KR101912158B1 - A positive-type photosensitive acrylic resin and positive-type photosensitive resin composition - Google Patents

Abstract

There is provided a resin capable of providing a positive photosensitive resin composition capable of forming a rectangular or nearly rectangular profile even after baking the formed pattern.
Insoluble or poorly soluble in an alkali developing solution containing a carboxyl group at the end of the main chain (main chain) and containing a repeating unit having a cyclic ether group of a 3-membered ring and / or a 4-membered ring, A positive photosensitive acrylic resin soluble in an alkali developing solution is used.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a positive type photosensitive acrylic resin and a positive type photosensitive resin composition,

The present invention relates to a positive photosensitive acrylic resin and a positive photosensitive resin composition using the positive photosensitive acrylic resin. The present invention also relates to a cured film produced by using a positive photosensitive resin composition and a method for producing the same. The present invention also relates to a pattern forming method using a positive photosensitive resin composition, a manufacturing method of a MEMS structure, a dry etching method, and a wet etching method. The present invention also relates to a process for producing a positive photosensitive acrylic resin.

A photosensitive resin composition is used in a manufacturing process of a display device such as a liquid crystal display device and an organic EL display device, an interlayer insulating film, a semiconductor device, MEMS (Micro Electro Mechanical Systems), and the like. In particular, chemically amplified positive resists are used vigorously because of their high resolution and high sensitivity.

As a conventional photosensitive resin composition, for example, JP-A-10-73923 discloses a positive photosensitive resin composition for etching resists, and JP-A-10-026829 discloses a positive photosensitive resin composition for etching resists Japanese Patent Application No. 2008-533510 discloses a resin composition for a positive interlayer insulating film material for use as a micro lens forming agent in Japanese Patent Application Laid-Open No. 2004-264623, which is an example of the production of a MEMS structure using a sacrificial layer resist, JP-A-2009-104040, JP-A-2010-111803, and JP-A-2005-122035 disclose a photosensitive resin composition characterized by the main chain end of a binder polymer.

For example, in the case of a sacrificial layer resist at the time of MEMS fabrication, the shape of the resist is reflected in the upper laminate structure as it is, so control of the shape of the resist is important.

Further, when used as an etching resist in a dry etching process, it is required to form a profile having a taper angle close to a rectangle in order to realize a precise pattern production by etching.

In addition, durability such as solvent resistance, chemical resistance, and mechanical strength is required to some extent in order to prevent the resist film from swelling, peeling, dissolution and disappearance in a dry etching or wet etching process.

When used as a thick film resist, a high sensitivity is required to obtain an appropriate pattern in a development process. Further, in a thick film, the influence of heat flow and curing shrinkage becomes large, so profile control technology becomes more important. The thick film is exemplified by the use of a resist having a dried film thickness of 4 to 100 mu m after solvent removal.

In the conventional etching resist, it is difficult to obtain a rectangular or rectangular profile when baking is performed to improve the hardened film strength.

For example, the photosensitive resin composition described in JP-A-10-73923 has a problem that a rectangular profile can not be obtained due to heat flow during baking.

Further, in Japanese Patent Application Laid-Open No. 2004-264623, the better the curve and the better the curvature of the pattern and the taper, the worse the evaluation becomes, the more the rectangular taper shape is evaluated.

A problem to be solved by the present invention is to provide a positive photosensitive resin composition capable of forming a rectangular or nearly rectangular profile even after baking the formed pattern.

Further, JP-A-2009-104040, JP-A-2010-111803, and JP-A-2005-122035 disclose positive-type photosensitive resin compositions using a polymer in which an end group of an end- However, when the present inventors have studied it, it has been found that there is a problem in the rectangularity and the taper angle.

An object of the present invention is to provide a positive photosensitive acrylic resin capable of providing a positive photosensitive resin composition capable of forming a rectangular or nearly rectangular profile even after baking the formed pattern The purpose.

As a result of a study by the inventors of the present invention, it has been found that a photosensitive resin composition containing a repeating unit having a cyclic ether group of a three-membered ring or a four-membered ring and having a carboxyl group at the end of the main chain, It has been found that it is possible to provide a positive photosensitive resin composition capable of forming a rectangular or nearly rectangular profile even after baking the formed pattern.

The reason why such a copolymer can form a rectangular or nearly rectangular profile even after baking the formed pattern is that the carboxyl group at the end of the polymer main chain is crosslinked (crosslinked) with the 3-membered ring or the 4-membered ring by baking , It can be considered that the polymers are arranged and crosslinked rather than merely having a carboxyl group in the polymer side chain.

More specifically, the above problems are solved by the following means <1>, preferably <2> to <21>.

&Lt; 1 > A positive resist composition comprising an alkali developing solution insoluble or hardly soluble in an alkali developing solution containing a carboxy group at the main chain end and containing a repeating unit having a cyclic ether group of a 3-membered ring and / A positive photosensitive resin composition containing an acrylic resin which becomes soluble.

<2> The positive photosensitive resin composition according to <1>, wherein the acrylic resin is a repeating unit having a cyclic ether group of a three-membered ring and / or a four-membered ring represented by the general formula (1).

In general formula (1)

(1), R ¹ represents a hydrogen atom or an alkyl group, L represents a divalent linking group, R ² to R ⁴ each represent a hydrogen atom, an alkyl group, or a phenyl group, n represents 1 or 2, R ² , R ³ or R ⁴ may be bonded to a substituent group of L to form a ring)

<3> The positive photosensitive resin composition according to <1> or <2>, wherein the acrylic resin has a weight average molecular weight of 5,000 or more.

<4> The acrylic resin according to <1>, wherein the acrylic resin has a repeating unit having a carboxyl group or a phenolic hydroxyl group having a residue protected with an acid-decomposable group, in addition to the repeating unit having a cyclic ether group of the 3-membered ring and / To < 3 > the positive photosensitive resin composition described in any one of &lt; 1 &gt;

<5> The positive photosensitive resin composition according to any one of <1> to <4>, further comprising a photoacid generator.

&Lt; 6 > The positive photosensitive resin composition according to < 5 >, wherein the photo acid generator is an onium salt and / or oxime sulfonate.

<7> The positive photosensitive resin composition according to any one of <1> to <6>, which further contains a crosslinking agent.

<8> The positive photosensitive resin composition according to any one of <1> to <7>, further containing a solvent.

<9> A cured film obtained by curing a positive photosensitive resin composition according to any one of <1> to <8> by applying at least one of light and heat.

&Lt; 10 > The cured film according to < 9 >, which is an interlayer insulating film.

(11) A process for producing a positive photosensitive resin composition, which comprises the steps of (1) applying the positive photosensitive resin composition described in any one of (1) to (8)

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

(3) a step of exposing the positive photosensitive resin composition from which the solvent has been removed to actinic radiation,

(4) a step of developing the exposed positive photosensitive resin composition with an aqueous developer, and

(5) A post-baking step of thermally curing the developed positive photosensitive resin composition.

<12> The method for forming a cured film according to <11>, wherein the developing step is performed without the heat treatment after the exposure in the exposure step.

<13> The positive-working photosensitive resin composition according to any one of <1> to <8>, which is used for an etching resist.

<14> The positive photosensitive resin composition according to any one of <1> to <8>, which is for a structural member for MEMS.

<15> A film forming process for removing a solvent from a positive photosensitive resin composition according to any one of <1> to <8> to form a film,

An exposure step of exposing the film in a pattern by an actinic ray,

A developing step of developing the exposed film with an aqueous developing solution to form a pattern, and

And a baking step of heating the pattern.

<16> A pattern forming method according to <15>, wherein the post-exposure step comprises exposing the pattern by an actinic ray before the baking step after the development step.

<17> A process for producing a structure using the pattern produced by the pattern forming method according to <15> or <16> as a sacrificial layer for laminating the structure, and

And removing the sacrificial layer by a plasma treatment.

<18> a step of performing dry etching using the pattern produced by the pattern forming method described in <15> or <16> as a resist for dry etching, and

And removing the pattern by a plasma treatment or a chemical treatment.

<19> A process for wet etching using a pattern produced by the pattern forming method according to <15> or <16> as a resist for wet etching,

And removing the pattern by a plasma treatment or a chemical treatment.

<20> A process for producing an acrylic resin as described in any one of <1> to <8>, which comprises producing an acrylic resin by using a chain transfer agent having a carboxyl group at the time of polymerization of the polymerizable monomer or by using a polymerization initiator having a carboxyl group A method for producing a positive photosensitive resin composition.

According to the present invention, it is possible to provide a positive photosensitive resin composition capable of forming a rectangular or nearly rectangular profile even after baking the formed pattern. Particularly, it is suitable for use as a thick film resist requiring rectangularity.

1 is a schematic view showing an example in which a pattern cross-sectional profile after heat treatment is good.
Fig. 2 is a schematic diagram showing an example in which a pattern cross-sectional profile after heat treatment is defective. Fig.
3 is a schematic view showing an example of a pattern cross-sectional profile after heat treatment;

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

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

In the present specification, the "repeating unit derived from (meth) acrylic acid or an ester thereof" is also referred to as "acrylic repeating unit". Further, (meth) acrylic acid is collectively referred to as methacrylic acid and acrylic acid.

&Lt; Positive photosensitive resin composition >

The positive photosensitive resin composition of the present invention (hereinafter, simply referred to as &quot; photosensitive resin composition &quot;) is a photosensitive resin composition containing a carboxyl group at the main chain end and a repeating unit having a cyclic ether group of three- A positive photosensitive resin composition characterized by containing an acrylic resin which is insoluble or sparingly soluble in an alkali developing solution and which is soluble in an alkali developing solution by the action of an acid. The positive photosensitive resin composition is characterized by comprising a chemically amplified positive photosensitive resin composition Resin composition) is particularly preferable.

The acrylic resin used in the present invention is an acrylic resin which is insoluble or hardly soluble in an alkaline developer containing a carboxyl group at the main chain end and contains a repeating unit having a cyclic ether group of a 3-membered ring and / or a 4-membered ring, (&Quot; specific polymer &quot;, also referred to as &quot; polymer A &quot;) soluble in an alkali developing solution.

In the acrylic resin used in the present invention, it is preferable that the carboxyl group or the phenolic hydroxyl group contains a residue protected with an acid-decomposable group, and the residue can be decomposed (deprotected) by the acid to form a carboxyl group or phenolic It is possible to generate a hydroxyl group. In the present invention, it is preferable that the carboxyl group or the phenolic hydroxyl group contains a repeating unit (a1) containing a residue protected by an acid-decomposable group.

The term "repeating unit" in the present invention includes not only a constituent unit formed by one molecule of a monomer but also a constituent unit formed by one molecule of a monomer, which is modified by a polymer reaction or the like.

Polymer A is preferably a resin that is alkali-insoluble and becomes alkali-soluble when the acid-decomposable group in the repeating unit (a1) is decomposed.

"Alkali solubility" in the present invention means that the coating film (thickness: 4 μm) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating the coating at 90 ° C. for 2 minutes at 23 ° C. Means that the dissolution rate of the compound (resin) in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 0.01 탆 / second or more is referred to as &quot; alkali insoluble &quot; The dissolution rate of the coating film (thickness 4 占 퐉) of the compound (resin) formed by heating in an aqueous solution of tetramethylammonium hydroxide at 0.4% by weight at 23 占 폚 is less than 0.01 占 퐉 / sec, preferably 0.005 占 퐉 / sec .

The weight average molecular weight (Mw) of the polymer A is preferably 5,000 or more, more preferably 7,000 or more, and most preferably 10,000 or more. It is preferably 1,000,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less. Within this range, a better rectangular or rectangular profile can be obtained even after the baking step. When the weight average molecular weight is 12,000 or more, the shape change in the baking step is small, and a profile close to a rectangular or rectangular shape can be obtained. When the weight average molecular weight is 80,000 or less, the pattern forming property at the time of development is more excellent.

In addition, 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 Super Hz3000 and TSKgel Super Hz M-M (all manufactured by TOSOH CORPORATION) as the column.

Polymer A is an acrylic polymer. The "acrylic polymer" in the present invention is a polymer of addition polymerization type and is a polymer containing a repeating unit derived from (meth) acrylic acid or an ester thereof, and is a repeating unit other than a repeating unit derived from (meth) acrylic acid or an ester thereof Unit, for example, a repeating unit derived from styrene, a repeating unit derived from a vinyl compound, or the like. Further, the polymer A may contain both a repeating unit derived from (meth) acrylic acid and a repeating unit derived from a (meth) acrylic acid ester. In the present invention, it is preferable that 90 mol% or more of the repeating units constituting the polymer A is a repeating unit derived from (meth) acrylic acid or an ester thereof.

&Lt; Recurring unit (a1) having a carboxy group or a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group >

More preferably, the polymer A has a repeating unit (a1) in which the carboxyl group or the phenolic hydroxyl group has a residue protected by an acid-decomposable group.

By having the polymer A having the repeating unit (a1), a highly sensitive photosensitive resin composition can be obtained. The repeating unit in which the carboxyl group has a moiety protected by an acid-decomposable group is characterized in that the phenolic hydroxyl group is faster than the repeating unit having a moiety protected with an acid-decomposable group. Therefore, when a rapid development is desired, a repeating unit in which the carboxyl group has a residue protected by an acid-decomposable group is preferable. Conversely, when it is desired to slow down the development, it is preferable to use a repeating unit having a residue protected by an acid-decomposable group with a phenolic hydroxyl group.

[Recurring unit (a1-1) in which a carboxyl group has a residue protected by an acid-decomposable group]

As the acid decomposable group, there can be used any known acid decomposable group in the positive resist for KrF and the positive resist for ArF, and there is no particular limitation. Conventionally, examples of the acid decomposable group include groups which are relatively easily decomposable by an acid (e.g., acetal-based functional groups such as tetrahydropyranyl) or groups which are relatively difficult to decompose by an acid (e.g., tert- Butyl-based functional groups such as butyl carbonate groups) are known.

Among these acid decomposable groups, it is preferable that the carboxyl group is a residue protected with an acetal, or a repeating unit having a carboxyl group protected ketal protected moiety. The basic properties of the resist, particularly the sensitivity and pattern shape, From the viewpoint of storage stability. Among the acid decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1). When the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1), the moiety has a structure of -C (= O) -O-CR ¹ R ² (OR ³ ) have.

(In the formula (a1-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, provided that when 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 connected to form a cyclic ether. The broken line indicates the bonding position with other structures)

In formula (a1-1), R ¹ to R ³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of linear, branched and cyclic. Wherein both of 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 the formula (a1-1), when R ¹ , R ² and R ³ represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

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

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

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group and an alkoxy group. When R ¹ , R ² and R ³ are a haloalkyl group, and when they have an aryl group as a substituent, R ¹ , R ² and R ³ are an aralkyl group when they have a halogen atom as a substituent.

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.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Specific examples thereof include a phenyl group, an? -Methylphenyl group, and a naphthyl group.

The aralkyl group is preferably an aralkyl group having 7 to 32 carbon atoms and more preferably an aralkyl group having 7 to 20 carbon atoms. Specifically, benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like can be exemplified.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.

When the alkyl group is an alkyl group having a cyclic structure, the alkyl group having the cyclic structure may have a straight or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group may be a linear or branched alkyl group , It may have an alkyl group having a cyclic structure having 3 to 12 carbon atoms as a substituent.

These substituents may be further substituted by 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. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms may be preferably exemplified. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.

Furthermore, R ¹ , R ² and R ³ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, and a tetrahydropyranyl group.

In formula (a1-1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.

The radically polymerizable monomer used for forming the repeating unit having a moiety represented by the formula (a1-1) may be a commercially available one, or a compound synthesized by a known method may be used. For example, by reacting (meth) acrylic acid with a vinyl ether in the presence of an acid catalyst.

Further, the above-mentioned synthesis may be carried out by previously copolymerizing (meth) acrylic acid with other monomers, and then reacting with vinyl ether in the presence of an acid catalyst.

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Li represents a carbonyl group or a phenylene group, and R ² each represent an alkyl group having 1 to 4 carbon atoms.) N1 and n2 are N3 is an integer of 1 to 4, and n4 is an integer of 1 to 3,

Each R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

Li represents a carbonyl group or a phenylene group, and a carbonyl group is more preferable.

R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

n1, n2, n3 and n4 are each preferably 0.

Among them, particularly (1), (2), (5) or (7) is preferable, (2) or (7) is more preferable and (7) is particularly preferable.

As specific preferred examples of the repeating unit (a1-1) having a carboxyl group-protected residue with an acid-decomposable group, the following repeating units can be exemplified. R represents a hydrogen atom or a methyl group. Among them, the repeating unit (a1-1-1), the repeating unit (a1-1-2) and the repeating unit (a1-1-7) are preferable from the viewpoint of sensitivity, , And the repeating unit (a1-1-7) is more preferable.

&Lt; Repeating unit (a1-2) in which the phenolic hydroxyl group has a residue protected by an acid-decomposable group>

As the acid decomposable group, known ones can be used as described above, and there is no particular limitation. Among the acid decomposable groups, the repeating units having a phenolic hydroxyl group protected with an acetal or a phenolic hydroxyl group protected with a ketal protected moiety are preferable because the basic properties of the resist, particularly the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, In view of the formation of contact holes. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the above formula (a1-1). In addition, when the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the above formula (a1-1), the residue has a structure of -Ar-O-CR ¹ R ² (OR ³ ) as a whole. Ar represents an arylene group.

Preferable examples of the acetal ester structure for protecting the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group and R ¹ = R ² = methyl group and R ³ = benzyl group.

Examples of the radically polymerizable monomer used for forming the repeating unit having a phenolic hydroxyl group having an acetal or ketal protected moiety include a 1-alkoxyalkyl protected 4-hydroxyphenyl methacrylate, a 4-hydroxyphenyl Alkoxyalkyl protected derivatives of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 4-hydroxybenzoic acid (1-methacryloyloxymethyl) -tetrahydrofuranyl protected derivatives of methacrylate, (2-methacryloyloxyethyl) ester of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, a protected tetrahydrothiopyranyl of ester Tetrahydrofuranyl protecting agent, a 1-alkoxyalkyl protected derivative of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, a tetrahydrofuran derivative of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) A pyranyl protecting group, 4-hydroxybenz Alkoxyalkyl protecting group of an acid (3-methacryloyloxy-2-hydroxypropyl) ester, a tetrahydrofuran of 4-hydroxybenzoic acid (3-methacryloyloxy- Nyl protective material is preferable from the viewpoint of transparency.

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

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

Specific preferred examples of the repeating unit (a1-2) include the following repeating units, but the present invention is not limited thereto.

The content of the repeating unit (a1) in the polymer A is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, and still more preferably 20 to 45 mol% based on all repeating units of the polymer A from the viewpoint of sensitivity % Is more preferable.

<Repeating unit (a2) having cyclic ether group of 3-membered ring and / or 4-membered ring>

Examples of the cyclic ether group in the repeating unit having a cyclic ether group of a 3-membered ring and / or a 4-membered ring used in the present invention include an epoxy group and an oxetanyl group. The cyclic ether group is more preferably the following structure.

In general formula (1)

(1), R ¹ represents a hydrogen atom or an alkyl group, L represents a divalent linking group, R ² to R ⁴ each represent a hydrogen atom, an alkyl group, or a phenyl group, n represents 1 or 2, R ² , R ³ or R ⁴ may be bonded to a substituent group of L to form a ring)

In the general formula (1), when n is 1, the groups represented by R ³ and R ⁴ are each one, and when n is 2, the groups represented by R ³ and R ⁴ are each two.

R ¹ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

L is preferably a divalent linking group containing an aryl group, an alkyl group, an ether linkage, an ester linkage, or a combination thereof. Examples of the substituent of L include an alkyl group, a phenyl group, an alkoxy group, a fluorine atom, and a bromine atom.

R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group may have a substituent.

It is more preferable that R ³ and R ⁴ are hydrogen atoms.

Examples of the radically polymerizable monomer used for forming the repeating unit (a2) are a monomer containing a methacrylate ester structure and a monomer containing an acrylic ester structure.

As the group having an epoxy group, a glycidyl group and a 3,4-epoxycyclohexylmethyl group can be preferably exemplified, as long as they have an epoxy ring, although there is no particular limitation.

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

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

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

Among these monomers, glycidyl methacrylate, glycidyl acrylate, compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and compounds described in JP-A-2001-330953 (Meth) acrylic acid esters having an oxetanyl group as described in paragraphs 0011 to 0016 of the publication.

Particularly preferable from the viewpoint of heat resistance transparency is a repeating unit derived from any of acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl.

These repeating units (a2) may be used singly or in combination of two or more.

Specific preferred examples of the repeating unit (a2) include the following repeating units, but are not limited to the following structures.

The content of the repeating unit (a2) in the polymer A is preferably from 3 to 90 mol%, more preferably from 5 to 80 mol%, and still more preferably from 20 to 70 mol% based on all repeating units of the polymer A from the viewpoint of sensitivity , More preferably from 25 to 40 mol%.

<Repeating unit (a4) having a cyclic structure>

Polymer A preferably contains a recurring unit (a4) having a ring structure from the viewpoints of dry etching resistance and chemical resistance. Note that (a4) excludes those corresponding to (a1) and (a2).

Examples of the monomer forming the repeating unit (a4) include (meth) acrylic acid cyclic alkyl esters such as styrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate and cyclohexyl Aromatic compounds and the like.

As the repeating unit (a4) having a cyclic structure, a repeating unit represented by the following formula (a4-1) or (a4-2) can be preferably exemplified.

The formula (a4-1)

(Wherein R ^A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R represents a hydrogen atom or a substituent)

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 the uniformity of polymerization rates of the respective monomers during polymerization. R is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a hydroxyl group, more preferably a hydrogen atom.

(A4-2)

(Wherein 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, a ring A represents a cyclopentane ring or a cyclopentane ring, You do not need to have it)

The R ^B in the formula (a4-2) is preferably a methyl group from the viewpoint of the uniformity of polymerization rates of the respective monomers at the time of polymerization.

X in the formula (a4-2) is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond.

The ring A in the formula (a4-2) preferably has a ring A, and is preferably a cyclopentane ring or a cyclopentane ring, more preferably a cyclopentane ring. The position of the double bond of the cyclopentene ring in Ring A is not particularly limited and may be any arbitrary position.

The content of the repeating unit (a4) in the polymer A is preferably 1 to 50 mol%, more preferably 5 to 35 mol%, and particularly preferably 10 to 30 mol%, based on all repeating units of the polymer A . By including the repeating unit (a4) in the above ratio, the resulting pattern has excellent dry etching resistance and chemical resistance.

<Repeating unit (a5) having a carboxyl group or hydroxyl group>

From the viewpoint of developability, the polymer A preferably has a repeating unit (a5) having a carboxyl group or a hydroxyl group. It should be noted, however, that those corresponding to the above (a1), (a2) and (a4) are excluded.

The repeating unit (a5) is preferably introduced in such a range that the polymer A does not become alkali soluble. The content of the repeating unit (a5) in the polymer A is preferably from 2 to 20 mol%, more preferably from 2 to 15 mol%, and particularly preferably from 3 to 15 mol%, based on all repeating units of the polymer A . By containing the repeating unit (a5) in the above ratio, a high sensitivity can be obtained and the developing property can be improved.

[Recurring unit having a carboxyl group (a5-1)]

Examples of the repeating unit (a5-1) having a carboxyl group include repeating units derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid.

As the unsaturated carboxylic acid used for obtaining the repeating unit (a5-1) having a carboxyl group, those exemplified below can be used.

That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid used for obtaining the repeating unit (a5-1) having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, and examples thereof include monosaccharide mono (2-acryloyloxyethyl), succinic acid mono Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like.

Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, from the viewpoint of developability, it is preferable to use acrylic acid or methacrylic acid in order to form the repeating unit (a5-1) having a carboxyl group.

The repeating unit (a5-1) having a carboxyl group can also be obtained by reacting a repeating unit (a5-2) having a hydroxyl group, which will be described later, with an acid anhydride.

As the acid anhydride, known ones can be used, and specific examples include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and anhydrous chloridic acid; Acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and biphenyltetracarboxylic anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride are preferable from the viewpoint of developability.

[Repeating unit having a hydroxyl group (a5-2)]

As the repeating unit (a5-2) having a hydroxyl group, a repeating unit (a5-2-1) having a phenolic hydroxyl group can be exemplified.

Examples of the radically polymerizable monomer used to form the repeating unit (a5-2-1) having a phenolic hydroxyl group in the repeating unit (a5-2) having a hydroxyl group include p-hydroxystyrene,? -Methyl p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 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 the radical polymerizable monomers used to form the repeating unit (a5-2-1) having a phenolic hydroxyl group, methacrylic acid, acrylic acid, a compound described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, Hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Patent Publication No. 2888454, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate Is more preferable, but methacrylic acid and acrylic acid are particularly preferable from the viewpoint of transparency. These repeating units may be used singly or in combination of two or more.

Of the repeating units (a5-2) having a hydroxyl group, any repeating unit having a hydroxyl group can be used as the repeating unit (a5-2-2) having a hydroxyl group other than the phenolic hydroxyl group, (Meth) acrylic acid ester of an alkyl group-terminated polyalkylene glycol, (meth) acrylic acid ester of an alkyl group-terminated polyalkylene glycol, and (meth) acrylic acid ester of an aryl-terminated polyalkylene glycol.

Examples of the hydroxyl group-containing (meth) acrylic acid esters include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Hydroxyalkyl esters of (meth) acrylic acid such as dihydroxypropyl and 4-hydroxybutyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate, polypropyleneglycol mono (meth) acrylate, poly Propylene glycol-mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) -mono (meth) acrylate, polyethylene glycol-polypropylene glycol- ) -Mono (meth) acrylate, and propylene glycol · polybutylene glycol-mono (meth) acrylate.

Examples of the (meth) acrylic acid esters of alkyl-terminated polyalkylene glycols include methoxypolyethylene glycol- (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, lauroxypolyethylene glycol- ) Acrylate, stearoxypolyethylene glycol- (meth) acrylate, and the like.

Examples of the (meth) acrylic acid ester of the aryl group-terminated polyalkylene glycol include phenoxypolyethylene glycol- (meth) acrylate, phenoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, nonylphenoxypolyethylene glycol (Meth) acrylate, nonylphenoxy-polypropylene glycol- (meth) acrylate and nonylphenoxy-poly (ethylene glycol-propylene glycol) - (meth) acrylate.

A commercially available (meth) acrylic acid ester of a hydroxyl group, a (meth) acrylic acid ester of an alkyl group-terminated polyalkylene glycol and a (meth) acrylic acid ester of an aryl-terminated polyalkylene glycol can be used. Representative examples include, but are not limited to, blemmers E, blemmer PE-90, blemmer PE-200, blemmer PE-350, blemmer p, blemmer PP-1000, Blemmer AE-200, Blemmer AE-400, Blemmer AP-300, Blemmer 70PEP-350, Blemmer 55PET-800, 150, Blemmer AP-400, Blemmer AP-550, Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, BLEMER PSE-400, BLEMMER PSE-1300, BLEMMER PAE-50, BLEMMER PAE-100, BLEMMER 43PAPE-600B, BLEMMER AME-400, BLEMMER ALE series, BLEMMER ANP-300, -600, Blemmer AAE-50, Blemmer AAE-300 (manufactured by Nichiyu Corporation), and the like.

The number of hydroxyl groups in the repeating unit (a5-2) is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

When the repeating unit (a5-2) has an alkyleneoxy group, the number of repeating units of the alkyleneoxy group is preferably from 1 to 25, more preferably from 1 to 15, and most preferably from 1 to 10.

Specific preferred examples of the radically polymerizable monomer used for forming the repeating unit (a5-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, methoxypolyethylene glycol- (meth) acrylate having 2 to 10 ethylene glycol repeating units, methoxypolypropylene glycol- (Meth) acrylate, methoxypolyethylene glycol-polypropylene glycol- (meth) acrylate wherein the sum of ethylene glycol repeating units and propylene glycol repeating units is 2 to 10, the sum of repeating units of ethylene glycol and propylene glycol is 2 (Meth) acrylate having 2 to 10 ethylene glycol mono (meth) acrylate repeating units, ethylene glycol mono Polypropylene glycol mono (meth) acrylate having 2 to 10 propylene glycol repeating units, poly (ethylene glycol-propylene glycol) -mono (meth) acrylate having a total of repeating units of ethylene glycol and propylene glycol of 3 to 10, Acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate having a sum of ethylene glycol repeating units and propylene glycol repeating units of 3 to 10, and the like.

Among these, preferred are (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl More preferably 2 to 10 methoxypolyethylene glycol- (meth) acrylates, and the sum of ethylene glycol repeating units and propylene glycol repeating units is 2 to 10 oxypropylene glycol-polypropylene glycol- (meth) acrylates , Methoxypolyethylene glycol (meth) acrylate having 2 to 10 ethylene glycol repeating units and 2-hydroxyethyl (meth) acrylate are particularly preferable.

The repeating unit (a5) may be used singly or in combination of two or more.

The content of the repeating unit (a5) in the polymer A is preferably 0.5 to 30 mol%, more preferably 0.5 to 25 mol%, and particularly preferably 1 to 25 mol%, based on all repeating units of the polymer A .

The content of the repeating unit (a5) in the polymer A is 3 to 30% by weight, more preferably 3 to 25% by weight, and particularly preferably 5 to 25% by weight based on the total weight of the polymer A. When the proportion of the repeating unit (a5) is contained in the above ratio, the developability is improved and a photosensitive composition with high sensitivity can be obtained. In particular, by combining the repeating unit (a2) and the repeating unit (a5) described above, a photosensitive resin composition having extremely high sensitivity can be obtained.

&Lt; Other repeating unit (a6) >

The polymer A may contain a repeating unit (a6) other than the repeating units (a1) to (a5) within the range not hindering the effect of the present invention.

Examples of the radically polymerizable monomer used for forming the repeating unit (a6) include the compounds described in paragraphs 0021 to 0024 of JP-A-4207604 (provided that the repeating units (a1) to (except for the monomers forming the monomer (a5)).

The polymer A may have one kind of the repeating unit (a6) alone or two or more kinds of the repeating unit (a6).

The content of the repeating unit (a6) in the polymer A is preferably 0 to 40 mol%, more preferably 0 to 10 mol%, based on all repeating units of the polymer A.

When the polymer A contains the repeating unit (a6), the content of the repeating unit (a5) in the polymer A is preferably 1 to 40 mol%, more preferably 5 to 30 mol% Mol, more preferably 5 to 25 mol%.

The weight average molecular weight in the present invention is the polystyrene reduced weight average molecular weight by gel permeation chromatography (GPC).

The method of introducing each repeating unit of the polymer 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, the radical-polymerizable (meth) acrylic polymer used for forming the repeating unit (a1), the repeating unit (a2), the repeating unit (a3), the repeating unit (a4), the repeating unit Can be synthesized by polymerization of a radically polymerizable monomer mixture containing a monomer in an organic solvent using a radical polymerization initiator.

In the polymer reaction method, a necessary functional group is introduced into the repeating unit by using a reactive group contained in the repeating unit of the obtained copolymer after the polymerization reaction.

The introduction of the repeating units (a1) to (a6) into the polymer A may be either a polymerization method or a polymer reaction method, and these two methods may be used in combination.

The polymer A can be used singly or in combination of two or more kinds in the photosensitive resin composition of the present invention.

&Lt; Method of introducing a carboxyl group at the resin main chain end &

As a method of introducing a carboxyl group into the resin main chain end, there are a method using a chain transfer agent having a carboxyl group at the time of polymerization and a method using a polymerization initiator having a carboxyl group.

In the method of using a chain transfer agent having a carboxyl group at the time of polymerization, a thiol compound having at least one carboxyl group is used in polymerization. Examples of the thiol compound having at least one carboxyl group include the following examples.

The chain transfer agent is preferably blended at a ratio of 1/100 to 2/3 of the amount of the initiator, more preferably at a rate of 1/20 to 1/3 of the mole of the initiator.

Although the molecular weight is adjusted by the total amount of initiator and chain transfer agent, it is preferably 0.05 to 10 mol%, more preferably 0.1 to 5 mol%, based on the total moles of all monomers.

The reaction temperature for the copolymerization reaction is preferably from 50 to 100 캜, more preferably from 60 to 95 캜.

As a method of using a polymerization initiator having a carboxyl group, a polymerization initiator having a carboxyl group is used as an initiator at the time of polymerization.

Examples of the polymerization initiator having a carboxyl group include VA-057 (Wako Pure Chemical Industries, Ltd.) and V-501 (Wako Pure Chemical Industries, Ltd.).

Such a polymerization initiator is preferably used in an amount of 0.05 to 10 mol%, more preferably 0.1 to 5 mol%, based on 100 mol of the polymerizable monomer.

The reaction temperature of the copolymerization reaction is preferably from 50 to 100 캜, more preferably from 60 to 100 캜.

The positive photosensitive resin composition of the present invention is preferably used for an etching resist, more preferably a photosensitive resin composition for a thick-film etching resist having a thickness of 4 to 100 mu m.

Further, 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 &quot; taper angle &quot; is an angle between the side surface of the pattern and the plane of the substrate 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, it is an angle formed by the tangent line at the half point of the film thickness on the pattern and the plane of the substrate. In addition, even when the cross-sectional shape of the side surface of the pattern is semicircular or arcuate, and the upper surface of the pattern is not recognized, the midpoint between the uppermost portion of the film and the substrate, And the plane of the plate substrate (plate substrate).

As a concrete example,? In each cross-sectional shape of the patterns shown in Figs. 1, 2, and 3 is a taper angle.

In the example of Fig. 3, since the upper surface of the pattern is not recognized, the angle formed by the tangent line at the midpoint between the uppermost portion of the film and the substrate, i.e., the point at which the film thickness is half, and the plane of the plate substrate is?.

The content of the polymer A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, more preferably 40 to 97% by weight, and more preferably 50 to 95% by weight, based on the total solid content of the photosensitive resin composition More preferably 50 to 80% by weight. When the content is within this range, the pattern forming property upon development becomes good. The solid content of the photosensitive resin composition means an amount excluding a volatile component such as a solvent.

In the photosensitive resin composition of the present invention, a resin other than the polymer A may be used in combination within a range not hindering the effect of the present invention. However, the content of the resin other than the polymer A is preferably smaller than the content of the polymer A from the viewpoint of developability.

Hereinafter, other components constituting the photosensitive resin composition will be described.

&Lt; (B) Photo acid generator >

The photosensitive resin composition of the present invention contains (B) a photoacid generator.

The photoacid generator is preferably a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but is not limited to the chemical structure thereof. Further, even in the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer if it is used in combination with a sensitizer so as to generate an acid upon exposure to an actinic ray having a wavelength of 300 nm or more have.

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

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

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

For example, the description of paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2010-282178 may be taken into consideration.

Examples of the compound having at least one oxime sulfonate residue represented by the formula (1) include oximesulfonate compounds represented by the following formulas (OS-3), (OS-4) or (OS-5) desirable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(In the formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom and R ⁸ represents a hydrogen atom, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom or a methyl group, a halogen atom, a chlorine atom, Lt; / RTI &

R ¹ in the above formulas (OS-6) to (OS-11) is synonymous with R ¹ in the above formulas (OS-3) to (OS-5).

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

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

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

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

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

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

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

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

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

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

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

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

Among them, R ¹ in the formulas (OS-1) and (OS-2) is more preferably a cyano group or an aryl group and is represented by the formula (OS-2), R ¹ is a cyano group, Or a naphthyl group is most preferable.

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

The oxime sulfonate compound is preferably an oxime sulfonate compound represented by the following formula (B-1).

(Wherein R ^B4 represents a hydrogen atom or a methyl group, and R ^B5 represents an alkyl group having 1 to 8 carbon atoms, a p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group or a nonafluorobutyl group)

R ^B4 in the formula (B-1) is preferably a methyl group.

The alkyl group having 1 to 8 carbon atoms and the nonafluorobutyl group in R ^B5 in the formula (B-1) may be straight chain or branched.

The number of carbon atoms of the alkyl group in R ^B5 is preferably 1 to 4, more preferably 1 to 3.

The bonding position of the camphoryl group and the sulfur atom in R ^B5 is not particularly limited, but is preferably in the 10 position. That is, the camphoryl group is preferably a 10-camphoryl group.

The R ^B5 in the formula (B-1) is preferably a methyl group, an n-propyl group, an n-octyl group, a p-toluyl group, or a camphoryl group, more preferably an n-propyl group, Or a camphoryl group, more preferably an n-propyl group or a p-toluyl group.

For details of these, reference may be made to the description of 0062 to 0066 of JP-A-2010-282178.

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

Examples of R ^3A in the formula (2-2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- N-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group is particularly preferable.

As the halogen atom represented by R ^4A , a fluorine atom, a chlorine atom or a bromine atom is preferable.

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

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

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

Among the compounds represented by the formula (2), preferred embodiments of the compound included in the compound represented by the formula (2-2) include those wherein R ^1A represents a phenyl group or a 4-methoxyphenyl group, R ^2A is a cyano group, and R ^3A is 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.

? - (methylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = methyl group)

? - (ethylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = ethyl group)

? - (n-propylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = n-propyl group)

? - (n-butylsulfonyloxyimino) benzyl cyanide (R ^1A = phenyl group, R ^2A = cyano group, R ^3A = n-butyl group)

(R ^1A = phenyl group, R ^2A = cyano group, R ^3A = 4-tolyl group)

methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl, R ^2A = cyano group, R ^3A = methyl group)

methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = ethyl group)

methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = n-propyl group)

methoxyphenyl] acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = n-butyl group)

methoxyphenyl) acetonitrile (R ^1A = 4-methoxyphenyl group, R ^2A = cyano group, R ^3A = 4-tolyl group)

In the positive photosensitive resin composition of the present invention, the photoacid generator represented by the formula (1) or (2) may also be used.

(Wherein R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aromatic group which may have a substituent, and in the case of an alkyl group, they may be connected to form a ring, and R ⁸ and R ⁹ are each independently , X ^- represents a monovalent anion represented by BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- , or the formula (3) or (4) Y each independently represent a halogen atom)

(Wherein R ²¹ , R ²² and R ²³ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or R ²¹ and R ²² , An alkylene group having 2 to 6 carbon atoms or an alkylene group having a fluorine atom having 2 to 6 carbon atoms)

As the alkyl group in R ⁵ , R ⁶ and R ⁷ in the formula (1), an alkyl group having 1 to 10 carbon atoms is preferable, and for example, a methyl group, an ethyl group and a tertiary butyl group (tert-butyl group) . When at least two of R ⁵ , R ⁶ and R ⁷ in the formula (1) are alkyl groups, it is preferable that the two or more alkyl groups are connected to each other to form a ring. (Thacyclopentane), and a 6-membered ring (thiacyclohexane) are more preferable, and a 5-membered ring is more preferable.

The aromatic group in R ⁵ , R ⁶ and R ⁷ is preferably an aromatic group having 6 to 30 carbon atoms and may have a substituent. Examples of such aromatic groups include a phenyl group, a naphthyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-tertiary butylphenyl group, Methoxy-1-naphthyl group, and 4- (4'-diphenylsulfonylphenylthio) phenyl group.

In the formula (2), preferred examples of the aromatic group in R ⁸ and R ⁹ are the same as those of R ⁵ , R ⁶ and R ⁷ .

As the substituent in R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , an aromatic group is particularly preferable, and specifically, phenyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 4- Phenylthio) phenyl group is particularly preferable.

The acid generator represented by the formula (1) or (2) may be bonded to any of R ⁵ to R ⁹ to form a multimer such as a dimer. For example, the 4- (4'-diphenylsulfonylphenylthio) phenyl group is an example of a dimer, and the relative anion in the 4- (4'-diphenylsulfonylphenylthio) phenyl group is BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- , or a monovalent anion represented by the formula (3) or (4).

Formula (1) and (2) of, X ^- in the _{^{BY 4 -, PY 6 -,}} AsY 6 -, SbY 6 - of the Y is a fluorine atom, a chlorine atom is preferred, and a fluorine atom in view of the negative ion stability Particularly preferred.

Examples of the alkyl group having 1 to 10 carbon atoms in R ²¹ , R ²² and R ²³ in the formulas (3) and (4) include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, Octyl group and the like. Examples of the fluorine atom-containing alkyl group having 1 to 10 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, a perfluoro And rouxthyl group. Of these, R ²¹ , R ²² and R ²³ are preferably an alkyl group having a fluorine atom of 1 to 10 carbon atoms, more preferably an alkyl group having a fluorine atom of 1 to 6 carbon atoms, An alkyl group having a fluorine atom of 4 is particularly preferable in terms of sensitivity.

Examples of the alkylene group having 2 to 6 carbon atoms in the formulas (3) and (4) when R ²¹ and R ²² bond together to form a ring include an ethylene group, a propylene group, a butylene group, a pentylene group, And a silylene group. Examples of the alkylene group containing a fluorine atom having 2 to 6 carbon atoms include a tetrafluoroethylene group, a hexafluoropropylene group, an octafluorobutylene group, a decafluoropentylene group, a dodecafluorohexylene group and the like . Among them, when R ²¹ and R ²² are bonded to each other to form a ring, they are preferably bonded with an alkylene group having a fluorine atom having 2 to 6 carbon atoms, and alkyl having a fluorine atom with 2 to 4 carbon atoms More preferably, they are bonded by an alkylene group, and it is particularly preferable from the viewpoint of sensitivity to bond with an alkylene group having a fluorine atom of 3 carbon atoms.

In the formulas (3) and (4), R ²¹ and R ²² are preferably an alkylene group having 2 to 6 carbon atoms or a ring bonded with an alkylene group having 2 to 6 carbon atoms and having a fluorine atom.

In the formulas (1) and (2), X ^- is preferably a monovalent anion represented by BY ₄ ^- , PY ₆ ^- or the formula (3) or (4) It is particularly preferable in terms of sensitivity that the monovalent anion to be displayed is,

As the acid generator represented by the formula (1), an acid generator represented by the following formula (5) may also be used.

(Wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent an alkyl group or aromatic group which may have a substituent, Ar ³ and Ar ⁴ each independently represent a divalent aromatic group which may have a substituent X ^{1 -} and X ^{2 -} are each independently selected from the group consisting of BY ₄ ^- , PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- or a monovalent anion represented by the formula (3) or the formula (4) And each Y independently represents a halogen atom)

Preferred embodiments of the alkyl group and the aromatic group in R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the formula (5) are the preferred embodiments of the alkyl group and the aromatic group in R ⁵ , R ⁶ and R ⁷ of formula (1) same.

The bivalent aromatic group in Ar ³ and Ar ⁴ in the formula (5) is preferably a phenylene group or a naphthylene group, and a phenylene group is particularly preferable.

Examples of compounds represented by formula (1) or formula (2) are given below. Among them, PAG-7, PAG-12 and PAG-14 are preferable, and PAG-12 is particularly preferable.

In addition to the above, compounds described in paragraphs 0036 to 0042 of Japanese Patent Application Laid-Open No. 2007-279585 can also be preferably used as the acid generator of the present invention.

The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as the photoacid generator (B) that is sensitive to an actinic ray. The reason is that the 1,2-quinonediazide compound generates a carboxy group by sequential fluorescent chemistry, but its quantum yield is 1 or less, and the sensitivity is lower than that of the oxime sulfonate compound.

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

In the photosensitive resin composition of the present invention, the photoacid generator (B) is preferably used in an amount of 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the polymer A, And most preferably 6 parts by weight.

(C) Solvent

The photosensitive resin composition of the present invention may contain (C) a solvent.

The photosensitive resin composition of the present invention is preferably prepared as a solution prepared by dissolving optional components of polymer A and component B, which are essential components, and various additives, which will be described later, in a solvent (C).

As the solvent (C) used in the photosensitive resin composition of the present invention, known solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, Dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

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

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

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

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

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

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

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

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

(D) Heat crosslinking agent

The photosensitive resin composition of the present invention preferably contains (D) a heat crosslinking agent, if necessary. (Component D) By adding a heat crosslinking agent, heat flow in the baking step can be suppressed. Further, (D) in the present invention is a polymer other than the polymer A.

As the thermal crosslinking agent, an alkoxymethyl group-containing crosslinking agent, a (meth) acrylic resin having an epoxy resin having an epoxy group and a carboxyl group to be described later, and the like can be preferably exemplified.

A crosslinking agent containing an alkoxymethyl group can also be suitably used, and preferably contains at least a methylol melamine compound.

The content of the 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, and more preferably 5 to 30 parts by weight, based on 100 parts by weight of the polymer A More preferable. In the above range, it is easy to obtain a profile close to a rectangle or a rectangle.

<Crosslinking agent containing alkoxymethyl group>

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These can be obtained by converting methylol melamine, methylol benzoguanamine, methylol glycoluryl, or the methylol group of the methylol moiety into 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 the amount of generated outgas, desirable.

Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine and alkoxymethylated glycoluril are preferable crosslinking compounds, and from the viewpoint of transparency, alkoxymethylated glycoluril is particularly preferable.

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

When an alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the amount of the alkoxymethyl group-containing crosslinking agent to be added is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the polymer A, More preferably 0.5 to 5 parts by weight. When added in this range, high sensitivity and favorable alkali solubility at the time of development can be obtained.

(E) a compound having an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group

In the photosensitive resin composition of the present invention, it is effective to add a compound having an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group in order to suppress the curing shrinkage of the film and obtain a rectangular profile after baking.

(E) is preferably a resin having a weight average molecular weight of 1,000 or more.

Specifically, a copolymer containing a repeating unit containing an epoxy group, an oxetanyl group, a hydroxyl group and / or a carboxyl group can be mentioned.

Further, a compound containing no such functional group as the homopolymer of polymethylmethacrylate (PMMA) can also be added as the component (E).

In the present invention, when (E) satisfies the definition of the crosslinking agent, it is classified into both of them. For example, when (E) is an epoxy resin, the epoxy resin is (D) a crosslinking agent and (E). Component (E) in the present invention is other than polymer A.

The epoxy equivalent, the oxetanyl equivalent, the hydroxyl group equivalent and the carboxyl group equivalent can be measured by a known method without any particular limitation. For example, the content of the group in a specific amount of the compound can be titrated ) Or the like. For example, by referring to the methods described in JIS K7236, K0070, and the like.

&Lt; Epoxy resin &

As the component (E), an epoxy resin is preferably used. By adding an epoxy resin, heat flow during baking can be suppressed. The epoxy resin preferably has a large epoxy equivalent because it suppresses curing shrinkage of the cross-linked film to obtain a profile close to a rectangular or rectangular shape. Specifically, it is preferably 400 g / eq or more, more preferably 400 to 1,000 g / eq, and particularly preferably 400 to 600 g / eq. In the above-mentioned range, since the curing shrinkage is small, a profile close to a rectangle or a rectangle can be obtained, and the permissible range of process conditions at the time of production of the cured film is large.

The method for measuring the epoxy equivalent is preferably in accordance with JIS K7236.

As the epoxy resin, commercially available ones and arbitrarily synthesized ones can be used. Specific examples of commercially available epoxy resins 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 and EXA-4822 (manufactured by DIC Corporation)

1004, 1004, 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 (Mitsubishi Kagaku Co.,

YD-012, YD-013, YD-014, YD-017, YD-019, YD-020G, YD-7011R, YD-901, YD- YDF-2001, YDF-2004, YDF-2005RL, YDB-400, YDB-405, YDB-400T60, YDB-400EK60, YDB-500EK80, FX-305EK70, ERF-001M30 Manufactured by Kagaku K.K.).

As the structure of the epoxy resin, it is preferable to have a BPA (bisphenol A) skeleton. Specifically, EPICLON 1050, 1055, 3050, 4050, EXA-4850-150, EXA-4850-1000, EXA- YD-013, YD-014 (manufactured by Mitsubishi Kagaku Co., Ltd.), epoxy resin 1001, 1002, 1003, 1055, 1004 and 1004AF (All manufactured by Shinnitetsu Kagaku Co., Ltd.).

The amount of the epoxy resin to be added 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 rectangular or rectangular profile, and to form a desired pattern by a developing 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, it is possible to inhibit volatilization in the solvent drying step or outflow in the developing step, and the effect of addition of the epoxy resin can be sufficiently obtained.

The epoxy resin may be used singly or in combination of two or more kinds.

The photosensitive resin composition of the present invention preferably contains an alkoxymethyl group-containing crosslinking agent and an epoxy resin from the viewpoint of obtaining a profile more nearly rectangular.

&Lt; (Meth) acrylic resin having carboxyl group >

As the component (E), a (meth) acrylic resin having a carboxyl group can be mentioned.

As the (meth) acrylic resin having a carboxyl group, it is preferable that the carboxyl group equivalent is large because the crosslinked film is prevented from hardening and shrinking to obtain a rectangular profile. Specifically, it is preferably 400 g / eq or more, more preferably 400 to 1,000 g / eq, and particularly preferably 400 to 600 g / eq.

The (meth) acrylic resin having a carboxyl group can be obtained by using a known (meth) acrylic monomer and adjusting the equivalence of the carboxyl group by adjusting the kinds and the ratio of the monomers.

As the acrylic monomer, for example, unsaturated monocarboxylic acid, (meth) acrylic acid esters, crotonic acid esters and (meth) acrylamides are preferable.

Specific examples of such monomers include the following compounds.

Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid,? -Chloroacrylic acid, and cinnamic acid.

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, diethyleneglycol monomethyl ether (meth) acrylate, di (meth) acrylate, di (meth) Ethylene glycol monoethyl ether (meth) acrylate, diethylene glycol (Meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate of polypropylene glycol monomethyl ether (meth) acrylate, a copolymer of ethylene glycol and propylene glycol , N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and the like.

Examples of the crotonic acid esters include butyl crotonate, hexyl crotonate and the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylacrylamide, N- (Meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide and (meth) acryloylmorpholine.

Among them, the (meth) acrylic resin having a carboxyl group is preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.

&Lt; Other components >

The photosensitive resin composition of the present invention may contain other components other than the above polymer A to component E.

As other components, it is preferable to contain a sensitizer (Component F) from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferable to add (P) a development accelerator.

The photosensitive resin composition of the present invention preferably contains an adhesion improver (Component H) in view of substrate adhesion, and preferably contains a basic compound (Component I) from the viewpoint of liquid storage stability, (Component J) preferably contains a surfactant (a fluorine-based surfactant, a silicon-based surfactant, etc.).

If necessary, the photosensitive resin composition of the present invention may further comprise (Component K) an antioxidant, (Component L) plasticizer, (Component M) thermal radical generator, (Component N) thermal acid generator, (Component O) acid Known additives such as an antioxidant, an antioxidant, an antioxidant, a growth agent, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.

In addition, the photosensitive resin composition of the present invention preferably contains a methylol cross-linking agent, an epoxy resin, a (Component H) adhesion improver, (Component I) a basic compound, and (Component J) a surfactant in order to obtain a profile more nearly rectangular And it is particularly preferable to contain an alkoxymethyl group-containing crosslinking agent, an epoxy resin, a (Component H) adhesion improver, (Component I) a basic compound and (Component J) a surfactant.

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

(Component F)

In the photosensitive resin composition of the present invention, it is preferable to add a sensitizer (Component F) in combination with the above-described (Component B) photoacid generator in order to accelerate the decomposition thereof. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer brought into the electron-excited state comes into contact with the photoacid generator to generate electron movement, energy transfer, heat generation, and the like. As a result, the photoacid generator decomposes by chemical change and generates acid.

Preferable examples of the sensitizer include those described in paragraphs 0162 to 0168 of Japanese Patent Application Laid-Open No. 2011-074314.

The sensitizer may be commercially available or may be synthesized by a known synthesis method.

The addition amount of the sensitizer is preferably from 20 to 300 parts by weight, particularly preferably from 30 to 200 parts by weight, per 100 parts by weight of the (B) photoacid generator from the viewpoints 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 phenomenon of promoting development may be used, but it is preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group, Or a compound having a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is most preferable.

The molecular weight of the component (G) of the development accelerator is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

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

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

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

(Component G) One type of the phenomenon promoting agent may be used alone, or two or more types may be used in combination.

In the photosensitive resin composition of the present invention, the addition amount of the (P) component is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the polymer A from the viewpoints of sensitivity and residual film ratio And most preferably 0.5 to 10 parts by weight.

(Component H) Adhesion improving agent

The photosensitive resin composition of the present invention preferably contains (Component H) an adhesion improver.

The adhesion improver (component H) that can be used in the photosensitive resin composition of the present invention can be obtained by a method in which an inorganic substance as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, Thereby improving adhesion. Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the (H) adhesion improver used in the present invention is intended to modify the interface and is not particularly limited, and a known silane coupling agent can be used.

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

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

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

The content of the (H) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer A. [

(Component I) The basic compound

The photosensitive resin composition of the present invention preferably contains (Component I) a basic compound.

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

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

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1, 2-diazabicyclo [4.3.0] -naphthalene, pyrazine, pyridazine, pyridine, pyrrolidine, piperidine, piperazine, morpholine, , 8-diazabicyclo [5.3.0] -7-undecene, and the like.

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

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

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

The content of the (basic component) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.002 to 0.2 parts by weight, per 100 parts by weight of the polymer A.

(Component J) Surfactants (fluorine surfactants, silicone surfactants, etc.)

The photosensitive resin composition of the present invention preferably contains (Component J) a surfactant (a fluorine-based surfactant, a silicon-based surfactant, etc.).

As the surfactant, a copolymer (3) containing the constituent unit A and the constituent unit B shown below may be mentioned as a preferable example. The weight average molecular weight (Mw) of the copolymer is preferably 1,000 to 10,000 or less, more preferably 1,500 to 5,000. 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 straight chain alkylene group having 1 to 4 carbon atoms and R ²⁴ represents a hydrogen atom or a C1- P represents an integer of not less than 10% by weight and not more than 80% by weight, q represents an amount of not more than 20% by weight, and L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages indicating a polymerization ratio, Or more and 90 weight% or less, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less.

L in the constituent 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 a surface to be coated, Is more preferable.

It is also preferable that the sum (p + q) of p and q is p + q = 100, that is, 100% by weight.

Specific examples of the fluorine-based surfactant and the silicon-based surfactant include those described in JP 62-36663 A, JP 61-226746 A, JP 61-226745 A, JP 62-170950 A, JP-B-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, 330953, and the like, and commercially available surfactants may be used. As commercial surfactants that can be used, for example, FEFFER EF301, EF303 (manufactured by Mitsubishi Materials Corporation), Fluorad FC 430 and 431 (manufactured by Sumitomo 3M Ltd.) Surfron S-382, SC101, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., Ltd.), Megafac F171, F173, F176, F189 and R08 Fluorine surfactants such as PolyFox series (OMNOVA SHAHASE), and silicone surfactants. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

These surfactants may be used singly or in combination of two or more. Further, a fluorine-based surfactant and a silicon-based surfactant may be used in combination.

The amount of the surfactant (fluorine surfactant, silicone surfactant, etc.) (component J) in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight More preferably 0.01 to 1 part by weight.

(Component K) Antioxidant

As the antioxidant used in the present invention, the description in paragraphs 0086 to 0078 of Japanese Patent Application Laid-Open No. 2011-170305 may be taken into consideration.

(Component L) Plasticizer

The photosensitive resin composition of the present invention may contain (Component L) plasticizer.

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

The content of (plasticizer) plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of polymer A. [

(Component M) Heat radical generator

The photosensitive resin composition of the present invention may contain (component M) a thermal radical generator, and when it contains an ethylenically unsaturated compound such as a compound having at least one ethylenically unsaturated double bond as described above (component M) It is preferable to contain a thermal radical generator. For details of the thermal radical generator, reference can be made to paragraph No. 0113 of Japanese Patent Application Laid-Open No. 2011-170305.

(Component M) One kind of thermal radical generator may be used singly or two or more kinds thereof may be used in combination.

The content of the heat radical generator (component M) in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer A, And most preferably 0.5 to 10 parts by weight.

(Component N) Thermal acid generator

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

A thermal acid generator is a compound which generates an acid by heat and is generally a compound having a thermal decomposition point in the range of 130 to 250 캜, preferably 150 to 220 캜, for example, by heating, a sulfonic acid, a carboxylic acid, (Low nucleophilic) acid such as imide.

As the generated acid, an alkylcarboxylic acid or an arylcarboxylic acid substituted with a sulfonic acid or an electron-withdrawing group (electron withdrawing group) having a pKa of 2 or less and a disulfonylimide similarly substituted with an electron-withdrawing group are 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 which generates an acid by heat without substantially generating an acid by irradiation with exposure light.

The fact that the acid is not substantially generated by the irradiation of the exposure light can be judged by the IR spectrum and the NMR spectrum before and after exposure of the compound to show that there is no change in the spectrum.

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

The sulfonic acid ester which can be used in the present invention may be a commercially available sulfonic acid ester or may be synthesized by a known method. Sulfonic acid esters can be synthesized, for example, by reacting a sulfonyl chloride or sulfonic 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, per 100 parts by weight of the polymer A. [

(Component O) Acid growth agent

In the photosensitive resin composition of the present invention, an acid generator (component O) may be used for the purpose of improving the sensitivity. The acid-proliferating agent used in the present invention is a compound capable of raising the acid concentration in the reaction system by generating an acid by an acid catalytic reaction, and is a compound stably present in the absence of acid. Such a compound accelerates the reaction progressively with the progress of the reaction because at least one acid increases in a single reaction, but since the generated acid itself induces self-decomposition, The strength of the generated acid is preferably 3 or less, more preferably 2 or less, as the acid dissociation constant, pKa.

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

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

The content of the acid proliferating agent in the photosensitive resin composition is preferably from 10 to 1,000 parts by weight based on 100 parts by weight of the (Component B) photoacid generator from the viewpoint of the dissolution contrast of the exposed portion and the unexposed portion, By weight is more preferable.

(Pattern Making Method)

The pattern making method of the present invention is not particularly limited as long as it is a method of producing a pattern using the photosensitive resin composition of the present invention. However, the pattern forming step of removing the solvent from the photosensitive resin composition of the present invention to form a film, A developing step of exposing the patterned film by a light beam, a developing step of developing the exposed film with an aqueous developer to form a pattern, and a baking step of heating the pattern.

The method of producing a pattern in the present invention preferably includes the following steps (1) to (6).

(1) a step of applying the photosensitive resin composition of the present invention on a substrate

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

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

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

(5) a step of exposing the developed photosensitive resin composition to an actinic ray (post exposure)

(6) Baking process for thermally curing 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 film can be formed by applying the photosensitive resin composition of the present invention to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). The substrate material that can be used in the present invention is silicon oxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper- Coated glass; Organic films such as polyimide and polyester; But are not limited to, metals, semiconductors, and any substrate containing a patterned region of an insulating material, and the like. In some cases, a baking step may be performed on the substrate to remove the absorbed moisture before applying the photosensitive resin composition of the present invention. The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spraying method, a roll coating method, and a spin coating method can be used. In the case of a large substrate, a slit coating method is preferable. Here, a large substrate refers to a substrate having a size of 1 m or more on each side.

In the solvent removing step of (2), the solvent is removed from the coated film by reduced pressure (baking) and / or heating to form a dried coating film on the substrate. The heating conditions are those in which the acid-decomposable group decomposes in the repeating unit (a1) in the polymer A in the unexposed portion and the polymer A is not soluble in the alkali developing solution. The heating conditions are different depending on the kinds and blending ratios of the respective components, Preferably about 70 to 120 DEG C for about 30 to about 300 seconds.

The photosensitive resin composition of the present invention can be suitably used as a so-called thick film resist having a thickness of 4 mu m or more after drying. This is because the present invention has high sensitivity and good shape controllability. The film thickness is preferably 4 to 500 mu m, particularly preferably 4 to 100 mu m.

(3) In the exposure step, an actinic ray of a predetermined pattern is irradiated to the substrate provided with the dry film. The exposure may be performed with a mask interposed, or a predetermined pattern may be directly drawn. An active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After the exposure process, PEB (post-exposure heat treatment) is performed as necessary.

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

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

When a laser is used, 343 nm and 355 nm are used in a solid-state (YAG) laser, 351 nm (XeF) is used in an excimer laser, and 375 nm and 405 nm are used in a semiconductor laser. Of these, 355 nm and 405 nm are more preferable in terms of stability and cost. The laser can be applied to the coating film one time or a plurality of times.

The energy density per pulse of the laser is preferably from 0.1 mJ / cm 2 to 10,000 mJ / cm 2. More preferably not less than 0.3 mJ / cm 2, most preferably not less than 0.5 mJ / cm 2, and preferably not more than 1,000 mJ / cm 2 in order to prevent the coating film from being decomposed by the ablation phenomenon Most preferably 100 mJ / cm &lt; 2 &gt; or less. The pulse width is preferably from 0.1 nsec to 30,000 nsec. In order to prevent decomposition of the chromaticity film due to ablation, it is more preferably 0.5 nsec or more, most preferably 1 nsec or more, and more preferably 1,000 nsec or less and 50 nsec or less Most preferred.

The frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less. In order to shorten the exposure processing time, more preferably 10 Hz or more, most preferably 100 Hz or more, and more preferably 10,000 Hz or less, and most preferably 1,000 Hz or less, in order to improve the fitting accuracy at the time of the scan exposure .

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

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

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

In order to accelerate the decomposition reaction in the region where the acid catalyst is generated, PEB (post-exposure heat treatment) can be performed if necessary. By PEB, the generation of carboxyl groups from the acid decomposable group can be promoted.

The acid decomposable group in the recurring unit (a1) in the present invention has a low activation energy for acid decomposition and is not necessarily subjected to PEB in order to easily decompose by an acid derived from an acid generator by exposure and to generate a carboxyl group, A positive image may be formed by development.

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

(4), the polymer A having a liberated carboxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed region containing a resin composition having a carboxyl group which is liable to dissolve in an alkaline developing solution.

Examples of the basic compound that can be used for the alkaline developer include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

The pH of the developing solution is preferably 10.0 to 14.0.

The developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method, and a shower method. After the development, it is preferable to carry out water washing for 10 to 90 seconds to form a desired pattern.

(5) A catalyst for accelerating crosslinking by re-exposure (post) exposure of the substrate on which a pattern has been formed by an actinic ray before the heat treatment to generate an acid from the photoacid generator present in the unexposed portion (component B) .

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

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

A cured film can be formed by thermally decomposing an acid-decomposable group in the recurring unit (a1) to produce a carboxyl group and then crosslinking the resulting positive image with an epoxy group and / or an oxetanyl group in the baking step of the step (6).

In order to obtain a profile close to a rectangle or a rectangle, it is preferable to perform so-called two-stage baking in which two stages of heating are performed at different temperatures. By performing the two-step baking, the film can be cured to some extent in the first stage baking to determine the shape, and the film can be baked by baking the second end to give necessary durability. The baking temperature in the first stage is preferably 90 占 폚 to 150 占 폚, and the time is preferably 10 to 60 minutes. The baking temperature of the second stage is preferably 180 to 250 캜, and the time is preferably 30 to 90 minutes.

It is also possible to carry out the baking step of three or more stages.

The taper angle in the cross-sectional shape of the pattern after the baking step is preferably 60 degrees or more, more preferably 70 degrees or more, and particularly preferably 80 degrees or more.

The photosensitive resin composition of the present invention is particularly useful as an etching resist since a profile close to a rectangle or a rectangle can be obtained even after the baking process.

(MEMS structure and its fabrication method, dry etching method, wet etching method, MEMS shutter device, and image display device)

A method for fabricating a MEMS (Micro Electro Mechanical Systems) structure of the present invention includes the steps of fabricating a structure by using a pattern produced by the pattern manufacturing method of the present invention as a sacrificial layer at the time of structure lamination, And a step of removing the silicon oxide film by a CVD method.

The MEMS structure of the present invention is a MEMS structure fabricated by using the pattern produced by the pattern making method of the present invention as a sacrificial layer for laminating structures.

The MEMS shutter device of the present invention is a MEMS shutter device manufactured by the manufacturing method of the 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 device or system or micromachine having a microstructure of micro-size or less. For example, a mechanical drive component, a sensor, an actuator, , An organic material, or the like.

As an image forming apparatus having a MEMS shutter device and a MEMS shutter device, those described in JP-A-2008-533510 can be exemplified.

When a pattern produced by the pattern manufacturing method of the present invention is used as a sacrificial layer for fabricating a MEMS structure, a metal, a metal oxide, a metal oxide, and a metal oxide are formed on the pattern by using various film forming processes such as coating, vapor deposition, sputtering, Inorganic compounds such as silicon compounds and semiconductors, and organic materials such as polyimide. In addition, two or more different materials may be laminated in multiple layers.

Examples of the base material of the MEMS sacrificial layer usable in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, , Copper-silicon alloy, indium-tin oxide coated glass; Organic films such as polyimide and polyester; But are not limited to, metals, semiconductors, and any substrate containing a patterned region of an insulating material, and the like. In some cases, a baking step may be performed on the substrate to remove the absorbed moisture before applying the photosensitive resin composition of the present invention.

When the pattern produced by the pattern making method of the present invention is used as a dry etching resist, dry etching such as ashing, plasma etching, and ozone etching 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 making method of the present invention as a dry etching resist and a step of removing the pattern by plasma treatment or chemical treatment desirable.

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

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

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

When the pattern produced by the pattern making method of the present invention is used as a wet etching resist, it is possible to carry out a wet etching treatment with a known agent such as an acid, an alkali, or a solvent.

The wet etching method of the present invention includes a step of performing wet etching using a pattern produced by the pattern producing method of the present invention as a resist for wet etching and a step of removing the pattern by plasma treatment or chemical treatment desirable.

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

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

When the pattern is peeled after the fabrication of the MEMS or after the etching process, it can be peeled off by a known wet process such as a known dry plasma process such as ashing or an alkali chemical process. Since the cured product of the present invention is cured through the baking process, peeling by the dry plasma process is particularly preferable.

When it is used as a sacrificial layer for MEMS, it is preferable to carry out delamination by a dry process in order to remove the resist from the complicated shape of the MEMS. In particular, oxygen plasma treatment is preferred.

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

(Example)

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

In the following Synthesis Examples and Table 1, the following abbreviations respectively represent the following compounds.

MATHF: 2-tetrahydrofuranyl methacrylate (synthetic)

MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

MATB: tertiary butyl methacrylate (TOKYO GASHI)

OXE-30: 3-ethyl-3-oxetanyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

THFCH ₂ OH: tetrahydrofurfuryl methacrylate (Tokyo Sagami)

St: Styrene

DCPM: Dicyclopentanyl methacrylate (Tokyo Gagai)

HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

V-65: 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

V-601: Dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

VA-057: 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] (manufactured by Wako Pure Chemical Industries, Ltd.)

V-501: 4,4'-azobis (4-cyanovaleric acid) (manufactured by Wako Pure Chemical Industries, Ltd.)

PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko)

Chain transfer agent A: Thiomalic acid (companion in Tokyo)

Chain transfer agent B: 3-mercaptopropionic acid (communicated in Tokyo)

Chain transfer agent C: Thiopronin (Tokyo)

Chain transfer agent D: Thioglycolic acid (companion Tokyo)

Chain transfer agent E: Captofuril (contact with Tokyo)

&Lt; Synthesis of Polymer A-1 &

&Lt; Synthesis Example 1: Synthesis of MATHF >

50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2 mol%) of camphorsulfonic acid were mixed in a three-necked flask and cooled to 15 캜. 41.00 g (0.585 mol) of 2,3-dihydrofuran was added dropwise to the solution. A saturated aqueous sodium bicarbonate solution (500 mL) was added to the reaction solution, extracted with ethyl acetate (500 mL), and dried over magnesium sulfate. The insoluble material was filtered and concentrated under reduced pressure at a temperature of 40 ° C or lower and the colorless oily substance of the residue was distilled under reduced pressure to obtain 73.02 g of a boiling point (bp) 54 to 56 ° C / 3.5 mmHg fraction Of MATHF.

&Lt; Synthesis Example 1: Synthesis of Specific Resin A >

A three-necked flask was charged with PGMEA (31.0 g), and the temperature was raised to 80 占 폚 in a nitrogen atmosphere. To the solution was added MATHF (19.5 g), HEMA (4.07 g), OXE-30 (17.27 g), V-601 (0.21 g, 0.38 mol% based on the monomer), thiomalic acid 1.5 mol%) was dissolved in PGMEA (31.0 g) and added dropwise over 2 hours. After completion of dropwise addition, stirring was performed for 4 hours, and the reaction was terminated. Thus, a specific resin A was obtained. The weight average molecular weight was 19,000.

<Synthesis of Polymers A-2 to A-29>

The respective monomers used for the synthesis of the polymer A-1 were changed to the monomers forming the respective repeating units (a1) to (a5) shown in Table 1, and the amounts of the monomers forming the respective repeating units were changed to those shown in Table 1 Except that the radical polymerization initiators V-601, VA-057, V-501 and V-65 were appropriately used depending on the substrate and the substrate and the chain transfer agent described in the table was used as required, -1, the polymers A-2 to A-29 were synthesized, respectively. The addition amounts of the radical polymerization initiators V-601, VA-057, V-501 and V-65 were adjusted so as to have the molecular weights shown in Table 1, respectively.

[Table 1]

The molar ratios shown in Table 1 are the copolymerization ratios of the repeating units derived from the respective monomers described in the category column. In Table 1, "-" indicates that the repeating unit is not used.

(Examples 1 to 39 and Comparative Examples 1 to 6)

(1) Preparation of Photosensitive Resin Composition

The components shown in Table 2 below were mixed. Here, as to the binder polymer, any of Polymers A-1 to A-29 shown in Table 3 below was used. For Comparative Example 3, the composition described in Example 1 of Japanese Patent No. 4302178 was employed.

The mixed components were made into a homogeneous solution and then filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to prepare photosensitive resin compositions of Examples and Comparative Examples. Using the photosensitive resin compositions of the obtained examples and comparative examples, evaluation described later was carried out. The evaluation results are shown in Tables 3 and 4.

[Table 2]

The abbreviations in Table 2 are as follows.

B1: CGI1397 (the following compound, Chiba Specialty Chemicals)

B2:? - (p-toluenesulfonyloxyimino) phenylacetonitrile (synthesis method is as shown below)

B3: Oxime sulfonate compound synthesized by the following synthesis method

B4: The structure shown below (synthesized by the method described in Chem. Commun., 2009, vol.7, p.827)

B5: The structure shown below (synthesized by the method described in US4329300A1)

F1: 9,10-dibutoxyanthracene (DBA) (9,10-dibutoxyanthracene, available from Kawasaki Chemical)

I1: 1,5-diazabicyclo [4.3.0] -5-nonene, manufactured by Tokyo Kasei K.K., D1313

I2: 2,4,5-triphenylimidazole (T0999, manufactured by TOKYO KASEI KABUSHIKI KAISHA)

E5: EPICLON EXA-4816 (epoxy equivalent: 403 g / eq)) D1: NIKARAKU MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)

E9: JER157S65 (manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: 200 to 220 g / eq)

J1: Compound W-3 shown below

H1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

C1: Propylene glycol monomethyl ether acetate

&Lt; Synthesis method of B2 &

Α- (p-toluenesulfonyloxyimino) phenylacetonitrile was synthesized according to the method described in paragraph 0108 of Japanese Patent Application No. 2002-528451.

&Lt; Synthesis method of B3 &

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

Acetic acid (7.3 g) and a 50% hydroxylamine aqueous solution (8.0 g) were added to the resulting suspension of the 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 mixture was heated to room temperature and reacted for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered out and then slurry was rinsed with methanol (20 mL), followed by filtration and drying to obtain B3 (2.3 g).

In addition, ¹ H-NMR spectrum of the B3 (300M㎐, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 ( (d, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d.1H), 5.6

&Lt; Evaluation of Photosensitive Resin Composition >

(1) Evaluation of sensitivity (without PEB)

The photosensitive resin composition was spin-coated on a silicon wafer having a silicon oxide film and then baked on a hot plate at 90 캜 for 120 seconds to form a coating film having a thickness of 4 탆.

Next, using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.), exposure was performed through a predetermined mask. The substrate was allowed to stand at room temperature for 10 minutes after the exposure, and then developed with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide at 23 占 폚 for 60 seconds by the liquid method, and further rinsed with ultra pure water for 45 seconds. With these operations, the optimum exposure amount (Eopt) when resolving a line-and-space of 10 mu m at a ratio of 1: 1 was taken as sensitivity. The smaller the sensitivity, the higher the sensitivity can be. In particular, it is preferable that the sensitivity is lower than 70 mJ / cm 2. Also, PEB is not implemented.

(2) Evaluation of taper angle and evaluation of pattern profile

The photosensitive resin composition was spin-coated on a silicon wafer having a silicon oxide film, and then prebaked on a hot plate at 90 캜 for 120 seconds to form a coating film having a thickness of 4 탆.

Next, an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.) was used to expose an integrated dose of 70 mJ / cm 2 through a predetermined mask. The substrate was allowed to stand at room temperature for 10 minutes after the exposure, and then developed with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide at 23 占 폚 for 60 seconds by the liquid method, and further rinsed with ultra pure water for 45 seconds. Next, a two-stage baking treatment (first stage: 140 DEG C, 30 minutes, second stage: 230 DEG C, 60 minutes) was performed and firing was performed.

Thereafter, a cross section of a line and space pattern of 10 mu m was observed with a scanning electron microscope (SEM), and the taper angle was measured.

In addition, the profile shape was evaluated based on the taper angle and the rectangularity of the whole. As the profile is closer to a rectangle, a structure of a desired shape (rectangular shape) can be laminated on the resist, if the resist is a MEMS resist. Further, if the resist is dry etching, the etch material can be precisely processed in the dry etching process. It is judged that evaluation points 3 to 5 are practically usable and problem-free level. An image of the shape is shown in Fig.

Further, in this evaluation, since it is aimed to form a rectangular line and space pattern, a high taper angle is judged to be excellent as described below. However, when the desired pattern is different, it is not necessarily rectangular.

5: a rectangular or nearly rectangular profile having a line section taper angle of 80 DEG to 90 DEG

4: a profile close to a rectangle whose taper angle of the line section is not less than 70 ° and less than 80 °

3: Profile of a trapezoid with a line section taper angle of 60 ° or more and less than 70 °

2: Profile having a line section taper angle of 40 ° or more and less than 60 °

1: Profile with a line section taper angle less than 40 °

(3) Evaluation of drug resistance

The film thickness (T1) of the cured film produced in the same process as the pattern profile evaluation was measured. Then, the substrate on which the cured film was formed was immersed in a 5% oxalic acid aqueous solution at 40 DEG C for 10 minutes. The film thickness t1 of the cured film after immersion was measured and the film thickness change rate {| t1-T1 | / T1} x 100 [%] by immersion was calculated. It is judged that evaluation points 3 to 5 are practically usable and problem-free level.

5: Film thickness change was less than ± 1%

4: Film thickness change was within ± 1% and less than 5%

3: Film thickness variation was within ± 5% and less than 10%

2: Film thickness change was more than ± 10%

1: Peeling was confirmed

(4) Evaluation of development defects

The photosensitive resin composition was spin-coated on a silicon wafer having a silicon oxide film, and then prebaked on a hot plate at 90 캜 for 120 seconds to form a coating film having a thickness of 4 탆.

Next, an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.) was used to expose an integrated dose of 70 mJ / cm 2 through a predetermined mask. The substrate was allowed to stand at room temperature for 10 minutes after the exposure, and then developed with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide at 23 占 폚 for 60 seconds by the liquid method. The developed substrate was observed with an optical microscope, and the number of development defects was counted.

5: 0 defects in developing / wafer

4: 1 to 3 development defects / wafer

3: development defects 4 to 10 / wafer

2: 11 to 20 development defects / wafer

1: 21 defects / wafer or more

[Table 3]

In Comparative Example 3, the photosensitive layer described in Example 1 of Japanese Patent No. 4302178 was employed.

(2) Evaluation of taper angle and pattern profile, and (5) Preparation of MEMS shutter display and evaluation of operation were carried out in the same manner as in Example 31, using the photosensitive resin composition of Example 3.

[Table 4]

(2) Evaluation of taper angle and pattern profile, (3) Evaluation of taper angle and pattern profile, (3) Evaluation of taper angle and pattern profile, (3) ), Evaluation of chemical resistance, and (4) evaluation of development defects.

[Table 5]

As is apparent from the above table, the photosensitive resin composition using the acrylic resin used in the present invention is excellent in sensitivity, close to a taper angle of 90 占 and close to a rectangle or a rectangle, I could.

In particular, when the binder polymer having a weight average molecular weight Mw of more than 5000 was used, the effect of the present invention was more effectively exhibited.

10: substrate
12: Pattern
14: center point between the top of the film and the substrate
θ: Taper angle

Claims (22)

Insoluble or poorly soluble in an alkali developing solution containing a carboxyl group at the end of the main chain (main chain) and containing a repeating unit having a cyclic ether group of a 3-membered ring and / or a 4-membered ring, Wherein the acrylic resin is soluble in an alkali developing solution. The method according to claim 1,
Wherein the acrylic resin is a repeating unit having a cyclic ether group of a 3-membered ring and / or a 4-membered ring represented by the general formula (1).
In general formula (1)

(1), R ¹ represents a hydrogen atom or an alkyl group, L represents a divalent linking group, R ² to R ⁴ each represent a hydrogen atom, an alkyl group, or a phenyl group, n represents 1 or 2, R ² , R ³ or R ⁴ may be bonded to a substituent group of L to form a ring) 3. The method according to claim 1 or 2,
Wherein the acrylic resin has a weight average molecular weight of 5000 or more. 3. The method according to claim 1 or 2,
Wherein the acrylic resin has a repeating unit having a carboxyl group or a residue protected with an acid-decomposable group by a phenolic hydroxyl group, in addition to the repeating unit having a cyclic ether group of the 3-membered ring and / or the 4-membered ring. 3. The method according to claim 1 or 2,
Wherein the positive photosensitive resin composition further contains a photoacid generator. 6. The method of claim 5,
Wherein the photoacid generator is an onium salt and / or oxime sulfonate. 3. The method according to claim 1 or 2,
A positive photosensitive resin composition further comprising a crosslinking agent. 3. The method according to claim 1 or 2,
Wherein the positive photosensitive resin composition further contains a solvent. 3. The method according to claim 1 or 2,
Wherein the acrylic resin has a weight average molecular weight of 5000 or more and has a repeating unit having a carboxyl group or a residue protected with an acid-decomposable group by a phenolic hydroxyl group in addition to the repeating unit having a cyclic ether group of the 3-membered ring and / A positive photosensitive resin composition. 3. The method according to claim 1 or 2,
Wherein the acrylic resin further contains a photoacid generator, and the weight average molecular weight of the acrylic resin is 5000 or more. A cured film obtained by curing a positive photosensitive resin composition according to any one of claims 1 to 3 by applying at least one of light and heat. 12. The method of claim 11,
A cured film which is an interlayer insulating film. (1) a step of applying the positive photosensitive resin composition according to any one of claims 1 to 3 on a substrate,
(2) a step of removing the solvent from the applied positive photosensitive resin composition,
(3) a step of exposing the positive photosensitive resin composition from which the solvent has been removed to actinic radiation,
(4) a step of developing the exposed positive photosensitive resin composition with an aqueous developer, and
(5) A post-baking step of thermally curing the developed positive photosensitive resin composition. 14. The method of claim 13,
Wherein the developing step is performed after the exposure in the exposure step without performing the heat treatment. 3. The method according to claim 1 or 2,
A positive type photosensitive resin composition for an etching resist. 3. The method according to claim 1 or 2,
A positive photosensitive resin composition for a structural member for MEMS. A film forming step of removing the solvent from the positive photosensitive resin composition according to claim 1 or 2 to form a film,
An exposure step of exposing the film to a pattern by an actinic ray,
A developing step of developing the exposed film with an aqueous developing solution to form a pattern, and
And a baking step of heating the pattern. 18. The method of claim 17,
And a post-exposure step of exposing the pattern by an actinic ray before the baking step after the development step. A step of fabricating a structure by using the pattern produced by the pattern forming method according to claim 17 as a sacrificial layer for laminating the structure, and
And removing the sacrificial layer by a plasma treatment. A step of performing dry etching using the pattern produced by the pattern forming method according to claim 17 as a resist for dry etching,
And removing the pattern by a plasma treatment or a chemical treatment. A step of performing wet etching using the pattern produced by the pattern forming method according to claim 17 as a resist for wet etching, and
And removing the pattern by a plasma treatment or a chemical treatment. A process for producing a positive photosensitive resin composition according to any one of claims 1 to 3, which comprises preparing an acrylic resin by using a chain transfer agent having a carboxyl group in polymerization of a polymerizable monomer or by using a polymerization initiator having a carboxyl group .

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