JP5871706B2 - Chemical amplification type positive photosensitive resin composition and interlayer insulating film - Google Patents

Description

The present invention relates to a chemically amplified positive photosensitive resin composition, a method for producing a cured film, a cured film, an organic EL display device, and a liquid crystal display device.
More specifically, a chemically amplified positive photosensitive resin composition suitable for the formation of a planarizing film, protective film or interlayer insulating film of electronic components such as organic EL display devices, liquid crystal display devices, integrated circuit elements, solid-state imaging devices, etc. The present invention relates to an article and a method for producing a cured film using the article.

Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In the formation of this interlayer insulating film, since the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained, a chemically amplified positive photosensitive resin composition is widely used. Yes.
The interlayer insulating film in the display device is required to have high transparency in addition to the properties of the cured film, such as excellent insulation, solvent resistance, heat resistance, and indium tin oxide (ITO) sputtering suitability. For this reason, an attempt has been made to use an acrylic resin having excellent transparency as a film forming component.
On the other hand, a microlens having a lens diameter of about 3 to 100 μm or an optical system material for an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state image sensor or the like, or a microlens thereof. A regularly arranged microlens array is used.
To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is as a lens, or by using the melt-flowed lens pattern as a mask and drying. A method of transferring a lens shape to a base by etching is known. For the formation of the lens pattern, a chemically amplified positive photosensitive resin composition is widely used.
An example of such a chemically amplified positive photosensitive resin composition is Patent Document 1.
On the other hand, Patent Document 2 is cited as a photosensitive resin composition used for forming a surface protective film and an interlayer insulating film of a semiconductor device.

JP 2011-209681 A JP 2011-13644 A

Here, the chemically amplified positive photosensitive resin composition is required to have high dry etching resistance while maintaining high sensitivity. An object of the present invention is to provide a chemically amplified positive photosensitive resin composition having high dry etching resistance while maintaining high sensitivity.
In addition, another problem to be solved by the present invention is a cured film using the chemically amplified positive photosensitive resin composition, a method for producing the cured film, an organic EL display device and a liquid crystal display device including the cured film. It is to provide.

  Under such circumstances, the present inventor has found that the above problem can be solved by using a monofunctional alkoxysilane compound having no reactive group.

Specifically, the above problem has been solved by the following means <1>, preferably <2> to <18>.
<1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,
(B) a photoacid generator,
(C) a compound represented by the following general formula (1), and
(D) A chemically amplified positive photosensitive resin composition containing a solvent.
General formula (1)
(In general formula (1), R ¹ is a hydrocarbon group having no reactive group, R ² is an alkyl group, and n is an integer of 1 to ^3. )
<2> The chemically amplified positive photosensitive resin composition according to <1>, wherein R ¹ is a hydrocarbon group.
<3> (C) The chemically amplified positive photosensitive resin composition according to <1>, wherein R ¹ in the general formula (1) is a hydrocarbon group having 4 or more carbon atoms.
<4> (C) The chemically amplified positive photosensitive resin composition according to <1>, wherein R ¹ in the general formula (1) is a hydrocarbon group having 6 or more carbon atoms.
<5> (C) The chemically amplified positive photosensitive resin composition according to <1>, wherein R ¹ in the general formula (1) is a hydrocarbon group having 6 or more carbon atoms and no aromatic ring. .
<6> The chemically amplified positive photosensitive resin composition according to any one of <1> to <5>, wherein R ¹ is an alkyl group having 4 or more carbon atoms.
<7> The chemically amplified positive photosensitive resin composition according to any one of <1> to <6>, wherein the acid-decomposable group is a group having a structure protected in the form of acetal.
<8> The chemically amplified positive photosensitive resin composition according to any one of <1> to <7>, wherein any of the polymer components (A) is a polymer further containing an acid group. .
<9> (a2) The crosslinkable group contained in the structural unit having a crosslinkable group is an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The chemically amplified positive photosensitive resin composition according to any one of <1> to <8>, which is at least one selected from the group represented by:
<10> The chemistry according to any one of <1> to <9>, wherein the polymer component (A) is a polymer having a structural unit (a4) having a hydroxyl group other than a phenolic hydroxyl group or an alkyleneoxy group. Amplification type positive photosensitive resin composition.
<11> The polymer component (A) is a structural unit (a1) having a residue in which a carboxyl group is protected by an acetal structure, a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, an epoxy group, or an oxetanyl group. The chemical amplification type according to any one of <1> to <10>, which is a polymer having a structural unit (a3) having a structural unit (a4) having a hydroxyl group other than a phenolic hydroxyl group or an alkyleneoxy group Positive photosensitive resin composition.
<12> The chemically amplified positive photosensitive resin composition according to any one of <1> to <11>, wherein the (B) photoacid generator is an oxime sulfonate compound.
<13> (1) A step of applying the chemically amplified positive photosensitive resin composition according to any one of <1> to <12> on a substrate,
(2) a step of removing the solvent from the applied chemically amplified positive photosensitive resin composition;
(3) a step of exposing the chemically amplified positive photosensitive resin composition from which the solvent has been removed with actinic rays;
(4) a step of developing the exposed chemically amplified positive photosensitive resin composition with an aqueous developer, and
(5) A post-baking step of thermally curing the developed chemically amplified positive photosensitive resin composition.
<14> The method for producing a cured film according to <13>, including a step of exposing the entire surface of the developed chemically amplified positive photosensitive resin composition after the developing step and before the post-baking step.
<15> (6) The method for producing a cured film according to <13> or <14>, further comprising a dry etching step of performing dry etching on a substrate having a cured film obtained by thermosetting.
<16> A cured film obtained by curing the chemically amplified positive photosensitive resin composition according to any one of <1> to <12>.
<17> The cured film according to <16>, which is an interlayer insulating film.
<18> A liquid crystal display device or an organic EL display device having the cured film according to <16> or <17>.

  According to the present invention, it is possible to provide a positive photosensitive resin composition having high sensitivity, low unexposed residual film ratio, low relative dielectric constant and excellent dry etching resistance.

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. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. 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.

  In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[Chemically amplified positive photosensitive resin composition]
The chemically amplified positive photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention” or “photosensitive composition”) is (A) the following (1) and (2) It contains a polymer component containing a polymer satisfying at least one, (B) a photoacid generator, (C) a compound represented by the following general formula (1), and (D) a solvent.
(1) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,
General formula (1)
(In general formula (1), R ¹ is a hydrocarbon group having no reactive group, R ² is an alkyl group, and n is an integer of 1 to ^3. )

<(A) component>
The photosensitive resin composition of this invention contains the polymer component which satisfy | fills at least one of (A) following (1) and (2) as (A) component.
(1) (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group

Here, in the above aspect (1), the polymer contains (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a crosslink. It is an aspect which has the structural unit which has a sex group. Such a polymer may further contain other repeating units. Each of the structural unit (a1) and the structural unit (a2) may include two or more types.
In the aspect (2), at least two types of polymers are included, at least one of the polymers has the structural unit (a1), and at least one other type of the polymer is the structural unit (a2). ).
Furthermore, in the aspect of (2), the polymer containing the structural unit (a1) may further contain the structural unit (a2) and other structural units. Similarly, the polymer containing the structural unit (a2) may contain the structural unit (a1) or another structural unit. In such a case, the aspect satisfies both (1) and (2). In the present specification, the term “component A” refers to any of the above polymer components without particular notice.

As a preferred first embodiment of the present invention, the component (A) contains two or more types of polymers, and at least one of the polymers has a residue in which at least an acid group is protected with an acid-decomposable group. It is a polymer having a structural unit, and at least one other polymer is a polymer having a structural unit having at least a crosslinkable group. From the viewpoint of the degree of freedom in molecular design, the polymer having a structural unit having a residue in which at least an acid group is protected with an acid-decomposable group is substantially free of the structural unit (a2) and is at least crosslinkable. More preferably, the polymer having a structural unit having a group does not substantially contain the structural unit (a1). Here, “substantially free” means, for example, that the ratio to the total structural units is 3 mol% or less, and further 1 mol% or less.
A preferred second embodiment of the present invention includes an aspect in which the polymer containing the structural unit (a1) contains the structural unit (a2) from the viewpoint of compatibility.
Furthermore, as the third aspect, an aspect in which the polymer of the first embodiment and the polymer of the second embodiment coexist can be considered as the polymer component (A).

The component (A) is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The component (A) preferably contains 50 mol% or more, and 90 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units in the polymer. Is more preferable, and a polymer composed only of structural units derived from (meth) acrylic acid and / or its ester is particularly preferable.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. “(Meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.

The copolymer (A) is preferably alkali-insoluble as a whole, and is preferably a resin that becomes alkali-soluble when the acid-decomposable group of the structural unit (a1) is decomposed. Here, the acid-decomposable group means a functional group that can be decomposed in the presence of an acid. That is, the structural unit having a protected carboxyl group in which the carboxyl group is protected with an acid-decomposable group can generate a carboxyl group by the decomposition of the protective group with an acid, and the phenolic hydroxyl group is an acid-decomposable group. The structural unit having a protected phenolic hydroxyl group protected with can generate a phenolic hydroxyl group by the decomposition of the protecting group with an acid. Here, in the present invention, “alkali-soluble” refers to 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 heating at 90 ° C. for 2 minutes with respect to a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. It means less than 0.01 μm / second.
The (A) copolymer may have a carboxyl group described later, a structure derived from a carboxylic anhydride, and / or other structural units having a phenolic hydroxyl group. However, when introducing an acidic group, it is preferable to introduce it in the range which keeps the whole (A) copolymer insoluble in alkali.

<< (a1) Structural Unit Having Residue Protected with Acid-Decomposable Group >>
The component (A) has (a1) at least a structural unit having a residue in which an acid group is protected with an acid-decomposable group. When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
The structural unit (a1) in the present invention preferably contains a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in this order. To do.

<<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a group.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group as a structural unit which can be used for the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, (a1-1-1) used as a structural unit having a carboxyl group, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) ethylene The structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.

<<<<< (a1-1-1) Constituent Unit Derived from Unsaturated Carboxylic Acid Having at least One Carboxyl Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, Alternatively, an unsaturated polycarboxylic acid anhydride or the like is preferably used, and acrylic acid or methacrylic acid is more preferably used.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.

<<<<< (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride reacts a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and the like. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

<<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
The acid-decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group can be any known acid-decomposable group, and is not particularly limited. Conventionally, as an acid-decomposable group, a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as a tetrahydropyranyl group) or a group that is relatively difficult to be decomposed by an acid (for example, a tert-butyl ester group, a tert-butyl ester group, -Tert-butyl functional groups such as butyl carbonate groups) are known.
Among these acid-decomposable groups, an acetal functional group is preferable from the viewpoint of basic physical properties of the photosensitive resin composition, particularly sensitivity, pattern shape, contact hole formability, and storage stability of the photosensitive resin composition. Further, among the protected carboxyl groups protected with an acid-decomposable group, the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-1) from the viewpoint of sensitivity. . In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-1), the entire protected carboxyl group is-(C = O) -O-CR ^101. The structure is R ¹⁰² (OR ¹⁰³ ).

Formula (a1-1)
(In formula (a1-1), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. R ¹⁰³ is an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

In the general formula (a1-1), R ^{101 to} R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched, or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the general formula (a1-1), when R ¹⁰¹ , R ^102, and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched, or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

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

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, (alpha) -methylphenyl group, a naphthyl group etc. can be illustrated. Examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, and a methoxy group or an ethoxy group is more preferable.
In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In the general formula (a1-1), when R ¹⁰¹ , R ^102, and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.

In the general formula (a1-1), any one of R ¹⁰¹ and R ¹⁰² is preferably a hydrogen atom or a methyl group.

A preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the formula (A2 ′).
Formula (A2 ′)
(Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents 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 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.

As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-1), a commercially available one may be used, or it may be synthesized by a known method. Things can also be used.
Preferable specific examples of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

<<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>>
The structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic component in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a hydroxyl group.

<<<< (a1-2-1) Structural unit having phenolic hydroxyl group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a structural unit in a hydroxystyrene-based structural unit and a novolac-based resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is, It is preferable from the viewpoint of transparency. Among the structural units having a phenolic hydroxyl group, the structural unit represented by the following general formula (a1-2) is preferable from the viewpoints of transparency and sensitivity.

Formula (a1-2)
(In General Formula (a1-2), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a straight chain having 1 to 5 carbon atoms or Represents a branched alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R ²²² is 2 or more, these R ²²² may be different from each other or the same.)

In General Formula (a1-2), R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²²¹ represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R ²²¹ may be exemplified alkylene groups, specific examples R ²²¹ is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Among these, it is preferable that R ²²¹ is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Moreover, although a represents the integer of 1-5, from the viewpoint of the effect of this invention and the point that manufacture is easy, it is preferable that a is 1 or 2, and it is more preferable that a is 1. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²²¹ is defined as the reference (first position).
R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
Specific examples include fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;

<<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
The acid-decomposable group that can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group has a protected carboxyl group protected with the acid-decomposable group. Similarly to the acid-decomposable group that can be used for the unit (a1-1), a known one can be used and is not particularly limited. Among acid-decomposable groups, the structural unit having a protected phenolic hydroxyl group protected in the form of an acetal is the basic physical properties of the resist, especially the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, the contact hole It is preferable from the viewpoint of formability.
Furthermore, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-1) from the viewpoint of sensitivity. When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of the acetal represented by the general formula (a1-1), the entire protected phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R. The structure is ¹⁰² (OR ¹⁰³ ). Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

Moreover, as a radically polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of acetal, for example, paragraph number 0042 of JP2011-215590A is disclosed. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

  Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.

  As the radical polymerizable monomer used to form the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group, a commercially available one may be used, or a known method may be used. What was synthesize | combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group include the following structural units, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit (a1) >>>
When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1). The mol% is preferable, and 30 to 90 mol% is more preferable.
When the polymer containing the structural unit (a1) contains the following structural unit (a2), the structural unit (a1) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, 3-70 mol% is preferable, and 10-60 mol% is more preferable. In particular, when the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the content is preferably 20 to 50 mol%, 30 -45 mol% is more preferable.

  The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred when developing quickly. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<< (a2) Structural Unit Having a Crosslinking Group >>
The component (A) has a structural unit (a2) having a crosslinking group. The crosslinking group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. Preferred embodiments of the structural unit having a bridging group were selected from the group consisting of an oxiranyl group, an oxetanyl group, —NH—CH ₂ —OR (where R is an alkyl group having 1 to 20 carbon atoms) and an ethylenically unsaturated group. Examples of the structural unit include at least one.
Among them, in the photosensitive resin composition of the present invention, the component (A) preferably contains a structural unit containing at least one of an oxiranyl group and an oxetanyl group, and contains a structural unit containing an oxetanyl group. Is particularly preferred. In more detail, the following are mentioned.

<<< (a2-1) Oxylanyl group and / or Oxetanyl group-containing unit >>>>
The (A) copolymer preferably contains a structural unit (structural unit (a2-1)) having an oxiranyl group and / or an oxetanyl group. The 3-membered cyclic ether group is also called an oxiranyl group, and the 4-membered cyclic ether group is also called an oxetanyl group. The structural unit (a2-1) having an oxiranyl group and / or oxetanyl group is preferably a structural unit having an alicyclic oxiranyl group and / or oxetanyl group, more preferably a structural unit having an oxetanyl group. preferable.
The structural unit (a2-1) having an oxiranyl group and / or oxetanyl group may have at least one oxiranyl group or oxetanyl group in one structural unit. It may have an oxetanyl group, two or more oxiranyl groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 oxiranyl groups and / or oxetanyl groups. It is more preferable to have one or two oxiranyl groups and / or oxetanyl groups, and it is even more preferable to have one oxiranyl group or oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxiranyl group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Fat And compounds containing an expression epoxy skeleton.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylic acid esters.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a2-1) having the oxiranyl group and / or oxetanyl group include a monomer having a methacrylate structure and an acrylate structure. It is preferable that it is a monomer to contain.

  Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraph Nos. 0034 to 0035 of Japanese Patent No. 4168443 and paragraph numbers 0011 to 0016 of JP-A No. 2001-330953. The (meth) acrylic acid ester having an oxetanyl group described in (1), and (meth) acrylic acid ester having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A-2001-330953 is particularly preferable. Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl, most preferred are (3-ethyloxetane-3-yl) methyl acrylate and (3-ethyloxetane-3-yl) methyl methacrylate. These structural units can be used individually by 1 type or in combination of 2 or more types.

  As the structural unit (a2-1) having the oxiranyl group and / or oxetanyl group, the description of paragraph numbers 0053 to 0055 of JP2011-215590A can be referred to.

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

  In the present invention, an oxetanyl group is preferable from the viewpoint of sensitivity. From the viewpoint of transmittance (transparency), an alicyclic oxiranyl group and an oxetanyl group are preferred. From the above, in the present invention, as the oxiranyl group and / or oxetanyl group, an alicyclic oxiranyl group and an oxetanyl group are preferable, and an oxetanyl group is particularly preferable.

<<< (a2-2) Structural unit having an ethylenically unsaturated group >>>
As one of the structural unit (a2) having a crosslinking group, there may be mentioned a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a2-2)”). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms. A structural unit having a side chain is more preferred, and a structural unit having a side chain represented by the following general formula (a2-2-1) is more preferred.

General formula (a2-2-1)
(In General Formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * represents a structural unit having a bridging group (a2 ) Represents a site linked to the main chain of.

R ³⁰¹ is a divalent linking group having 1 to 13 carbon atoms and includes an alkenyl group, a cycloalkenyl group, an arylene group, or a combination of these, and includes an ester bond, an ether bond, an amide bond, a urethane bond, and the like. Bonds may be included. The divalent linking group may have a substituent such as a hydroxy group or a carboxyl group at an arbitrary position. Specific examples of R ³⁰¹ include the following divalent linking groups.

Among the side chains represented by the general formula (a2-2-1), an aliphatic side chain including the divalent linking group represented by R ³⁰¹ is preferable.

  Other (a2-2) Regarding the structural unit having an ethylenically unsaturated group, the description of paragraph numbers 0077 to 0090 of JP2011-215580A can be referred to.

<<< constituent unit having a partial structure represented by (a2-3) -NH-CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms) >>
The copolymer used in the present invention is also preferably a structural unit (a2-3) having a partial structure represented by —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms). By having the structural unit (a2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit (a2) is more preferably a structural unit having a group represented by the following general formula (1).
General formula (1)
(In the above formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)
R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

<<< Preferred Aspect of Structural Unit (a2) >>>
When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a1) is 5 to 90 in the polymer containing the structural unit (a1). Mol% is preferable and 20-80 mol% is more preferable.
When the polymer containing the structural unit (a2) contains the structural unit (a1), the structural unit (a1) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, 3-70 mol% is preferable, and 10-60 mol% is more preferable.
In this invention, it is preferable to contain 3-70 mol% of structural units (a2) in all the structural units of (A) component irrespective of any aspect, and it is more preferable to contain 10-60 mol%. preferable.
Within the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and ITO sputtering resistance.

<< (a3) Other structural units >>
In the present invention, the component (A) may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer (1) and / or (2). In addition to the polymer (1) or (2), a polymer component having another structural unit (a3) may be included. When the polymer having another structural unit (a3) is included separately from the polymer (1) or (2), the blending amount of the polymer component is 60% by mass or less in the total polymer component. Is preferable, it is more preferable that it is 40 mass% or less, and it is further more preferable that it is 20 mass% or less.

  There is no restriction | limiting in particular as a monomer used as another structural unit (a3), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.

  Hereinafter, preferred embodiments of the polymer component of the present invention will be described, but it is needless to say that the present invention is not limited to these.

(First embodiment)
The aspect in which the polymer (1) further has one or more other structural units (a3).
(Second Embodiment)
The polymer having a structural unit having a residue in which the (a1) acid group of the polymer (2) is protected with an acid-decomposable group further has one or more other structural units (a3). Aspect.
(Third embodiment)
The aspect which the polymer which has a structural unit represented by (a2) following general formula (I) of polymer (2) further has 1 type, or 2 or more types of other structural units.

(Fourth embodiment)
In any one of the first to third embodiments, the other structural unit includes a structural unit containing at least an acid group.

(Fifth embodiment)
In any one of the first to third embodiments, the polymer (1) and / or the polymer (2) includes a structural unit containing at least an acid group as the other structural unit.

(Sixth embodiment)
The aspect which has the polymer which has another structural unit (a3) separately from the said polymer (1) or (2). Examples of the other structural unit (a3) in this case include a structural unit containing an acid group and a structural unit having a crosslinkable group.

(Seventh embodiment)
The form which consists of two or more combinations of the said 1st-6th embodiment.

  The structural unit (a3) is specifically styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a structural unit due. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  Moreover, the group which has styrenes and an aliphatic cyclic skeleton as another structural unit (a3) is preferable from a viewpoint of an electrical property. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

  Furthermore, (meth) acrylic acid alkyl ester is preferable as another structural unit (a3) 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), the content of the structural unit (a3) 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.

The other structural unit (a3) preferably 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 containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the resin, alkali solubility tends to increase.
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 containing 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, 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 to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.

  The structural unit containing an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 40 mol%, and particularly preferably 5 to 30 mol% of the structural units of all polymer components. 5 to 20 mol% is particularly preferable.

  In the present invention, in addition to the polymer (1) or (2), a polymer having another structural unit (a3) may be included. Examples of the other structural unit (a3) in this case include a structural unit containing an acid group and a structural unit having a crosslinkable group.

  As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used.
These polymers may contain only 1 type and may contain 2 or more types.

  SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON are commercially available as these polymers. UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncry 690, Joncry 678, Joncry 67, Joncry 586 (above, made by BASF) You can also.

<< (A) Molecular Weight of Copolymer >>
(A) The molecular weight of a copolymer is a polystyrene conversion weight average molecular weight, Preferably it is 1,000-200,000, More preferably, it is the range of 2,000-50,000. Within the above numerical range, the sensitivity and ITO suitability are good.
The ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< (A) Copolymer Production Method >>
Various methods for synthesizing the component (A) are known. To give an example, the component (A) is used to form at least the structural units represented by (a1) and (a2). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

As a specific example of the copolymer (A), as an example satisfying (1), 1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate Polymer (45/8/35/12),
1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / allyl methacrylate / dicyclopentanyl methacrylate / styrene copolymer (35/10/30/5/15/15),
1-cyclohexyloxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer (40/8/35/12/5),
Tetrahydrofuran-2-yl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer (35/10/15/15/15 / 10),
1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / N-methoxymethylacrylamide / 2-hydroxyethyl methacrylate copolymer (40/5/40/5/10) ,
Tetrahydropyran-2-yl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate / dicyclopentanyl methacrylate copolymer (42/11/25/18 / 4),
As an example that satisfies (2),
1-ethoxyethyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate methacrylate (60/10/10/20) and methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / A combination of 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (60/10/10/20),
Tetrahydropyran-2-yl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate / dicyclopentanyl methacrylate copolymer (65/5/10/20) and glycidyl methacrylate / N-methoxymethylacrylamide / methacrylic acid / Dicyclopentanyl methacrylate / styrene copolymer (50/15/5/15/15).

<(B) Photoacid generator>
The photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. 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, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.
The component (B) is preferably an oxime sulfonate compound from the viewpoint of sensitivity.

  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, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. 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 0077 to 0078 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 (B1).

General formula (B1)
(In the general formula (B1), R ²¹ represents an alkyl group, an aryl group, a fluorinated alkyl group, or a fluorinated alkyl 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 represented by R ²¹ is 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 or the like It may be substituted with a cyclic 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 (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).

(In the formula (B2), R ⁴² represents an alkyl group, an aryl group, a fluorinated alkyl group, or a fluorinated alkyl group, X represents an alkyl group, an alkoxy group, or a halogen atom; 3 represents an integer of 3 and when m4 is 2 or 3, a plurality of X may be the same or different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1.
In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

  The compound containing the oxime sulfonate structure represented by the general formula (B1) is more preferably an oxime sulfonate compound represented by the following general formula (B3).

(In formula (B3), R ⁴³ has the same meaning as R ⁴² in formula (B2), and X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano A group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and 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 (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). ) 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- Toluene sulfonyl) -4-methoxyphenyl] can be mentioned 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.

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

  Preferable examples of the compound represented by the general formula (OS-1) include general formulas described in paragraph numbers 0194 to 0202 of JP2011-22196A and exemplary compounds thereof.

  In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (B1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.

(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.
In the general formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have a substituent. Here, the substituent that the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have may be the alkyl group or aryl group in R ²² , R ²⁵ and R ²⁸ described above. Examples of the same group as a good substituent can be given.

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 preferably, it 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.

Examples of the halogen atom for R ²³ , R ²⁶ and R ²⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Among these, a chlorine atom and a bromine atom are preferable.

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 addition, for the preferred ranges of general formulas (OS-3) to (OS-5) and exemplary compounds, the description in paragraph numbers 0171 to 0200 of JP2011-227449A can be referred to.

  In the photosensitive resin composition of the present invention, (B) the photoacid generator is added to 100 parts by mass of all resin components (preferably solid content, more preferably (A) copolymer) in the photosensitive resin composition. On the other hand, it is preferable to use 0.1-10 mass parts, and it is more preferable to use 0.5-10 mass parts. Two or more kinds can be used in combination.

<Compound represented by the general formula (1)>
The composition of this invention has a compound represented by General formula (1). By blending the compound represented by the general formula (1), high dry etching resistance can be maintained while maintaining sensitivity. Furthermore, applicability and adhesion to the substrate can also be improved.
General formula (1)
(In general formula (1), R ¹ is a hydrocarbon group having no reactive group, R ² is an alkyl group, and n is an integer of 1 to ^3. )

R ¹ is a hydrocarbon group having no reactive group, preferably a hydrocarbon group having 4 or more carbon atoms, and more preferably a hydrocarbon group having 6 or more carbon atoms. The upper limit value is not particularly defined, but may be, for example, 20 or less, and further 10 or less. In particular, when the hydrocarbon group has 6 or more carbon atoms, the compatibility with the polymer component is improved, and the coating property and the dry etching resistance tend to be further improved.
R ¹ is preferably a hydrocarbon group having no aromatic ring. When there is no aromatic ring, the compatibility with the polymer component is improved and the coating property and the dry etching resistance tend to be further improved.
R ¹ is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group, preferably an alkyl group, and preferably a linear or branched alkyl group.
R ² is an alkyl group, preferably a linear or branched alkyl group, and more preferably a linear alkyl group. The carbon number of the alkyl group as R ² is 1 to 10, more preferably 1 to 5, more preferably 1 to 3, still more preferably a methyl group or an ethyl group, a methyl group is particularly preferred.
n is preferably 2 or 3, and more preferably 3.

The compound represented by the general formula (1) used in the present invention is preferably composed of Si, O, C and H.
The molecular weight of the compound represented by the general formula (1) used in the present invention is preferably 100 to 500, and more preferably 150 to 300.
80-250 degreeC is preferable and, as for the boiling point of the compound represented by General formula (1) used by this invention, 100-220 degreeC is more preferable.
Although the compound represented by General formula (1) preferably used for this invention below is illustrated, it cannot be overemphasized that this invention is not limited to these.

In the above, Ph is a phenyl group.

  In the photosensitive resin composition of the present invention, the compound represented by the general formula (1) is preferably 0.1 to 7% by mass with respect to the total solid content of the photosensitive resin composition, 0.3 More preferably, it is -5 mass%, and it is most preferable that it is 0.5-3 mass%. Two or more kinds can be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<(D) Solvent>
The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the components (A) to (D), which are essential components, and optional components are dissolved in a solvent (D).
As the solvent (D) 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.

As a (D) solvent used for the photosensitive resin composition of this invention, description of the paragraph numbers 0166-0169 of Unexamined-Japanese-Patent No. 2011-215580 can be referred, for example.
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, and propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether are most preferably used in combination.

Component D is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. A solvent having a boiling point of 130 ° 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 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 (D) in the photosensitive resin composition of the present invention is 100 parts by mass of all resin components (preferably solid content, more preferably the (A) copolymer) in the photosensitive resin composition. It is preferably 50 to 3,000 parts by mass, more preferably 100 to 2,000 parts by mass, and even more preferably 150 to 1,500 parts by mass.

<Other ingredients>
In addition to the component (A), the component (B), the component (C) and the component (D), the positive photosensitive resin composition of the present invention includes a sensitizer, a crosslinking agent, and an adhesive as necessary. An improver, a basic compound, and a surfactant 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, a development accelerator, a thermal base generator, and an organic Or well-known additives, such as an inorganic precipitation inhibitor, can be added.

<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. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by weight, and 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.

<Crosslinking agent>
It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. (Excluding component A). For example, a compound selected from an alkoxymethyl group-containing crosslinking agent, a compound having two or more epoxy groups or oxetanyl groups in the molecule, a compound having at least one ethylenically unsaturated double bond, and a blocked isocyanate compound. preferable.

-Alkoxymethyl group-containing crosslinking agent-
Specific examples of the alkoxymethyl group-containing crosslinking agent preferably include alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively.
The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of outgas generation amount, A methyl group is particularly preferred.
Among these alkoxymethyl group-containing crosslinking agents, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferred alkoxymethyl group-containing crosslinking agents, and from the viewpoint of chemical resistance effect, alkoxymethylated melamine Is particularly preferred.
These alkoxymethyl group-containing crosslinking agents are available as commercial products. For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarac MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

  When the photosensitive resin composition of the present invention contains an alkoxymethyl group-containing crosslinking agent, the addition amount of the alkoxymethyl group-containing crosslinking agent in the photosensitive resin composition of the present invention is the total solid content of the photosensitive resin composition. On the other hand, it is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, and most preferably 0.5 to 5% by mass.

-Compounds having two or more epoxy groups or oxetanyl groups in the molecule-
The photosensitive resin composition of the present invention preferably contains, as Component C, a compound having two or more epoxy groups or oxetanyl groups in the molecule.
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy compounds, and the like. Can do. The aliphatic epoxy compound is a resin having a linear and / or branched carbon chain and an epoxy group, and in addition to a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, and the like are bonded to the carbon chain. You may do it. The aliphatic epoxy compound is particularly preferably a resin composed of a linear and / or branched carbon chain, a hydrogen atom, and an epoxy group, or a resin in which a hydroxyl group is substituted on the resin. 1-4 are preferable and, as for the number of an epoxy group, 2 or 3 is more preferable.

  These are available as commercial products. For example, as a bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1004, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1055 And bisphenol F-type epoxy resins such as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Co., Ltd.), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.) As the phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (or higher) The cresol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), etc., and as an aliphatic epoxy resin, ADEKA RESIN EP -4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), aliphatic epoxy compounds include Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, and PB 4700 (The above is made by Daicel Chemical Industries, Ltd.). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation) and the like can be mentioned.

  Moreover, as an aliphatic epoxy compound, the compound represented by a following formula (X-1) is mentioned.

(In formula (X-1), A represents a linear or branched hydrocarbon group, may have a hydroxyl group as a substituent, and n represents an integer of 1 to 4.)

1-20 are preferable, as for carbon number of A in Formula (X-1), 1-15 are more preferable, 2-10 are more preferable, and 2-6 are especially preferable.
N in Formula (X-1) represents an integer of 1 to 4, and 2 or 3 is preferable.

  The aliphatic epoxy compound is more preferably a compound represented by the following formula (X-2).

(In Formula (X-2), A ′ represents a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n represents an integer of 1 to 4.)

1-18 are preferable, as for carbon number of A 'in Formula (X-2), 1-13 are more preferable, and 2-8 are more preferable.
N in Formula (X-2) represents an integer of 1 to 4, and 2 or 3 is preferable.

Examples of the aliphatic epoxy compound that can be preferably used in the present invention include Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX- 421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-321L, EX-850L, EX-211L, EX-946L, EX-946L, DLC- 201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 , Manufactured by Nagase ChemteX (Ltd.)), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, Nippon Steel Chemical Co., Ltd.) and the like.
Of these, trimethylolpropane triglycidyl ether or neopentyl glycol diglycidyl ether shown below is particularly preferable. Among these, EX-321, EX-321L, EX-211, EX-211L (above, manufactured by Nagase ChemteX Corporation) correspond to these.

These can be used alone or in combination of two or more.
Among these, an epoxy resin and an aliphatic epoxy compound are preferably mentioned, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and an aliphatic epoxy compound are more preferred, and bisphenol A Particularly preferred are type epoxy resins and aliphatic epoxy compounds.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.
When the compound having two or more epoxy groups or oxetanyl groups in the molecule is used in the photosensitive resin composition of the present invention, the photosensitive resin composition of the compound having two or more epoxy groups or oxetanyl groups in the molecule 0.1-50 mass parts is preferable with respect to 100 mass parts of component A, as for the addition amount to a thing, 0.5-30 mass parts is more preferable, and 1-20 mass parts is further more preferable.

-Compound having at least one ethylenically unsaturated double bond-
As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. be able to.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.

  When using the compound which has one ethylenically unsaturated double bond in the photosensitive resin composition of this invention, it has at least 1 ethylenically unsaturated double bond in the photosensitive resin composition of this invention. The proportion of the compound used is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of Component A. By containing at least one compound having an ethylenically unsaturated double bond at such a ratio, the heat resistance and surface hardness of the cured film obtained from the photosensitive resin composition of the present invention can be improved. it can. When adding a compound having at least one ethylenically unsaturated double bond, it is preferable to add the aforementioned thermal radical generator.

-Block isocyanate compounds-
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as an adhesion improving agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said block isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanate may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 , 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound and a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

  Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.

  Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, and the like. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (and above) , Manufactured by Asahi Kasei Chemicals Corporation, Death Module BL 100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.), etc. are preferably used can do.
In the photosensitive resin composition of this invention, when mix | blending a block isocyanate compound, it is preferable that it is 0.1-8 mass% with respect to the total solid of the photosensitive resin composition, 0.2-7 mass% It is more preferable that it is 0.5 to 5% by mass. Two or more kinds can be used in combination. When using 2 or more types together, it is preferable that a total amount is the said range.

<Adhesion improver>
The photosensitive resin composition of the present invention may contain an adhesion improving agent. Adhesion improvers that can be used in the photosensitive resin composition of the present invention are inorganic substances that serve as substrates, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, metals such as gold, copper, aluminum, molybdenum, and titanium. It is a compound that improves the adhesion between the insulating film and the insulating film. 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.
Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. 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 preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. Part is more preferred. When using 2 or more types together, it is preferable that a total amount is the said range.

<Basic compound>
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound 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 thereof include compounds described in paragraph numbers 0204 to 0207 of JP2011-221494A.

  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.

  The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is ˜1 part by mass.

<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.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
Further, as the surfactant, compounds described in paragraph numbers 0185 to 0188 of JP2011-215580A can also be employed.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of (I) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.001 It is more preferable that it is -10 mass parts, and it is still more preferable that it is 0.01-3 mass parts.

<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.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, saccharides, nitrites, sulfites, thiosulfates, Examples include hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.

Examples of commercially available phenolic antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 and ADK STAB AO manufactured by ADEKA Corporation. -80, ADK STAB AO-330, Sumitizer Chemical Co., Ltd., Sumilizer GM, Sumilizer GS, Sumilizer MDP-S, Sumizer ZBM-S, Sumizer ZX, IRGANOX10 NO. IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, IR ANOX1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295, Yoshinox BHT, Yoshinox BB, Yoshinox T3, Yoshinox T3, Yoshinox T3, Is mentioned.
Among them, ADK STAB AO-60, ADK STAB AO-80 (manufactured by ADEKA, Inc.), and Irganox 1098 (manufactured by Ciba Japan Co., Ltd.) are preferable.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. 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.

<Acid multiplication agent>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-A-9-512498. The compounds described on the 12th line to the 47th line on the 2nd line can be mentioned.
In particular
Etc.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
The content of the acid proliferating agent in the photosensitive resin composition is 10 to 1,000 parts by weight with respect to 100 parts by weight of the photoacid generator, from the viewpoint of dissolution contrast between the exposed part and the unexposed part. To 20 to 500 parts by weight is more preferable.

<Development accelerator>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, the compounds described in JP-A-2012-042837, paragraph numbers 0171 to 0172 can be used.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass when the component (A) is 100 parts by mass from the viewpoints of sensitivity and residual film ratio. 20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.
<Thermal radical generator, thermal acid generator, thermal base generator>
As other additives, the thermal radical generator and the thermal acid generator described in paragraphs 0120 to 0121 of JP2012-8223A can be used.
Moreover, as a thermal base generator, the nitrogen containing compound as described in WO2011136074A1 can be used.
The content of the thermal radical generator, thermal acid generator and thermal base generator in the photosensitive resin composition is 0.5 to 20 parts by weight when the total content of component (A) is 100 parts by weight. Preferably, 1 to 10 parts by weight is more preferable.

[Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the chemical amplification type positive photosensitive resin composition of this invention on a board | substrate,
(2) a step of removing the solvent from the applied chemically amplified positive photosensitive resin composition;
(3) a step of exposing the chemically amplified positive photosensitive resin composition from which the solvent has been removed with actinic rays;
(4) a step of developing the exposed chemically amplified positive photosensitive resin composition with an aqueous developer, and
(5) Post-baking process of thermosetting the developed chemically amplified positive photosensitive resin composition Each process will be described in order below.

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

  In the exposure step (3), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, (B) the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the copolymer (A) is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.

  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”) is performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.

  The acid-decomposable group in the structural unit represented by the formula (a1-1) in the present invention has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from an acid generator by exposure to a carboxyl group or phenol. A positive image can also be formed by development without necessarily carrying out PEB, since a functional hydroxyl group is generated. However, in the method for producing a cured film of the present invention, the photosensitive resin composition of the present invention is used. By performing the post-bake process, the obtained cured film can reduce heat flow. Therefore, when the cured film obtained by the method for producing a cured film of the present invention is used for a substrate as a resist, for example, even if the cured film of the present invention is heated together with the substrate, the resolution of the pattern hardly deteriorates. In the present specification, “heat flow” means that the cross-sectional shape of a patterned cured film formed by exposure and development steps is to heat the cured film (preferably 180 ° C. or more, more preferably 200 ° C. to 240 ° C. ) When deformed and the dimensions, taper angle, etc. deteriorate.

In the developing step (4), a 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.
In the post-baking step of (5), the obtained positive image is heated to thermally decompose the acid-decomposable group in the structural unit (a1) to generate a carboxyl group or a phenolic hydroxyl group, thereby forming the structural unit (a2). A cured film can be formed by crosslinking with a crosslinking group, a crosslinking agent, or the like. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 240 ° 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 120 minutes.
When a step of irradiating the entire surface with actinic rays, preferably ultraviolet rays, is added before the post-baking step, the crosslinking reaction can be promoted by an acid generated by actinic ray irradiation.
Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
When the cured film obtained by thermal curing in the post-baking step (5) is used as a dry etching resist, dry etching processing such as ashing, plasma etching, ozone etching, or the like can be performed as the etching processing.
Furthermore, the forming method of the present invention may include (6) a dry etching step of performing dry etching on a substrate having a cured film obtained by thermosetting.
Next, the manufacturing method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition is prepared by mixing the essential components (A) to (D) at a predetermined ratio and by any method, and stirring and dissolving. For example, it is possible to prepare a resin composition by mixing the components (A) to (C) in advance in a solution in which the components (A) to (C) are previously dissolved in the solvent (D) and mixing them at a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Coating process and solvent removal process>
It is preferable to wash the substrate before applying the photosensitive resin resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after washing the substrate. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate is improved. Further, the method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor.
Examples of the substrate include glass, quartz, silicone, silicon nitride, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and a hydrogenated product thereof. The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a side of 1 m or more on each side. Moreover, when manufacturing a high-definition panel, the board | substrate of the magnitude | size called a medium-small size with each side being 1 m or less may be used, and the spin coating method and the slit and spin method are preferable in that case. A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking).

  Further, the heating condition of the solvent removal step is a range in which the acid-decomposable group is not decomposed in the structural unit (a1) in the component (A) in the unexposed part and the component (A) is not soluble in the alkali developer. Although it varies depending on the type and mixing ratio of each component, it is preferably about 70 to 130 ° C. for 30 to 300 seconds.

<Exposure process and development process (pattern formation method)>
In the exposure step, 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 the development step, the 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 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.

  The developer used in the development step 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 developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid piling method and a dipping method. After development, washing with running water is performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

<Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 180 to 250 ° C., for a predetermined time, for example, 5 to 90 minutes on the hot plate, In the case of an oven, a protective film or an interlayer insulating film having excellent heat resistance, hardness, etc. can be formed by carrying out a heat treatment for 30 to 120 minutes to cause a crosslinking reaction. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to the heat treatment, the substrate on which the pattern is formed is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) to generate an acid from the component (B) present in the unexposed portion, thereby crosslinking. It is preferable to function as a catalyst that accelerates the process.
That is, it is preferable that the manufacturing method of the cured film of this invention includes the re-exposure process reexposed with actinic light between a image development process and a post-baking process. The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, the entire surface is exposed on the side of the substrate on which the film is formed by the photosensitive resin composition of the present invention. It is preferable.
A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

[Curing film]
The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.

[Organic EL display device, Liquid crystal display device]
The organic EL display device and the liquid crystal display device of the present invention are characterized by including the cured film of the present invention.
The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that they have a planarizing film, an interlayer insulating film, and a partition formed by using the photosensitive resin composition of the present invention, and various types are available. Examples include various known organic EL display devices and liquid crystal display devices having a structure.
Specific examples of the organic EL display device having a planarizing film, an interlayer insulating film, and a partition formed using the photosensitive resin composition of the present invention are formed using the photosensitive resin composition of the present invention. An organic EL device having a bank layer (16) and a planarizing film (57) described in FIG. 2 of JP2011-107476A, and a partition wall (12 shown in FIG. 4A of JP2010-9793A). ) And a planarizing film (102), an organic EL device having a bank layer (221) and a third interlayer insulating film (216b) shown in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591, -128577, the organic EL device having the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A, and the flat structure described in FIG. 3 of JP 2010-182638 A Chemical film (1 ) And an organic EL device and the like having a pixel isolation insulating film (14).

For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
The liquid crystal display device that can be used by the liquid crystal display device of the present invention includes a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, An OCB (Optical Compensated Bend) method may be used.
Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.

  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 the organic EL element. 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. Unless otherwise specified, “part” and “%” are based on mass.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: tetrahydrofuran-2-yl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (synthetic product)
MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
StOEVE: 4- (1-ethoxyethyloxy) styrene (synthetic product)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (Wako Pure Chemical Industries, Ltd.)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
BzMA: benzyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
MAEE: 2-ethoxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
V-601: Dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
HS-EDM: Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Co., Ltd., High Solve EDM)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)

<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 gave 125 g of tetrahydrofuran-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 MAEVE>
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower. .) 134.0 parts of 1-ethoxyethyl methacrylate in the 43-45 ° C./7 mmHg fraction were obtained as a colorless oil.

  MATHP and StOEVE were synthesized in the same manner as MATHF and MAEVE except that the corresponding compound of ethyl vinyl ether was changed or methacrylic acid was changed to hydroxystyrene.

[Synthesis of Polymer A1]
HS-EDM (82 parts) was heated and stirred at 90 ° C. under a nitrogen stream. MATHF (43 parts (40.5 mol% equivalent)), OXE-30 (48 parts (37.5 mol% equivalent)), MAA (6 parts (9.5 mol% equivalent)), HEMA (11 parts (12 0.5 mol% equivalent)), radical polymerization initiator V-601 (trade name, 4.3 parts by Wako Pure Chemical Industries, Ltd.) and PGMEA (82 parts) were added dropwise over 2 hours, By further reacting at 90 ° C. for 2 hours, a PGMEA solution of polymer A1 (solid content concentration: 40%) was obtained.
The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained polymer A1 was 15,000.

<Synthesis of other polymers A2 to A14>
Each copolymer was synthesized in the same manner as the synthesis of polymer A1, except that each monomer used and the amount used thereof were changed to those shown in the following table. A13 and A14 used the commercial item.

  In the above table, the numerical values not particularly given in the table are in mol%. The numerical value of a polymerization initiator and an additive is mol% when a monomer component is 100 mol%. The solid content concentration is shown as monomer weight / (monomer weight + solvent weight) × 100 (unit weight%). When V-601 was used as the polymerization initiator, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.

<Examples and Comparative Examples>
(1) Preparation of photosensitive resin composition After mixing each component shown in the following table to obtain a uniform solution, a polytetrafluoroethylene filter having a pore size of 0.1 µm was used as a solvent (D1 described later). It dissolved and mixed until it became solid content concentration 32%, and it filtered, and prepared the solution of the photosensitive resin composition of an Example and a comparative example, respectively.

In addition, the symbol in the following table | surface is as follows.
<Photo acid generator>
B1: CGI-1397 (Ciba Japan Co., Ltd.)
B2: PAI-101 (manufactured by Midori Chemical Co., Ltd.)
B3: Compounds shown below (Synthesis examples will be described later)
B4: Compounds shown below (Synthesis examples will be described later)
B5: Compounds shown below (Synthesis examples will be described later)
B6: Compound shown below (Synthesis examples will be described later)

<Alkoxysilane compound>
C1: KBM-3063 (hexyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
C2: KBM-3103 (decyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
C3: KBM-103 (phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
C4: Z-2306 (isobutyltrimethoxysilane, manufactured by Toray Dow Corning Co., Ltd.)
C5: Z-6321 (ethyltrimethoxysilane, manufactured by Toray Dow Corning Co., Ltd.)

<Crosslinking agent>
O1: JER-157S65 (Polyfunctional novolac type epoxy resin, cross-linking agent, manufactured by Mitsubishi Chemical Corporation)
O2: JER-828 (bisphenol A type epoxy resin, cross-linking agent, manufactured by Mitsubishi Chemical Corporation)
O3: JER-1007 (bisphenol A type epoxy resin, cross-linking agent, manufactured by Mitsubishi Chemical Corporation)
O4: Denacol EX-321L (Liquid aliphatic epoxy compound, manufactured by Nagase ChemteX Corporation)
O5: Denacol EX-211L (Liquid aliphatic epoxy compound, manufactured by Nagase ChemteX Corporation)
O6: Coronate AP stable M (block isocyanate compound, manufactured by Nippon Polyurethane Industry Co., Ltd.)
O7: Death Module BL-4265 (Block isocyanate compound, manufactured by Sumika Bayer Urethane Co., Ltd.)
O8: TEPIC-SP (epoxy compound, manufactured by Nissan Chemical Industries, Ltd.)

<Solvent>
D1: Propylene glycol monomethyl ether acetate <sensitizer>
E1: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Chemical Industry Co., Ltd.)

<Basic compound>
F1: 1,5-diazabicyclo [4,3,0] -5-nonene (the following structure, manufactured by Tokyo Chemical Industry Co., Ltd.)
F2: Compound having the following structure (manufactured by Toyobo Co., Ltd.)

<Silane coupling agent>
H1: KBM-403 (trade name, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
H2: KBM-5103 (trade name, 3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.))

<Antioxidant>
I1: Irganox 1726 (Antioxidant, manufactured by BASF)
I2: Irganox 1035 (Antioxidant, manufactured by BASF)
I3: Irganox 1098 (Antioxidant, manufactured by BASF)
I4: ADK STAB AO-60 (Antioxidant, manufactured by ADEKA Corporation)
I5: ADK STAB AO-70 (Antioxidant, manufactured by ADEKA Corporation)

<Surfactant>
W1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula W2: Silicone surfactant SH-8400 (Toray Dow Corning Silicone)

[Synthesis of B3]
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain B3 (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B3 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 ( d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2 .4 (s, 3H), 1.7 (d, 3H).

[Synthesis of B4]
2-Naphthol (20 g) is dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) are added and reacted at 100 ° C. for 2 hours. It was. To the reaction solution are added water (300 mL) and ethyl acetate (200 mL), and the mixture is separated. The organic layer is concentrated, and then a 48 mass% aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) are added. The reaction was performed for 2 hours. The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid, and then 30 g of polyphosphoric acid was added and reacted at 170 ° C. for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added for liquid separation, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).
Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the resulting ketone compound (10.0 g) and methanol (100 mL) for 24 hours. Heated to reflux. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was separated four times with 80 mL of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g). Got.
The obtained oxime (3.1 g) was sulfonated in the same manner as B3 to obtain B4 (3.2 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B4 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 ( d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H), 2 .4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4 to 1.2 (m, 8H), 0.8 (t, 3H) .

[Synthesis of B5]
1-1. Synthesis of Synthetic Intermediate B5A 2-Aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C.). Next, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour and then at 100 ° C. for 2 hours to cause a reaction. 500 mL of water was added to the resulting reaction solution to dissolve the precipitated salt, the toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B5A.

1-2. Synthesis of B5 After 2.25 g of the synthetic intermediate B5A obtained as described above was mixed with tetrahydrofuran: 10 mL (manufactured by Wako Pure Chemical Industries, Ltd.), the reaction solution was cooled to 5 ° C. or lower by placing in an ice bath. . Next, 4.37 g (25 mass% methanol solution, manufactured by Alfa Acer) of tetramethylammonium hydroxide was added dropwise to the reaction solution, and the mixture was stirred for 0.5 hour in an ice bath to be reacted. Further, 7.03 g of isopentyl nitrite was added dropwise while maintaining the internal temperature at 20 ° C. or lower, and after completion of the dropwise addition, the reaction solution was warmed to room temperature and stirred for 1 hour.
Subsequently, after cooling the reaction liquid to 5 ° C. or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred for 1 hour while maintaining 10 ° C. or lower. Thereafter, 80 mL of water was added and stirred at 0 ° C. for 1 hour. After filtration of the resulting precipitate, 60 mL of isopropyl alcohol (IPA) was added, heated to 50 ° C., stirred for 1 hour, filtered while hot, and dried to obtain 1.8 g of B5 (the aforementioned structure). Obtained.
The ¹ H-NMR spectrum (300 MHz, deuterated DMSO ((D ₃ C) ₂ S═O)) of the obtained B5 is δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.0. 00 (m, 1H), 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).
From the above ¹ H-NMR measurement results, it is estimated that the obtained B5 is a single geometric isomer.

[Synthesis of B6]
B6: Compound having the following structure (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)

In the above table, the numerical values not particularly given in the table are in parts by mass.

(2) Evaluation of photosensitive resin composition <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 4.0 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 resin composition layer was developed with an alkali developer (0.4 wt% 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. The evaluation criteria are as follows. “A” and “B” are levels that have no practical problem. The results are shown in the table below.
A: Eopt is less than 40 mJ / cm ² B: Eopt is 40 mJ / cm ² or more and less than 60 mJ / cm ² C: Eopt is 60 mJ / cm ² or more and less than 80 mJ / cm ² D: Eopt is 80 mJ / cm ² or more

<Evaluation of coatability>
In each photosensitive resin composition preparation, a photosensitive resin composition was prepared in the same manner except that the amount of solvent was adjusted to a viscosity of 9.0 mPa · s.
About each photosensitive resin composition, applicability | paintability was evaluated as follows. Using CL1700 manufactured by Tokyo Electron Ltd., a glass substrate of 1,500 mm × 1,800 mm was slit coated so that the coating thickness after drying was 4.0 μm. Drying was performed on a hot plate at 90 ° C. for 90 seconds. The coated surface was visually observed to count the number of streaky irregularities and evaluated according to the following criteria. The results are shown in the table. A, B, and C are acceptable.
A: No streak-like unevenness on the coated surface B: 1 to 3 streaky unevenness C: 4 to 5 D: 6 or more

<Evaluation of dry etching resistance (film loss)>
After each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 4 A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
The obtained photosensitive resin composition layer is subjected to a cumulative irradiation amount of 100 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. The cured film is dry etched using a dry etching apparatus “CDE-80N (manufactured by Shibaura Mechatronics Co., Ltd.)” under the conditions of etching gas CF ₄ 50 ml / min, O ₂ 10 ml / min, output 400 mW, etching time 90 seconds. The film thickness before and after the treatment was measured, and the amount of film loss due to dry etching was calculated. The evaluation criteria are as follows. A to C are practical ranges, and D is not practical.
A: Less than 0.2 μm B: 0.2 μm or more and less than 0.4 μm C: 0.4 μm or more and less than 0.8 μm D: 0.8 μm or more

<Evaluation of dry etching resistance (surface roughness)>
The surface roughness (Ra, unit nm) of the surface of the substrate (the surface of the photosensitive resin composition layer) whose etching resistance was evaluated using an atomic force microscope (AFM) was measured. The smaller the value, the smoother the surface.
The ranking was based on the following criteria. A to C are practical, and D is not practical.
A: Ra is less than 2.0 nm B: Ra is 2.0 nm or more and less than 4.0 nm C: Ra is 4.0 nm or more and less than 7.0 nm D: Ra is 7.0 nm or more

<Development adhesion>
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 4.0 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 resin composition layer was developed with an alkali developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
When exposed to the optimum i-line exposure amount (Eopt) when resolving 3 μm line and space by 1: 1 by these operations, the development adhesion to the underlying substrate was evaluated by the pattern residual ratio of 3 μm line. The larger the pattern remaining rate, the higher the development adhesion with the base substrate. The evaluation criteria are as follows, and “A” and “B” are practically unproblematic levels. The results are shown in the table below.
A: Pattern remaining rate of 3 μm line is 100%
B: Pattern remaining rate of 3 μm line is 80% or more and less than 100% C: Pattern remaining rate of 3 μm line is 50% or more and less than 80% D: Pattern remaining rate of 3 μm line is less than 50%

As is apparent from the above table, when the composition of the present invention was used (Examples 1 to 50), a composition excellent in both sensitivity and dry etching resistance was obtained. Furthermore, it was excellent in applicability and cured film adhesion.
On the other hand, when the compound (alkoxysilane) represented by the general formula (1) was not added (Comparative Examples 1 to 6), the dry etching resistance was remarkably inferior. Furthermore, the coating property and the development adhesion were also inferior. Further, Comparative Examples 7 to 8 to which bisalkoxysilane was added were found to be inferior in sensitivity, dry etching resistance, coating property and development adhesion.

<Example 51>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed 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 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 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 of Example 41 on a substrate, pre-baking (90 ° C. × 2 minutes) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes. 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, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film, the photosensitive resin composition of Example 41 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process can be prevented.

  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 active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied through the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

<Example 52>
In the active matrix type liquid crystal display device shown 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 52 was obtained.
That is, using the photosensitive resin composition of Example 23, 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 the above Example.

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

<Example 53>
In Example 52, only the following coating process was changed to obtain a similar liquid crystal display device.
That is, after applying the photosensitive resin composition of Example 46 by the slit and spin method (SF-700G manufactured by Dainippon Screen Mfg. Co., Ltd.), the solvent was removed by heating on a hot plate at 90 ° C./120 seconds. A photosensitive resin composition layer having a film thickness of 4.0 μm was formed. The obtained coating film was flat and had a good surface shape without unevenness. Moreover, the performance as a liquid crystal display device was also good.

Claims (17)

(A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,
(B) a photoacid generator,
(C) a compound represented by the following general formula (1), and
(D) A chemically amplified positive photosensitive resin composition containing a solvent.
General formula (1)
(In general formula (1), R ¹ is a hydrocarbon group having no substituent , R ² is an alkyl group, and n is an integer of 1 to ^3. ) (C) The chemically amplified positive photosensitive resin composition according to claim 1, wherein R ¹ in the general formula (1) is a hydrocarbon group having 4 or more carbon atoms having no substituent . (C) The chemically amplified positive photosensitive resin composition according to claim 1, wherein R ¹ in the general formula (1) is a hydrocarbon group having 6 or more carbon atoms that has no substituent . (C) is R ¹ in the general formula (1), a hydrocarbon group having no substituent group, having 6 or more carbon atoms, and a hydrocarbon group not having an aromatic ring, according to claim 1 A chemically amplified positive photosensitive resin composition. The chemical amplification type positive photosensitive resin composition according to any one of claims 1 to 4 , wherein R ¹ is an alkyl group having 4 or more carbon atoms having no substituent . Acid-decomposable group is a group having a protected structure in the form of acetal, a chemically amplified positive photosensitive resin composition according to any one of claims 1-5. (A) the polymer component is, furthermore, a polymer containing acid groups, chemically amplified positive photosensitive resin composition according to any one of claims 1-6. (A2) The crosslinkable group contained in the structural unit having a crosslinkable group is represented by an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7 , which is at least one selected from the group described above.   The chemical amplification type positive according to any one of claims 1 to 8, wherein the polymer component (A) is a polymer having a structural unit (a4) having a hydroxyl group other than a phenolic hydroxyl group or an alkyleneoxy group. Type photosensitive resin composition. The (A) polymer component has a structural unit (a1) having a residue in which a carboxyl group is protected by an acetal structure, a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, an epoxy group or an oxetanyl group. The chemically amplified positive photosensitive resin according to any one of claims 1 to 9 , which is a polymer having a unit (a3) and a structural unit (a4) having a hydroxyl group other than a phenolic hydroxyl group or an alkyleneoxy group. Resin composition. The chemical amplification type positive photosensitive resin composition according to any one of claims 1 to 10 , wherein the (B) photoacid generator is an oxime sulfonate compound. (1) applying a chemically amplified positive photosensitive resin composition according to the substrate in any one of claims 1 to 11,
(2) a step of removing the solvent from the applied chemically amplified positive photosensitive resin composition;
(3) a step of exposing the chemically amplified positive photosensitive resin composition from which the solvent has been removed with actinic rays;
(4) a step of developing the exposed chemically amplified positive photosensitive resin composition with an aqueous developer, and
(5) A post-baking step of thermally curing the developed chemically amplified positive photosensitive resin composition. The manufacturing method of the cured film of Claim 12 including the process of exposing the developed chemical amplification type positive photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process. (6) The manufacturing method of the cured film of Claim 12 or 13 which further includes the dry etching process of performing dry etching with respect to the board | substrate which has a cured film obtained by thermosetting. Cured film obtained by curing the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 11. The cured film according to claim 15 , which is an interlayer insulating film. A liquid crystal display device or an organic EL display device having the cured film according to claim 15 or 16 .