JP5313285B2 - Positive photosensitive resin composition, pattern manufacturing method, MEMS structure and manufacturing method thereof, dry etching method, wet etching method, MEMS shutter device, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition capable of forming a rectangular or nearly rectangular profile even after the formed pattern is baked. <P>SOLUTION: The positive photosensitive resin composition contains: (component A) a polymer having a monomer unit (a1) having a residue comprising a carboxyl group or a phenolic hydroxyl group protected with an acid decomposable group, a monomer unit (a2) having an epoxy group and/or an oxetanyl group, and a monomer unit (a3) having a structure selected from a group consisting of an amino group, amide group, imide group, sulfonimide group, sulfonamide group, imino group, urethane bond and ureido bond; (component B) a photoacid generator; and (component C) a solvent. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

  The present invention relates to a positive photosensitive resin composition, a pattern manufacturing method, a MEMS structure and a manufacturing method thereof, a dry etching method, a wet etching method, a MEMS shutter device, and an image display device.

In a manufacturing process of a liquid crystal display device, an organic EL display device, a semiconductor device, a MEMS, or the like, a photosensitive resin composition is used as an etching resist. In particular, chemically amplified positive resists are actively used in etching resist applications because of their high resolution and high sensitivity.
As a conventional photosensitive resin composition, for example, Patent Document 1 proposes a positive photosensitive resin composition for an etching resist. Patent Document 2 proposes a positive photosensitive resin composition for an etching resist. Patent Document 3 shows an example of manufacturing a MEMS structure using a sacrificial layer resist. Moreover, the resin composition for positive type | mold interlayer insulation film materials of the microlens formation agent use of patent document 4 is mentioned.

Japanese Patent Laid-Open No. 10-73923 Japanese Patent No. 3693199 Special table 2008-533510 gazette Japanese Patent No. 4207604

For example, in the case of a sacrificial layer resist at the time of producing a MEMS, the resist shape is reflected in the upper laminated structure as it is, and therefore, resist shape control is important.
In addition, when used as an etching resist in a dry etching process, a profile that is close to a rectangle and has a large taper angle is required in order to realize precise patterning by etching.
Furthermore, durability such as a certain degree of solvent resistance, chemical resistance and mechanical strength is required so that the resist film does not swell and peel off or dissolve and disappear in a dry etching or wet etching process.
When used as a thick film resist, high sensitivity is required in order to obtain an appropriate pattern in the development process, and the influence of heat flow and cure shrinkage increases in the thick film. It becomes even more important. In addition, a thick film refers to the usage form of the resist whose dry film thickness after solvent removal is 4-100 micrometers.

With a conventional etching resist, it is difficult to obtain a rectangle or a profile close to a rectangle when a baking process for improving the strength of the cured film is performed.
For example, the photosensitive resin composition described in Patent Document 1 has a problem that a rectangular profile cannot be obtained due to the heat flow during baking.
On the other hand, in Patent Document 4, the evaluation is better as the curve of the pattern and the taper is better, and the evaluation is worse as the taper shape is rectangular.
The problem to be solved by the present invention is to provide a positive photosensitive resin composition capable of forming a rectangular shape or a profile close to a rectangular shape even after the formed pattern is baked.

The above-described problems of the present invention have been solved by means described in the following <1>, <9>, or <13> to <18>. It describes below with <2>-<8> and <10>-<12> which are preferable embodiments.
<1> (Component A) A monomer unit (a1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group, a monomer unit (a2) having an epoxy group and / or an oxetanyl group, amino A monomer unit (a3) having a structure selected from the group consisting of a group, an amide group, an imide group, a sulfonimide group, a sulfonamide group, an imino group, a urethane bond and a ureido bond, (Component B) A positive-type photosensitive resin composition comprising a photoacid generator, and (Component C) a solvent;
<2> The positive photosensitive resin composition according to <1>, wherein the monomer unit (a3) is a monomer unit having a structure selected from the group consisting of the following structures (S1) to (S14):

（構造（Ｓ１）〜（Ｓ１４）中のＲ、Ｒ’及びＲ”はそれぞれ独立に、水素原子又は炭素数１〜２０の置換基を表し、＊は他の構造との連結部を表す。）

(R, R ′ and R ″ in the structures (S1) to (S14) each independently represent a hydrogen atom or a substituent having 1 to 20 carbon atoms, and * represents a connecting portion with another structure.)

<3> The positive photosensitive resin composition according to <1> or <2>, wherein the weight average molecular weight of component A is 5,000 or more,
<4> The positive photosensitive resin according to any one of <1> to <3>, wherein the content of the monomer unit (a3) in the component A is 50 mol or less with respect to all the monomer units in the component A. Functional resin composition,
<5> The positive photosensitive resin composition according to any one of the above <1> to <4>, wherein the component A is a polymer further having a monomer unit (a5) having a carboxy group or a hydroxyl group,
<6> (Component D) The positive photosensitive resin composition according to any one of <1> to <5>, further including a thermal crosslinking agent,
<7> The positive photosensitive resin composition according to any one of the above <1> to <6>, which is a positive photosensitive resin composition for an etching resist,
<8> The positive photosensitive resin composition according to any one of <1> to <6>, which is a photosensitive resin composition for a structural member for MEMS,
<9> A film forming step of forming a film by removing the solvent from the positive photosensitive resin composition according to any one of <1> to <8>, and exposing the film in a pattern with an actinic ray A pattern preparation method including an exposure step, a development step of developing the exposed film with an aqueous developer to form a pattern, and a baking step of heating the pattern;
<10> The pattern preparation method according to <9>, including a post-exposure step of exposing the pattern with actinic rays after the development step and before the baking step,
<11> The pattern preparation method according to <9> or <10>, wherein a taper angle in a cross-sectional shape of the pattern after the baking step is 70 ° or more.
<12> The pattern preparation method according to any one of the above <9> to <11>, wherein the film thickness of the pattern after the baking step is 4 to 100 μm,
<13> A step of producing a structure using the pattern produced by the pattern production method according to any one of <9> to <12> as a sacrificial layer at the time of stacking the structure, and the sacrificial layer A method of manufacturing a MEMS structure including a step of removing by plasma treatment,
<14> A MEMS structure produced using the pattern produced by the pattern production method according to any one of <9> to <12> as a sacrificial layer at the time of stacking the structure,
<15> A step of performing dry etching using the pattern produced by the pattern production method according to any one of <9> to <12> as a resist for dry etching, and plasma treatment or chemical treatment of the pattern A dry etching method including a step of removing by
<16> A step of performing wet etching using the pattern produced by the pattern production method according to any one of <9> to <12> as a resist for wet etching, and the pattern is subjected to plasma treatment or chemical treatment A wet etching method including a step of removing by
<17> A MEMS shutter device manufactured by the method for manufacturing a MEMS structure according to <16> above,
<18> An image display device comprising the MEMS shutter device according to <17>.

  According to the present invention, it is possible to provide a positive photosensitive resin composition capable of forming a rectangular shape or a profile close to a rectangular shape even after the formed pattern is baked. It is particularly suitable for thick film resist applications that require rectangularity.

It is a schematic diagram which shows an example whose pattern cross-sectional profile after heat processing is favorable. It is a schematic diagram which shows an example in which the pattern cross-sectional profile after heat processing is unsatisfactory. It is a schematic diagram which shows an example of the pattern cross-sectional profile after heat processing.

Hereinafter, the positive photosensitive resin composition of the present invention will be described in detail.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
In the present invention, “(Component A) a monomer unit (a1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group, and a monomer unit (a2 having an epoxy group and / or an oxetanyl group) And a monomer unit (a3) having a structure selected from the group consisting of an amino group, an amide group, an imide group, a sulfonimide group, a sulfonamide group, an imino group, a urethane bond and a ureido bond. Are also simply referred to as “component A” and the like, “monomer unit (a1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group”, etc., or simply “monomer unit (a1)” or the like. Also called.

(Positive photosensitive resin composition)
The positive photosensitive resin composition of the present invention (hereinafter also simply referred to as “photosensitive resin composition”) has a residue in which (Component A) a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group. It consists of a monomer unit (a1), a monomer unit (a2) having an epoxy group and / or an oxetanyl group, an amino group, an amide group, an imide group, a sulfonimide group, a sulfonamide group, an imino group, a urethane bond and a ureido bond. And a monomer unit (a3) having a structure selected from the group, (Component B) a photoacid generator, and (Component C) a solvent.
The positive photosensitive resin composition of the present invention is particularly preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

The positive photosensitive resin composition of the present invention is preferably used for an etching resist, and more preferably a photosensitive resin composition for a thick film etching resist having a film thickness of 4 to 100 μm.
Moreover, the positive photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition capable of forming a baking cross-sectional shape having a taper angle of 70 ° or more.
The “taper angle” is an angle formed between the side surface of the pattern and the substrate plane on which the pattern is formed in the cross-sectional shape after the pattern is formed and the baking process is performed. When the cross-sectional shape of the side surface of the pattern is not a straight line, the angle between the tangent line at the point where the film thickness on the pattern is half and the substrate plane is the cross-sectional shape. Even if the cross-sectional shape of the side surface of the pattern is a semicircle or arcuate shape, and the upper surface of the pattern is not recognized, the tangent line and the plate substrate at the middle point between the top of the film and the substrate, that is, at the point of 1/2 the film thickness The angle with the plane.
As a specific example, θ in each pattern cross-sectional shape shown in FIGS. 1, 2, and 3 is a taper angle.
In the example of FIG. 3, since the pattern cross-sectional shape is not observed and the upper surface of the pattern is not recognized, the angle between the tangent at the top of the film and the midpoint of the substrate, that is, the half of the film thickness, and the plane of the plate substrate is θ It is said.

Hereinafter, each component which comprises the photosensitive resin composition is demonstrated.
In addition, in the description of the 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).

(Component A) Specific polymer The photosensitive resin composition of the present invention comprises (Component A) a monomer unit (a1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group, an epoxy group, and And / or a monomer unit (a2) having an oxetanyl group and a monomer unit having a structure selected from the group consisting of an amino group, an amide group, an imide group, a sulfonimide group, a sulfonamide group, an imino group, a urethane bond and a ureido bond (A3) and a polymer (also referred to as “specific polymer”).
Component A contains, in addition to the monomer units (a1), (a2) and (a3), a monomer unit (a4) having a ring structure and / or a monomer unit (a5) having a carboxy group or a hydroxyl group. Is preferred.
Component A may contain a monomer unit (a6) other than the monomer units (a1) to (a5).
The “monomer unit” in the present invention includes not only a structural unit formed from one monomer molecule but also a structural unit obtained by modifying a structural unit formed from one monomer molecule by a polymer reaction or the like.
Moreover, the residue in which the carboxy group or the phenolic hydroxyl group is protected with an acid-decomposable group may generate a carboxy group or a phenolic hydroxyl group by decomposing (deprotecting) the acid-decomposable group with an acid. it can.

Component A is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group in the monomer unit (a1) is decomposed.
The term “alkali-soluble” in the present invention refers to a coating film (thickness 4 μm) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. ) In a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 0.01 μm / second or more. “Alkali insoluble” means that the solution of the compound (resin) is a substrate. The dissolution rate of a coating film (thickness: 4 μm) of the compound (resin) formed by coating on the substrate and heating at 90 ° C. for 2 minutes in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. It means less than 0.01 μm / second, preferably less than 0.005 μm / second.

The weight average molecular weight (Mw) of Component A is preferably 5,000 or more, more preferably 12,000 or more, and most preferably 14,000 or more. Further, it is preferably 1,000,000 or less, more preferably 80,000 or less, and still more preferably 60,000 or less. Within the above range, a good rectangle or a profile close to a rectangle can be obtained even after the baking step. Further, when the weight average molecular weight is 12,000 or more, the shape change in the baking process is small, and a rectangle or a profile close to a rectangle can be obtained. Further, when the weight average molecular weight is 80,000 or less, the pattern formability during development is excellent.
The weight average molecular weight is a value in terms of polystyrene measured by GPC (gel permeation chromatography). It is preferable to use THF as the solvent and TSKgel SuperHZ3000 and TSKgel SuperHZM-M (both manufactured by Tosoh Corporation) as the column.

Component A is preferably an acrylic polymer.
The “acrylic polymer” in the present invention is an addition polymerization type resin, is a polymer containing a monomer unit derived from (meth) acrylic acid or an ester thereof, and is derived from (meth) acrylic acid or an ester thereof. You may have monomer units other than a monomer unit, for example, the monomer unit derived from styrenes, the monomer unit derived from a vinyl compound, etc. Component A may contain both a monomer unit derived from (meth) acrylic acid and a monomer unit derived from (meth) acrylic acid ester.
In the present specification, the “monomer unit derived from (meth) acrylic acid or its ester” is also referred to as “acrylic monomer unit”. (Meth) acrylic acid is a generic term for methacrylic acid and acrylic acid.

  Component A preferably has an acetal structure or a ketal structure, and may have both an acetal structure and a ketal structure. In the acetal structure or ketal structure, an acetal structure is more preferable from the viewpoint of process stability. Hereinafter, the monomer units (a1) to (a6) will be described.

<Monomer unit (a1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group>
Component A has at least a monomer unit (a1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group.
When component A has a monomer unit (a1), a highly sensitive photosensitive resin composition can be obtained. A monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group is characterized by faster development than a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Therefore, a monomer unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferable for rapid development. Conversely, when it is desired to delay development, it is preferable to use a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group.

[Monomer unit (a1-1) having a residue in which a carboxy group is protected with an acid-decomposable group]
As the acid-decomposable group, known acid-decomposable groups in the positive resist for KrF and the positive resist for ArF can be used and are 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 t-butyl ester group, t -T-butyl functional groups such as butyl carbonate groups) are known.
Among these acid-decomposable groups, the basic physical properties of the resist, in particular the sensitivity and pattern, are residues having a residue in which the carboxy group is protected with an acetal or a residue in which the carboxy group is protected with a ketal. From the viewpoints of shape, contact hole formability, and storage stability of the photosensitive resin composition, it is preferable. Furthermore, among acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxy group is a residue protected with an acetal or ketal represented by the following formula (a1-1). In addition, when the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1), the entire residue is —C (═O) —O—CR ¹ R ² ( OR ³ ).

（式（ａ１−１）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子又はアルキル基を表し、ただし、Ｒ¹とＲ²とが共に水素原子の場合を除く。Ｒ³は、アルキル基を表す。Ｒ¹又はＲ²
と、Ｒ³とが連結して環状エーテルを形成してもよい。また、波線部分は、他の構造との
結合位置を表す。）

(In formula (a1-1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group, except that R ¹ and R ² are both hydrogen atoms. R ³ represents an alkyl group. R ¹ or R ²
And R ³ may be linked to form a cyclic ether. Moreover, a wavy line part represents the coupling | bonding position with another structure. )

In formula (a1-1), R ^{1 to} R ³ each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, both R ¹ and R ² do not represent a hydrogen atom, and at least one of R ¹ and R ² represents an alkyl group.
In formula (a1-1), when R ¹ , R ² and R ³ 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, t-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 ¹ , R ² and R ³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹ , R ² and R ³ 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 and a C6-C12 aryl group is more preferable. Specific examples include a phenyl group, an α-methylphenyl group, and a naphthyl group.
As the aralkyl group, an aralkyl group having 7 to 32 carbon atoms is preferable, and an aralkyl group having 7 to 20 carbon atoms is more preferable. Specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is further preferable.
Further, 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 formula (a1-1), when R ¹ , R ² and R ³ 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 ¹ , R ² and R ³ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydro group. A pyranyl group etc. can be mentioned.
In formula (a1-1), either R ¹ or R ² is preferably a hydrogen atom or a methyl group.

As the radical polymerizable monomer used for forming the monomer unit having a residue represented by the formula (a1-1), a commercially available one may be used, or one synthesized by a known method may be used. You can also. For example, it can be synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst.
In the above synthesis, (meth) acrylic acid may be previously copolymerized with other monomers and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the monomer unit (a1-1) having a residue in which a carboxy group is protected with an acid-decomposable group include the following monomer units. R represents a hydrogen atom or a methyl group. Among these, from the viewpoint of sensitivity, the monomer unit (a1-1-1), the monomer unit (a1-1-2), and the monomer unit (a1-1-7) are preferable, and the monomer unit (a1-1-2) and the monomer are preferable. The unit (a1-1-7) is more preferable.

[Monomer unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group (a1-2)]
As the acid-decomposable group, a known group can be used as described above, and is not particularly limited. Among acid-decomposable groups, the basic physical properties of the resist, in particular the sensitivity and pattern shape, are residues having a phenolic hydroxyl group protected with an acetal or a residue having a phenolic hydroxyl group protected with a ketal. From the viewpoint of storage stability of the photosensitive resin composition and formability of the contact hole. Furthermore, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably a residue protected with an acetal or ketal represented by the above formula (a1-1) from the viewpoint of sensitivity. In addition, when the phenolic hydroxyl group is a residue protected with an acetal or ketal represented by the formula (a1-1), the entire residue is -Ar-O-CR ^1.
The structure is R ² (OR ³ ). Ar represents an arylene group.
Preferred examples of the acetal ester structure for protecting the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group, and R ³ = benzyl group.

  Moreover, as a radically polymerizable monomer used for forming a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acetal or ketal, a 1-alkoxyalkyl protected form of 4-hydroxyphenyl methacrylate, 4- Tetrahydropyranyl protected form of hydroxyphenyl methacrylate, 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, Tetrahydropyranyl protected form of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester 1-alkoxyalkyl protected, 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester tetrahydropyranyl protected, 4-hydroxybenzoic acid 1-alkoxyalkyl protector of benzoic acid (3-methacryloyloxypropyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy- The 1-alkoxyalkyl protector of 2-hydroxypropyl) ester and the tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester are preferred from the viewpoint of transparency.

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

  A commercially available thing may be used for the radically polymerizable monomer used in order to form a monomer unit (a1), and what was synthesize | combined by the well-known method 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 monomer unit (a1-2) include the following monomer units, but the present invention is not limited thereto.

  The content of the monomer unit (a1) in Component A is preferably from 3 to 70 mol%, more preferably from 5 to 60 mol%, more preferably from 20 to 45 mol%, based on the total monomer units of Component A, from the viewpoint of sensitivity. Further preferred.

<Monomer unit (a2) having epoxy group and / or oxetanyl group>
Component A has a monomer unit (a2) having an epoxy group and / or an oxetanyl group. Component A may have both a monomer unit having an epoxy group and a monomer unit having an oxetanyl group.
The group having an epoxy group is not particularly limited as long as it has an epoxy ring, but a glycidyl group and a 3,4-epoxycyclohexylmethyl group can be preferably exemplified.
The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.
The monomer unit (a2) may have at least one epoxy group or oxetanyl group in one monomer unit, one or more epoxy groups and one or more oxetanyl groups, two or more epoxy groups, or Although it may have two or more oxetanyl groups and is not particularly limited, it preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of 1 or 2 epoxy groups and / or oxetanyl groups It is more preferable to have one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the monomer unit having an epoxy 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, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, cycloaliphatic described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Compounds containing an epoxy skeleton It is.
Examples of the radical polymerizable monomer used for forming the monomer unit having an oxetanyl group include, for example, (meth) acrylic acid having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include esters.

Examples of the radical polymerizable monomer used to form the monomer unit (a2) are preferably a monomer containing a methacrylic ester structure and a monomer containing an acrylate ester structure.
Among these monomers, more preferred are glycidyl methacrylate, glycidyl acrylate, compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443, and JP-A No. 2001-330953. Examples include (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of the publication.
Particularly preferable from the viewpoint of heat-resistant transparency is a monomer unit derived from either (3-ethyloxetane-3-yl) methyl acrylate or methyl (3-ethyloxetane-3-yl) methacrylate. is there.
These monomer units (a2) can be used singly or in combination of two or more.

  Preferable specific examples of the monomer unit (a2) include the following monomer units.

  The content of the monomer unit (a2) in Component A is preferably from 15 to 55 mol%, more preferably from 20 to 55 mol%, particularly preferably from 30 to 50 mol%, based on all monomer units of Component A. By containing the monomer unit (a2) at the above ratio, the physical properties of the cured film are improved.

<Monomer unit (a3) having a structure selected from the group consisting of amino group, amide group, imide group, sulfonimide group, sulfonamide group, imino group, urethane bond and ureido bond>
Component A is a structure selected from the group consisting of an amino group, an amide group, an imide group, a sulfonimide group, a sulfonamide group, an imino group, a urethane bond, and a ureido bond (hereinafter, also referred to as “hydrogen bonding structure”). The monomer unit (a3) having
In the photosensitive resin composition of the present invention, since the component A has the monomer unit (a3), the hydrogen bonding structure in the monomer unit (a3) acts as a hydrogen bond acceptor or a donor to form a hydrogen bond in the pattern. It is presumed that the formation of the above causes an increase in pseudo cross-linking points and pseudo high molecular weight, and a rectangle or a profile close to a rectangle can be obtained even after baking the pattern.
The hydrogen bonding structure is preferably a structure selected from the group consisting of an amino group, an imide group, a sulfonamide group, a sulfonimide group, and a ureido bond, and an imide group, a sulfonamide group, a sulfonimide group, and a ureido bond. More preferably, the structure is selected from the group consisting of a sulfonamide group and / or a ureido bond.
The monomer unit (a3) is preferably a monomer unit having a structure selected from the group consisting of the following structures (S1) to (S14), and the following structures (S1), (S2), (S4) , (S5), (S6), (S8), (S9), (S10), and (S11), more preferably a monomer unit having a structure selected from the group consisting of the following structures (S1), ( More preferably, it is a monomer unit having a structure selected from the group consisting of (S4), (S5), (S6), (S10) and (S11), and comprises the following structures (S5) and / or (S6). A monomer unit having a structure selected from the group is particularly preferred. In the above aspect, a rectangle or a profile closer to the rectangle can be obtained even after the pattern is baked.

（構造（Ｓ１）〜（Ｓ１４）中のＲ、Ｒ’及びＲ”はそれぞれ独立に、水素原子又は炭素数１〜２０の一価の有機基を表し、＊は他の構造との連結部を表す。）

(R, R ′ and R ″ in the structures (S1) to (S14) each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and * represents a connecting portion with another structure. Represents.)

R, R ′ and R ″ in the structures (S1) to (S14) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an alkyl group having 6 to 15 carbon atoms. It is preferably an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 8 carbon atoms, and a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. It is particularly preferred.
The alkyl group, cycloalkyl group and aryl group represented by R, R ′ and R ″ may have a substituent.
Examples of the substituent for the alkyl group include an alkyl group, a halogen atom, a cyano group, a hydroxyl group, and an alkoxy group.
Examples of the substituent of the cycloalkyl group include an alkyl group, a halogen atom, a cyano group, an optionally protected hydroxyl group or an alkoxy group.
Examples of the substituent for the aryl group include an alkyl group, a halogen atom, a cyano group, a hydroxyl group, and an alkoxy group.
In the structure (S7), at least one of R and R ″ is preferably a monovalent organic group having 1 to 20 carbon atoms. That is, R and R ″ are preferably not hydrogen atoms at the same time.
The monomer unit (a3) preferably has a hydrogen bonding structure in the side chain of the polymer. The monomer unit (a3) is preferably a monomer unit derived from a (meth) acrylate compound or a (meth) acrylamide compound, and a (meth) acrylate having a hydrogen bonding structure in a portion other than the (meth) acryloyl group. More preferably, it is a monomer unit derived from a (meth) acrylamide compound having a hydrogen bonding structure in a portion other than the compound or the (meth) acrylamide group.

  A commercially available thing may be used for the radically polymerizable monomer used in order to form a monomer unit (a3), and what was synthesize | combined by the well-known method can also be used. For example, 4-methacrylamideamidobenzenesulfonamide can be synthesized by reaction of methacrylic acid chloride and sulfanilamide.

  Preferable specific examples of the monomer unit (a3) include the following monomer units, but the present invention is not limited thereto. In the following, Ph represents a phenyl group.

  Among these, X1 to X4, X8 to X11, X16 and X20 are preferable, and X1 to X4 and X8 to X11 are more preferable.

  The content of the monomer unit (a3) in Component A is preferably from 0.1 to 50 mol%, preferably from 0.5 to 30 mol%, based on all monomer units of Component A, from the viewpoint of sensitivity and solubility in synthesis. Is more preferable, and 0.5 to 15 mol% is particularly preferable.

<Monomer unit having a ring structure (a4)>
Component A preferably contains a monomer unit (a4) having a ring structure from the viewpoint of improving dry etching resistance and chemical resistance.
Examples of the monomer forming the monomer unit (a4) include cyclic alkyl (meth) acrylates such as styrenes, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Examples thereof include esters and unsaturated aromatic compounds.
Preferred examples of the monomer unit (a4) having a ring structure include monomer units represented by the following formula (a4-1) or formula (a4-2).

（式中、Ｒ^Aは水素原子又は炭素原子数１〜６のアルキル基を表す。）

(In the formula, R ^A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

R ^A in the formula (a4-1) is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, from the viewpoint of uniformity of the polymerization rate of each monomer during polymerization.

（式中、Ｒ^Bは水素原子又はメチル基を表し、Ｘは単結合又は炭素原子数１〜４のアルキ
レン基を表し、環Ａはシクロペンタン環又はシクロペンテン環を表し、環Ａを有していても、有していなくともよい。）

(In the formula, R ^B represents a hydrogen atom or a methyl group, X represents a single bond or an alkylene group having 1 to 4 carbon atoms, Ring A represents a cyclopentane ring or a cyclopentene ring, and has ring A. Or do not have to.)

R ^B in the formula (a4-2), from the viewpoint of the uniformity of the polymerization rate of each monomer during the polymerization is preferably a methyl group.
X in the formula (a4-2) is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond.
Ring A in formula (a4-2) is preferably a cyclopentane ring.
The formula (a4-2) preferably has a ring A. The position of the double bond of the cyclopentene ring in ring A is not particularly limited and may be any position.

  The content of the monomer unit (a4) in Component A is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, particularly preferably from 10 to 20 mol%, based on all monomer units of Component A. By including the monomer unit (a4) at the above ratio, the resulting pattern is excellent in dry etching resistance and chemical resistance.

<Monomer unit (a5) having carboxy group or hydroxyl group>
Component A preferably has a monomer unit (a5) having a carboxy group or a hydroxyl group from the viewpoint of developability.
The monomer unit (a5) is preferably introduced in such a range that the component A is not alkali-soluble. The content of the monomer unit (a5) in Component A is preferably from 2 to 20 mol%, more preferably from 2 to 15 mol%, particularly preferably from 3 to 15 mol%, based on all monomer units of Component A. By containing the monomer unit (a5) at the above ratio, high sensitivity can be obtained and developability is also improved.

[Monomer unit having carboxy group (a5-1)]
Examples of the monomer unit (a5-1) having a carboxy group include unsaturated carboxylic acids having at least one carboxy group in the molecule, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid. The monomer unit derived from is mentioned.
As unsaturated carboxylic acid used in order to obtain the monomer unit (a5-1) which has a carboxy group, what is illustrated below is used.
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 monomer unit (a5-1) which has a carboxy 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. For example, 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 a dicarboxy polymer at both terminals, 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 these, from the viewpoint of developability, it is preferable to use acrylic acid or methacrylic acid in order to form the monomer unit (a5-1) having a carboxy group.

Moreover, the monomer unit (a5-1) which has a carboxy group can be obtained also by making the monomer unit (a5-2) which has a hydroxyl group mentioned later, and an acid anhydride react.
As the acid anhydride, known ones can be used. Specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. Examples include basic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.

[Monomer unit having a hydroxyl group (a5-2)]
Examples of the monomer unit (a5-2) having a hydroxyl group include a monomer unit (a5-2-1) having a phenolic hydroxyl group.
Among the monomer units (a5-2) having a hydroxyl group, examples of the radical polymerizable monomer used for forming the monomer unit (a5-2-1) having a phenolic hydroxyl group include p-hydroxystyrene, Hydroxystyrenes such as α-methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, and 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 Preferred examples include an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, and the like.

  Among radical polymerizable monomers used for forming a monomer unit (a5-2-1) having a phenolic hydroxyl group, methacrylic acid, acrylic acid, described in paragraphs 0011 to 0016 of JP-A-2008-40183 Compound, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid and glycidyl acrylate Addition reactants are more preferred, but methacrylic acid and acrylic acid are particularly preferred from the viewpoint of transparency. These monomer units can be used singly or in combination of two or more.

  Among the monomer units having a hydroxyl group (a5-2), any monomer unit having a hydroxyl group other than the phenolic hydroxyl group (a5-2-2) may be used as long as it is a monomer unit having a hydroxyl group. Preferred examples include monomer units derived from a hydroxyl group-containing (meth) acrylic acid ester, a (meth) acrylic acid ester of an alkyl group-terminated polyalkylene glycol, a (meth) acrylic acid ester of an aryl group-terminated polyalkylene glycol, and the like. be able to.

  Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2,3 (meth) acrylic acid. -Hydroxyalkyl esters of (meth) acrylic acid such as dihydroxypropyl, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / propylene glycol)- Mono (meth) acrylate, polyethylene glycol / polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) -mono (meth) acrylate, poly (propylene glycol) Le tetramethylene glycol) - mono (meth) acrylate, propylene glycol polybutylene glycol - may be mentioned as preferred examples of the mono (meth) acrylate.

Examples of (meth) acrylic acid esters of alkyl group-terminated polyalkylene glycols include methoxypolyethylene glycol- (meth) acrylate, octoxypolyethyleneglycol-polypropyleneglycol- (meth) acrylate, lauroxypolyethyleneglycol- (meth) acrylate, and steer. Roxypolyethylene glycol- (meth) acrylate can be mentioned as a preferred example.
Examples of the (meth) acrylic acid ester of the aryl group-terminated polyalkylene glycol include, for example, phenoxy polyethylene glycol- (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol- (meth) acrylate, nonylphenoxy-polyethylene glycol- (meth) acrylate, and nonyl. Preferable examples include phenoxy-polypropylene glycol- (meth) acrylate and nonylphenoxy-poly (ethylene glycol-propylene glycol)-(meth) acrylate.

  Commercially available hydroxyl group-containing (meth) acrylic acid esters, alkyl group-terminated polyalkylene glycol (meth) acrylic acid esters and aryl group-terminated polyalkylene glycol (meth) acrylic acid esters can be used. Representative examples are Blemmer E, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer P, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer 50 PEP-300, Blemmer 70 PEP- 350B, Blemmer 55PET-800, Blemmer PPT series, Blemmer 10PPB-500B, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer PME-100 , Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer 50POEP-800B, Blemmer PLE-200, Blemmer PSE-4 0, Blemmer PSE-1300, Blemmer PAE-50, Blemmer PAE-100, Blemmer 43PAPE-600B, Blemmer AME-400, Blemmer ALE series, Blemmer ANP-300, Blemmer 75ANP-600, Blemmer AAE-50, Blemmer AAE-300 (Above, manufactured by NOF Corporation).

In the monomer unit (a5-2), the number of hydroxyl groups is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
Moreover, when the monomer unit (a5-2) has an alkyleneoxy group, the number of repeating units of the alkyleneoxy group is preferably 1 to 25, more preferably 1 to 15, and most preferably 1 to 10.

Preferable specific examples of the radical polymerizable monomer used for forming the monomer unit (a5-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) 3-hydroxypropyl acrylate, 2,3-dihydroxypropyl (meth) acrylate, methoxypolyethylene glycol- (meth) acrylate having 2 to 10 ethylene glycol repeating units, and methoxypolypropylene having 2 to 10 propylene glycol repeating units Glycol- (meth) acrylate, ethylene glycol repeating unit and propylene glycol repeating unit of 2-10 methoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, ethylene glycol repeating unit and pro 2-10 octoxypolyethyleneglycol-polypropyleneglycol- (meth) acrylate, lenglycol repeating unit sum, 2-10 ethylene glycol repeating unit polyethylene glycol mono (meth) acrylate, 2 propylene glycol repeating units 10 polypropylene glycol mono (meth) acrylates, poly (ethylene glycol / propylene glycol) -mono (meth) acrylate with 3 to 10 total of ethylene glycol repeating units and propylene glycol repeating units, ethylene glycol repeating units and propylene glycol Examples include polyethylene glycol / polypropylene glycol / mono (meth) acrylate having 3 to 10 repeating units.
Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, ethylene glycol repeating unit Is more preferably 2-10 methoxypolyethylene glycol- (meth) acrylates, more preferably 2-10 octoxypolyethyleneglycol-polypropyleneglycol- (meth) acrylates having a sum of ethylene glycol repeating units and propylene glycol repeating units, ethylene glycol Methoxy polyethylene glycol- (meth) acrylate and 2-hydroxyethyl (meth) acrylate having 2 to 10 repeating units are particularly preferred.
A monomer unit (a5) can be used individually by 1 type or in combination of 2 or more types.

The content of the monomer unit (a5) in Component A is preferably 0.5 to 30 mol%, more preferably 0.5 to 25 mol%, particularly 1 to 25 mol%, based on all monomer units of Component A. preferable.
In addition, the content of the monomer unit (a5) in Component A is 3 to 30% by weight, more preferably 3 to 25% by weight, and particularly preferably 5 to 25% by weight with respect to the total weight of Component A. By incorporating the monomer unit (a5) at the above ratio, the developability becomes good and a highly sensitive photosensitive composition can be obtained. In particular, by combining the monomer unit (a2) and the monomer unit (a5), a photosensitive resin composition with very high sensitivity can be obtained.

<Other monomer units (a6)>
Component A may contain monomer units (a6) other than the monomer units (a1) to (a5) as long as the effects of the present invention are not hindered.
Examples of the radical polymerizable monomer used to form the monomer unit (a6) include the compounds described in paragraphs 0021 to 0024 of Patent No. 4207604 (however, the above-described monomer unit ( excluding the monomers forming a1) to (a5)).
Component A may have one type of monomer unit (a6) alone or two or more types.

The content of the monomer unit (a6) in Component A is preferably 0 to 40 mol% with respect to all the monomer units of Component A.
Moreover, when component A contains a monomer unit (a6), 1-40 mol% is preferable with respect to all the monomer units of component A, and, as for content of the monomer unit (a5) in component A, 5-30 mol% Is more preferable, and 5 to 25 mol% is particularly preferable.
In addition, the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

The method for introducing each monomer unit of component A may be a polymerization method or a polymer reaction method.
In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. That is, radical polymerization used to form the monomer unit (a1), the monomer unit (a2), the monomer unit (a3), the monomer unit (a4), the monomer unit (a5), and if necessary, the monomer unit (a6). It can be synthesized by polymerizing a radically polymerizable monomer mixture containing a polymerizable monomer in an organic solvent using a radical polymerization initiator.
In the polymer reaction method, after a polymerization reaction is performed, a necessary functional group is introduced into the monomer unit using a reactive group contained in the monomer unit of the obtained copolymer.
The monomer units (a1) to (a6) described above may be introduced into the component A by a polymerization method or a polymer reaction method, or these two methods may be used in combination.
Component A can be used alone or in combination of two or more in the photosensitive resin composition of the present invention.

The content of Component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, and preferably 40 to 97% by weight, based on the total solid content of the photosensitive resin composition. More preferred is 50 to 95% by weight. When the content is within this range, the pattern formability upon development is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
In addition, in the photosensitive resin composition of this invention, you may use together resin other than the component A in the range which does not prevent the effect of this invention. However, the content of the resin other than Component A is preferably smaller than the content of Component A from the viewpoint of developability.

(Component B) Photoacid Generator The photosensitive resin composition of the present invention contains (Component B) a photoacid generator.
Component B 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.
Component B 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.
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 high sensitivity. These photoacid generators can be used singly or in combination of two or more.

Specific examples of these include the following.
As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methyl) Butylphenyl) ethenyl] - bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaphthyl) - bis (4,6-trichloromethyl) -s-triazine.

  Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl-4- (2′-hydroxy-1) '-Tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-) Tetradecaoxy) phenyliodonium p-toluenesulfonate and the like.

  Examples of triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoro. Lomethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

  As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate and the like.

  Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, and bis (p-toluenesulfonyl) diazomethane.

  Examples of imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-ene-dicarboximide, succinimide trifluoromethyl sulfonate, phthalimido trifluoromethyl sulfonate, N-hydroxynaphthalimide methane sulfonate, N- Hydroxy-5-norbornene-2,3-dicarboximide propane sulfonate and the like.

  The photosensitive resin composition of the present invention preferably contains an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following formula (1) as (Component B) a photoacid generator.

The oxime sulfonate compound having at least one oxime sulfonate residue represented by the formula (1) is preferably a compound represented by the following formula (2).
^{R 1A -C (R 2A) =} N-O-SO 2 -R 3A (2)

In the formula (2), R ^1A is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or a 2-thienyl group. Represents an alkoxy group having 1 to 4 carbon atoms or a cyano group. When R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups include a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a nitro group. It may be substituted with a substituent selected from the group consisting of groups.
In the formula (2), R ^2A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents a substituted alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, an anthranyl group optionally substituted with W, a dialkylamino group, a morpholino group, or a cyano group. R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be bonded to a benzene ring.
In the formula (2), R ^3A represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents an alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

The alkyl group having 1 to 6 carbon atoms represented by R ^1A may be a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- A butyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, or a 2-ethylbutyl group is exemplified.
Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ^1A include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^1A include a methoxy group or an ethoxy group.
When R ^1A represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, and a carbon atom having 1 to 4 carbon atoms. Alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group), alkoxy groups having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group) , N-propoxy group, i-propoxy group, n-butoxy group) and a nitro group may be substituted.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^2A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^2A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group and n-octyl. An oxy group, n-decyloxy group, etc. are mentioned.
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^2A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, a perfluoro group. Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted by W represented by R ^2A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group , P- ( -Butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i -Amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2, 4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group And p-biphenylyl group.

Specific examples of the naphthyl group optionally substituted by W represented by R ^2A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted with W represented by R ^2A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

^Examples of the dialkylamino group represented by R ^2A include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^3A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group and n-octyl. An oxy group, n-decyloxy group, etc. are mentioned.
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^3A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, a perfluoro group. Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted by W represented by R ^3A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group , P- ( -Butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i -Amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2, 4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group And p-biphenylyl group.

Specific examples of the naphthyl group optionally substituted by W represented by R ^3A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted with W represented by R ^3A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy having 1 to 5 carbon atoms represented by W Specific examples include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and the number of carbon atoms represented by R ^2A or R ^3A. The thing similar to what was mentioned as a specific example of the halogenated alkoxy group of 1-5 is mentioned.

R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring.
When R ^2A and R ^1A are bonded to each other to form a 5-membered ring or a 6-membered ring, examples of the 5-membered ring or 6-membered ring include a carbocyclic group and a heterocyclic ring group. It may be a cyclopentane, cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered ring or 6-membered ring may be bonded to an optionally substituted benzene ring, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene, and thiol. Xanthene ring system. The 5-membered or 6-membered ring may contain a carbonyl group, examples of which include cyclohexadienone, naphthalenone and anthrone ring systems.

  The compound having at least one oxime sulfonate residue represented by the formula (1) is an oxime sulfonate compound represented by the following formula (OS-3), formula (OS-4) or formula (OS-5). It is preferable that

（式（ＯＳ−３）〜（ＯＳ−５）中、Ｒ¹はアルキル基、アリール基、又はヘテロアリール基を表し、複数存在するＲ²はそれぞれ独立に、水素原子、アルキル基、アリール基、又はハロゲン原子を表し、複数存在するＲ⁶はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基、又はアルコキシスルホニル基を表し、ＸはＯ又はＳを表し、ｎは１又は２を表し、ｍは０〜６の整数を表す。）

(In the formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ² are each independently a hydrogen atom, an alkyl group, an aryl group, Or a plurality of R ⁶ independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, X represents O or S, n Represents 1 or 2, m represents an integer of 0-6.)

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group represented by R ¹ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
In the formulas (OS-3) to (OS-5), the aryl group represented by R ¹ is preferably an aryl group having 6 to 30 carbon atoms in total which may have a substituent.
In the formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent. There may be at least one heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be condensed.
Examples of the substituent that the alkyl group, aryl group or heteroaryl group represented by R ¹ may have include a halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryl Examples thereof include an oxycarbonyl group and an aminocarbonyl group.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the formulas (OS-3) to (OS-5), it is preferable that one or two of R ² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
In the formulas (OS-3) to (OS-5), the alkyl group or aryl group represented by R ² may have a substituent.
Examples of the substituent that the alkyl group or aryl group represented by R ² may have include the same groups as the substituent that the alkyl group or aryl group in R ¹ may have.

In the formulas (OS-3) to (OS-5), the alkyl group represented by R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent. It is more preferable that it is a C1-C6 alkyl group which may have a group.
As the alkyl group represented by R ² , a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are preferable, and a methyl group is more preferable.

In the formulas (OS-3) to (OS-5), the aryl group represented by R ² is preferably an aryl group having 6 to 30 carbon atoms in total which may have a substituent.
The aryl group represented by R ² is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
In the formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.
In the formulas (OS-3) to (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferable.

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group represented by R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
The alkyloxy group represented by R ⁶ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group.
Examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
Examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

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

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

  The compound represented by the formula (OS-3) is particularly preferably a compound represented by the following formula (OS-6), (OS-10) or (OS-11). The compound represented by OS-4) is particularly preferably a compound represented by the following formula (OS-7), and the compound represented by the formula (OS-5) is represented by the following formula (OS-8). ) Or (OS-9) is particularly preferable.

（式（ＯＳ−６）〜（ＯＳ−１１）中、Ｒ¹はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ⁷は、水素原子又は臭素原子を表し、Ｒ⁸は水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒ⁹は水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒ¹⁰は水素原子又はメチル基を表す。）

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

R ¹ in the formulas (OS-6) to (OS-11) has the same meaning as R ¹ in the formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ⁸ in the above formulas (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or Represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferred is a methyl group.
R ⁹ in the formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ¹⁰ in the formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.

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

  As another preferred embodiment of the oxime sulfonate compound having at least one oxime sulfonate residue represented by the formula (1), a compound represented by the following formula (OS-1) may be mentioned.

In the formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or heteroaryl. Represents a group. R ² represents an alkyl group or an aryl group.
Is -O X -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or -CR ⁶ R ⁷ - represents, R ⁵ to R ⁷ is an alkyl group, or Represents an aryl group.
R ^{21 to} R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or represents an aryl group. Two of R ^{21 to} R ²⁴ may be bonded to each other to form a ring.
R ^{21 to} R ²⁴ are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R ^{21 to} R ²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R ^{21 to} R ²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the above-described substituents may further have a substituent.

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

In the formula ^{(OS-2), R 1} , R 2, R 21 ~R 24 are respectively synonymous with ^{R 1, R 2, R 21} ~R 24 in the general formula (OS-1), preferred examples thereof are also The same is true.
Among these, an embodiment in which R ¹ in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), and R ¹ is a cyano group, The embodiment which is a phenyl group or a naphthyl group is most preferable.

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

Moreover, one of the suitable aspects of the compound represented by said Formula (2) is a compound represented by following formula (2-1). The compound represented by the formula (2-1) is a compound in which R ^2A and R ^1A in the formula (2) are bonded to form a 5-membered ring.

（式（２−１）中、Ｒ^3Aは、式（２）におけるＲ^3Aと同義であり、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｔは、０〜３の整数を表し、ｔが２又は３であるとき、複数のＸは同一でも異なっていてもよい。）

(In formula (2-1), R ^3A has the same meaning as R ^3A in formula (2), X represents an alkyl group, an alkoxy group or a halogen atom, t represents an integer of 0 to 3, When t is 2 or 3, the plurality of X may be the same or different.)

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.
t is preferably 0 or 1.
In formula (2-1), t is 1, X is a methyl group, the substitution position of X is an ortho position, R ^3A is a linear alkyl group having 1 to 10 carbon atoms, 7,7 A compound having a -dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (2-1) include the following compound (i), compound (ii), compound (iii), compound (iv) and the like. One species may be used alone, or two or more species may be used in combination. Compounds (i) to (iv) can be obtained as commercial products.
It can also be used in combination with other types of photoacid generators.

As one of the preferable embodiments of the compound represented by the formula (2),
R ^1A represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group, or an anthranyl group;
R ^2A represents a cyano group;
R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, or a carbon atom number of 1 Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

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

In formula (2-2), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and L represents an integer of 0 to 5. Represent. R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, a carbon number of 1 to 1 Represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ^3A in the formula (2-2) 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 may be methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group. Particularly preferred.
The halogen atom represented by R ^4A is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms represented by R ^4A is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by R ^4A is preferably a methoxy group or an ethoxy group.
As L, 0-2 are preferable, and 0-1 are particularly preferable.

Among the compounds represented by formula (2), as a preferred embodiment of the compound included in the compound represented by formula (2-2), in formula (2), R ^1A is a phenyl group or 4-methoxy. This is an embodiment in which a phenyl group is represented, R ^2A represents a cyano group, and R ^3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 4-tolyl group.

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

α- (Methylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = methyl group)
α- (ethylsulfonyloxyimino) benzylcyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = ethyl group)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = n-propyl group)
α- (n-butylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = n-butyl group)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = 4-tolyl group)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = methyl group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = ethyl group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = n-propyl group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = n-butyl group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = 4-tolyl group)

The photosensitive resin composition of the present invention preferably does not contain a 1,2-quinonediazide compound as a photoacid generator (component B) sensitive to actinic rays. The reason is that the 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is 1 or less and is less sensitive than the oxime sulfonate compound.
On the other hand, the oxime sulfonate compound acts as a catalyst for the deprotection of the acidic group protected in response to the actinic ray, so that the acid generated by the action of one photon Contributing to the deprotection reaction, the quantum yield exceeds 1, for example, a large value such as a power of 10, and it is assumed that high sensitivity is obtained as a result of so-called chemical amplification.

  In the photosensitive resin composition of the present invention, (Component B) the photoacid generator is preferably used in an amount of 0.1 to 15 parts by weight, and 0.1 to 10 parts by weight, based on 100 parts by weight of Component A. It is more preferable to use 0.5 to 6 parts by weight.

(Component C) Solvent The photosensitive resin composition of the present invention contains (Component C) a solvent.
The photosensitive resin composition of the present invention is prepared as a solution in which components A and B, which are essential components, and optional components of various additives described below which are preferable components are dissolved in a (component C) solvent. Is preferred.
As the (Component C) solvent 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 Examples include glycol monoalkyl ether acetates, esters, ketones, amides, and lactones.

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

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

  (11) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate; (12) methyl lactate, lactic acid Lactic acid esters such as ethyl, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, N-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate , Ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate and the like; (14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxypropionmethyl, 3-methoxypropionethyl, 3-ethoxypropionmethyl, 3-ethoxypropionethyl, 3-methoxybutylacetate, 3- Others such as methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate Esters;

  (15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; (16) N-methylformamide, N, N-dimethyl Examples include amides such as formamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and (17) lactones such as γ-butyrolactone.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.
Of the above-mentioned solvents, diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.
These solvents can be used alone or in combination of two or more.

  The content of the (Component C) solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight and more preferably 100 to 2,000 parts by weight per 100 parts by weight of Component A. The amount is preferably 150 to 1,500 parts by weight.

(Component D) Thermal crosslinking agent The photosensitive resin composition of the present invention preferably contains (Component D) a thermal crosslinking agent, if necessary. (Component D) The heat flow in a baking process can be suppressed by adding a thermal crosslinking agent. Component D in the present invention is other than component A.
Preferable examples of the thermal crosslinking agent include a blocked isocyanate crosslinking agent, an alkoxymethyl group-containing crosslinking agent, an epoxy resin having an epoxy group, a (meth) acrylic resin having a carboxy group, and the like.
Among these, a blocked isocyanate crosslinking agent is particularly preferable from the viewpoints of resist sensitivity and storage stability. Moreover, an alkoxymethyl group-containing crosslinking agent can also be suitably used, and preferably contains at least a methylolated melamine compound.

<Block isocyanate cross-linking agent>
The block isocyanate-based crosslinking agent is not particularly limited, and a hexamethylene diisocyanate (HDI) skeleton, an isophorone diisocyanate (IPDI) skeleton, and a prepolymer type skeleton compound derived from HDI or IPDI are used. be able to. From the viewpoint of curability, a compound having two or more blocked isocyanate groups in one molecule is preferable.
The blocking group of the isocyanate group is not particularly limited, and active methylene protection, diester protection, oxime protection, caprolactam protection, an amine protector and the like can be used. From the viewpoint of reactivity, active methylene protection and diester protection are particularly preferred.

  These blocked isocyanate crosslinking agents are available as commercial products, for example, Duranate MF-K60X, MF-K60B, MF-B60X, 17B-60P, TPA-B80E, E402-B80B, SBN-70D, K6000 (or more , Manufactured by Asahi Kasei Chemicals Co., Ltd.), Death Module BL3272, BL3575 / 1, BL3475, BL3370, BL4265, BL5375, VPLS2376 / 1, VPLS2257, VPLS2578 / 1, VPLS2352 / 1, Sumidur BL3175 (above, Sumika Bayer Urethane) (Made by Co., Ltd.), Urehyper PUR-1804 (made by DIC Corporation), etc. can be used preferably. Among these, Duranate MF-K60X, MF-K60B, SBN-70D, and K6000 are particularly preferable.

  When the blocked isocyanate crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the blocked isocyanate crosslinking agent is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of component A. More preferably, it is -20 weight part, It is still more preferable that it is 3-15 weight part. By adding in this range, high sensitivity and preferable alkali solubility during development can be obtained.

<Alkoxymethyl group-containing crosslinking agent>
As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. 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 crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.

  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. Among these, Nicalac MX-270 and Nicalac MW-100LM are particularly preferable.

  When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the alkoxymethyl group-containing crosslinking agent is preferably 0.05 to 50 parts by weight with respect to 100 parts by weight of Component A. 0.5 to 10 parts by weight is more preferable, and 0.5 to 5 parts by weight is even more preferable. By adding in this range, high sensitivity and preferable alkali solubility during development can be obtained.

(Component E) Compound having a functional group equivalent of 400 g / eq or more of the total of epoxy group, oxetanyl group, hydroxyl group and carboxy group The photosensitive resin composition of the present invention suppresses curing shrinkage of the film and is a rectangular after baking. In order to obtain a profile, it is effective to add a compound having a functional group equivalent of 400 g / eq or more of the total of epoxy group, oxetanyl group, hydroxyl group and carboxy group.
Component E is preferably a resin having a weight average molecular weight of 1,000 or more.
Specific examples include a copolymer containing a monomer unit containing an epoxy group, an oxetanyl group, a hydroxyl group and / or a carboxy group.
Further, a compound that does not contain any of the above functional groups, such as a homopolymer of polymethyl methacrylate (PMMA), can be added as component E.
In addition, in this invention, when the component E satisfy | fills the definition of the said component D, it classify | categorizes into both. For example, when the component E is an epoxy resin having an epoxy equivalent of 400 g / eq or more, the epoxy resin is the component D and the component E. Component E in the present invention is other than component A.
Moreover, there is no restriction | limiting in particular as a measuring method of an epoxy equivalent, an oxetanyl equivalent, a hydroxyl group equivalent, and a carboxy group equivalent, A well-known method can be used, for example, titration of content of the said group in a specific amount of compounds etc. It can be calculated by measuring according to For example, it can be measured with reference to the method described in JIS K7236, K0070, etc.

<Epoxy resin>
Component E is preferably an epoxy resin. By adding an epoxy resin, the heat flow at the time of baking can be suppressed. Further, the epoxy resin preferably has a large epoxy equivalent in order to obtain a rectangular shape or a profile close to a rectangular shape by suppressing curing shrinkage of the crosslinked film. Specifically, 400 g / eq or more is preferable, 400 to 1,000 g / eq is more preferable, and 400 to 600 g / eq is particularly preferable. Within the above range, since the curing shrinkage is small, a rectangular shape or a profile close to a rectangular shape can be obtained, and the allowable range of process conditions during the production of the cured film is large.
In addition, it is preferable that the measuring method of epoxy equivalent conforms to JIS K7236.

As an epoxy resin, what is marketed and what was synthesize | combined arbitrarily can be used. Specific examples of commercially available epoxy resins having an epoxy equivalent of 400 g / eq or more are shown below.
EPICLON 1050, 1055, 3050, 4050, 7050, AM-020-P, AM-040-P, HM-091, HM-101, 1050-70X, 1050-75X, 1055-75X, 1051-75M, 7070-40K HM-091-40AX, 152, 153, 153-60T, 153-60M, 1121N-80M, 1123P-75M, TSR-601, 1650-75MPX, 5500, 5800, 5300-70, 5500-60, EXA-4850 -150, EXA-4850-1000, EXA-4816, EXA-4822 (manufactured by DIC Corporation),
Epoxy resins 1001, 1002, 1003, 1055, 1004, 1004AF, 1007, 1009, 1010, 1003F, 1004F, 1005F, 1009F, 1004FS, 1006FS, 1007FS, 1001B80, 1001X70, 1001X75, 1001T75, 4004P, 4005P, 4007P, 4010P 1256, 4250, 4275, 5046B80, 5047B75, 5050T60, 5050, 5051, 871, 872, 872X75 (manufactured by Mitsubishi Chemical Corporation),
YD-011, YD-012, YD-013, YD-014, YD-017, YD-019, YD-020G, YD-7011R, YD-901, YD-902, YD-903N, YD-904, YD- 907, YD-6020, YDF-2001, YDF-2004, YDF-2005RL, YDB-400, YDB-405, YDB-400T60, YDB-400EK60, YDB-500EK80, FX-305EK70, ERF-001M30 (above, New Day Sakai Chemical Co., Ltd.).

  The structure of the epoxy resin preferably has a BPA (bisphenol A) skeleton, specifically, EPICLON 1050, 1055, 3050, 4050, EXA-4850-150, EXA-4850-1000, EXA-4816, EXA. -4822 (above, manufactured by DIC Corporation), epoxy resins 1001, 1002, 1003, 1055, 1004, 1004AF (above, manufactured by Mitsubishi Chemical Corporation), YD-011, YD-012, YD-013, YD- 014 (manufactured by Nippon Steel Chemical Co., Ltd.).

  The addition amount of the epoxy resin is preferably 10 to 50% by weight, particularly preferably 20 to 40% by weight or more based on the total solid content of the photosensitive resin composition. Within the above range, it is easy to obtain a rectangle or a profile close to a rectangle and to form a desired pattern by a development process.

The molecular weight (weight average molecular weight) of the epoxy resin is preferably 500 or more. When the molecular weight is 500 or less, volatilization in the solvent drying step or outflow in the development step can be suppressed, and the effect of adding the epoxy resin can be sufficiently obtained.
An epoxy resin can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.
In addition, the photosensitive resin composition of the present invention preferably contains an alkoxymethyl group-containing crosslinking agent and an epoxy resin having an epoxy equivalent of 400 g / eq or more, from the viewpoint of obtaining a more rectangular profile.

<(Meth) acrylic resin having carboxy group>
Component E includes a (meth) acrylic resin having a carboxy group.
As the (meth) acrylic resin having a carboxy group, one having a large carboxy group equivalent is preferable in order to obtain a rectangular profile by suppressing curing shrinkage of the crosslinked film. Specifically, 400 g / eq or more is preferable, 400 to 1,000 g / eq is more preferable, and 400 to 600 g / eq is particularly preferable.
The (meth) acrylic resin having a carboxy group can be obtained by using a known (meth) acrylic monomer, and adjusting the carboxy group equivalent by adjusting the type and amount ratio of the monomer.
As the acrylic monomer, for example, unsaturated monocarboxylic acid, (meth) acrylic acid esters, and crotonic acid esters (meth) acrylamides are preferable.
Specific examples of such a monomer include the following compounds.
Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate , Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, tri Ethylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, monomethyl copolymer of ethylene glycol and propylene glycol Ether (meth) acrylate, N, N- Methylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate.

Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
(Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butylacryl (meth) amide, N- tertbutyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- Examples include phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, and the like.
Among these, the (meth) acrylic resin having a carboxy group is preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.

  The content of Component E in the photosensitive resin composition of the present invention is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, with respect to 100 parts by weight of Component A. More preferably, it is -30 weight part. Within the above range, it is easy to obtain a rectangle or a profile close to a rectangle.

<Other ingredients>
The photosensitive resin composition of the present invention may contain other components other than the components A to E.
As another component, it is preferable to contain the (component F) sensitizer from a sensitivity viewpoint. From the viewpoint of sensitivity, it is preferable to add (Component G) a development accelerator.
Furthermore, the photosensitive resin composition of the present invention preferably contains (Component H) an adhesion improver from the viewpoint of substrate adhesion, and contains (Component I) a basic compound from the viewpoint of liquid storage stability. From the viewpoint of applicability, it is preferable to contain (Component J) a surfactant (such as a fluorine-based surfactant or a silicone-based surfactant).
Furthermore, if necessary, the photosensitive resin composition of the present invention includes (Component K) an antioxidant, (Component L) a plasticizer, (Component M) a thermal radical generator, and (Component N) a thermal acid. Known additives such as a generator, (Component O) acid proliferator, an ultraviolet absorber, a thickener, and an organic or inorganic suspending agent can be added.
The photosensitive resin composition of the present invention is an epoxy resin having an epoxy equivalent of 400 g / eq or more, (Component H) an adhesion improver, (Component I) a basic compound, from the viewpoint of obtaining a profile closer to a rectangle. (Component J) It is preferable to contain a surfactant, an alkoxymethyl group-containing crosslinking agent, an epoxy resin having an epoxy equivalent of 400 g / eq or more, (Component H) an adhesion improver, (Component I) a basic compound, and (Component J) It is particularly preferable to contain a surfactant.
Hereinafter, other components that can be included in the photosensitive resin composition of the present invention will be described.

(Component F) Sensitizer In the photosensitive resin composition of the present invention, in the combination with the above-mentioned (Component B) photoacid generator, (Component F) a sensitizer is added to promote the decomposition thereof. Is preferred. 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 the 350 nm to 450 nm region.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone) ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg , Acridine orange, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, acridone) Torakinon), squaryliums (e.g., squarylium), styryl compounds, base styryl, coumarins (e.g., 7-diethylamino-4-methylcoumarin). Among these sensitizers, preferred are sensitizers that absorb actinic rays or radiation to be in an electronically excited state and have an electron transfer action to a photoacid generator, such as polynuclear aromatics, acridones, coumarins, base styryl. Are particularly preferred.

A commercially available sensitizer may be used, or it may be synthesized by a known synthesis method.
The addition amount of the sensitizer is preferably 20 to 300 parts by weight, particularly preferably 30 to 200 parts by weight, with respect to 100 parts by weight of (Component B) the photoacid generator, from the viewpoint of both sensitivity and transparency.

(Component G) Development accelerator The photosensitive resin composition of the present invention preferably contains (Component G) a development accelerator.
(Component G) As the development accelerator, any compound having a development acceleration effect can be used, but the compound has at least one structure selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and an alkyleneoxy group. The compound having a carboxy group or a phenolic hydroxyl group is more preferable, and the compound having a phenolic hydroxyl group is most preferable.
Further, the molecular weight of the (component G) development accelerator is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

Examples of development accelerators having an alkyleneoxy group include polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, polybutylene glycol, Examples thereof include polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and compounds described in JP-A-9-222724.
Examples of compounds having a carboxy group include compounds described in JP-A 2000-66406, JP-A 9-6001, JP-A 10-20501, JP-A 11-338150, and the like.
Examples of those having a phenolic hydroxyl group include JP-A No. 2005-346024, JP-A No. 10-133366, JP-A No. 9-194415, JP-A No. 9-222724, JP-A No. 11-171810, Examples thereof include compounds described in JP 2007-121766, JP-A-9-297396, JP-A 2003-43679, and the like. Among these, a phenol compound having 2 to 10 benzene rings is preferable, and a phenol compound having 2 to 5 benzene rings is more preferable. Particularly preferred is a phenolic compound disclosed as a dissolution accelerator in JP-A-10-133366.

(Component G) One type of development accelerator may be used alone, or two or more types may be used in combination.
The addition amount of (Component G) development accelerator in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of Component A from the viewpoint of sensitivity and residual film ratio, and 0.2 -20 parts by weight is more preferable, and 0.5-10 parts by weight is most preferable.

(Component H) Adhesion Improving Agent The photosensitive resin composition of the present invention preferably contains (Component H) an adhesion improving agent.
The (component H) adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic substance that serves as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. It is a compound that improves adhesion to an insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the (component H) adhesion improver 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.
Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

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 (Component H) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of Component A.

(Component I) Basic Compound The photosensitive resin composition of the present invention preferably contains (Component I) a basic compound.
(Component I) The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The basic compounds 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. Preferably, two kinds of heterocyclic amines are used in combination.
The content of the (Component I) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, and 0.002 to 0.2 part by weight with respect to 100 parts by weight of Component A. More preferably, it is a part.

(Component J) Surfactant (fluorine surfactant, silicone surfactant, etc.)
The photosensitive resin composition of the present invention preferably contains (Component J) a surfactant (such as a fluorine-based surfactant or a silicone-based surfactant).
As a surfactant, a copolymer (3) containing the structural unit A and the structural unit B shown below can be given as a preferred example. The weight average molecular weight (Mw) of the copolymer is preferably 1,000 or more and 10,000 or less, and more preferably 1,500 or more and 5,000 or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

In the copolymer (3), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a linear alkylene group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% to 80% by weight. Q represents a numerical value of 20% by weight to 90% by weight, r represents an integer of 1 to 18 and n represents an integer of 1 to 10.
L in the structural unit B is preferably an alkylene group represented by the following formula (4).

In the formula (4), R ²⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3.
The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by weight.

  Specific examples of fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950. , JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2001-330953, etc. An activator can be mentioned and a commercially available surfactant can also be used. Commercially available surfactants that can be used include, for example, F-top EF301, EF303 (Mitsubishi Materials Electronics Kasei Co., Ltd.), Florard FC430, 431 (Sumitomo 3M Co., Ltd.), MegaFuck F171, F173 , F176, F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox series (produced by OMNOVA), etc. Fluorine-based surfactant or silicone-based surfactant. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

These surfactants can be used individually by 1 type or in mixture of 2 or more types. Moreover, you may use together a fluorine-type surfactant and a silicone type surfactant.
The amount of (Component J) surfactant (fluorine-based surfactant, silicone-based surfactant, etc.) added to the photosensitive resin composition of the present invention is 10 parts by weight or less with respect to 100 parts by weight of Component A. Is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 1 part by weight.

(Component K) Antioxidant The photosensitive resin composition of the present invention may contain (Component K) an antioxidant.
(Component K) As antioxidant, a well-known antioxidant can be contained. By adding the (component K) antioxidant, there is an advantage that coloring of the cured film can be prevented, or a reduction in film thickness due to decomposition can be reduced, and heat resistance transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and 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.

  As a commercial item of a phenolic antioxidant, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (made by Ciba Japan Co., Ltd.) are mentioned, for example.

The content of (Component K) antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is preferably 0.5 to 4% by weight. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
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.

(Component L) Plasticizer The photosensitive resin composition of the present invention may contain (Component L) a plasticizer.
Examples of (Component L) plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The content of the (component L) plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of component A, and preferably 1 to 10 parts by weight. More preferred.

(Component M) Thermal radical generator The photosensitive resin composition of the present invention may contain (Component M) a thermal radical generator, and is a compound having at least one ethylenically unsaturated double bond as described above. When such an ethylenically unsaturated compound is contained, it is preferable to contain (Component M) a thermal radical generator.
As the thermal radical generator, a known thermal radical generator can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.
(Component M) A thermal radical generator may be used alone or in combination of two or more.
The content of the (component M) thermal radical generator in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight when the component A is 100 parts by weight from the viewpoint of improving film properties. 0.1 to 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

(Component N) Thermal acid generator In the present invention, (Component N) a thermal acid generator may be used in order to improve film physical properties and the like at low temperature curing.
The thermal acid generator is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C., for example, sulfonic acid, It is a compound that generates a low nucleophilic acid such as carboxylic acid or disulfonylimide.
As the generated acid, sulfonic acid, an alkylcarboxylic acid substituted with an electron withdrawing group or an arylcarboxylic acid having a strong pKa of 2 or less, and a disulfonylimide substituted with an electron withdrawing group are also preferable. Examples of the electron withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by exposure to exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by measuring IR spectrum and NMR spectrum before and after exposure of the compound.
The molecular weight of the thermal acid generator is preferably 230 to 1,000, more preferably 230 to 800.

As the sulfonic acid ester usable in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by weight, particularly preferably 1 to 15 parts by weight, based on 100 parts by weight of Component A.

(Component O) Acid Proliferator The photosensitive resin composition of the present invention can use (Component O) an acid multiplier for the purpose of improving sensitivity. The acid proliferating agent 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. 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 paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-T 9-512498. Examples of the compounds described in the first to page 47, line 2 are listed.

  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 multiplier in the photosensitive resin composition is 10 to 1,000 parts by weight with respect to 100 parts by weight of (Component B) photoacid generator. From the viewpoint of contrast, it is preferably 20 to 500 parts by weight.

(Pattern preparation method)
The pattern production method of the present invention is not particularly limited as long as it is a method for producing a pattern using the photosensitive resin composition of the present invention, but the solvent is removed from the photosensitive resin composition of the present invention to form a film. A film forming step, an exposure step of exposing the film to a pattern with actinic rays, a developing step of developing the exposed film with an aqueous developer to form a pattern, and a baking step of heating the pattern It is preferable.
The pattern production method in the present invention more preferably includes the following steps (1) to (6).
(1) Application process for applying the photosensitive resin composition of the present invention onto a substrate (2) Solvent removal process for removing the solvent from the applied photosensitive resin composition (3) Photosensitive resin composition from which the solvent has been removed An exposure step of exposing the product in a pattern with actinic rays (4) A development step of developing the exposed photosensitive resin composition with an aqueous developer (5) A step of exposing the developed photosensitive resin composition with actinic rays (Post exposure)
(6) Baking step of thermosetting the developed photosensitive resin composition The film forming step is preferably the coating step and the solvent removing step.
Each step will be described below in order.

  (1) A desired dry coating film can be formed by applying the photosensitive resin composition of the present invention to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking). Substrate materials that can be used in the present invention, silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper-silicon alloys, Indium-tin oxide coated glass; organic films such as polyimide and polyester; including but not limited to any substrate containing patterned areas of metal, semiconductor, and insulating material. Optionally, a baking step can be performed on the substrate to remove absorbed moisture before applying the photosensitive resin composition of the present invention. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. In the case of a large substrate, the slit coat method is particularly preferable. Here, the large substrate means a substrate having a side of 1 m or more on each side.

(2) In the solvent removing step, the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating condition is a range in which the acid-decomposable group is decomposed in the monomer unit (a1) in the component A in the unexposed area and the component A is not soluble in the alkaline developer. Depending on the temperature, it is preferably about 70 to 120 ° C. for about 30 to 300 seconds.
The photosensitive resin composition of this invention is used suitably as what is called a thick film resist whose film thickness after drying is 4 micrometers or more. This is because the present invention has high sensitivity and good shape controllability. The film thickness is preferably 4 to 500 μm, particularly preferably 4 to 100 μm.

(3) In the exposure step, the substrate provided with the dry coating film is irradiated with an actinic ray having a predetermined pattern. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. After the exposure step, PEB (post-exposure heat treatment) is performed as necessary.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.

When a laser is used, 343 nm and 355 nm are used for a solid (YAG) laser, 351 nm (XeF) is used for an excimer laser, and 375 nm and 405 nm are used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoint of stability and cost. The coating can be irradiated with the laser once or a plurality of times.
The energy density per pulse of the laser is preferably 0.1 mJ / cm ² or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is most preferable. To prevent the coating film from being decomposed by an ablation phenomenon, 1,000 mJ / cm ² is preferable. cm ² or less is more preferable, and 100 mJ / cm ² or less is most preferable. The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. In order not to decompose the color coating film due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable, and in order to improve the alignment accuracy at the time of scanning exposure, 1,000 nsec or less is more preferable, Most preferred is 50 nsec or less.
Furthermore, the frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less. In order to shorten the exposure processing time, 10 Hz or more is more preferable, and 100 Hz or more is most preferable. In order to improve the alignment accuracy at the time of scanning exposure, 10,000 Hz or less is more preferable, and 1,000 Hz or less is most preferable.
Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus that can be used in the present invention. Commercially available exposure apparatuses include Callisto (manufactured by Buoy Technology), AEGIS (manufactured by Buoy Technology), and DF2200G (Dainippon). Screen Manufacturing Co., Ltd.) can be used. Further, devices other than those described above are also 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.

In order to accelerate the decomposition reaction in the region where the acid catalyst is generated, PEB (post-exposure heat treatment) can be performed as necessary. PEB can promote the formation of a carboxy group from an acid-decomposable group.
Since the acid-decomposable group in the monomer unit (a1) in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxy group, PEB is necessarily performed. Alternatively, a positive image can be formed by development.
In addition, by performing PEB at a relatively low temperature, hydrolysis of an acid-decomposable group can be promoted without causing a crosslinking reaction. 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 90 ° C. or lower.

(4) In the developing step, the component A having a liberated carboxy group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxy group that is easily dissolved in an alkaline developer.
Examples of basic compounds that can be used in the alkaline developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate, Alkali metal bicarbonates such as potassium bicarbonate; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide; and aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, a shower method, and the like. After the development, washing with running water is preferably performed for 10 to 90 seconds to form a desired pattern.

(6) A catalyst that promotes cross-linking by re-exposing (post-exposure) to the substrate on which the pattern has been formed with an actinic ray prior to the baking step, and generating an acid from the (component B) photoacid generator present in the unexposed portion. It is preferable to function as.
That is, the method for forming a cured film in the present invention preferably includes (5) a re-exposure step (post-exposure step) in which exposure is performed with actinic rays between the development step and the baking step.
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 of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable. A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

(6) In the baking step, by heating the obtained positive image, the acid-decomposable group in the monomer unit (a1) is thermally decomposed to form a carboxy group and crosslinked with an epoxy group and / or an oxetanyl group. Thus, a cured film can be formed.
In order to obtain a rectangular shape or a profile close to a rectangular shape, it is preferable to perform so-called two-stage baking in which two-stage heating is performed at different temperatures. By performing the two-stage baking, the film is first cured to some extent by the first-stage baking to determine the shape, and further, the film is baked by the second-stage baking to give the necessary durability. The first baking temperature is preferably 90 ° C. to 150 ° C., and the time is preferably 10 to 60 minutes. The second baking temperature is preferably 180 to 250 ° C., and the time is preferably 30 to 90 minutes.
It is also possible to perform a baking process of three or more stages.
The taper angle in the cross-sectional shape of the pattern after the baking step is preferably 60 ° or more, more preferably 70 ° or more, and particularly preferably 80 ° or more.

  Since the photosensitive resin composition of the present invention can obtain a rectangle or a profile close to a rectangle even after the baking step, it is particularly useful as an etching resist.

(MEMS structure and manufacturing method thereof, dry etching method, wet etching method, MEMS shutter device, and image display device)
The manufacturing method of the MEMS (Micro Electro Mechanical Systems) structure of the present invention includes a step of manufacturing a structure using a pattern manufactured by the pattern manufacturing method of the present invention as a sacrificial layer at the time of stacking the structure, and the sacrificial layer. It is preferable to include the process of removing by plasma processing.
The MEMS structure of the present invention is a MEMS structure manufactured using a pattern manufactured by the pattern manufacturing method of the present invention as a sacrificial layer at the time of stacking structures.
The MEMS shutter device of the present invention is a MEMS shutter device manufactured by the method for manufacturing a MEMS structure of the present invention.
The image forming apparatus of the present invention preferably includes the MEMS shutter device of the present invention.
MEMS (Micro Electro Mechanical System) refers to an electromechanical element or system or micromachine having a micro structure of a micro size or less. For example, a mechanical drive component, a sensor, an actuator, and an electronic circuit are included in one silicon substrate, glass Examples include devices integrated on a substrate, an organic material, or the like.
Examples of the MEMS shutter device and the image forming apparatus provided with the MEMS shutter device include those described in JP-T-2008-533510.

When the pattern produced by the pattern production method of the present invention is used as a sacrificial layer for producing a MEMS structure, a metal film is formed on the pattern using various film formation processes such as coating, vapor deposition, sputtering, CVD, and plating. Further, inorganic materials such as metal oxides, silicon compounds, and semiconductors, and organic materials such as polyimide can be stacked. Two or more different materials can be laminated in multiple layers.
In addition, as a base material for the MEMS sacrificial layer that can be used in the present invention, silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron Steel, copper-silicon alloy, indium-tin oxide coated glass; organic films such as polyimide and polyester; including, but not limited to, any substrate containing patterned regions of metals, semiconductors, and insulating materials . Optionally, a baking step can be performed on the substrate to remove absorbed moisture before applying the photosensitive resin composition of the present invention.

When the pattern produced by the pattern production method of the present invention is used as a dry etching resist, dry etching treatment such as ashing, plasma etching, ozone etching and the like can be performed as the etching treatment. In particular, it is preferably used as an etching resist in a dry etching process using a fluorine-based gas.
The dry etching method of the present invention includes a step of performing dry etching using a pattern produced by the pattern production method of the present invention as a resist for dry etching, and a step of removing the pattern by plasma treatment or chemical treatment. preferable.
Examples of dry etching materials that can be used in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, and steel. , Copper-silicon alloys, indium-tin oxide coated glass; including but not limited to metals, semiconductors, and any substrate containing a patterned region of insulating material.

There is no restriction | limiting in particular as a generation method of plasma, Both a low pressure plasma method and an atmospheric plasma method are applicable.
In the plasma etching, for example, an inert gas selected from helium, argon, krypton, and xenon, O ₂ , CF ₄ , C ₂ F ₄ , N ₂ , CO ₂ , SF ₆ , CHF ₃ , at least O A reactive gas containing N, F, or Cl can be preferably used.

When the pattern produced by the pattern production method of the present invention is used as a wet etching resist, a wet etching treatment with a known agent such as an acid, an alkali, or a solvent can be performed.
The wet etching method of the present invention includes a step of performing wet etching using the pattern produced by the pattern production method of the present invention as a resist for wet etching, and a step of removing the pattern by plasma treatment or chemical treatment. Is preferred.
Examples of wet etching materials that can be used in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, and steel. , Copper-silicon alloys, indium-tin oxide coated glass; including but not limited to metals, semiconductors, and any substrate containing a patterned region of insulating material.

  Examples of the wet etching include an oxidative etching treatment with a sodium permanganate aqueous solution, a strong alkaline aqueous solution treatment such as sodium hydroxide, and a hydrofluoric acid treatment.

When the pattern is peeled after the fabrication of the MEMS or after the etching process, peeling can be performed by a known dry plasma process such as ashing or a known wet process such as alkaline chemical treatment. Since the cured product of the present invention is cured through a baking process, peeling by a dry plasma process is particularly preferable.
When used as a sacrificial layer for MEMS, it is preferable to perform peeling by a dry process in order to remove the resist from the complicated shape of the MEMS. In particular, oxygen plasma treatment is preferable.
Even when a resist for wet etching or dry etching is used as a planar resist, oxygen plasma treatment is preferably used, but the resist can be peeled and removed by heat treatment with a chemical solution.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on weight.

In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile)
V-601: Dimethyl-2,2′-azobis (2-methylpropionate)
GMA: Glycidyl methacrylate PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis of Polymer A-1>
<Synthesis Example 1: Synthesis of MATHF>
In a three-necked flask, 50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2 mol%) of camphorsulfonic acid were mixed and cooled to 15 ° C. To the solution, 41.00 g (0.585 mol) of 2,3-dihydrofuran was added dropwise. Saturated aqueous sodium hydrogen carbonate solution (500 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (500 mL) and dried over magnesium sulfate. Insoluble matter was filtered, and the filtrate was concentrated under reduced pressure at 40 ° C. or lower, and the colorless oily residue was distilled under reduced pressure to obtain 73.02 g of MATHF having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg fraction.

<Synthesis Example 1: Synthesis of specific resin A>
PGMEA (50.0 g) was placed in a three-necked flask and heated to 80 ° C. in a nitrogen atmosphere. MAA (9.5 g), MATHF (36.5 g), (X-1) (2.40 g), HEMA (4.07 g), OXE-30 (17.27 g), V-601 (1. 72 g, 3 mol% with respect to the monomer) was dissolved in PGMEA (36.0 g) and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 4 hours. Thereby, specific resin A was obtained. The acid value was 39.5 mgKOH / g, and the weight average molecular weight was 16,000.

<Synthesis of Polymers A-2 to A-39>
Each monomer used in the synthesis of polymer A-1 was changed to a monomer that forms each monomer unit (a1) to (a5) shown in Table 1, and the amount of monomer used to form each monomer unit is shown in Table 1. The polymer A-2 was synthesized in the same manner as the synthesis of the polymer A-1, except that the radical polymerization initiator V-601 or V-65 was appropriately used depending on the substrate. ~ A-39 were synthesized respectively. The amount of radical polymerization initiator V-601 or V-65 added was adjusted so as to have the molecular weight shown in Table 1, respectively.

<Polymer A-40>
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 40 parts by weight of 1- (cyclohexyloxy) ethyl methacrylate, 5 parts by weight of styrene, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, and 3 parts by weight of α-methylstyrene dimer were charged, and then gently. Stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-40).

<Polymer A-41>
(Styrene / methacrylic acid / t-butyl methacrylate / methacrylic acid 2-hydroxyethyl copolymer)
Using a flask equipped with a reflux condenser, the inside of the flask was purged with nitrogen, and then 200 parts by weight of a solution prepared by dissolving 7.0 parts by weight of 2,2′-azobisisobutyronitrile in ethyl lactate as a polymerization initiator. The flask was charged. Next, 35 parts by weight of styrene, 20 parts by weight of methacrylic acid, 30 parts by weight of t-butyl methacrylate and 15 parts by weight of 2-hydroxyethyl methacrylate were charged, and the temperature of the liquid was raised to 70 ° C. while gently stirring. The monomer was copolymerized while maintaining this temperature for 7 hours to obtain 300 parts by weight of a copolymer solution (A-41).

In addition, the molar ratio described in Table 1 is a copolymerization ratio of monomer units derived from each monomer described in the type column. In Table 1, “-” indicates that the monomer unit is not used.
Abbreviations in Table 1 are as follows.
MAEVE: 1-ethoxyethyl methacrylate MATHF: tetrahydrofuran-2-yl methacrylate MACHOE: 1- (cyclohexyloxy) ethyl methacrylate GMA: glycidyl methacrylate OXE-30: (3-ethyloxetane-3-yl) methyl methacrylate ( Osaka Organic Chemical Industry Co., Ltd.)
Protected phenol 1: Ethyl acetal protector of phenolic hydroxyl group obtained in the following synthesis example St: Styrene DCPM: Dicyclopentanyl methacrylate HEMA: 2-hydroxyethyl methacrylate MAA: Methacrylic acid X1, X3, X4, X6, X9, X10, X11, X13, X14, X15, X16, X20 and X23: The following compounds (Ph represents a phenyl group)

<Synthesis of Protected Phenol 1 (Ethyl Acetal Protected Body of 4-Hydroxybenzoic Acid (2-Methacryloyloxyethyl) Ester)>
To a 100 ml acetonitrile solution of 21 g of 4-hydroxybenzoic acid (2-hydroxyethyl) ester, 20 ml of N, N-dimethylacetamide was added with stirring, and 20 g of methacrylic acid chloride was further added. After reacting with stirring at 35 ° C. for 8 hours, the reaction mixture was poured into ice water, the precipitated crystals were collected by filtration, recrystallized from ethyl acetate / n-hexane, and 4-hydroxybenzoic acid (2-methacryloyloxy). Ethyl) ester was obtained.
The phenol obtained as described above was reacted with ethyl vinyl ether in the presence of an acid catalyst to obtain an ethyl acetal protector (protected phenol 1) of a phenolic hydroxyl group.

(Examples 1-45 and Comparative Examples 1-9)
(1) Preparation of photosensitive resin composition Each component shown in Table 2 below was mixed to obtain a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.1 µm. The photosensitive resin composition of 1-45 and Comparative Examples 1-9 was prepared, respectively. The obtained photosensitive resin compositions of Examples 1 to 45 and Comparative Examples 1 to 9 were used, and evaluations described later were performed. The evaluation results are shown in Tables 3 and 4.

In addition, the symbol in Table 2 is as follows.
B1: CGI1397 (the following compound, manufactured by Ciba Specialty Chemicals)
B2: α- (p-Toluenesulfonyloxyimino) phenylacetonitrile (the synthesis method is as shown below)
B3: Oxime sulfonate compound synthesized by the following synthesis method C1: Propylene glycol monomethyl ether acetate D1: Nicalac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
D3: Duranate MF-K60X (block isocyanate-based crosslinking agent, active methylene-protected polyfunctional type, manufactured by Asahi Kasei Chemicals Corporation)
D4: Duranate MF-B60X (block isocyanate-based crosslinking agent, oxime-protecting polyfunctional type, manufactured by Asahi Kasei Chemicals Corporation)
E5: EPICLON EXA-4816 (manufactured by DIC Corporation, epoxy equivalent: 403 g / eq))
E9: JER157S65 (Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq)
F1: 9,10-dibutoxyanthracene (DBA)
H1: 3-glycidoxypropyltrimethoxysilane (KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.))
I1: 1,5-diazabicyclo [4.3.0] -5-nonene I2: Triphenylimidazole J1: Compound W-3 shown below

<Synthesis of B2>
Α- (p-toluenesulfonyloxyimino) phenylacetonitrile was synthesized according to the method described in paragraph 0108 of JP-T-2002-528451.

<Method for synthesizing 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 50% 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).

<Evaluation of photosensitive resin composition>
(1) Evaluation of sensitivity (without PEB)
A photosensitive resin composition was spin-coated on a silicon wafer having a silicon oxide film, and then prebaked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 4 μm.
Next, exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.). After exposure, the substrate was allowed to stand at room temperature (23 ° C.) for 10 minutes, and then developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, followed by rinsing with ultrapure water for 45 seconds. By these operations, the optimum exposure amount (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity. It can be said that the smaller the sensitivity, the higher the sensitivity. In particular, it is preferable that the sensitivity is lower than 70 mJ / cm ² . PEB is not implemented.

(2) Evaluation of taper angle and pattern profile After a photosensitive resin composition is spin-coated on a silicon wafer having a silicon oxide film, it is pre-baked on a hot plate at 90 ° C. for 120 seconds to have a film thickness of 4 μm. Formed.
Next, using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.), 70 mJ exposure was performed through a predetermined mask. After exposure, the substrate was allowed to stand at room temperature (23 ° C.) for 10 minutes, and then developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, followed by rinsing with ultrapure water for 45 seconds. Next, a two-stage baking process (first stage: 140 ° C.-30 minutes, second stage: 230 ° C.-60 minutes) was performed and baked.
Thereafter, a cross section of a 10 μm line & space pattern was observed with a scanning electron microscope (SEM), and the taper angle was measured.
Furthermore, the profile shape was evaluated based on the taper angle and the overall rectangularity. If the profile is closer to a rectangle, a structure having a shape (rectangular shape) that is originally desired for a MEMS resist can be laminated on the resist, and if a resist for dry etching, the material to be etched in the dry etching process. Can be processed precisely. At that time, a 10-level sensitivity evaluation was performed from the viewpoint that “the rectangular portion is worse if it is a curve, and it is better that it is an acute angle”.
Evaluation points 6 to 10 are determined to be practically acceptable levels. The image of the pattern shape is shown in FIGS. FIG. 1 is an image of a shape in the case of FIG. 1 where evaluation is 10, FIG. 2 is evaluation 6 and FIG.

(3) Evaluation of chemical resistance The thickness change before and after immersing the cured film produced in the same process as the pattern profile evaluation in a 5% oxalic acid aqueous solution at 40 ° C. for 10 minutes was evaluated. Evaluation points 7 to 10 are determined to be practically acceptable and no problem level.
10: Change in film thickness was less than ± 1%.
9: Change in film thickness was ± 1% or more and less than 3%.
8: Change in film thickness was ± 1% or more and less than 5%.
7: Change in film thickness was ± 5% or more and less than 7%.
6: Change in film thickness was ± 7% or more and less than 9%.
5: Change in film thickness was ± 9% or more and less than 11%.
4: The film thickness change was ± 11% or more and less than 15%.
3: The change in film thickness was ± 15% or more and less than 20%.
2: The film thickness change was ± 20% or more.
1: Film peeling was confirmed.

(4) Evaluation of Development Defects A photosensitive resin composition was spin-coated on a silicon wafer having a silicon oxide film, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 4 μm.
Next, using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.), 70 mJ exposure was performed through a predetermined mask. After the exposure, the substrate was left at room temperature (23 ° C.) for 10 minutes, and then developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds by a puddle method. The substrate after development was observed with an optical microscope, and the number of development defects was counted.
10: Development defects 0 / wafer 9: Development defects 1-2 / wafer 8: Development defects 3-5 / wafer 7: Development defects 6-10 / wafer 6: Development defects 11-15 Pieces / wafer 5: development defects 16-20 pieces / wafer 4: development defects 21-25 pieces / wafer 3: development defects 26-30 pieces / wafer 2: development defects 31-40 pieces / wafer 1: development 41 defects / wafer or more

(5) Fabrication and operation evaluation of MEMS shutter display (evaluation of display unevenness)
Using the obtained photosensitive resin composition as a sacrificial layer, a display device using a MEMS shutter device and a 5-inch MEMS shutter device was produced by the method described in JP-T-2008-533510. The produced display device was driven, and the display unevenness was judged sensuously by visual evaluation, and the following 10 stages of evaluation were performed.
10: Display unevenness is 10 or less 9: Display unevenness is 11 to 20 8: Display unevenness is 21 to 30 7: Display unevenness is 31 to 40 6: Display unevenness is 41 to 50 5: Display unevenness 51 to 60 4: Display unevenness 61 to 70 3: Display unevenness 71 to 80 2: Display unevenness 81 to 90 1: Display unevenness 91 or more

  Further, except that the photosensitive resin composition of Example 32 was used and the conditions for the two-stage baking treatment in the (2) taper angle evaluation and pattern profile evaluation were changed to the conditions shown in Table 5, the examples described above were used. 32, (2) taper angle evaluation and pattern profile evaluation, and (5) MEMS shutter display production and operation evaluation were performed.

  In Examples 1 and 32, the same operation was performed except that the film thickness of the coating film was changed from 4 μm to 10 μm, 50 μm, and 100 μm, respectively. (2) Taper angle evaluation and pattern profile evaluation, (3) Chemical resistance Table 6 shows the results of evaluation and (4) evaluation of development defects.

10: Substrate 12: Pattern 14: Midpoint between the top of the film and the substrate θ: Taper angle

Claims (16)

(Component A) a monomer unit (a1) having a residue in which a carboxy group or a phenolic hydroxyl group is protected with an acid-decomposable group, a monomer unit (a2) having an epoxy group and / or an oxetanyl group, an amino group, an amide A monomer unit (a3) having a structure selected from the group consisting of a group, an imide group, a sulfonimide group, a sulfonamide group, an imino group, a urethane bond and a ureido bond, and a monomer unit (a5) having a carboxy group or a hydroxyl group , a polymer having a,
(Component B) Photoacid generator ,
(Component C) solvent, and
A positive photosensitive resin composition comprising (Component D) a thermal crosslinking agent . The positive photosensitive resin composition according to claim 1, wherein the monomer unit (a3) is a monomer unit having a structure selected from the group consisting of the following structures (S1) to (S14).

(R, R ′ and R ″ in the structures (S1) to (S14) each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and * represents a connecting portion with another structure. Represents.)   The positive photosensitive resin composition according to claim 1, wherein the component A has a weight average molecular weight of 5,000 or more. The positive photosensitive resin composition of any one of Claims 1-3 whose content of the monomer unit (a3) in the component A is 50 mol % or less with respect to all the monomer units of the component A.   The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the monomer unit (a3) is a monomer unit having a sulfonamide group and / or a ureido bond.   The positive photosensitive resin composition of any one of Claims 1-5 in which the component B contains an oxime sulfonate compound.   Component D is a compound selected from the group consisting of a blocked isocyanate crosslinking agent, a crosslinking agent having an alkoxymethyl group, an epoxy resin having an epoxy group, and a (meth) acrylic resin having a carboxy group. 6. The positive photosensitive resin composition according to any one of 6 above. The positive photosensitive resin composition according to any one of claims 1 to 7 , which is a positive photosensitive resin composition for an etching resist. A MEMS structural member for a photosensitive resin composition The positive photosensitive resin composition according to any one of claims 1-7. A film forming step of forming a film by removing the solvent from the positive photosensitive resin composition according to any one of claims 1 to 9 ,
An exposure step of exposing the film in a pattern with an actinic ray;
A developing step of developing the exposed film with an aqueous developer to form a pattern; and
A baking step of heating the pattern;
A pattern manufacturing method including: The pattern preparation method according to claim 10 , further comprising a post-exposure step of exposing the pattern with actinic rays after the developing step and before the baking step. The pattern preparation method according to claim 10 or 11 , wherein a taper angle in a cross-sectional shape of the pattern after the baking step is 70 ° or more. The pattern preparation method according to any one of claims 10 to 12 , wherein a film thickness of the pattern after the baking step is 4 to 100 µm. A step of producing a structure using the pattern produced by the pattern production method according to any one of claims 10 to 13 as a sacrificial layer at the time of stacking the structure, and
Removing the sacrificial layer by plasma treatment;
A method for manufacturing a MEMS structure including: A step of performing dry etching using the pattern produced by the pattern production method according to any one of claims 10 to 13 as a resist for dry etching; and
Removing the pattern by plasma treatment or chemical treatment;
A dry etching method including: A step of performing wet etching using the pattern produced by the pattern production method according to any one of claims 10 to 13 as a resist for wet etching, and
Removing the pattern by plasma treatment or chemical treatment;
A wet etching method including:

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