JP5589101B2 - Photosensitive resin composition and method for producing pattern using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a method for producing a pattern using the same. Furthermore, it is related with the pattern manufactured by the manufacturing method of an organic EL (organic electroluminescence) display apparatus or a liquid crystal display device including this pattern manufacturing method, and a pattern manufacturing method. More specifically, the present invention relates to a positive photosensitive resin composition suitable for forming resist etching of electronic parts such as liquid crystal display devices and organic EL display devices, and a pattern manufacturing method using the same.

  An organic EL display device, a liquid crystal display device, and the like are provided with a metal wiring pattern such as a patterned ITO film. A widely known method for forming a pattern such as an ITO film is to apply a photosensitive resin composition on the ITO film, remove the solvent, expose and develop, and etch the ITO film using the formed pattern as a mask for processing. It has been.

  In recent years, high resolution of ITO processing has been demanded in order to make organic EL display devices and liquid crystal display devices have high-definition display characteristics. In order to finely process ITO with high definition, high resolution of a photosensitive resin composition that functions as a mask during etching is required.

  As a photosensitive resin composition capable of obtaining a high-definition and fine pattern shape, for example, Patent Document 1 discloses a constituent unit of a hydroxystyrene monomer and a constituent unit of a hydroxystyrene monomer in which a hydroxyl group is protected with an acid-decomposable group. The radiation sensitive resin composition containing the copolymer which consists of is disclosed. Patent Document 2 discloses a positive photo compound in which a photoacid generator and a tertiary amine compound having an ether bond are blended with a resin that becomes alkali-soluble by the action of an acid from an insoluble or hardly soluble state to alkali. A resist composition is disclosed.

JP 9-325473 A Japanese Patent Laid-Open No. 10-326015

  Here, as a development trend in recent years, there has been a tendency to pursue a composition having an absorption region in a short wave as the exposure wavelength is shortened, and to seek a material having no absorption in the visible region. However, such a composition requires the use of an expensive exposure apparatus with good resolving power such as an i-line stepper. The present invention has been accomplished in view of such circumstances, and it is possible to achieve high sensitivity, resolution, and rectangularity using an inexpensive low NA (aperture) exposure apparatus (NA = 0.1 or less). An object is to provide an excellent photosensitive resin composition.

  Under such circumstances, as a result of intensive studies by the inventor of the present application, by blending a polymer having a structural unit having an acid group and a protected acid group with a PHS polymer, all of these structural units are obtained. Is included in one type of polymer (1 binder system) and each of the three structural units is a separate polymer (3 binder system), phase separation (entangled state of polymer chains in the resist film) The situation was different and the sensitivity and resolution were improved. Furthermore, surprisingly, it has been found that by using a blend system, rectangularity is improved, and the present invention has been completed.

Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <12>.
<1> (A-1) a structural unit having an acid group and a polymer having a structural unit represented by formula (a-1), (A-2) represented by formula (a-2) A polymer having a structural unit;
(B) a photoacid generator,
(C) solvent,
Containing a photosensitive resin composition.
Formula (a-1)
(In General Formula (a-1), R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group; ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond Or represents an arylene group.)
Formula (a-2)
(In the general formula (a-2), R ⁴ is a hydrogen atom or a methyl group.)
<2> (A-2) The photosensitive resin composition as described in <1> in which a polymer further has a structural unit represented by general formula (a-3).
Formula (a-3)
(In the general formula (a-3), R ⁴ is a hydrogen atom or a methyl group. R ⁵ is a linear, branched, or cyclic alkyl group, and at least one —O— is present in the alkyl group. Including)
<3> The photosensitive resin composition according to <2>, wherein R ⁵ in the general formula (a-3) is represented by the general formula (a-4) or (a-5). Formula (a-4)
(In the general formula (a-4), R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. It binds to the general formula (a-3) at the position of the US mark.)
Formula (a-5)
(In the general formula (a-5), it is combined with the general formula (a-3) at the position of the US mark.)
<4> The photosensitive resin composition according to any one of <1> to <3>, further comprising (D) a sensitizer.
<5> (D) The photosensitive resin composition as described in <4> whose sensitizer is a compound represented by the following general formula (O) or general formula (P).
(In the general formula (0), R ¹ and R ² each represent an aryl group or a heterocyclic structure having one or more ethylene bonds. L ¹ is a 2-4 valent group having 2-4 ethylene bonds. Represents a linking group, and n and m each represent 1 or 2.)
General formula (P)
(In the general formula (P), each R is an alkyl group having 1 to 8 carbon atoms.)
<6> (B) The photosensitive resin composition according to any one of <1> to <5>, wherein the photoacid generator is an oxime sulfonate compound.
<7> The photosensitive resin composition according to any one of <1> to <6>, further comprising an epoxy resin.
<8> (1) The process of applying the photosensitive resin composition in any one of <1>-<7> on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) a step of etching the substrate using the formed resist pattern as a mask; and
(6) A method for producing a pattern, comprising a step of peeling the resist pattern. <9> The method for producing a pattern according to <8>, including a step of post-baking the resist pattern at 100 to 160 ° C. after the developing step and before the etching step.
<10> The method for producing a pattern according to <8> or <9>, wherein the substrate is an ITO substrate, a molybdenum substrate, a silicon substrate, a Cu substrate, an Al substrate, or a single crystal sapphire substrate.
<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <7>. <12> A method for producing an organic EL display device or a liquid crystal display device, comprising the method for producing a pattern according to any one of <8> to <11>.

  According to the present invention, it is possible to provide a photosensitive resin composition having high sensitivity and excellent resolution and rectangularity. In particular, an inexpensive low NA (aperture) exposure apparatus (NA = 0.1) can be used without using an expensive exposure apparatus with good resolving power such as an i-line stepper or a short-wave exposure light source. The present invention is highly valuable in that these performances can be achieved.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL display device in the present invention refers to an organic electroluminescence display device. The polydispersity in the present invention refers to the value of Mw / Mn.

The photosensitive resin composition of the present invention comprises (A-1) a polymer having a structural unit having an acid group and a structural unit represented by the general formula (a-1), (A-2) a general formula (a -2) a polymer having a structural unit represented by:
It contains (B) a photoacid generator and (C) a solvent.
Formula (a-1)
(In General Formula (a-1), R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group; ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond Or represents an arylene group.)
Formula (a-2)
(In the general formula (a-2), R ⁴ is a hydrogen atom or a methyl group.)

Conventionally, the structural unit having an acid group, the structural unit represented by the general formula (a-1), and the structural unit represented by the general formula (a-2) In the case of inclusion in a coalescence (1 binder system) was common, but in the present invention, (A-1) a structural unit having an acid group and a weight having a structural unit represented by the general formula (a-1) are used. By using a blend system of the polymer and the polymer having the structural unit represented by (A-2) general formula (a-2), the state of phase separation differs, and the sensitivity, resolution, and rectangularity are improved. It has succeeded in making it happen.
The photosensitive resin composition of the present invention is preferably used as a chemically amplified positive photosensitive resin composition.
Hereinafter, the composition of the present invention will be described in detail.

<(A) Polymer component>
The photosensitive resin composition of the present invention contains (A-1) and (A-2) as essential components as a polymer component, and may further contain another polymer (A-3). Hereinafter, these polymer components will be described. In the present specification, “component (A)” and “polymer component” are blends of (A-1), (A-2) and (A-3) unless otherwise specified.

  (A) The polymer component is preferably alkali-insoluble, and is preferably a resin that becomes alkali-soluble when the acid-decomposable group of the structural unit represented by formula (a-1) is decomposed. . Here, the acid-decomposable group means a functional group that can be decomposed in the presence of an acid. That is, since the general formula (a-1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected with an acid-decomposable group, the carboxyl group can be generated by the decomposition of the protective group with an acid. is there. Here, in the present invention, “alkali-soluble” means a coating film (thickness) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. 3 μm) is a dissolution rate in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. of 0.01 μm / second or more. “Alkali insoluble” means that the solution of the compound (resin) is a substrate. The dissolution rate of the coating film (thickness 3 μm) of the compound (resin) formed by applying the coating on the substrate and heating at 90 ° C. for 2 minutes in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. It means less than 0.01 μm / second.

(A-1) A structural unit having an acid group and a polymer having a structural unit represented by formula (a-1) The polymer (A-1) in the present invention comprises a structural unit having an acid group, and It has a structural unit represented by general formula (a-1).

(Acid group)
The polymer (A-1) contains an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the resin as a structural unit having an acid group using a monomer capable of forming an acid group. Inclusion of such a structural unit having an acid group in the resin tends to increase alkali solubility.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit having an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid and / or an ester thereof. .

  In the present invention, it is particularly preferable from the viewpoint of sensitivity that a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group is contained, and a structural unit having a carboxyl group is more preferable.

  The structural unit having an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, further preferably 5 to 40 mol%, and more preferably 5 to 30 mol% of the structural unit of the polymer (A-1) component. % Is particularly preferable, and 5 to 20 mol% is particularly preferable.

(Polymer having structural unit represented by general formula (a-1))
(A-1) polymer used by this invention has a polymer which has a structural unit represented by general formula (a-1).
Formula (a-1)
(In General Formula (a-1), R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group; ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond Or represents an arylene group.)

When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.

Preferable specific examples of the structural unit represented by the general formula (a-1) include the following structural units. R represents a hydrogen atom or a methyl group.

  The structural unit represented by the general formula (a-1) is preferably 10 to 80 mol%, more preferably 20 to 80 mol%, and more preferably 30 to 70 mol% of the structural unit of the polymer (A-1) component. More preferred.

  The polymer (A-1) in the present invention may have other structural units within the range not departing from the gist of the present invention (except for those corresponding to the general formula (a-2)).

  As another structural unit, (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.

  In the structural unit constituting the polymer (A-1), the content of the other structural unit is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

  (A-1) The protection rate of the polymer is preferably 1 to 60%, more preferably 5 to 50%, and still more preferably 10 to 40%. By setting it as such a range, a sensitivity improves and the difference (discrimination) of the solubility of an exposed part and an unexposed part becomes favorable. A protection rate means the molar ratio of the protected group by making all the structural units in a polymer (A-1) into 100 mol%.

  The weight average molecular weight (Mw) of the (A-1) polymer is preferably in the range of 2000 to 15000, more preferably 5000 to 12000, and still more preferably 7500 to 12000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 15000 or less, an effect that sensitivity and PED characteristics are improved is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A-1) is preferably 1.0 to 4.0, more preferably 1.5 to 3.5, 2.0 to 3.0 are more preferable. By setting it as such a range, it is excellent in rectangularity.

(A-2) Polymer having structural unit represented by general formula (a-2) The (A-2) polymer used in the present invention has a structural unit represented by general formula (a-2). Has a polymer.
Formula (a-2)
(In the general formula (a-2), R ⁴ is a hydrogen atom or a methyl group.)
R ⁴ is preferably a hydrogen atom.
The OH group may be any of p-, m- and o-, but is preferably bonded to the p-position.

  The structural unit represented by the general formula (a-2) is preferably 5.0 to 30 mol%, more preferably 10 to 20 mol% of the structural unit of the polymer (A-2) component. If the amount is less than this, the effect cannot be obtained. If the amount is too large, the sensitivity becomes too high and the exposure process margin becomes narrow.

The polymer (A-2) in the present invention may have other structural units within a range not departing from the gist of the present invention. However, the other structural unit is not a structural unit having an acid group and a structural unit represented by the general formula (a-1). It is preferable that another structural unit has a structural unit represented by general formula (a-3).
Formula (a-3)
(In the general formula (a-3), R ⁴ is a hydrogen atom or a methyl group. R ⁵ is a linear, branched, or cyclic alkyl group, and at least one —O— is present in the alkyl group. Including)
R ⁵ is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. R ⁵ preferably contains one —O— in the alkyl group.
R ⁵ in the general formula (a-3) is preferably represented by the general formula (a-4) or (a-5).

Formula (a-4)
(In the general formula (a-4), R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. It binds to the general formula (a-3) at the position of the US mark.)

R ² is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
Formula (a-5)
(In the general formula (a-5), it is combined with the general formula (a-3) at the position of the US mark.)

Below, the preferable example of the structural unit represented by general formula (a-3) is shown below. However, it goes without saying that the present invention is not limited to these examples.

  Among the structural units constituting the polymer (A-2), the structural unit represented by the general formula (a-3) is preferably 5 to 40 mol% of the structural unit of the polymer (A-2) component. -40 mol% is more preferable, and 20-35 mol% is more preferable.

The polymer (A-2) may further have other structural units. Examples of other structural units include styrenes, (meth) acrylic acid alkyl esters, and (meth) acrylic acid cyclic alkyls. Esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated Examples thereof include dicarboxylic acid anhydrides and other unsaturated compounds.
Moreover, the structural unit which has an acid group, and the structural unit which has a crosslinkable group can also be mentioned.
The compounding amount of these structural units is preferably 30 mol% or less, more preferably 10 mol% or less, based on all the structural units of the polymer (A-2).

  (A-2) The protection rate of the polymer is preferably 1 to 60%, more preferably 5 to 50%, and still more preferably 10 to 40%. By setting it as such a range, an image disk, a sensitivity, and resolution become favorable. A protection rate means the molar ratio of the protected group by making all the structural units in a polymer (A-2) 100 mol%.

  The weight average molecular weight (Mw) of the polymer (A-2) is preferably in the range of 2000 to 15000, more preferably 5000 to 12000, and still more preferably 7500 to 12000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 15000 or less, an effect that sensitivity and PED characteristics are improved is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A-2) is preferably 1.0 to 4.0, more preferably 1.5 to 3.5, 2.0 to 3.0 are more preferable. By setting it as such a range, rectangularity improves.

(A-1) and (A-2) compounding ratio Although the photosensitive resin composition of this invention contains (A-1) and (A-2) as a polymer component, these mass ratios are as follows. 1: 6 to 6: 1 is preferable, and 2: 5 to 8: 1 is more preferable. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

Other polymers (A-3)
In the present invention, other polymer (A-3) may be included in addition to the above polymer. For example, a styrene polymer is exemplified. These polymers are preferably 10% by weight or less of the total polymer components.

  The composition of the present invention preferably contains (A) the polymer component in a proportion of 60% by weight or more, more preferably 80% by weight or more, based on the total solid content.

<(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.

  Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, from the viewpoint of insulation, it is preferable to use an onium salt compound and an oxime sulfonate compound, and an oxime sulfonate compound is more preferable. When the oxime sulfonate compound is used, a significantly superior effect is obtained as compared with the case where the onium salt compound is used. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A. It can be illustrated.

  Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B-1).

Formula (B-1)
(In general formula (B-1), R ²¹ represents an alkyl group or an aryl group. The wavy line represents a bond with another group.)

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group for R ²¹ is a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group, etc.). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate structure represented by the general formula (B-1) is also preferably an oxime sulfonate compound represented by the following general formula (B-2).

General formula (B-2)
(In the general formula (B-2), R ⁴² represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. And when m4 is 2 or 3, the plurality of X may be the same or different.)

Preferred ranges of R ^42, the same as the preferable range of the R ^21.
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1.
In the general formula (B-2), m4 is 1, X is a methyl group, the substitution position of X is an ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

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

General formula (B-3)
(In General Formula (B-3), R ⁴³ has the same meaning as R ⁴² in Formula (B-2), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or 1 to 1 carbon atoms. 4 represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—. A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, 0-2 are preferable and 0-1 are especially preferable.

  Specific examples of the compound represented by the general formula (B-3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyl). Oxyimino) benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] Acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino)- 4-methoxyphenyl] acetonitrile, α-[(4 It can be given toluenesulfonyl) -4-methoxyphenyl] acetonitrile.

  Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii) and the like, and these can be used alone or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

  As a compound containing the oxime sulfonate structure represented by the said general formula (B-1), it is also preferable that it is a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
As R ^{121 to} R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

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

In the general formula (OS-2), R ¹⁰¹ , R ¹⁰² , R ^{121 to} R ¹²⁴ are respectively synonymous with those in the formula (OS-1), and preferred examples are also the same.
Among these, an embodiment in which R ¹⁰¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). And R ¹⁰¹ is most preferably a cyano group, a phenyl group, or a naphthyl group.

  In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

  Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include the compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to 1). b-34), but the present invention is not limited thereto.

  In this invention, as a compound containing the oxime sulfonate structure represented by the said general formula (B-1), the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-) The oxime sulfonate compound represented by 5) is preferred.

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents an integer of 0 to 6 Represents.)

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.

In the general formulas (OS-3) to (OS-5), as the aryl group in R ²² , R ²⁵ and R ^28, an aryl group having 6 to 30 carbon atoms which may have a substituent may be used. preferable.

Further, in the above general formula (OS-3) ~ (OS -5), as the heteroaryl group in R ^1, heteroaryl group having a total carbon number of 4-30 which may have a substituent is preferable.

In the general formulas (OS-3) to (OS-5), at least one ring of the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be a heteroaromatic ring. For example, a heteroaromatic ring and benzene The ring may be condensed.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. preferable.
In the general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

In the general formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n ^{1 to} n ³ each independently represent 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ are each independently 1 is preferable, and when X ^{1 to} X ³ are S, n ^{1 to} n ³ are preferably 2 each independently.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Represent. Among them, R ²⁴ , R ²⁷ and R ³⁰ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

In the general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.

In the general formulas (OS-3) to (OS-5), m ^{1 to} m ³ each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
Further, with respect to each of the substituents of (OS-3) to (OS-5), the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A. The preferred range of groups is likewise preferred.

  Moreover, the compound containing the oxime sulfonate structure represented by the general formula (B-1) is an oxime sulfonate compound represented by any one of the following general formulas (OS-6) to (OS-11). Is particularly preferred.

(In the formulas (OS-6) to (OS-11), R ^{301 to} R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.)

  Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.

  Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.

  In the photosensitive resin composition of the present invention, (B) the photoacid generator is based on 100 parts by mass of all resin components (preferably a solid content, more preferably a total of copolymers) in the photosensitive resin composition. 0.1 to 10 parts by mass is preferably used, and 0.5 to 10 parts by mass is more preferably used. Two or more kinds can be used in combination.

<(C) Solvent>
The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the components (A) and (B), which are essential components, and other components described below are dissolved in a solvent (C). As a solvent used for the preparation of the composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the solvent (C) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. Moreover, as a specific example of the solvent used for the photosensitive resin composition of this invention, the solvent of paragraph number 0174-0178 of Unexamined-Japanese-Patent No. 2011-221494, paragraph number 0167-0168 of Unexamined-Japanese-Patent No. 2012-194290. And the contents thereof are incorporated herein by reference.

Specific examples of the (C) solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers [0174] to [0178] of JP2011-221494A.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.

The component (C) is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof, a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., and a boiling point of 160 ° C. A solvent having a boiling point of 200 ° C. or lower or a mixture thereof is more preferable, and a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and a solvent having a boiling point of 160 ° C. or higher and 200 ° C. or lower is still more preferable.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

  The content of the solvent (C) in the photosensitive resin composition of the present invention is 50 per 100 parts by weight of all resin components (preferably solid content, more preferably the (A) polymer) in the photosensitive resin composition. It is preferably ˜3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and even more preferably 150 to 1,500 parts by weight.

<Other ingredients>
In addition to the component (A), the component (B), and the component (C), the positive photosensitive resin composition of the present invention includes (D) a sensitizer and (E) a basic compound as necessary. (F) Adhesion improver, (G) surfactant, (H) antioxidant can be preferably added. Further, the positive photosensitive resin composition of the present invention includes a plasticizer, a thermal radical generator, an antioxidant, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives can be added.

<(D) Sensitizer>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (B) the photoacid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Among the polynuclear aromatics, compounds represented by the following general formula (O) or general formula (P) are most preferable.
(In the general formula (0), R ¹ and R ² each represent an aryl group or a heterocyclic structure having one or more ethylene bonds. L ¹ is a 2-4 valent group having 2-4 ethylene bonds. Represents a linking group, and n and m each represent 1 or 2.)
General formula (P)
(In the general formula (P), each R is an alkyl group having 1 to 8 carbon atoms.)

(About general formula (O))
R ¹ and R ² each preferably represents an aryl group or a heterocyclic structure having one or more ethylene bonds, and at least one of R ¹ and R ² preferably represents a heterocyclic structure having one or more ethylene bonds. More preferably, R ¹ and R ² both represent a heterocyclic structure having one or more ethylene bonds. The heterocycle preferably contains a sulfur atom.
The cyclic structure possessed by R ¹ and R ² may be a single ring or a condensed ring. In the present invention, each of the heterocyclic structures having one or more aryl groups or ethylene bonds in R ¹ and R ² preferably includes only a single ring as the cyclic structure. In this case, the structure may be such that only one monocycle or two or more monocycles are linked directly or via a linking group, and preferably 1 to 4 monocycles and more preferably one monocycle.
The ring contained in R ¹ and R ² is exemplified by two or more condensed rings of a 5-membered ring, a 6-membered ring, a 5-membered ring and a 6-membered ring, and a 5-membered ring or a 6-membered ring is preferable.

R ¹ and R ² are each preferably a phenyl group which may have a substituent, or a group represented by the following general formula (O-1).
Formula (O-1)
(In general formula (O-1), R represents a substituent, and r is an integer of 0 to 2.)

As for the substituent which the phenyl group may have and the substituent in the general formula (O-1), the mass of one substituent portion per molecule is preferably 250 or less, and 100 or less. Is more preferable. The substituent that the phenyl group may have and the substituent in the general formula (O-1) are each preferably a halogen atom, an alkoxy group, an alkyl group, or an amino group. Are more preferable, and an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 4 carbon atoms is more preferable.
The phenyl group preferably has no substituent.
r is preferably 0 or 1, more preferably 0.

R ¹ and R ² are preferably the same group.

  n and m each represent 1 or 2, each is preferably 1, and both are more preferably 1.

L ¹ preferably has at least an alkenylene group or a heterocyclic structure having one or more ethylene bonds, and more preferably a group represented by the following general formula (O-2) or (O-3). More preferably, it is represented by the general formula (O-2).
The number of ethylene bonds in L ¹ is preferably 2 to 3, and more preferably 3.

Formula (O-2)
(In general formula (O-2), S1 is an integer of 1-6.)
S1 is preferably an integer of 1 to 4, and more preferably 1.
General formula (O-3)
(In general formula (O-3), S2 is an integer of 2 to 4.)
S2 is preferably 2 or 3.

The compound represented by the general formula (O) is preferably a compound represented by any one of the following general formulas (O-4) to (O-6).
General formula (O-4)
General formula (O-5)
General formula (O-6)
(In general formulas (O-4) to (O-6), R ^{1 to} R ⁶ are each a hydrogen atom or a substituent.)
In general formulas (O-4) to (O-6), R ^{1 to} R ⁶ are each more preferably a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. An alkoxy group or an alkyl group having 1 to 4 carbon atoms is more preferable, and a hydrogen atom is more preferable.

  In the general formula (O), the number of ethylene bonds is preferably 4 to 14, and more preferably 5 to 10.

Although the compound represented by general formula (O) preferably used for this invention below is illustrated, it cannot be overemphasized that this invention is not limited to these. In the following, Me represents a methyl group.

(About the compound represented by the general formula (P))
In general formula (P), R is respectively a C1-C8 alkyl group, and a C2-C6 alkyl group is more preferable.

The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by weight, preferably 10 to 500 parts by weight, with respect to 100 parts by weight of the photoacid generator of the photosensitive resin composition. It is more preferable that it is 50 to 200 parts by weight.
Two or more kinds can be used in combination.

<(E) Basic compound>
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound used in the present invention can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Specific examples of the basic compound include the compounds described in paragraph numbers 0052 to 0056 of JP-A-2009-98616, the contents of which are incorporated herein.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.

In the present invention, the basic compound is preferably at least one of compounds represented by the following general formulas (Qa), (Qb), and (Qc).
(In the general formula (Qa), R ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom. Y ¹ represents an oxygen atom. Or -NH- group, p1 represents an integer of 1 to 3)
The basic compound used in the present invention is a compound having a structural feature of having a partial structure represented by at least one urea or thiourea bond in the molecule and containing a morpholino group or a piperazino group. is there.

The basic compound is preferably a thiourea compound represented by the following general formula (Q-a2), in which X is a sulfur atom, that is, a partial structure represented by a thiourea bond.
(In the general formula (Q-a2), R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Y ² represents an oxygen atom or an —NH— group. Represents an integer of 1 to 3)

More preferably, the basic compound is a thiourea compound represented by the following general formula (Q-a3), that is, it contains a morpholino group.
(In the general formula (Q-a3), R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. P3 represents an integer of 1 to 3)

Examples of the alkyl group having 1 to 6 carbon atoms in R ^{2 to} R ⁴ of the compounds represented by the general formulas (Qa) to (Qa3) include a methyl group, an ethyl group, a propyl group, and n-butyl. C1-C4 alkyl groups, such as a group, a sec-butyl group, and a t-butyl group, are preferable, a linear C1-C4 alkyl group is more preferable, and a methyl group is especially preferable.

Examples of the cycloalkyl group having 3 to 10 carbon atoms in R ^{2 to} R ⁴ of the compounds represented by the general formulas (Qa) to (Qa3) include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. A cycloalkyl group having 3 to 10 carbon atoms such as cycloalkyl group having 5 to 10 carbon atoms is more preferable, and a cyclohexyl group is particularly preferable.

  Specific examples of the basic compound represented by the general formula (Qa) include the following compounds (C-1) to (C-7), but the present invention is limited to these. It is not something.

  These basic compounds can be used alone or in admixture of two or more.

In general formula (Qb), R < ⁸ >, R <^9> , R < ¹⁰ > has a hydrogen atom and the C1-C6 alkyl group which may have a substituent, and a substituent each independently. Or an aryl group which may be substituted or a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent.

Examples of the alkyl group or aryl group having 1 to 6 carbon atoms in R ^{8 to} R ¹⁰ of the compound represented by the general formula (Qb) include a methyl group, an ethyl group, a propyl group, an n-butyl group, sec -A butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group and the like are preferable, a linear alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is particularly preferable.

Examples of the cycloalkyl group having 3 to ¹⁰ carbon atoms in R ^{8 to} R ¹⁰ of the compound represented by the general formula (Qb) include 3 to 3 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. A cycloalkyl group having 10 carbon atoms is preferable, a cycloalkyl group having 5 to 10 carbon atoms is more preferable, and a cyclohexyl group is particularly preferable.

The alkyl group, the substituent which may be aryl groups have at R ⁸ to R ¹⁰ of the compound represented by general formula (Q-b), the alkyl group of R ³ in the general formula (Q-a2) It is the same as the preferable substituent which may have.

  In the present invention, the addition amount of the basic compound is all resin components (preferably solid content, more preferably the (A) polymer in the photosensitive resin composition) from the viewpoint of satisfying all of sensitivity and resolution. ) Is usually used in the range of 0.001 to 20% by weight, preferably 0.005 to 10% by weight, and most preferably 0.01 to 5% by weight.

<(F) Adhesion improver>
The photosensitive resin composition of the present invention may contain an adhesion improving agent. The adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As a preferable silane coupling agent, for example, the description of paragraph number 0175 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification. These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
The content of the adhesion improving agent in the photosensitive resin composition of the present invention is based on 100 parts by weight of all resin components (preferably solid content, more preferably (A) copolymer) in the photosensitive resin composition. 0.1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable.

<(G) Surfactant>
The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
As preferable examples of the surfactant, for example, the description of paragraph numbers 0184 to 0196 in JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of (G) surfactant in the photosensitive resin composition of the present invention is 100 weights of all resin components (preferably solid content, more preferably (A) copolymer) in the photosensitive resin composition. The amount is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 1 part by weight with respect to parts.

<(H) Antioxidant>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
As such an antioxidant, for example, the description of paragraph numbers 0194 to 0196 in JP 2012-042837 A can be referred to, and the contents thereof are incorporated in the present specification.

The content of the antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by weight. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

[Pattern manufacturing method]
Next, the pattern manufacturing method of the present invention will be described.
The pattern manufacturing method of the present invention includes the following steps (1) to (6).
(1) The process of applying the photosensitive resin composition of this invention on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) etching the substrate using the formed resist pattern as a mask, and
(6) A step of removing the resist pattern.
Each step will be described below in order.

In the step (1), the positive photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
In the step (2), the solvent is removed from the applied film by decompression (vacuum) and / or heating to form a dry coating film on the substrate.

  (3) In the exposing step, the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm to 450 nm. In this step, (B) the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the hydroxy group protected by the acid-decomposable group (protected carboxyl group) of the structural unit (a-1) having an acid group contained in the component (A-1) is hydrolyzed. A phenolic hydroxyl group is formed.

  In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed as necessary. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The pattern production method of the present invention preferably includes a step of post-baking and thermosetting the resist pattern after the development step and before the etching step.

The hydroxy group of the structural unit (A-2) of hydroxystyrene contained in the component (A) in the present invention has low activation energy for acid decomposition, and is easily decomposed by an acid derived from a photoacid generator by exposure, Since a phenolic hydroxyl group is generated, a positive image can be formed by development without necessarily performing PEB. However, in the method for producing a pattern of the present invention, the above-described post-baking is performed using the photosensitive resin composition of the present invention. It is preferable to perform a process.
In the pattern production method of the present invention, it is preferable to promote hydrolysis of acid-decomposable groups without causing a crosslinking reaction by performing PEB at a relatively low temperature. The temperature for performing PEB is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 110 ° C, and particularly preferably 50 ° C to 100 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 1 to 60 minutes.

(4) In the developing step, the copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
By performing PEB at a relatively low temperature, it is preferable to promote hydrolysis of the acid-decomposable group without causing a crosslinking reaction. The temperature for performing PEB is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 110 ° C, and particularly preferably 50 ° C to 80 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.
In the pattern manufacturing method of the present invention, it is preferable that a post-baking step is included between (4) the developing step and an etching step described later, and (4) the resist pattern after the developing step and before the etching step. It is more preferable to include a step of post-baking at 100 to 160 ° C. (4) By heating the obtained positive image in the post-baking step after the developing step, the effect of improving etching dimensional stability can be obtained.
The post-baking step after the step (4) developing and before the step (5) etching is more preferably 120 to 150 ° C. By performing PEB at a relatively low temperature, an effect of improving etching dimensional stability without causing heat flow of the resist pattern can be obtained.
The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 1 to 60 minutes.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Method for preparing photosensitive resin composition>
The essential components and optional components of (A) to (C) are mixed at a predetermined ratio and by an arbitrary method, stirred and dissolved to prepare a photosensitive resin composition. For example, the resin composition can be prepared by mixing each component in a predetermined ratio after preparing each solution in advance in the above-described solvent. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 μm.

<(1) Step of applying photosensitive resin composition on substrate and (2) Step of removing solvent>
A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by decompression and / or heating (pre-baking). Examples of the substrate include, for example, a glass plate in which a polarizing plate, a black matrix layer and a color filter layer are provided as necessary, and a transparent conductive circuit layer is further provided in the production of a liquid crystal display element. Although there is no restriction | limiting in particular as a method of applying the photosensitive resin composition to a board | substrate, Among these, it is preferable to apply | coat a touristic resin composition to a board | substrate in this invention. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Manufacturing with a large substrate is preferable because of high productivity. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  Further, the heating condition in the step (2) is that the acid-decomposable group is decomposed in the structural unit (a-1) in the component (A) in the unexposed part, and the component (A) is soluble in the alkali developer. Although not depending on the type and blending ratio of each component, it is preferably about 80 to 130 ° C. for about 30 to 120 seconds.

<(3) Step of exposing and (4) Step of developing (pattern forming method)>
In the step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in step (4), an exposed area is removed using an alkaline developer to form an image pattern.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm such as) can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the mask used in the step (3), it is preferable to use a halftone phase mask capable of obtaining a pattern having a plurality of thicknesses at a time.

  The developer used in the step (4) preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.

<(5) Step of etching>
The pattern manufacturing method of the present invention includes the step (5) of etching the substrate using the formed resist pattern as a mask.
There is no restriction | limiting in particular as a method of etching the said board | substrate using the said resist pattern as a mask, A well-known method can be used.

<(6) Step of peeling resist pattern>
The pattern production method of the present invention includes the step (6) of peeling the resist pattern.
There is no restriction | limiting in particular as a peeling method of the said resist pattern, A well-known method can be used.

<Board>
The substrate used in the pattern manufacturing method of the present invention is not particularly limited. For example, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, an indium oxide (ITO) film doped with tin oxide, or tin oxide. Film, Ni, Cu, Fe, Al, etc. metal substrate; quartz, glass, silicon nitride film, silicone, silicone nitride, polysilicone, silicone oxide, amorphous silicone film, SOG, silicon wafer for semiconductor device manufacturing, liquid crystal device manufacturing Silicon substrates such as glass square substrates for use; Polymer substrates such as paper, polyester film, polycarbonate film, polyimide film, and other polymer substrates used in organic EL display devices; used for ceramic materials, Ti substrates, Al substrates, LED lighting Use single crystal sapphire substrate Rukoto can. Among them, in the present invention, an ITO substrate, a molybdenum substrate, a silicon substrate, a Cu substrate, an Al substrate, or a single crystal sapphire substrate is preferable, and an ITO substrate, a molybdenum substrate, a silicon substrate, or a single crystal sapphire substrate is preferable. More preferably, it is an ITO substrate or a single crystal sapphire substrate.
The shape of the substrate may be a plate shape or a roll shape.

[Curing film]
In the present invention, (4) after the developing step, the pattern corresponding to the unexposed area obtained by development is predetermined at a predetermined temperature, for example, 180 to 250 ° C., using a heating device such as a hot plate or an oven. For example, 5 to 60 minutes on a hot plate and 30 to 90 minutes on an oven to form a cured film such as a protective film or an interlayer insulating film having excellent heat resistance and hardness. Can do.
Moreover, when performing heat processing, transparency of a cured film can also be improved by performing in nitrogen atmosphere.
Prior to the heat treatment, it is preferable that the substrate having the cured film formed in a pattern is re-exposed with actinic rays and then heated.

That is, in order to form the cured film of the present invention, it is preferable to include a step of re-exposing with actinic rays between the developing step and the thermosetting step.
The exposure in the re-exposure step may be performed by the same means as in the exposure step. However, in the re-exposure step, the entire surface of the substrate on the side where the film is formed by the photosensitive resin composition of the present invention is used. It is preferable to perform exposure. A preferable exposure amount for the re-exposure step is 100 to 1,000 mJ / cm ² .

[pattern]
The pattern of this invention is a pattern obtained by etching the said board | substrate using the resist pattern obtained by hardening | curing the photosensitive resin composition of this invention as a mask. The pattern of the present invention can be preferably used as an ITO pattern, a molybdenum pattern or a silicon pattern, and more preferably used as an ITO pattern.
Since the photosensitive resin composition of the present invention is excellent in sensitivity, resolution and exposure margin, a resist pattern having excellent rectangularity can be obtained. Since the pattern of the present invention is obtained by the method for producing a pattern of the present invention using the resist pattern, it can be finely processed, and an organic EL display device or a liquid crystal display device can have high definition display characteristics.

[Organic EL display device, Liquid crystal display device]
The photosensitive resin composition of the present invention can also be used as an interlayer insulating film, and an organic EL display device and a liquid crystal display device can be manufactured by the pattern manufacturing method of the present invention. The organic EL display device and the liquid crystal display device of the present invention preferably have an ITO pattern.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, 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 imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual diagram illustrating an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
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 then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

  FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-601: Dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
MAEVE: 1-ethoxyethyl methacrylate MATHF: tetrahydro-2H-furan-2-yl methacrylate MATHP: 2-tetrahydropyranyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
StOEVE: 4- (1-Ethoxyethyloxy) styrene THF FMA: Tetrahydrofurfuryl methacrylate MMA: Methyl methacrylate MAA: Methacrylic acid

(Synthesis Example 1: Synthesis of a-1-1 (MATHF / MMA / MAA = 60/15/25))
<Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.
<Synthesis of a-1-1>
In a three-necked flask, 50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2 mol%) of camphorsulfonic acid were mixed and cooled to 15 ° C. To the solution, 41.00 g (0.585 mol) of 2,3-dihydrofuran was added dropwise. Saturated aqueous sodium hydrogen carbonate solution (500 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (500 mL) and dried over magnesium sulfate. Insoluble matter was filtered, and the filtrate was concentrated under reduced pressure at 40 ° C. or lower. The colorless oily residue was distilled under reduced pressure to obtain 73.02 g of MATHF in a boiling point (bp.) 54-56 ° C./3.5 mmHg fraction.
PGMEA (29.6 g) was placed in a three-necked flask and heated to 80 ° C. in a nitrogen atmosphere. MATHF (28.1 g), MMA (7.51 g), MAA (3.87 g), V-601 (1.93 g, 2.8 mol% based on monomer) were dissolved in PGMEA (29.6 g) in the solution. And added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, a-1-1 was obtained. The weight average molecular weight was 15,000. The polydispersity was 2.60.

(Synthesis Example 2: Synthesis of a-1-2)
The same procedure as in Synthesis Example 1 was performed except that the molar ratio of MATHF, MAA, and MMA was changed to 15 mol, 15 mol, and 70 mol.

(Synthesis Example 3: Synthesis of a-1-3)
The same procedure as in Synthesis Example 1 was performed except that the molar ratio of MATHF, MAA, and MMA was changed to 25 mol, 15 mol, and 60 mol.

(Synthesis Example 4: Synthesis of a-1-4)
The same procedure as in Synthesis Example 1 was performed except that the molar ratio of MATHF, MAA, and MMA was changed to 35 mol, 15 mol, and 50 mol.

(Synthesis Example 5: Synthesis of a-1-5)
The same procedure as in Synthesis Example 1 was performed except that the molar ratio of MATHF, MAA, and MMA was changed to 45 mol, 15 mol, and 40 mol.

(Synthesis Example 6: Synthesis of a-1-6 (THF / EVE / PHS / MAA = 33/15/37/15))
<Synthesis of Resin (R-1)>
110.3 g (0.68 mol) of p-acetoxystyrene and 10.3 g (0.12 mol) of methacrylic acid were dissolved in 140 g of propylene glycol monomethyl ether acetate (PGMEA) and heated to 65-75 ° C. under a nitrogen stream and stirring. Then, a PGMEA solution of 6.5 g (0.028 mol) of dimethyl 2,2′-azobis (2-methylpropionate) (V-601) was added and stirring was continued for 6 hours to carry out the polymerization reaction. It was. It melt | dissolved in 200 ml of methanol, 14 g of sodium methoxide methanol solutions (SM-28) were added, and it was made to react for 3 hours. The mixture was neutralized with hydrochloric acid, diluted with 200 ml of water, diluted with 300 ml of ethyl acetate, and washed three times with water. Thereafter, a white resin was deposited. The resin was filtered off, washed with water and dried. Furthermore, it melt | dissolved in 200 ml of acetone, and it dripped and reprecipitated, stirring to a 3 liter hexane / ethyl acetate = 10/1 solution. The obtained resin was dried in a vacuum dryer at 40 ° C. for 24 hours to obtain poly (p-hydroxystyrene) / MAA alkali-soluble resin (R-1). The obtained resin had a weight average molecular weight of 15000 and a polydispersity of 2.60.

<Synthesis of Polymer THF / EVE / PHS / MAA>
23.0 g of the alkali-soluble resin (R-1) obtained above and 94.4 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask, distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 4.17 g of 2,3-dihydrofuran, 2.08 g of ethyl vinyl ether and 0.025 g of p-toluenesulfonic acid were added and stirred at room temperature for 4 hours. Thereto was added 0.090 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water. Then, ethyl acetate and water were removed by distillation under reduced pressure, and a polymer (a-1- 6) was obtained.

(Synthesis Example 7: Synthesis of polymer PHS-EVE)
20 g of alkali-soluble resin (Marcalinker MS-4P manufactured by Maruzen Petrochemical Co., Ltd.) and 320 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 4.48 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto, 0.28 g of triethylamine was added to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water, and then ethyl acetate, water, and azeotropic PGMEA were distilled off by distillation under reduced pressure to obtain a polymer PHS-EVE. The weight average molecular weight of the obtained resin was 11,000. The polydispersity was 2.6.
The structure of PHS-EVE is a 1-ethoxyethyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).
PHS-EVE

(Synthesis Example 8: Synthesis of polymer PHS-THF)
15.6 g of alkali-soluble resin (Marcalinker MS-4P: manufactured by Maruzen Chemical Industry Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) are dissolved in a flask and distilled under reduced pressure to azeotropically distill water and PGMEA. Left. After confirming that the water content was sufficiently low, 2.7 g of 2,3-dihydrofuran and 0.015 g of p-toluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.090 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water, and then ethyl acetate and water were distilled off under reduced pressure to obtain a polymer PHS-THF, which is a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 2.6.
The structure of PHS-THF is a 2-tetrahydrofuranyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (25 mol% / 75 mol%).
PHS-THF

(Synthesis Example 9: Synthesis of Polymer a-1-7 (MATHP / MAA / MMA = 60/15/25))
In the synthesis of the polymer a-1-1, the polymer a-1-7 (MATHP / MAA /) was changed in the same manner except that MATH was changed to MATHP and the addition amount was adjusted in accordance with the molar ratio of the target polymer. MMA = 60/15/25) was synthesized.

(Synthesis Example 10: Synthesis of Polymer a-1-8 (MAEVE / MAA / MMA = 60/15/25))
In the synthesis of polymer a-1-1, polymer a-1-8 (MAEVE / MAA /) was similarly prepared except that MATHF was changed to MAEVE and the addition amount was adjusted in accordance with the molar ratio of the target polymer. MMA = 60/15/25) was synthesized.

Polymer a-1-9: BuVE / MAA / MMA = 60/15/25 (the following structure)

Polymer a-1-10: CyHexVE / MAA / MMA = 60/15/25 (the following structure)

Polymer PHS: (Maruzen Chemical Co., Ltd., Marcalinker MS-4P)

Photoacid generator (B-1) The following compound α- (p-toluenesulfonyloxyimino) phenylacetonitrile was synthesized according to the method described in paragraph No. [0108] of JP-T-2002-528451.
(B-2) The following compound (manufactured by BASF, CGI-1397)
(B-3) The following structure (manufactured by BASF, Irgacure 250)

Sensitizer DBA: Anthracular (manufactured by Kawasaki Chemical Industries)

Sensitizer A (Tokyo Chemical Industry, T1196)

Sensitizer B (Tokyo Chemical Industry, D2077)

Epoxy resin JER157S65, made by Japan Epoxy Resin
EPICLON N-695, made by DIC

(Adjustment of photosensitive resin composition)
Each component was dissolved and mixed so that it might become a composition shown in the following table | surface, and it filtered with the filter made from a polytetrafluoroethylene with a diameter of 0.2 micrometer, and obtained the photosensitive resin composition of an Example and a comparative example. The blending ratio was as shown in the following table. In addition, Example 14 is a reference example.
(A) Polymer (A-1) and (A-2) were blended at the ratio (weight ratio) shown in the table.
-(B) Photoacid generator (A) 2.7 parts by weight with respect to 100 parts by weight of polymer-Sensitizer (A) With respect to 100 parts by weight of polymer, the amounts shown in the following table were blended. .
・ Epoxy resin (JER157S65, manufactured by Japan Epoxy Resin) (A) 2.7 parts by weight with respect to 100 parts by weight of polymer.

  Each evaluation shown below was performed about the photosensitive resin composition of each Example obtained by the above and each comparative example.

<Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness A photosensitive resin composition layer having a thickness of 1.5 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive composition layer was developed with an alkali developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity.
Evaluation was made according to the following criteria.
1: 100mJ / cm ² or more ^2: 45mJ / cm 2 or more 100 mJ / cm ² less than 3: 2.0mJ / cm ² or more 45 mJ / cm ² less than 4: 1.0mJ / cm ² or more 2.0 mJ / cm ² less than 5 : 0.01mJ / cm ² or more 1.0mJ / cm less than ²

<Evaluation of resolution>
A photosensitive resin composition having a film thickness of 1.3 μm was applied to a glass substrate that had been cleaned and treated with HMDS, exposed and developed through a mask, and the smallest pattern that could be resolved in the line and space pattern was defined as the resolution.
1 point: resolution 5 μm or more 2 points: 3.0 μm resolves but 2.5 μm does not resolve 3 points: 2.5 μm resolves but 2.0 μm does not resolve 4 points: 2.0 μm Resolved but 1.5 μm not resolved 5 points: 1.5 μm resolved.

<Evaluation of rectangularity>
A photosensitive resin composition is applied to a cleaned and HMDS-treated glass substrate with a film thickness of 1.3 μm, exposed and developed through a mask, then post-baked at 140 ° C., and 2.5 μm line and space after post-baking. The rectangularity of the shape of the pattern part was evaluated.
1 point: Dome-shaped cross section with no corners and taper angle of less than 45 ° 2 points: Dome shape with cross-sections with no corners and taper angle of 45 ° to less than 60 ° Tapering angle of 60 ° or more and less than 75 ° 4 points: Cross section has an angle and taper angle of 60 ° or more and less than 75 ° 4.5 points: Section shape has an angle and taper angle of 75 ° or more and less than 80 ° 5 points : Cross section has corners and taper angle is 80 ° or more

<Overall performance>
The numerical values of the sensitivity, resolution, and rectangularity were summed up, and the total performance was evaluated according to the following criteria.
5: Level that can be used without any problems.
4.5 Level that can be used without problems.
4: Level that can be used without problems.
3: Level that can be used by process handling.
2: Level that cannot be used.
1: Level that cannot be used at all.

  As shown in the above table, the photosensitive resin composition of each example is excellent in any evaluation of sensitivity, resolution, and rectangularity in comparison with the photosensitive resin composition of each comparative example. It was found that the results were obtained. In particular, when only one type of polymer was included (Comparative Example 4), the effect of the present invention was not achieved at all.

(Example 100)
<Organic EL display device>
An organic EL display device having an ITO pattern 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 so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition described in Example 1 of JP-A-2009-98616 on a substrate and pre-baking (90 ° C. × 2 minutes), after irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a high-pressure mercury lamp from above the mask, developing with an alkaline aqueous solution to form a pattern at 230 ° C. A heat treatment for 60 minutes was performed.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, the photosensitive resin composition of Example 1 was spin-coated on an ITO substrate, pre-baked on a hot plate (90 ° C. × 2 minutes), and then i-line (365 nm) was 20 mJ from above the mask using a high-pressure mercury lamp. After irradiation with / cm ² (illuminance 20 mW / cm ² ), the pattern was formed by developing with an alkaline aqueous solution. Then, the post-baking heat processing for 3 minutes were performed at 140 degreeC before the etching process. Using this resist pattern as a mask, ITO was patterned by wet etching by dipping in an ITO etchant (3% aqueous oxalic acid solution) at 40 ° C./1 min. Thereafter, the resist pattern was peeled off by being immersed in a resist stripping solution (MS2001, manufactured by Fuji Film Electronics Materials Co., Ltd.) at 70 ° C. for 7 minutes. 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 8, the photosensitive resin composition described in Example 1 of JP2009-98616A was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an organic EL display device having an active matrix type ITO pattern formed by connecting each organic EL element to TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 101)
<Liquid crystal display device>
A liquid crystal display device having an ITO pattern was produced by the following method.
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 200 was obtained.
That is, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 100.

  When a drive voltage was applied to the obtained liquid crystal display device having the ITO pattern, it was found that the liquid crystal display device showed good display characteristics and high reliability.

(Example 102)
<Patterned sapphire substrate>
After applying the photosensitive resin composition of Example 4 on a single crystal sapphire substrate with a spin coater, pre-baking on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, the photosensitive resin composition having a film thickness of 2.5 μm A physical layer was formed. Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using an i-line stepper exposure machine (NSR-2005i9C) manufactured by Nikon Corporation. The exposed photosensitive composition layer was developed with an alkaline developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, rinsed with ultrapure water for 20 seconds, and 1.0 μm in thickness. A line and space pattern was obtained. The pattern was rectangular and the remaining film rate was 100%. The substrate was post-baked at 140 ° C. for 3 minutes, and then the sapphire substrate was dry-etched using a mixed gas of BCl ₃ / HBr / Ar to obtain a sapphire substrate having a 1.0 μm line and space pattern. The shape of the obtained pattern was good.

  Recent development trends have tended to pursue a composition having an absorption region in the short wave with the shortening of the exposure wavelength, and to seek a material having no absorption in the visible region. There has been a tendency to use an expensive exposure apparatus such as an i-line stepper with a good resolving power, a short-wave exposure light source, and a photoacid generator with little absorption in the exposure region. However, in the present invention, by using a sensitizer having an absorption region in a long wave (ghi line, gh line), an inexpensive low NA (aperture) exposure apparatus (NA = 0.1 or less) can be used. Thus, it has become possible to provide a photosensitive resin composition having high sensitivity and excellent resolution and rectangularity. Such a photosensitive resin composition also has an advantage that an improved version of an existing apparatus can be adopted. The sensitizer used in the present invention is colored in the visible range, but there is no problem as long as it is used as an etching material.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened 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 (11)

(A-1) a polymer having a structural unit having an acid group and a structural unit represented by formula (a-1);
(A-2) a polymer having a structural unit represented by the general formula (a-2) and a structural unit represented by the general formula (a-3) ,
(B) a photoacid generator,
(C) solvent,
Containing a photosensitive resin composition.
Formula (a-1)
(In General Formula (a-1), R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group; ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond Or represents an arylene group.)
Formula (a-2)
(In the general formula (a-2), R ⁴ is a hydrogen atom or a methyl group.)
Formula (a-3)
(In the general formula (a-3), R ⁴ is a hydrogen atom or a methyl group. R ⁵ is a linear, branched, or cyclic alkyl group, and at least one —O— is present in the alkyl group. Including) R ⁵ in the general formula (a-3) is the general formula (a-4) or (a-5) represented by the photosensitive resin composition of claim 1.
Formula (a-4)
(In the general formula (a-4), R ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. It binds to the general formula (a-3) at the position of the US mark.)
Formula (a-5)
(In the general formula (a-5), it is combined with the general formula (a-3) at the position of the US mark.) Further characterized in that it comprises (D) Sensitizer The photosensitive resin composition according to claim 1 or 2. (D) The photosensitive resin composition of Claim 3 whose sensitizer is a compound represented by the following general formula (O) or general formula (P).
(In the general formula (0), R ¹ and R ² each represent an aryl group or a heterocyclic structure having one or more ethylene bonds. L ¹ is a 2-4 valent group having 2-4 ethylene bonds. Represents a linking group, and n and m each represent 1 or 2.)
General formula (P)
(In the general formula (P), each R is an alkyl group having 1 to 8 carbon atoms.) (B) The photosensitive resin composition of any one of Claims 1-4 whose photo-acid generator is an oxime sulfonate compound. Furthermore, epoxy resin is included, The photosensitive resin composition of any one of Claims 1-5 characterized by the above-mentioned. (1) The process of applying the photosensitive resin composition of any one of Claims 1-6 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer,
(5) a step of etching the substrate using the formed resist pattern as a mask; and
(6) A method for producing a pattern, including a step of peeling the resist pattern. The manufacturing method of the pattern of Claim 7 including the process of post-baking the said resist pattern at 100-160 degreeC after the said image development process and before an etching process. Wherein the substrate, ITO substrate, molybdenum substrate, a silicon substrate, Cu substrate, Al substrate, or a manufacturing method of a pattern according to claim 7 or 8, that wherein a single crystal sapphire substrate. The cured film formed by hardening the photosensitive resin composition of any one of Claims 1-6 . Including the claims 7 to pattern producing method according to any one of 9, a method of manufacturing the organic EL display device or a liquid crystal display device.