) may be performed, if necessary, to accelerate the above decomposition reaction. By PEB, generation of an acid group from the acid decomposable group can be promoted.

The acid decomposable group in the structural unit (a1) in the specific resin is low in the activation energy of acid decomposition and is easily decomposed by an acid derived from the photoacid generator due to exposure to generate an acid cycle. There is no. Therefore, it is preferable to carry out the above developing step without performing the heat treatment after the exposure step. More specifically, it is preferable to form a positive image by performing development by the developing process of (4) without performing PEB after the exposure process of (3).

Further, by performing PEB at a relatively low temperature, the decomposition of the acid decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 90 占 폚.

In the developing step of the developing roller 4, it is preferable to develop the component A having an advantageous acid group and the component B having an acid group using an alkaline developing solution. A positive image can be formed by removing the exposed region containing the photosensitive resin composition having an acid group easily dissolvable in an alkaline developing solution.

(A2) obtained by thermally decomposing an acid group and an acid-decomposable group in the constituent unit (a1), for example, by heating the obtained positive image in the post-baking step of the constituent unit (5) And the structural unit (b2) to form a cured film. This heating is preferably carried out at a high temperature of 150 ° C or higher, more preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 250 ° C. The heating time can be appropriately set depending on the heating temperature and the like, but is preferably within a range of 10 to 90 minutes.

The cured film obtained from the photosensitive resin composition of the present invention can be suitably used as a dry etching resist.

When the cured film obtained by thermal curing by the post-baking process of step (5) is used as a dry etching resist, dry etching such as ashing, plasma etching, ozone etching and the like can be performed as the etching process.

In the dry etching process of the step (6), a reactive gas etching process in which etching is performed by exposing a substrate in a reaction gas, a reactive ion etching (RIE) process in which a reactive gas is ionized and radicalized by plasma, A known dry etching treatment can be exemplified. These gas species and etching methods may be appropriately selected depending on the material to be dry-etched, desired speed, precision, and the like. As a device for performing dry etching, a known device can be used.

In addition, it is preferable to include a step of exposing the developed photosensitive resin composition to the whole before the post-baking step, and when a step of irradiating the pattern of the developed photosensitive resin composition with an actinic ray, preferably ultraviolet light, The crosslinking reaction can be promoted by the acid generated by irradiation of the crosslinking agent.

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

[Method for preparing photosensitive resin composition]

The photosensitive resin composition is prepared by mixing an essential component of a specific resin and an acid generator, if necessary, with a solvent in a predetermined ratio and optionally by stirring and dissolving. For example, a photosensitive resin composition may be prepared by preparing a solution in which a specific resin or acid generator is dissolved in each solvent in advance, and mixing them in a predetermined ratio. The solution of the photosensitive resin composition prepared as described above may be used after being filtered using a filter having a pore diameter of 0.1 mu m or the like.

<Layer Formation Process and Solvent Removal Process>

A desired dry film can be formed by forming a film layer on a predetermined substrate using a photosensitive resin composition and removing the solvent by reduced pressure and / or heating (prebaking). As the substrate, for example, in the production of a liquid crystal display device, a polarizing plate, a further glass plate provided with a black matrix layer and a color filter layer as necessary, and a transparent conductive circuit layer provided thereon can be exemplified. The method for forming the layer on the substrate is not particularly limited, and for example, a coating method such as a slit coating method, a spray method, a roll coating method, and a spin coating method can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, a large substrate refers to a substrate having a size of 1 m or more on each side.

The heating conditions for the solvent removal step (2) are those in which the acid-decomposable group decomposes in the constituent unit (a1) in the component A in the unexposed portion and the component A is not soluble in the alkali developer, But it is preferably about 70 to 120 DEG C for about 30 to about 300 seconds.

<Exposure Step>

(3) In the exposure step, the substrate provided with the dried coating film of the photosensitive resin composition is irradiated with a predetermined pattern of actinic rays. The exposure may be performed through a mask, or a predetermined pattern may be directly drawn. An active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After the exposure process, PEB may be performed if necessary.

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

When a mercury lamp is used, an actinic ray having a wavelength of g-line (436 nm), i-line (365 nm) and h-line (405 nm) can be preferably used. The mercury lamp is preferable in that it is suitable for exposure of a large area as compared with a laser.

When a laser is used, 343 nm and 355 nm can be used as a solid-state (YAG) laser, and 351 nm (XeF) can be suitably used as an excimer laser. . Of these, 355 nm and 405 nm are more preferable from the standpoints of stability and cost. The laser can be irradiated onto the coating film by dividing it into one or a plurality of circuits.

The energy density per pulse of the laser is preferably from 0.1 mJ / cm2 to 10,000 mJ / cm2. More preferably not less than 0.3 mJ / cm 2, most preferably not less than 0.5 mJ / cm 2, and more preferably not more than 1,000 mJ / cm 2 in order to prevent the coating film from being decomposed by the abrasion phenomenon, Most preferably 100 mJ / cm 2 or less.

The pulse width is preferably from 0.1 nsec to 30,000 nsec. In order to prevent the chromaticity film from being decomposed by the ablation phenomenon, it is more preferably 0.5 nsec or more, most preferably 1 nsec or more, and more preferably 1,000 nsec or less and 50 nsec or less Most preferred.

The frequency of the laser is preferably 1 Hz to 50,000 Hz, more preferably 10 Hz to 1,000 Hz.

In order to shorten the exposure processing time, the frequency of the laser is more preferably 10 Hz or more, most preferably 100 Hz or more, and more preferably 10,000 Hz or less in order to improve the fitting accuracy at the time of the scan exposure, And most preferably 1,000 Hz or less.

Compared with a mercury lamp, a laser is preferable in that it is easy to narrow the focus, and a mask for forming a pattern in the exposure process is unnecessary and cost can be reduced.

Examples of the exposure apparatus that can be used in the present invention include, but are not limited to, those sold by Callisto (manufactured by V Technology), AEGIS (manufactured by V Technology) and DF2200G (manufactured by Dainippon Screen- ) Can be used. Also, devices other than those described above can be used suitably.

If necessary, the irradiation light may be adjusted by passing through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

<Development Process>

(4) In the developing process, an exposed pattern area is removed by using a basic developing solution to form an image pattern. Examples of the basic compound used in the developer 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 developer is not particularly limited as far as development is feasible, but it is preferably 10.0 to 14.0.

It is preferable to develop it in an aqueous solution of 0.2 to 2.38% by weight of tetramethylammonium hydroxide, more preferably in an aqueous solution of 0.4% by weight, 0.5% by weight, 0.7% by weight and 2.38% by weight.

The developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method, and a shower method. After the development, a desired pattern can be formed by conducting water washing for 10 to 90 seconds.

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 adhering developer and residual developing residue. As the rinsing method, a known method can be used. For example, a shower rinse or a deep rinse.

&Lt; Post baking step (crosslinking step) >

The pattern corresponding to the unexposed area obtained by the development is heated at a predetermined temperature, for example, 180 to 250 占 폚 for a predetermined time, for example, 60 minutes and an oven for 30 to 90 minutes to decompose an acid-decomposable group in a specific resin to generate a carboxyl group and / or a phenolic hydroxyl group, and react with a crosslinkable group which is an epoxy group and / or an oxetanyl group in a specific resin By crosslinking, a protective film or an interlayer insulating film excellent in heat resistance, hardness and the like can be formed. In addition, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

Post-baking may be performed after baking at a relatively low temperature before the post-baking (addition of the middle baking step). In the case of performing the middle baking, post baking is preferably performed at a high temperature of 200 DEG C or more after heating at 90 to 150 DEG 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 devising such a middle baking and post baking. For these heating, a known heating method such as a hot plate, an oven, and an infrared heater can be used.

Prior to the heat treatment, the substrate on which the pattern is formed is re-exposed by an actinic ray, and then an acid is generated from the acid generator (B) present in the unexposed portion by post-baking (re-exposure / post-baking) , And to function as a catalyst for promoting crosslinking.

That is, the method for forming a cured film in the present invention preferably includes a step of re-exposure by an actinic ray between the developing step and the post-baking step.

The exposure in the re-exposure step may be performed by the same means as in the exposure step, but in the re-exposure step, it is preferable to perform the entire exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention. The preferable exposure amount of the re-exposure process is 100 to 1,000 mJ / cm &lt; 2 &gt;.

<Dry Etching Process>

The dry etching step in the present invention is a step of performing dry etching on a substrate having a cured film obtained by thermal curing in the post baking step. The cured film obtained from the photosensitive resin composition of the present invention is excellent in dry etching resistance, so that even when exposed to dry etching conditions, the amount of film reduction is small.

In the dry etching process, as described above,

Examples of the feed-lye etching material usable in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, - tin oxide coated glass; But are not limited to, metals, semiconductors, and any substrate containing a patterned region of an insulating material, and the like.

The generation method of the plasma is not particularly limited, and both the reduced-pressure plasma method and the atmospheric plasma method can be applied.

The plasma etching may be performed by using an inert gas selected from, for example, helium, argon, krypton, and xenon, an inert gas selected from O ₂ , CF ₄ , C ₂ F ₄ , N ₂ , CO ₂ , SF ₆ , CHF ₃ , A reactive gas containing F or Cl can be preferably used.

In the dry etching process, for example, when the underlying layer is a silicon-based layer such as SiN _x or SiO ₂ , it is preferable to use a fluorine-based reaction gas such as O ₂ , CF ₄ or SiF ₆ .

The substrate in the dry etching step and the substrate in the coating step may be the same or different. For example, the substrate in the coating step may be a virtual substrate, and the cured film may be transferred onto another substrate before the dry etching step.

The cured film obtained by curing the photosensitive resin composition of the present invention can also be suitably used as a sacrifice layer for etching treatment such as dry etching or wet etching. When the cured film is peeled off after the etching treatment, It is possible to carry out delamination by a known wet process such as a dry plasma process or an alkaline chemical process. Since the cured film of the present invention is cured through the baking process, peeling by the dry plasma process is particularly preferable.

Even when used as a flat resist as an etching resist, an oxygen plasma treatment can be suitably used, but it is also possible to peel off the resist by a heat treatment with a chemical solution.

The cured film obtained by curing the photosensitive resin composition of the present invention can be particularly suitably used as a dry etching resist.

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention and can be suitably used as an interlayer insulating film. The cured film of the present invention is preferably a cured film obtained by the method of forming a cured film of the present invention.

With the photosensitive resin composition of the present invention, it is possible to obtain a cured film having a high sensitivity, suppressing the generation of residues during development, and having a surface with excellent smoothness, and the cured film is useful as an interlayer insulating film. Further, the interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency, can form a pattern of a good shape, and is also excellent in the smoothness of its surface. Therefore, an organic EL display device, a liquid crystal display . &Lt; / RTI &gt;

As the organic EL display device or liquid crystal display device to which the photosensitive resin composition of the present invention can be applied, the cured film formed using the photosensitive resin composition of the present invention is particularly limited except that the cured film is used as a planarizing film, a protective film, And various known organic EL display devices and liquid crystal display devices having various structures can be given.

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

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a structural conceptual diagram showing an example of an organic EL display device using the photosensitive resin composition of the present invention. Fig. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device and has a planarization film 4.

A bottom gate type TFT 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3 and a wiring 2 (height 1.0 mu m) connected to the TFT 1 is formed on the insulating film 3 with this contact hole interposed therebetween Respectively. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in a subsequent step to the TFT 1. [

The flattening film 4 is formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities due to the formation of the wirings 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 via the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing the insulating film 8, the first electrode 5 and the second electrode Can be prevented.

Although not shown in Fig. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited by a desired pattern mask. Subsequently, a second electrode made of Al is formed on the entire upper side of the substrate, An organic EL display device of an active matrix type in which an organic EL element is sealed by bonding using a glass plate for ultraviolet curing type epoxy resin and the TFT 1 for driving each organic EL element is connected can be obtained.

Fig. 2 is a conceptual cross-sectional view showing an example of the 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 is a liquid crystal display panel in which all of the two glass substrates 14 and 15 that are stuck Elements of the TFT 16 corresponding to the pixel are disposed. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 which passes through the contact hole 18 formed in the cured film 17 and forms a pixel electrode. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are arranged is provided.

[Example]

Next, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" are by weight.

&Lt; Synthesis Example 1 &

In a flask equipped with a cooling tube and a stirrer, 150 parts by weight of diethylene glycol ethyl methyl ether was added and the temperature was raised to 90 占 폚 under a nitrogen atmosphere. To the solution, 41.3 parts by weight of 1-ethoxyethyl methacrylate, 31.0 parts by weight of 3-ethyl-3-oxetanylmethyl methacrylate, 5.6 parts by weight of methacrylic acid, 2-ethylhexyl methacrylate And 10.0 parts by weight of dimethyl-2,2'-azobis (2-methylpropionate) as a polymerization initiator were dissolved and dissolved dropwise over 2 hours. After completion of dropwise addition, stirring was continued for 2 hours. 2.5 parts by weight of dimethyl-2,2'-azobis (2-methylpropionate) was further added to the solution, and the mixture was further stirred for 2 hours to terminate the reaction. Thus, Copolymer A-1 was obtained. The weight average molecular weight was 11,000.

&Lt; Synthesis Examples 2 to 41 &

2 to A-15, a-1 to a-5, B-1 to B-5 shown in Tables 1 and 2, except that the monomers used and the amounts thereof were changed, 16, and b-1 to b-5, respectively. The composition ratios (mol%) and the weight average molecular weight (Mw) of each of the synthesized copolymers are shown in Tables 1 and 2.

[Table 1]

[Table 2]

The abbreviations in Tables 1 and 2 are as follows.

MAEVE: 1-ethoxyethyl methacrylate

MATHF: tetrahydrofuran-2-yl methacrylate

MACHOE: 1- (cyclohexyloxy) ethyl methacrylate

MATHP: tetrahydro-2H-pyran-2-yl methacrylate

PHSEVE: 1-ethoxyethyl protective group of p-hydroxystyrene

OXE-30: Methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

GMA: glycidyl methacrylate

NBMA: n-butoxymethyl acrylamide

VBGE: p-vinylbenzyl glycidyl ether

MAA: methacrylic acid

PHS: p-hydroxystyrene

HEMA: 2-ethylhexyl methacrylate

AA: Acrylic acid

THFFMA: tetrahydrofurfuryl methacrylate

St: Styrene

α-MeSt: α-methylstyrene

MmA: methyl methacrylate

DCPM: methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl)

(Examples 1 to 68 and Comparative Examples 1 to 11)

(Solid content) shown in Tables 3 to 5 was dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid concentration became 27% by weight, And filtered through a membrane filter having a pore size of 0.2 탆 to prepare photosensitive resin compositions of Examples 1 to 68 and Comparative Examples 1 to 11, respectively.

[Table 3]

[Table 4]

[Table 5]

In the above table, the abbreviations of various additives are as follows.

C-1: Compound of the following structure (synthesized product)

C-2: Compound of the following structure (synthesized product)

C-3: Compound of the following structure (synthesized product)

C-4: CGI-1397 (BASF)

C-5: Compound of the following structure (synthesized according to the method described in paragraph 0108 of Japanese Patent Application No. 2002-528451)

C-6: PAI-1001 (manufactured by Midori Kagaku Co., Ltd.)

C-7: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

<Synthesis of C-1>

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

Acetic acid (7.3 g) and a 50 wt% hydroxylamine aqueous solution (8.0 g) were added to the suspension of the resulting ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated under reflux for 10 hours. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).

The resulting oxime compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was heated to room temperature and reacted for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered and then slurry was reslurried with methanol (20 mL), followed by filtration and drying to obtain C-1 (2.3 g).

In addition, ^C-1 1 H-NMR spectrum (300M㎐, CDCl ₃₎ of the, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), (D, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

<Synthesis of C-2>

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

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g) and magnesium sulfate (4.5 g) were added to the resulting suspension of the ketone compound (10.0 g) and methanol (100 mL) and the mixture was refluxed for 24 hours. After allowing to cool, water (150 mL) and ethyl acetate (150 mL) were added to separate the layers. The organic layer was separated into four portions of 80 mL of water, concentrated, and then purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

The obtained oxime (3.1 g) was sulfonated as in C-1 to obtain C-2 (3.2 g).

In addition, ¹ H-NMR spectrum (300M㎐, CDCl3) of the C-2 is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 ddt, 1H), 1.4-1.2 (m, 8H), 0.8 (t, 3H).

<Synthesis of C-3>

C-3 was synthesized in the same manner as C-1, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in C-1.

In addition, C-3 ¹ H-NMR spectrum (300M㎐, CDCl ₃₎ of the, δ = 8.3 (d, 1H ), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), (D, 1H), 7.1 (d, 1H), 5.6 (q, 1H), 1.7 (d, 3H).

E-1: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

E-2: DETX (diethyl thioxanthone)

F-1: 1,5-diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

F-2: Compound of the following structure

G-1: JER157S65 (manufactured by Mitsubishi Kagaku Co., Ltd.)

G-2: JER1031S (manufactured by Mitsubishi Kagaku Co., Ltd.)

G-3: Denacol EX-612 (manufactured by Nagase ChemteX Corporation)

G-4: Denacol EX-321L (manufactured by Nagase ChemteX Corporation)

G-5: MF-K60X (manufactured by Asahi Kasei Chemical Co., Ltd.)

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

H-2: 3-glycidoxypropyltriethoxysilane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

H-3: 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)

I-1: Compound of the following structure

I-2: Silicone surfactant SH-8400FLUID (manufactured by Toray Dow Corning Co., Ltd.)

&Lt; Evaluation of chemical resistance (release liquid resistance) >

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to obtain a photosensitive resin composition Layer.

The obtained photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure device (ultra high pressure mercury lamp) manufactured by Canon Inc., At 230 占 폚 for 1 hour to obtain a cured film.

The cured film was immersed in monoethanolamine at 60 DEG C for 5 minutes, the film was pulled up to wipe out the liquid on the surface, and the film thickness was immediately measured. The film thickness before immersion and the film thickness after immersion were compared, and the increased ratio was expressed as a percentage. The results are shown in Tables 6 to 8. The smaller the numerical value is, the better the peel solution resistance of the cured film is, and A or B is preferable.

Swelling rate (%) = film thickness after immersion (占 퐉) / film thickness before immersion (占 퐉) 占 100

A: 100% or more and less than 105%

B: 105% or more and less than 110%

C: 110% or more

&Lt; Evaluation of chemical resistance (NMP resistance) >

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to obtain a photosensitive resin composition Layer.

The obtained photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure device (ultra high pressure mercury lamp) manufactured by Canon Inc., At 230 占 폚 for 1 hour to obtain a cured film.

The cured film was immersed in NMP at 80 DEG C for 10 minutes, the film was pulled up to wipe out the liquid on the surface, and the film thickness was immediately measured. The film thickness before immersion and the film thickness after immersion were compared, and the increased ratio was expressed as a percentage. The results are shown in Tables 6 to 8. The smaller the numerical value is, the better the NMP resistance of the cured film is, and A or B is preferable.

Swelling rate (%) = film thickness after immersion (占 퐉) / film thickness before immersion (占 퐉) 占 100

A: 100% or more and less than 105%

B: 105% or more and less than 110%

C: 110% or more

&Lt; Adhesion of cured film &

Each of the photosensitive resin compositions was coated with a slit on an ITO (indium tin oxide) substrate, a Mo (molybdenum) substrate, and a titanium (Ti) substrate and then the solvent was removed by heating on a hot plate at 90 deg. Mu m of the photosensitive resin composition layer. The obtained photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure device (ultra high pressure mercury lamp) manufactured by Canon Inc., At 230 占 폚 for 1 hour to obtain a cured film. A cutter was used for the cured film, a nick was formed at intervals of 1 mm in the vertical and horizontal directions, 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. The results are shown in Tables 6 to 8. 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 of 5% or more

&Lt; Dry etching resistance >

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to obtain a photosensitive resin composition Layer.

The resulting photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure device (ultra high pressure mercury lamp) manufactured by Canon Inc., At 230 占 폚 for 1 hour to obtain a cured film. The cured film was subjected to etching with a dry etching apparatus "CDE-80N (Shibaura Mechatronics Co., Ltd.)" as an etching gas under conditions of CF ₄ 50 ml / min, O ₂ 10 ml / min, output 400 mW, Dry etching was performed. The etching rate was calculated from the film reduction amount. The results are shown in Tables 6 to 8. The smaller the numerical value is, the higher the dry etching resistance is, and A or B is preferable.

A: 30 Å / sec to 35 Å / sec

B: 35 Å / sec or more and less than 40 Å / sec

C: 40 Å / sec to 45 Å / sec

&Lt; Evaluation of sensitivity &

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a 90 ° C / 120 sec hot plate to volatilize the solvent to obtain a photosensitive resin composition Layer.

Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure device (ultra-high pressure mercury lamp) manufactured by CANON CO., LTD. Then, the exposed photosensitive composition layer was developed with an alkaline developer (0.3 wt% tetramethylammonium hydroxide aqueous solution) at 23 DEG C for 60 seconds, and rinsed with ultrapure water for 20 seconds.

With these operations, the optimum i-line exposure amount (Eopt) when resolving a line-and-space of 13 mu m at a ratio of 1: 1 was taken as sensitivity. The results are shown in Tables 6 to 8. The smaller the numerical value is, the more preferable A and B are the levels at which there is no practical problem, and C is not preferable from the viewpoint of productivity.

A: Less than 50 mJ / cm 2

B: 50 mJ / cm 2 or more and less than 300 mJ / cm 2

C: 300 mJ / cm 2 or more

<Evaluation of Display Performance in Display Device>

A liquid crystal display device using a thin film transistor (TFT) was produced by the following method (see Fig. 2). 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 while covering the TFT 1. Next, after a contact hole was formed in the insulating film 3, a wiring 2 (height 1.0 mu m) connected to the TFT 1 via the contact hole was formed on the insulating film 3.

In order to planarize the irregularities due to the formation of the wirings 2, the flattening film 4 was formed on the insulating film 3 in a state in which the irregularities by the wirings 2 were filled. The planarizing film 4 on the insulating film 3 was formed by spin coating each of the photosensitive resin compositions of Examples 1 to 57 and Comparative Examples 1 to 9 on the substrate and prebaking (90 DEG C x 2 minutes) on a hot plate, After irradiating i-line (365 nm) with 25 mJ / cm 2 (roughness 20 mW / cm 2) using a high-pressure mercury lamp on the mask, the pattern was formed by developing with an aqueous alkaline solution and heat treatment was performed at 230 ° C. for 60 minutes. The coating properties upon application of the photosensitive resin composition were satisfactory, and wrinkles and cracks were not observed in the cured films obtained after exposure, development and firing. In addition, the average step of the wiring 2 was 500 nm, and the film thickness of the prepared planarization film 4 was 2,000 nm.

A driving voltage was applied to the obtained liquid crystal display device, and a gray display at the time of inputting a gray test signal was visually observed to evaluate the occurrence of display unevenness. The results are shown in Tables 6 to 8. A and B are levels at which there is no practical problem.

A: No irregularities at all (very good)

B: The display shows faint non-uniformity, but the practical level (good)

C: Strong unevenness on the display (poor)

[Table 6]

[Table 7]

[Table 8]

It was found that the photosensitive resin composition of the present invention had a high sensitivity, a high resistance to peeling liquid and NMP, good adhesion to a transparent electrode film and a metal, and excellent dry etching resistance.

(Example 69)

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

A bottom gate type TFT 1 was formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ was formed while covering the TFT 1. Next, 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 via the contact hole is formed on the insulating film 3 . The wirings 2 are for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

In order to planarize the irregularities formed by the formation of the wirings 2, the planarization layer 4 was formed on the insulating film 3 in a state in which irregularities by the wirings 2 were filled. The planarizing film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking it on a hot plate (90 占 폚 for 2 minutes), and then using a high- , Irradiated with i-line (365 nm) at 45 mJ / cm 2 (illuminance: 20 mW / cm 2), developed with an aqueous alkaline solution to form a pattern, and subjected to heat treatment at 230 ° C for 60 minutes. The coating properties upon application of the photosensitive resin composition were good, and wrinkles and cracks were not observed in the cured films obtained after exposure, development and firing. In addition, the average step of the wiring 2 was 500 nm, and the film thickness of the prepared planarization film 4 was 2,000 nm.

Next, 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 being connected to the wiring 2 through the contact hole 7. Thereafter, the resist was coated and 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 ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film, the insulating film 8 was formed in the same manner as above using the photosensitive resin composition of Example 3. By providing this insulating film, a short circuit can be prevented between the first electrode 5 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 deposited through a desired pattern mask in a vacuum vapor deposition apparatus. Subsequently, a second electrode made of Al was formed on the entire surface above 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 organic EL display device of an active matrix type in which the TFTs 1 for driving the organic EL elements were connected to each organic EL element was obtained. When a voltage was applied through the driving circuit, good display characteristics were exhibited and it was found that the organic EL display device was highly reliable.

(Example 70)

An organic EL device was produced in the same manner as in Example 69 except that the photosensitive resin composition of Example 16 was replaced with the photosensitive resin composition of Example 16. Exhibited good display characteristics, indicating that the organic EL display device is highly reliable.

(Example 71)

An organic EL device was prepared in the same manner as in Example 69 except that the photosensitive resin composition of Example 31 was replaced with the photosensitive resin composition of Example 31. Exhibited good display characteristics, indicating that the organic EL display device is highly reliable.

(Example 72)

In the active matrix type liquid crystal display device described 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 of Example 72. [

That is, the photosensitive resin composition of Example 1 was used to form a cured film 17 as an interlayer insulating film in the same manner as in the method of forming the planarization film 4 of the organic EL display device in Example 69.

When the driving voltage was applied to the obtained liquid crystal display device, good display characteristics were exhibited and it was found that the liquid crystal display device was highly reliable.

(Example 73)

A liquid crystal display device was manufactured in the same manner as in Example 72 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 16. And exhibited good display characteristics, indicating that the liquid crystal display device is highly reliable.

(Example 74)

A liquid crystal display device was prepared in the same manner as in Example 72 except that the photosensitive resin composition of Example 31 was replaced with the photosensitive resin composition of Example 31. And exhibited good display characteristics, indicating that the liquid crystal display device is highly reliable.

(Example 75)

A liquid crystal display was manufactured in the same manner as in Example 72 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 60. [ And exhibited good display characteristics, indicating that the liquid crystal display device is 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 (18)

(Component A) a copolymer having at least (a1) a structural unit having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group,
(Component B) a copolymer having at least (a1) a structural unit having an acidic group and (b2) a structural unit having a crosslinkable group, wherein the acid group has no structural unit having a residue protected by an acid-
(Component C) photoacid generator, and
(Component D) a solvent,
, The crosslinkable groups in the structural unit (a2) and the structural unit (b2) are each independently an epoxy group, an oxetanyl group or an N-alkoxymethyl group,
Component C is a compound selected from the group consisting of trichloromethyl-s-triazine, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. The method according to claim 1,
Wherein the structural unit (a1) is a structural unit having a carboxyl group in a form protected with an acetal or ketal moiety. The method according to claim 1,
Wherein the structural unit (a1) is a structural unit represented by the formula (a1-1).

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, R ² and R ³ may be connected to form a ring.) The method according to claim 1,
Wherein the structural unit (a2) is a structural unit having an epoxy group and / or an oxetanyl group. The method according to claim 1,
Wherein the acid group of the structural unit (b1) is a carboxyl group or a phenolic hydroxyl group. The method according to claim 1,
Wherein the structural unit (b2) is a structural unit having an epoxy group and / or an oxetanyl group. The method according to claim 1,
Wherein the component B further comprises the structural unit represented by the formula (b3).

(Wherein R ⁴ represents a hydrogen atom or a methyl group). The method according to claim 1,
When the content W _A and W _B of the content weight ratio of component B in component _{A W A / W B = 98} / 2~20 / 80 of a positive photosensitive resin composition. The method according to claim 1,
Wherein the component C is the oxime sulfonate photo-acid generator represented by the formula (c1).

(In the formula (c1), R ⁵ and R ⁶ each independently represent a monovalent organic group, R ⁵ and R ⁶ may be connected to form a ring, and R ⁷ represents an alkyl group, a cycloalkyl group or an aryl group. ) The method according to claim 1,
Wherein the component C is a compound represented by the formula (OS-3), the formula (OS-4), the formula (OS-5) or the formula (c4).

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ² each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ¹ represents an alkyl group, an aryl group or a heteroaryl group, ⁶ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents 0 to 6 Represents an integer.)

(Wherein R ^B1 represents an alkyl group, an alkoxy group or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.) The method according to claim 1,
A positive photosensitive resin composition further comprising a photosensitizer. (1) a layer forming step of forming a film-like layer on a substrate by using the positive photosensitive resin composition according to any one of claims 1 to 11,
(2) a solvent removing step of removing the solvent from the applied photosensitive resin composition,
(3) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray,
(4) a developing step of developing the exposed photosensitive resin composition with an aqueous developing solution, and
(5) A post-baking step of thermally curing the developed photosensitive resin composition. 13. The method of claim 12,
And a step of exposing the developed photosensitive resin composition to the whole surface after the development step and before the post-baking step. 13. The method of claim 12,
(6) A method for forming a cured film, which further comprises a dry etching step of performing dry etching on the substrate having the cured film obtained by thermosetting. A cured film formed by the method according to claim 12. 16. The method of claim 15,
A cured film which is an interlayer insulating film. An organic EL display device comprising the cured film according to claim 15. A liquid crystal display device comprising the cured film according to claim 15.

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