KR101772945B1 - Photosensitive resin composition, cured film, method for producing cured film, organic el display device and liquid crystal display device - Google Patents

Abstract

Disclosed is a photosensitive resin composition which is excellent in storage stability, sensitivity and tolerance of a solvent removal process of a photosensitive resin composition, and which gives a cured film excellent in transparency and solvent resistance. Another object of the present invention is to provide an organic EL display device and a liquid crystal display device which are provided with a cured film formed of the photosensitive resin composition as an interlayer insulating film and have high reliability and productivity.
(A) a monomer unit (1) in which a carboxyl group is protected with an acid-decomposable group and a monomer unit (2) in which a phenolic hydroxyl group is protected with an acid-decomposable group, And a monomer unit (3) having at least one of a cyclic ether residue of a 3-membered ring or a cyclic ether residue of a 4-membered ring, (B) a photoacid generator, and (C) .

Description

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

The present invention relates to a photosensitive resin composition, a cured film, a method of forming a cured film, an organic EL display device, and a liquid crystal display device.

In an organic EL display device, a liquid crystal display device, or the like, a patterned interlayer insulating film is provided. In forming the interlayer insulating film, the number of steps for obtaining a desired pattern shape is small, and furthermore, a sufficient level of flatness is obtained, so that a photosensitive resin composition is widely used.

A patterned interlayer insulating film or a planarizing film using the above photosensitive resin composition is required to have a highly reliable cured film having excellent solvent resistance in addition to transparency.

As such a photosensitive resin composition, for example, Patent Document 1 discloses a composition comprising (A) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) a radically polymerizable compound having an epoxy group, and (c) A resin soluble in an aqueous chain alkaline solution and (B) a radiation-sensitive (radiation-sensitive) acid-generating compound.

Examples of the photosensitive resin composition capable of securing the storage stability, sensitivity and high reliability of the formed cured film as the photosensitive resin composition include (meth) acrylic acid ester compounds having an acetal structure or a ketal structure, radically polymerizable compounds having an epoxy group, And a radiation-sensitive resin composition containing a resin that is a copolymer of another radical polymerizable compound and a compound that generates an acid having a pKa of 4.0 or less by irradiation with radiation (see, for example, Patent Document 2).

Japanese Patent Application Laid-Open No. 5-165214 Japanese Patent No. 4207604

The photosensitive resin composition described in Patent Document 1 has poor storage stability and has a problem of productivity of an organic EL display device or a product of a liquid crystal display device because of insufficient sensitivity.

In the photosensitive resin composition described in Patent Documents 1 and 2, when the solvent removal temperature and time fluctuate in the solvent removal step of removing the solvent from the applied photosensitive resin composition, the photosensitive resin composition is patterned The line width of the interlayer insulating film or the flattening film fluctuates greatly and the tolerance of the solvent removal process is insufficient. This proved to be a major problem in terms of product yield.

Therefore, at present, a photosensitive resin composition having high tolerance in the solvent removal step can not be obtained while securing storage stability, sensitivity, high reliability (transparency, solvent resistance, etc.) of the formed cured film.

A problem to be solved by the present invention is to provide a photosensitive resin composition which is excellent in storage stability, sensitivity and tolerance of a solvent removal step of a photosensitive resin composition, and which gives a cured film excellent in transparency and solvent resistance. Another object of the present invention is to provide an organic EL display device and a liquid crystal display device each having a cured film formed by the photosensitive resin composition as an interlayer insulating film and having high reliability and productivity.

It should be noted that the tolerance of the solvent removal process is not limited to the solvent removal which can form a good pattern without changing the line width even if the following (1) or (2) occurs in the solvent removal step of removing the solvent from the applied photosensitive resin composition: And has a tolerance in the process.

(1) Solvent removal time is shorter or longer than optimum time

(2) The solvent removal temperature is lower or higher than the optimum temperature

The above problem of the present invention is solved by the means described in the following <1>, <12> - <14>, <16> and <17>. <2> to <11> and <15> which are preferred embodiments are described below.

(A) a monomer unit (1) having a carboxyl group protected by an acid-decomposable group, a monomer unit (2) having a phenolic hydroxyl group protected by an acid-decomposable group, a cyclic ether residue of 3-membered ring or 4 (B) a photoacid generator, and (C) a solvent, wherein the photosensitive resin composition contains a monomer unit (3) having at least any one of a cyclic ether residue,

&Lt; 2 > A photosensitive resin composition according to < 1 >, which is a chemically amplified positive photosensitive resin composition,

<3> The method according to <3>, wherein the monomer unit (1) has at least one residue selected from the group consisting of a residue in which a carboxyl group is protected with a tertiary alkyl group, a residue in which a carboxyl group is protected with an acetal, and a residue in which a carboxyl group is protected with a ketal Wherein the monomer unit (2) is selected from the group consisting of a residue in which the phenolic hydroxyl group is protected with a tertiary alkyl group, a residue in which the phenolic hydroxyl group is protected with an acetal, and a residue in which the phenolic hydroxyl group is ketal protected The photosensitive resin composition according to < 1 > or &lt; 2 &gt;, which is a monomer unit having at least one selected residue,

The monomer unit (1) is preferably a copolymer wherein the carboxyl group is protected with a tertiary alkyl group represented by the following formula (a) and / or a carboxyl group is protected with an acetal or ketal represented by the following formula (b) And the monomer unit (2) is a residue in which the phenolic hydroxyl group is protected with a tertiary alkyl group represented by the following formula (a) and / or a residue in which the phenolic hydroxyl group is replaced with an acetal The photosensitive resin composition according to any one of < 1 > to < 3 >, wherein the photosensitive resin composition has a ketal-

In formula (a), R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring.

In the formula (b), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, but R ⁴ and R ⁵ do not form a hydrogen atom together, R ⁶ represents an alkyl group, and R ⁴ or R ⁵ and R &lt; ⁶ &gt; may be connected to form a cyclic ether.

<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the monomer unit (3) has a residue selected from the group consisting of the following formulas (3a) and (3b)

R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represents a hydrogen atom or an alkyl group, and R ^1b and R ^6b independently represent a hydrogen atom or an alkyl group, An atom, a halogen atom, an alkyl group, or an aryl group.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the photoacid generator (B) is a compound which generates an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more and 450 nm or less,

<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the photoacid generator (B) is a compound having an oxime sulfonate residue represented by the following formula (4)

In the formula (4), R ⁵ represents an alkyl group or an aryl group.

<8> The photosensitive resin according to any one of <1> to <7>, wherein the photo acid generator (B) is a compound represented by formula (OS-3), formula (OS- The composition,

Expression (OS-3) ~ formula (OS-5) of, R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ² are, each independently, a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ Each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, In the formula (OS-4), m represents an integer of 0 to 6, and in the formula (OS-5), m represents an integer of 0 to 4.

<9> The photosensitive resin composition according to any one of <1> to <7>, wherein the photoacid generator (B) is a compound represented by the following formula (5)

Equation (5) of, R ⁵ is, represents an alkyl group or an aryl group, X is an alkyl group, an alkoxy group, or a halogen atom, m is, as an integer of 0~3, m is 2 or 3, The plural Xs may be the same or different.

<10> The photosensitive resin composition according to any one of <1> to <9>, further containing (D) an antioxidant,

<11> The photosensitive resin composition according to any one of <1> to <10>, further comprising (E) a crosslinking agent,

<12> A photosensitive resin composition according to any one of <1> to <11>, wherein the cured film formed by imparting light and /

(1) a step of applying the photosensitive resin composition described in any one of <1> to <11> on a substrate, (2) a solvent removing step of removing the solvent from the applied photosensitive resin composition, (3) (4) a developing step of developing with an aqueous developing solution; and (5) a post-baking step of thermally curing. The method for forming a cured film,

<14> A cured film formed by the method described in <13>

<15> A cured film according to <12> or <14> which is an interlayer insulating film,

The organic EL display device according to any one of < 16 > < 12 >, < 14 &

<17> A liquid crystal display device comprising a cured film according to any one of <12>, <14> and <15>.

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in storage stability, sensitivity and tolerance of a solvent removal step of a photosensitive resin composition, and which gives a cured film excellent in transparency and solvent resistance. In addition, it is possible to provide an organic EL display device and a liquid crystal display device which are provided with a cured film formed of the photosensitive resin composition as an interlayer insulating film and have high reliability and productivity.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.
2 is a conceptual diagram showing an example of the configuration of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.

The photosensitive resin composition of the present invention comprises (A) a monomer unit (1) in which a carboxyl group is protected with an acid-decomposable group, a monomer unit (2) in which a phenolic hydroxyl group is protected with an acid-decomposable group and a monomer unit (B) a photoacid generator, and (C) a monomer containing a monomer unit (3) having at least one of a cyclic ether residue or a cyclic ether residue of a 4-membered ring And a solvent.

Hereinafter, each of the components represented by (A) to (C) is also referred to as "(A) component" to "(C) component".

The photosensitive resin composition of the present invention is a positive photosensitive resin composition.

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

It is preferable that the photosensitive resin composition of the present invention does not contain a 1,2-quinonediazide compound as a photoacid generator sensitive to an actinic ray. The 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is necessarily 1 or less.

On the other hand, the photoacid generator (B) used in the present invention acts as a catalyst for deprotection of an acid-protected acid generated in response to an actinic ray, Contributing to the deprotection reaction, the quantum yield exceeds 1, for example, becomes a large value such as several powers of 10, and high sensitivity is obtained as a result of so-called chemical amplification.

Further, from the viewpoint of the solvent resistance, the photosensitive resin composition of the present invention preferably further contains a crosslinking agent (E) described later.

By containing the components (A) to (C), the photosensitive resin composition of the present invention is excellent in storage stability, has high sensitivity, and is a photosensitive resin composition excellent in tolerance in a solvent removal step. Further, it is possible to provide a photosensitive resin composition which can obtain a cured film excellent in solvent resistance and heat-resistant transparency.

Hereinafter, the present invention will be described in detail.

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). Here, the permissible substituent is inert, does not change the original chemical function of the compound containing the specific group, and examples of the permissible substituent include a halogen atom, an alkoxy group and a hydroxyl group.

In the present invention, "(meth) acrylic acid ester" means an acrylic acid ester and / or methacrylic acid ester. (Meth) acrylic acid &quot; and the like.

In the present invention, "lower limit to upper limit" in the numerical range indicates "lower limit and higher limit, lower limit" unless otherwise specified. That is, it means a numerical range including a lower limit and an upper limit which are end points.

(A) Copolymer

The copolymer (A) contained in the photosensitive resin composition of the present invention is preferably a copolymer

(1): a monomer unit in which the carboxyl group is protected with an acid-decomposable group (hereinafter also referred to as monomer unit (1)),

(2): a monomer unit in which the phenolic hydroxyl group is protected with an acid-decomposable group (hereinafter also referred to as monomer unit (2)),

(3): a monomer unit having at least any one of a cyclic ether residue of a 3-membered ring and a cyclic ether residue of a 4-membered ring (hereinafter also referred to as a monomer unit (3)

&Lt; / RTI &gt;

The copolymer (A) may have the above monomer unit (1) to monomer unit (3) as essential components and may have other monomer unit (4). From the viewpoint of achieving the effect of the present invention, the ratio of the monomer units (1) to the monomer units (3) in the (A) copolymer is preferably 60% by mole or more based on the total monomer units of the copolymer , And more preferably 80 mol% or more.

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

In the copolymer of the component (A), introduction of the monomer unit (1), the monomer unit (2) and the monomer unit (3) into the copolymer (A) Both of these methods may be used together.

In the polymerization method, an ethylenically unsaturated compound having a carboxyl group protected by an acid-decomposable group, an ethylenically unsaturated compound having a phenolic hydroxyl group protected by an acid-decomposable group and an ethylenically unsaturated compound having an epoxy group and / or an oxetanyl group Are mixed and subjected to addition polymerization to obtain a desired copolymer.

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

The acid-decomposable group of the (A) copolymer represents a functional group capable of decomposing in the presence of an acid. That is, a monomer unit having a carboxyl group-protected residue by an acid-decomposable group is a monomer unit in which a carboxyl group can be produced by decomposition of a protecting group by an acid and a phenolic hydroxyl group is protected by an acid-decomposable group, By which the phenolic hydroxyl group can be generated.

In the present invention, the (A) copolymer is preferably a resin that is alkali-insoluble and becomes alkali-soluble when the acid decomposable group of the monomer unit (1) and the monomer unit (2) is decomposed. The term "alkali solubility" in the present invention means that the coating film (thickness: 3 μm) of the compound (resin) formed by applying the solution of the compound (resin) on a substrate and heating the same at 90 ° C. for 2 minutes at 23 ° C. Refers to a dissolution rate in an aqueous solution of 0.4% tetramethylammonium hydroxide in an aqueous solution of the compound (resin) in an aqueous solution of the compound Refers to a dissolution rate of a coating film (thickness 3 占 퐉) of the compound (resin) formed by heating in an aqueous solution of 0.4% tetramethylammonium hydroxide at 23 占 폚 of less than 0.005 占 퐉 / second.

The above-mentioned (A) copolymer does not exclude the introduction of an acidic group, but may contain other monomer units (4) having a carboxyl group, a carboxylic acid anhydride residue and the like, as long as the whole copolymer (A) remains alkali- And the like.

The (A) copolymer is preferably a polymer of addition polymerization type, more preferably a polymer containing monomer units derived from (meth) acrylic acid and / or an ester thereof. It may also contain monomer units other than the monomer units derived from (meth) acrylic acid and / or esters thereof, for example, monomer units derived from styrene, monomer units derived from vinyl compounds, and the like.

The (A) copolymer preferably contains 50 mol% or more of monomer units derived from (meth) acrylic acid and / or its ester, relative to all monomer units in the polymer, and more preferably 90 mol% or more (Meth) acrylic acid and / or an ester thereof, and it is particularly preferable that the polymer is a polymer comprising only monomer units derived from (meth) acrylic acid and / or an ester thereof.

The "monomer unit derived from (meth) acrylic acid and / or its ester" is also referred to as "acrylic monomer unit".

Hereinafter, each of the monomer unit (1), the monomer unit (2) and the monomer unit (3) will be described.

(1) a monomer unit (monomer unit (1)) in which the carboxyl group has a moiety protected with an acid-

Examples of the monomer unit having a carboxyl group-protected residue with an acid-decomposable group include a monomer unit in which a carboxyl group of a monomer unit having a carboxyl group is protected with an acid-decomposable group, specifically, a monomer unit derived from (meth) acrylic acid, And monomer units protected with an acid decomposer. This will be described in detail below.

(1-1) Monomer unit having a carboxyl group

Examples of the monomer unit having a carboxyl group include a monomer unit derived from an unsaturated carboxylic acid having at least one carboxyl group in a 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 monomer unit having a carboxyl group, those exemplified below are 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 to obtain the monomer unit 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, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono Oxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like.

Further, the unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymer thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate 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, in order to form the monomer unit (1-1) having a carboxyl group, it is preferable to use acrylic acid, methacrylic acid, or an anhydride of an unsaturated polycarboxylic acid or the like and use acrylic acid or methacrylic acid .

The monomer unit (1-1) having a carboxyl group may be composed of one kind alone, or may be composed of two or more kinds.

(1-2) a monomer unit having an ethylenic unsaturated group and an acid anhydride moiety together

The monomer unit (1-2) having both an ethylenic unsaturated group and an acid anhydride residue is preferably a unit derived from a monomer obtained by reacting a hydroxyl group present in a monomer unit having an ethylenic unsaturated group 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.

The monomer for forming a monomer unit having a hydroxyl group and an ethylenic unsaturated group is not particularly limited and may be appropriately selected from known monomers.

The reaction rate of the acid anhydride to the hydroxyl group is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, from the viewpoint of developability.

(1-3) a monomer unit having a carboxyl group protected with an acid-decomposable group

The monomer unit in which the carboxyl group has a moiety protected by an acid-decomposable group is a monomer unit having a moiety in which the carboxyl group described in (1-1) or (1-2) above is protected by an acid-decomposable group described in detail below.

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 so far, and there is no particular limitation.

Conventionally, examples of the acid decomposable group include groups which are relatively easily decomposable by an acid (for example, an acetal functional group such as a tetrahydropyranyl group) or groups which are relatively difficult to decompose by an acid (for example, a t- t-butyl functional group such as t-butyl carbonate group) are known.

Among these acid decomposable groups, the basic properties of the resist, particularly the sensitivity and pattern shape, are not particularly limited. Among these acid decomposable groups, a carboxyl group is protected with a tertiary alkyl group, a carboxyl group is protected with an acetal or a carboxyl group is protected with a ketal- And the storage stability of the photosensitive resin composition.

Among the acid decomposable groups, the carboxyl group is a residue protected with a tertiary alkyl group represented by the following formula (a), or an acetal or ketal-protected residue represented by the following formula (b) .

When the carboxyl group is a residue protected with a tertiary alkyl group represented by the following formula (a), the whole of the residue is a structure of -C (= O) -O-CR ¹ R ² R ³ , Is an acetal or ketal-protected residue represented by the following formula (b), the structure of the residue is -C (= O) -O-CR ⁴ R ⁵ (OR ⁶ ) as a whole.

In formula (a), R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring.

In the formula (a), 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 even 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 still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group and an alkoxy group. When R ¹ , R ² and R ³ are a haloalkyl group and 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 6 to 12 carbon atoms. Specific examples thereof include a phenyl group, an? -Methylphenyl group, a naphthyl group and the like, Examples of the alkyl group as a whole, that is, the aralkyl group, include a benzyl group, an a-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

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

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the alkyl group is a straight chain or branched chain alkyl group, Or a cycloalkyl group having 1 to 12 carbon atoms.

These substituents may be further substituted by the above substituents.

In the formula (a), 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 can be preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned.

Further, R ¹ , R ² and R ³ may combine with each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure in the case where 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, And examples thereof include a t-butyl group and a tetrahydropyranyl group.

As a preferable example of the tertiary alkyl ester structure of carboxylic acid, a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group and R ³ = benzyl group can be exemplified.

In formula (b), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, but R ⁴ and R ⁵ do not become a hydrogen atom together. R ⁶ represents an alkyl group. R ⁴ or R ⁵ and R ⁶ may be connected to form a cyclic ether.

In formula (b), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of linear, branched and cyclic. Here, both of R ⁴ and R ⁵ do not represent a hydrogen atom, and at least one of R ⁴ and R ⁵ represents an alkyl group.

The alkyl group is the same as the alkyl group represented by R ¹ to R ³ in formula (a), and the preferable range is also the same. It is preferable that either R ⁴ or R ⁵ is a hydrogen atom or a methyl group.

In the formula (b), R ⁶ represents an alkyl group, and the alkyl group is the same as the alkyl group represented by R ¹ to R ³ in formula (a), and the preferable range is also the same.

Examples of the radical polymerizable monomer used for forming the monomer unit having a moiety represented by the formula (b) include 1-alkoxyalkyl acrylate, 1-alkoxyalkyl methacrylate, 1- (haloalkoxy) alkyl Acrylate, 1- (haloalkoxy) alkyl methacrylate, 1- (aralkyloxy) alkyl acrylate, 1- (aralkyloxy) alkyl methacrylate, tetrahydropyran- Pyran-2-yl, acrylic tetrahydrofuran-2-yl, methacrylic acid tetrahydrofuran-2-yl and the like. Among them, preferred are 1-alkoxyalkyl acrylate, 1-alkoxyalkyl methacrylate, tetrahydropyran-2-yl acrylate, tetrahydropyran-2-yl methacrylate, tetrahydrofuran-2-yl acrylate, Furan-2-yl is preferable, and 1-alkoxyalkyl acrylate, 1-alkoxyalkyl methacrylate, tetrahydrofuran-2-acrylate, methacrylic acid tetrahydrofuran-2-yl is particularly preferable.

Specific examples of the 1-alkoxyalkyl acrylate and 1-alkoxyalkyl methacrylate include 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1- Methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1- , 1-benzyloxyethyl methacrylate, etc. These may be used alone or in combination of two or more.

As the radically polymerizable monomer used for forming the monomer unit having a moiety represented by the formula (b), commercially available ones may be used, or those synthesized by known methods may be used. For example, it can be synthesized by reacting (meth) acrylic acid with a vinyl ether in the presence of an acid catalyst as shown below.

R ¹¹ represents a hydrogen atom or an alkyl group, and the alkyl group is the same as the alkyl group represented by R ¹ to R ³ in formula (a). As R ¹¹ , a hydrogen atom or a methyl group is preferable.

R ¹² and R ¹³ are -CH (R ¹² ) (R ¹³ ), which is synonymous with R ⁵ in formula (b), and R ¹⁴ is the same as R ⁴ in formula (b) , R &lt; ¹⁵ &gt; is the same as R &lt; ⁶ &gt; in formula (b)

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.

Specific preferred examples of the monomer unit (1) include the following monomer units, but the present invention is not limited thereto.

The content of the monomer unit (1) among the monomer units constituting the component (A) is preferably from 3 to 70 mol%, more preferably from 5 to 60 mol%, from the viewpoint of excellent sensitivity and tolerance in the solvent removal step , More preferably from 10 to 50 mol%.

(2) a monomer unit (monomer unit (2)) having a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group

(2-1) Monomer unit having a phenolic hydroxyl group

The monomer unit having a phenolic hydroxyl group is preferably derived from an ethylenic unsaturated group and has a phenolic hydroxyl group. The introduction of the phenolic hydroxyl group into the monomer unit may be carried out by addition polymerization of an ethylenically unsaturated compound having a phenol-based hydroxyl group synthesized in advance, and addition of a monomer unit derived from an ethylenically unsaturated compound having a reactive side chain by a polymer reaction A phenolic hydroxyl group may be introduced into the side chain. Examples of the former include adduct polymerization of a hydroxystyrene monomer, and the latter examples include a monomer unit in which a phenolic hydroxyl group is introduced by a polymer reaction into a (co) polymer derived from glycidyl (meth) acrylate can do. Among these, monomer units derived from (meth) acrylate having? -Methylhydroxystyrene and a phenolic hydroxyl group are preferable from the viewpoint of transparency of the cured film.

Examples of the monomer unit having a phenolic hydroxyl group include a monomer unit constituting a hydroxystyrene-based or novolak-based resin, and among these, a monomer unit derived from -methylhydroxystyrene is preferable from the viewpoint of transparency .

Among the monomer units having a phenolic hydroxyl group, monomer units represented by the following formula (2) are preferable from the viewpoint of transparency and tolerance of the solvent removal step.

Formula (2) of, R ²⁰ is a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² represents a halogen atom or an alkyl group, a is an integer of 1~5, b is Represents an integer of 0 to 4, and a + b is 5 or less. When two or more R &lt; ²² &gt; are present, these R &lt; ²² &gt; may be the same or different.

In the formula (2), R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

R ²¹ represents a single bond or a divalent linking group which may have a substituent. The linking group is exemplified by an alkylene group having 1 to 10 carbon atoms, and the alkylene group may be either straight chain or branched chain. Specific examples of R ²¹ as the alkylene group include methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, tert-butylene, pentylene, have. Among them, R ²¹ is preferably a single bond or an alkylene group having 1 to 5 carbon atoms, more preferably a single bond, a methylene group or an ethylene group. Particularly, in the case of a single bond, the sensitivity can be improved and the transparency of the cured film can be improved, which is preferable.

The alkylene group may have a substituent, and examples of the substituent include a hydroxyl group, an alkoxy group and a halogen atom.

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

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

R ²² is preferably a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, chlorine atom, bromine atom, methyl group or ethyl group is preferable in view of easiness of production.

B represents an integer of 0 to 4, preferably 0.

As the linking group for R ²¹ , an alkyleneoxycarbonyl group and the like can be preferably exemplified (from the side of the main chain of the copolymer) in addition to the alkylene group. In this case, the monomer unit having a phenolic hydroxyl group is preferably represented by the following formula (3) .

In the formula (3), R ³⁰ is the same as R ²⁰ in the formula (2), R ³² is the same as R ²² in the formula (2), and a and b are as defined in the formula a and b, respectively. The preferred range is also the same.

In the formula (3), R ³³ represents a divalent linking group, and an alkylene group can be preferably exemplified. The alkylene group may be either linear or branched and preferably has 2 to 6 carbon atoms, and examples thereof include an ethylene group, a propylene group, an isopropylene group, an n-butylene group, a tert-butylene group, A neopentylene group, a hexylene group, and the like. The alkylene group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

Of these, R ^{33 is preferably an} ethylene group, a propylene group or a 2-hydroxypropylene group in view of the sensitivity and tolerance of the solvent removal step.

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

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

As the acid decomposable group, known ones can be used as the acid decomposable group in the positive resist for KrF and the positive resist for ArF, and are not particularly limited.

Conventionally, examples of the acid decomposable group include groups which are relatively easily decomposable by an acid (for example, an acetal functional group such as a tetrahydropyranyl group) or groups which are relatively difficult to decompose by an acid (for example, a t- t-butyl functional group such as t-butyl carbonate group) are known.

Of the acid-decomposable groups, the basic unit of the resist is a monomer unit in which a phenolic hydroxyl group is protected with a tertiary alkyl group, a phenolic hydroxyl group is protected with an acetal, or a phenolic hydroxyl group is protected with a ketal, In view of sensitivity and pattern shape and storage stability of the photosensitive resin composition.

Among the acid decomposable groups, the phenolic hydroxyl group is a residue protected with a tertiary alkyl group represented by the above formula (a), or an acetal or ketal-protected residue represented by the above formula (b) It is more preferable from the standpoint of tolerance.

When the phenolic hydroxyl group is a residue protected with a tertiary alkyl group represented by the above-mentioned formula (a), the total of the residues is a structure of -Ph-O-CR ¹ R ² R ³ (wherein Ph is phenyl And when the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the above formula (b), the residue entirely has the structure of -Ph-O-CR ⁴ R ⁵ (OR ⁶ ) .

These monomer units can be obtained, for example, by esterifying (meth) acrylic acid with an alcohol having a phenolic hydroxyl group to a monomer previously protected with a tertiary alcohol, acetal or ketal, and then copolymerizing with another monomer Can be introduced into the copolymer of component (A).

A known method may be employed in order to previously introduce the hydroxyl group into a tertiary alcohol or a monomer protected with acetal or ketal. For example, the hydroxyl group may be protected with an acetal or a ketal by reacting a (meth) acrylic acid ester having a phenolic hydroxyl group with a vinyl ether compound in the presence of an acid catalyst.

Preferred examples of the tertiary alkyl ether structure of the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group and R ³ = benzyl group.

Examples of the radical polymerizable monomer used for forming a monomer unit having a phenolic hydroxyl group having an acetal or ketal protected moiety include a 1-alkoxyalkyl protected product of hydroxystyrene, a tetrahydrofuran derivative of hydroxystyrene A tetrahydropyranyl protecting group of hydroxystyrene, a 1-alkoxyalkyl protecting group of? -Methylhydroxystyrene, a tetrahydropyranyl protecting group of? -Methylhydroxystyrene,? -Methylhydroxystyrene Hydroxyphenylmethacrylate, a tetrahydrofuranyl protected derivative of 4-hydroxyphenylmethacrylate, a tetrahydroxyphenylmethacrylate protected derivative of 4-hydroxyphenylmethacrylate, a tetrahydrofuranyl protected derivative of 4- (1-methacryloyloxymethyl) ester of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, a 1-alkoxyalkyl protected derivative of 4-hydroxybenzoic acid (1-methacryloyloxyethyl) ester of 4-hydroxybenzoic acid (1-methacryloyloxyethyl) ester, a tetrahydrofuranyl protected derivative of 4- (2-methacryloyloxyethyl) ester of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, a tetrahydrofuranyl protected derivative of 4- Alkoxyalkyl protecting group of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, tetrahydropyranyl protecting group of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester (3-methacryloyloxypropyl) ester of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, a tetrahydrofuranyl protected derivative of 4- Alkoxyalkyl protecting group, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxy Profile) and the tetra ester of tetrahydro pyranyl be protected, 4-hydroxy-benzoic acid (3-meth-yloxy-2-hydroxypropyl methacrylate with) tetrahydrofuranyl protection package of the ester and the like.

Among them, a 1-alkoxyalkyl protected form of 4-hydroxyphenyl methacrylate, a tetrahydropyranyl protected form of 4-hydroxyphenyl methacrylate, a tetrahydrofuranyl protected form of 4-hydroxyphenyl methacrylate , A 1-alkoxyalkyl protected product of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, a tetrahydropyranyl protected product of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) Alkoxyalkyl protected derivatives of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, tetrahydrofuranyl protected derivatives of 4-hydroxybenzoic acid (1-methacryloyloxyethyl) Tetrahydrofuranyl protected derivatives of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, tetrahydrofuranyl protected derivatives of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) (3-methacryloyloxypropyl) ester of 1-alkoxy (3-methacryloyloxypropyl) ester of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, tetrahydropyranyl protecting group of 4-hydroxybenzoic acid Alkoxyalkyl protected derivatives of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy- ) Tetrahydrofuranyl protecting agent of ester, and a tetrahydrofuranyl protected derivative of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester are preferable from the viewpoint of transparency.

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

As the radically polymerizable monomer used for forming the monomer unit (2), commercially available ones may be used, or those synthesized by known methods may be used. For example, a compound having a phenolic hydroxyl group can be synthesized by reacting 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.

The desired monomer unit (2) can be introduced into the copolymer of the component (A) by copolymerizing such an ethylenically unsaturated compound protected with an acid-decomposable group, preferably a derivative of a (meth) acrylic acid ester . Specific examples of the monomer unit (2) thus introduced include the following monomer units, but the present invention is not limited thereto.

The content of the monomer unit (2) in the monomer units constituting the component (A) is preferably from 3 to 70 mol%, more preferably from 5 to 60 mol%, from the viewpoint of sensitivity and tolerance in the solvent removal step , More preferably from 10 to 50 mol%.

(3) a monomer unit (monomer unit (3)) having at least one of a cyclic ether residue of a 3-membered ring or a cyclic ether residue of a 4-membered ring;

The copolymer (A) contains a monomer unit (monomer unit (3)) having at least one of a cyclic ether residue of a 3-membered ring or a cyclic ether residue of a 4-membered ring.

The cyclic ether residue of the three-membered ring is also called an epoxy group, and the cyclic ether residue of the four-membered ring is also called an oxetanyl group.

The monomer unit (3) having an epoxy group and / or an oxetanyl group is preferably a monomer unit having an alicyclic epoxy group and / or an oxetanyl group, and more preferably a monomer unit having an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring, and specific examples thereof include 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3-epoxycyclopentyl group, etc. .

The group having an oxetanyl group is not particularly limited as long as it has an oxetane group, and (3-ethyloxetan-3-yl) methyl group is preferably exemplified.

The monomer unit having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one monomer unit, and may contain at least one epoxy group and at least one oxetanyl group, two or more epoxy groups, And it is preferable to have one to three epoxy groups and / or oxetanyl groups in total, more preferably one or two epoxy groups and / or oxetanyl groups in total, more preferably epoxy group or oxetanyl group, More preferably has one aryl group.

Specific examples of the radical polymerizable monomer used for forming the monomer unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Epoxycyclohexyl methacrylate, glycidyl acrylate, glycidyl? -N-butyl acrylate,? -Epoxybutyl acrylate,? -Epoxybutyl methacrylate, Epoxy heptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton described in Nos. 0031 to 0035, and the like.

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

As specific examples of the radical polymerizable monomer used for forming the monomer unit having an epoxy group and / or an oxetanyl group, a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure are preferable.

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

It is preferable that the monomer unit (3) has a residue selected from the group consisting of the following formulas (3a) and (3b).

The fact that the monomer unit (3) has any of the three residues represented by the above formula (3a) ((3a-1), (3a-2), (3a-3) Quot; means a group having one or more hydrogen atoms removed from the structure.

It is more preferable that the monomer unit (3) has a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group and a 2,3-epoxycyclopentyl group.

R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represents a hydrogen atom or an alkyl group, and R ^1b and R ^6b independently represent a hydrogen atom or an alkyl group, An atom, a halogen atom, an alkyl group, or an aryl group.

In formula (3b), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms Alkyl group &quot;).

R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, more preferably a fluorine atom and a chlorine atom, and more preferably a fluorine atom.

The alkyl group may be any of linear, branched and cyclic, and may have a substituent. The straight chain and branched chain alkyl groups preferably have 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The cyclic alkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 5 to 7 carbon atoms. The linear or branched alkyl group may be substituted with a cyclic alkyl group, and the cyclic alkyl group may be substituted with a straight chain and / or branched chain alkyl group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.

Examples of the substituent which the alkyl group may have include a halogen atom and an aryl group. Examples of the substituent which the aryl group may have include a halogen atom and an alkyl group.

R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, More preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

As the residue represented by the formula (3b), a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

As specific preferred examples of the monomer unit (3), the following monomer units can be exemplified, but the present invention is not limited to these specific examples.

The content of the monomer unit (3) among the monomer units constituting the component (A) is preferably from 5 mol% to 60 mol%, more preferably from 10 mol% to 55 mol%, from the viewpoint of various resistance and transparency of the formed film , More preferably from 20 mol% to 50 mol%.

(4) Other monomer units (monomer unit (4))

The copolymer (A) may further contain a monomer unit (4) other than the above (1) to (3) (hereinafter also referred to as "(4) other monomer units") within the range not hindering the effect of the present invention .

(4) Examples of the radical polymerizable monomer used for forming other monomer units include the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623. (3) is excluded).

Among them, (meth) acrylic acid esters containing an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate and cyclohexyl acrylate, (meth) acrylic acid, methyl (meth) acrylate, -Hydroxyethyl, styrene and the like can be preferably exemplified. Among them, (meth) acrylic acid, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and styrene can be more preferably exemplified, and (meth) acrylic acid can be more preferably exemplified.

(4) When the other monomer unit has a free acid group, the free acid group is preferably a carboxyl group, and it is preferable that the free acid group does not have a phenolic hydroxyl group. That is, it is preferable not to use a monomer having a phenolic hydroxyl group which is not protected with an acid-decomposable group, such as hydroxystyrene, as a monomer used for forming (4) other monomer units.

These monomer units (4) may be used singly or in combination of two or more.

The content of the monomer unit (4) in the case where the monomer unit (4) is contained among all the monomer units constituting the copolymer (A) is preferably from 1 to 50 mol%, more preferably from 3 to 40 mol% , And particularly preferably from 5 to 30 mol%.

The weight average molecular weight of the copolymer (A) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000. The weight average molecular weight in the present invention is preferably a polystyrene reduced weight average molecular weight determined by gel permeation chromatography (GPC).

Various methods are also known for the synthesis of the above copolymer (A). For example, there are known methods for synthesizing the radical polymerizable (meth) acrylate copolymer (A) used for forming at least the monomer unit (1), the monomer unit Can be synthesized by polymerization of a radically polymerizable monomer mixture containing a monomer in an organic solvent using a radical polymerization initiator.

Preferable examples of the (A) copolymer used in the present invention are illustrated below, but the present invention is not limited thereto.

The weight average molecular weight of the (A) copolymer shown below is preferably 2,000 to 50,000.

Ethyl acetal protected product of 4-hydroxybenzoic acid (2-methacryloyloxymethyl) ester / 1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid / hydroxyethyl methacrylate

A protective group of ethyl acetal of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester / 1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid / hydroxyethyl methacrylate

Ethyl acetal protection of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid / hydroxyethyl methacrylate

A protective group of ethyl acetal of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid / Methacrylate

A protective group of ethyl acetal of 4-hydroxyphenyl methacrylate / 1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid / hydroxyethyl methacrylate

A protective group of ethyl acetal of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid / Methacrylate / methyl methacrylate

A tetrahydro pyranyl protected product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / glycidyl methacrylate / methacrylic acid / Roxy ethyl methacrylate

A protective group of ethyl acetal of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / tetrahydropyran-2-yl methacrylate / glycidyl methacrylate / methacrylic acid / Ethyl methacrylate

A protective group of ethyl acetal of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / methacrylic acid tetrahydrofuran-2-yl / glycidyl methacrylate / methacrylic acid / Ethyl methacrylate

Ethyl acetal protected product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / Acid / hydroxyethyl methacrylate

Ethyl acetal protected product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / 3- (methacryloyloxymethyl) Oxetane / methacrylic acid / hydroxyethyl methacrylate

Ethyl acetal protected product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / 3- (methacryloyloxymethyl) - oxetane / methacrylic acid / hydroxyethyl methacrylate / methyl methacrylate

A tetrahydrofuranyl protected product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / 3- (methacryloyloxymethyl) -3 -Ethyloxetane / methacrylic acid / hydroxyethyl methacrylate

A tetrahydrofuranyl protected product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / 3- (methacryloyloxymethyl) -3 -Ethyloxetane / methacrylic acid / hydroxyethyl methacrylate

(Methacryloyloxymethyl) -3-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester protected by ethyl acetal / methacrylic acid tetrahydropyran- Ethyl-oxetane / methacrylic acid / hydroxyethyl methacrylate

(3-methacryloyloxymethyl) -3-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester protected with ethyl acetal / methacrylic acid tetrahydrofuran- Ethyl oxetane / methacrylic acid / hydroxyethyl methacrylate

Ethyl acetal protection product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / tert-butyl methacrylate / 3- (methacryloyloxymethyl) / Methacrylic acid / hydroxyethyl methacrylate

Ethyl acetal protected product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / 3- (methacryloyloxymethyl) Butyl tert-butyl ester of oxetane / methacrylic acid / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl)

Ethyl acetal protected product of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester / 1-ethoxyethyl methacrylate / 3- (methacryloyloxymethyl) Oxetane / methacrylic acid / tert-butyl methacrylate

The (A) copolymers may be used alone or in combination of two or more.

The content of the copolymer (A) in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, more preferably 50 to 97% by weight, and more preferably 70 to 95% by weight based on the total solid content of the photosensitive resin composition. More preferably in weight%. When the content is within this range, the tolerance of the solvent removal step at the time of development becomes good. The solid content of the photosensitive resin composition means an amount excluding volatile components such as a solvent.

(B)

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

As the photoacid generator (also referred to as "component (B)") used in the present invention, a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or longer, preferably 300-450 nm is preferable, . In the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more by using in combination with a sensitizer can be preferably used in combination with a sensitizer.

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

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

Specific examples thereof include the following.

As trichloromethyl-s-triazine, there can be mentioned 2- (3-chlorophenyl) bis (4,6-trichloromethyl) (4-methylthiophenyl) bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy -? - styryl) bis , 2-piperonylbis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) bis (4,6- 6-trichloromethyl) -s-triazine and the like;

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

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate; and the like;

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

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

As the imide sulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hepto-5-endocarboximide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate, N -Hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidopropane sulfonate and the like;

As the oxime sulfonate compound, the following compounds.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate moiety, a compound containing an oxime sulfonate moiety represented by the formula (4) can be preferably exemplified.

In the formula (4), R ⁵ represents an alkyl group or an aryl group. The alkyl group in R &lt; ⁵ &gt; may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.

The alkyl group of R ⁵ is preferably an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including bridged alicyclic groups such as a 7,7-dimethyl-2-oxonorbornyl group) , Preferably a bicycloalkyl group, etc.).

As the aryl group for R ^5, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The compound containing an oxime sulfonate residue represented by the formula (4) is more preferably an oxime sulfonate compound represented by the following formula (5).

Equation (5) of, R ⁵ is and R ⁵ and consent of the formula (4), X is an alkyl group, an alkoxy group, or a halogen atom, m represents an integer of 0~3, m is 2 or 3, plural Xs may be the same or different.

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

The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

m is preferably 0 or 1.

In the formula (5), m is 1, X is a methyl group, X is a substituted position in an ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group Or a p-tolyl group is particularly preferable.

Specific examples of the oxime sulfonate compound include the following compounds (i), (ii), (iii), (iv) and the like, and they can be used singly or in combination of two or more kinds. have. The compounds (i) to (iv) are commercially available. It may also be used in combination with other types of (B) photoacid generators.

The compound containing the oxime sulfonate residue represented by the formula (4) is also preferably the photo acid generator represented by the formula (II).

In formula (II), 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, a cyano group 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, A phenyl group, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, An alkoxy group, 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 (II) include methyl, ethyl, n-propyl, n-butyl, n-octyl, N-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and 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.

As L, an integer of 0 to 2 is preferable, and 0 or 1 is particularly preferable.

Equation (Ⅱ) As a preferred embodiment of the compounds included in the photo-acid generator represented by, R ^3A is methyl group, ethyl group, n- propyl group, an n- butyl group, or represents a 4-tolyl, R ^4A is a hydrogen atom or a methoxy And L is a sun of 0 or 1.

Hereinafter, particularly preferred examples of the compound included in the photoacid generator represented by the formula (II) are shown, but the present invention is not limited thereto.

? - (methylsulfonyloxyimino) benzyl cyanide (R ^3A = methyl group, R ^4A = hydrogen atom)

? - (ethylsulfonyloxyimino) benzyl cyanide (R ^3A = ethyl group, R ^4A = hydrogen atom)

? - (n-propylsulfonyloxyimino) benzyl cyanide (R ^3A = n-propyl group, R ^4A = hydrogen atom)

? - (n-butylsulfonyloxyimino) benzyl cyanide (R ^3A = n-butyl group, R ^4A = hydrogen atom)

? - (4-toluenesulfonyloxyimino) benzyl cyanide (R ^3A = 4-tolyl group, R ^4A = hydrogen atom)

? - [(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = methyl group, R ^4A = methoxy group)

? - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = ethyl group, R ^4A = methoxy group)

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

? - [(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-butyl group, R ^4A =

? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = 4-tolyl group, R ^4A =

The compound containing an oxime sulfonate residue represented by the above formula (4) is also preferably a compound represented by the formula (OS-1).

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

X is ^{-O-, -S-, -NH-, -NR 5} -, -CH 2 -, -CR 6 H-, or, -CR ⁶ R ⁷ - represents a, R ⁵ ~R ⁷ is an alkyl group, or , And an aryl group.

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 functional groups 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).

In the formula (OS-2), R ¹ , R ² and R ²¹ to R ²⁴ are the same as those in the formula (OS-1), and preferred examples are also the same.

Of these, formula (OS-1) and the equation is R ¹ in (OS-2) a cyano group, or, more preferably an aryl group sun, and is represented by the expression (OS-2), R ¹ is a cyano group , A phenyl group or a naphthyl group is most preferable.

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

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

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

The oxime sulfonate residue-containing compound represented by the formula (4) is preferably an oxime sulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5).

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each of R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ represents independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, In the formula (OS-4), m represents an integer of 0 to 6, and in the formula (OS-5), m represents an integer of 0 to 4)

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

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

Examples of the substituent which the alkyl group in 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.

Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, N-decyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, A phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Of these, preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

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

Examples of the substituent which the aryl group in R ¹ may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group,

Examples of the aryl group for R ¹ include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, Phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group.

Among them, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group are preferable.

Among the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.

The substituent which R ¹ may have as a heteroaryl group may be a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, A sulfonyl group, and an alkoxysulfonyl group.

Of the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ may be at least one of the rings may be a heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be coordinated.

Examples of the heteroaryl group for R ¹ include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzoimidazole ring which may have a substituent A group in which one hydrogen atom is removed from the ring selected in the group.

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 the 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 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 in R ² may have a substituent.

Examples of the substituent which the alkyl group or the aryl group in R ² may have include a group such as the substituent which the alkyl group or aryl group in R ¹ may have.

The alkyl group in R ² is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent and more preferably an alkyl group having 1 to 6 carbon atoms in total which may have a substituent.

Specific examples of the alkyl group for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, A perfluorohexyl group, a chloromethyl group, a bromomethyl group, a methoxymethyl group, a benzyl group, a phenoxyethyl group, a methylthioethyl group, a naphthyl group, a naphthyl group, , A phenylthioethyl group, an ethoxycarbonylethyl group, a phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Among them, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s- , A benzyl group is preferable and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- butyl group, Propyl group, n-butyl group and n-hexyl group are more preferable, and methyl group is particularly preferable.

The aryl group in R ² is preferably an aryl group having a total of 6 to 30 carbon atoms which may have a substituent.

Specific examples of the aryl group for R ² include a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, Thiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group.

Among them, a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group are preferable.

Examples of the halogen atom in R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, a chlorine atom and a bromine atom are 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 ring member is a 5-membered ring or a 6-membered ring.

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

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

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

Examples of the substituent which the alkyl group in 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.

Examples of the alkyl group for R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- N-decyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, A phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Of these, preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

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

Examples of the substituent which the alkyloxy group of 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.

Examples of the alkyloxy group for R ⁶ include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, an ethoxyethyloxy group, a methylthioethyloxy group, A phenylthioethyloxy group, an ethoxycarbonylethyloxy group, a phenoxycarbonylethyloxy group, and a dimethylaminocarbonylethyloxy group.

Of these, methyloxy, ethyloxy, butyloxy, hexyloxy, phenoxyethyloxy, trichloromethyloxy or ethoxyethyloxy groups are preferred.

In the formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, .

Of the above-mentioned formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxycarbonyl group, a propyloxysulfonyl group and a butyloxysulfonyl group.

In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6 in the formulas (OS-3) to , m represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

The oximesulfonate residue-containing compound represented by the formula (4) is particularly preferably an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom or a lower alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, Methyl group)

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

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

R ⁸ in 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 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 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, either or both of the stereostructure (E, Z) of oxime may be used.

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.

In the photosensitive resin composition of the present invention, the photoacid generator (B) is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the copolymer (A) .

The photosensitive resin composition of the present invention may contain a photoacid generator other than the photoacid generator (B), if necessary, as a photoacid generator that is sensitive to an actinic ray, but it may contain a photoacid generator that does not contain a 1,2-quinonediazide compound . The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is always 1 or less and the sensitivity is low. On the other hand, in the case of the photoacid generator (B), the acid generated by the action of the actinic ray acts as a catalyst against the deprotection of the protected acidic group, so that the acid generated by the action of one photon activates a number of deprotection reactions And the quantum yield is greater than 1, for example, a large value such as several powers of 10, and it is presumed that a high sensitivity is obtained as a result of so-called chemical amplification.

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator (B) in order to accelerate the decomposition thereof.

The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator to generate electron transfer, energy transfer, heat generation, and the like. As a result, the photoacid generator decomposes by causing a chemical change to generate an acid.

Examples of preferred sensitizers include compounds having an absorption wavelength anywhere in the wavelength range of 350 nm to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Anthracene, xanthone, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, and the like), xanthone Thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, (For example, thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavine), acridones -Butyl-2-chloroacridone), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squalium), styryls, (For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizine-11-pne).

Among these sensitizers, polynuclear aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatic compounds are more preferable. Among the polynuclear aromatic compounds, an anthracene derivative is most preferable.

(C) Solvent

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

The photosensitive resin composition of the present invention is a photosensitive resin composition comprising the components (A) and (B) as essential components, the component (D) and / or the component (E) ) &Lt; / RTI &gt; solvent.

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.

As the solvent (C) used in the photosensitive resin composition of the present invention, for example,

(A) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;

(B) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether;

(C) 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;

(D) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

(E) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(F) 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;

(G) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

(A) 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;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

(Carboxy) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(K) 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;

(L) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, isobutyl lactate, isobutyl lactate, n-amyl lactate, and lactic acid /

(Par) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetic acid, ethyl propionate, n-propyl propionate, isopropyl propionate, n- 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;

(Lower) ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxypropionate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate;

(Er) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;

Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;

(More) lactones such as? -Butyrolactone.

These solvents may also contain, 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, Solvents such as octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may also be added.

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

As the solvent usable in the present invention, propylene glycol monoalkyl ether acetate is particularly preferable.

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, and most preferably 150 to 1,500 parts by weight per 100 parts by weight of the component (A) More preferable.

&Lt; Other components >

(D) an antioxidant, (E) a cross-linking agent, (C) an antioxidant, and (C) an antioxidant as described below as optional components, in addition to the components (A) F) a contact modifier, (G) a basic compound, (H) a surfactant, (I) a plasticizer, and (J) a thermal radical generator and a thermal acid generator, an ultraviolet absorber, a thickener, A known additive such as an inhibitor may be added.

(D) Antioxidants

The photosensitive resin composition of the present invention preferably contains (D) an antioxidant.

As the antioxidant (D), a known antioxidant may be contained. (D) the addition of an antioxidant can prevent the cured film from being colored, or can reduce the film thickness reduction due to decomposition, and has an advantage of being excellent in heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiosulfate, And a hydroxyamine derivative. Among them, a phenol-based antioxidant is particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used alone, or two or more kinds may be mixed and used.

Examples of commercially available phenolic antioxidants include ADEKA STOP AO-60 (manufactured by ADEKA), ADEKA STOP AO-80 (manufactured by ADEKA), Irganox 1098 (manufactured by Chiba Japan Co., ).

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

As the additives other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in "New developments of the polymer additive (Nikken Kogyo Shinbashi Co., Ltd.") may be added to the photosensitive resin composition of the present invention.

(E) Crosslinking agent

The photosensitive resin composition of the present invention preferably contains a crosslinking agent (E), if necessary.

As the crosslinking agent (E), for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond may be added. By adding the crosslinking agent (E), the cured film can be made into a stronger film.

&Lt; Compounds having two or more epoxy groups or oxetanyl groups in the molecule &

A compound having two or more epoxy groups or oxetanyl groups in a molecule is generally a compound called an epoxy resin, oxetane resin.

Specific examples of the compound containing two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin and the like.

These are available as commercial products. Examples of the bisphenol A epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Co., Ltd.), and the like can be used as the bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 JER152, JER154, JER157S65, and JER157S70 (all manufactured by Japan Epoxy Resins Co., Ltd.) (manufactured by Nippon Kayaku K.K.), phenol novolak type epoxy resin EPICLONN-740, EPICLONN-770 and EPICLONN-775 (manufactured by DIC Corporation), and EPICLONN-660, EPICLONN-665, EPICLONN- Examples of the aliphatic epoxy resin include ADEKARESINEP-4080S, EPICLONN-680, EPICLONN-690, EPICLONN-690, EPICLONN- 695 (manufactured by DIC Corporation), EOCN- EP-4085S (Manufactured by Daicel Chemical Industries, Ltd.), EP-4088S (manufactured by ADEKA, Inc.), Suloxide 2021P, Suloxide 2081, Suloxide 2083, Suloxide 2085, EHPE 3150, EPOLEADPB3600 and PB4700 . In addition, ADEKARESINEP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- , EPPN-502 (manufactured by ADEKA Co., Ltd.), and the like. These may be used alone or in combination of two or more.

Of these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin and phenol novolak type epoxy resin. Particularly, bisphenol A type epoxy resins, aliphatic epoxy resins and phenol novolak type epoxy resins are preferable.

As a specific example of the compound containing two or more oxetane groups in the molecule, Aromoxetane OXT-121, OXT-221, OX-SQ and PNOX (manufactured by DOA GOSEI CO., LTD.) Can be used.

The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to be added to the photosensitive resin composition is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the total amount of the component (A) .

<Crosslinking agent containing alkoxymethyl group>

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycolauryl and alkoxymethylated elements are preferable. These are obtained by converting methylol melamine, methylol benzoguanamine, methylol fatty acid glycoluril, or the methylol group of methylol moiety into an alkoxymethyl group, respectively. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of out-gas generation, , And particularly preferably a methoxymethyl group.

Of these crosslinking compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycolyuril are preferable crosslinking compounds, and from the viewpoint of transparency, alkoxymethylated glycolauryl 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, UFR65, 300 (manufactured by Mitsui Cyanamid Co.), Nigalak MX-750, -032, -706, -708, -40, -31, -270, -280, -290 , Nicalac MS-11, Nicalac MW-30HM, -100 LM, -390 (manufactured by Sanwa Chemical Co., Ltd.), and the like can be preferably used.

When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the amount of the alkoxymethyl group-containing crosslinking agent to be added is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the component (A) desirable. The addition in this range provides a favorable alkali solubility at the time of development and excellent solvent resistance of the film after curing.

&Lt; Compounds having at least one ethylenically unsaturated double bond >

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

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

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

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

These compounds having at least one ethylenic unsaturated double bond are used singly or in combination of two or more.

The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the component (A) Do. By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, (J) a heat radical generator is preferably added.

(F) Adhesion improver

The photosensitive resin composition of the present invention may contain (F) an adhesion improver.

The (F) adhesion improver that can be used in the photosensitive resin composition of the present invention can be obtained by reacting an inorganic substance to be a base material, 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 (F) 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,? -Methacryloxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Alkoxysilane, and vinyltrialkoxysilane.

Among 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 (F) 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 component (A).

(G) Basic compound

The photosensitive resin composition of the present invention may contain (G) a basic compound.

As the basic compound (G), any of those used as a chemically amplified resist may be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Examples of the aliphatic amine include aliphatic amines such as 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 heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, Benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8- 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, pyrrolidine, piperidine, piperazine, morpholine, 1,8-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. have.

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 usable in the present invention may be used singly or in combination of two or more kinds, but two or more kinds thereof are preferably used in combination, more preferably two kinds of them, and heterocyclic amines are substituted with 2 More preferably in combination.

The content of the (G) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.2 part by weight, per 100 parts by weight of the component (A).

(H) Surfactant

The photosensitive resin composition of the present invention may contain (H) a surfactant.

As the surfactant (H), any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Goeisha Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megapack (manufactured by DIC Corporation) (Manufactured by Asahi Glass Co., Ltd.) and PolyFox (manufactured by OMNOVA Co., Ltd.), and the like.

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

(Wherein R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ represents a hydrogen atom or a C1- P represents an alkylene group having 3 to 6 carbon atoms, p and q represent weight percentages indicating polymerization ratios, p represents a value of 10 to 80 wt%, q represents 20 wt% Or more and 90% or less by weight, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less)

It is preferable that L is a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, and an alkyl group having 2 or 3 carbon atoms More preferable. It is preferable that the sum (p + q) of p and q is p + q = 100, that is, 100% by weight.

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

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

The amount of the surfactant (H) added to 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, and even more preferably 0.01 to 1 part by weight based on 100 parts by weight of the component (A) It is more desirable to be negative.

(I) a plasticizer

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

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

The amount of the plasticizer (I) added to 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, per 100 parts by weight of the component (A).

(J) Thermal radical generator

The photosensitive resin composition of the present invention may contain (J) 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, (J) a thermal radical It is preferable to contain the generator.

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

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

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

As the thermal radical generator (J), one type may be used alone, or two or more types may be used in combination.

The amount of the heat radical generator (J) to be added to 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 copolymer (A) More preferably 0.5 to 10 parts by weight.

(Method of forming a cured film)

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

The method for forming a cured film of the present invention is characterized by including the following steps (1) to (5).

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

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

(3) an exposure process for exposing by an actinic ray

(4) a development step of developing with an aqueous developer

(5) Post-baking process for thermosetting

Each step will be described below in order.

(1), the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent.

In the solvent removing step (2), the solvent is removed from the coated film by reduced pressure (vacuum) and / or heating to form a dried coating film on the substrate.

In the exposure step of (3), an active ray having a wavelength of 300 nm or more and 450 nm or less is irradiated to the obtained coating film. In this step, (B) the photoacid generator is decomposed to generate acid. The acid-decomposable group in the monomer unit (1) and the monomer unit (2) contained in the (A) copolymer is hydrolyzed by the catalytic action of the generated acid to produce a carboxyl group and a phenolic hydroxyl group.

Post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) may be performed as needed in order to accelerate the hydrolysis reaction in the region formed by the acid catalyst. With PEB, the generation of a carboxyl group and a phenolic hydroxyl group from the acid decomposable group can be promoted.

The acid decomposable group in the monomer unit (1) and the monomer unit (2) in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to form a carboxyl group and a phenolic hydroxyl group A positive image can be formed by development without necessarily performing PEB.

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 80 占 폚.

(4), the free (liberated) carboxyl group and the polymer having a phenolic hydroxyl group are developed using an alkaline developer. A positive image is formed by removing the exposed region containing a resin composition having a carboxyl group and a phenolic hydroxyl group which is easily dissolved in an alkaline developing solution.

(1) and the monomer unit (2) by thermal decomposition of the acid-decomposable group in the post-baking step of the step (5) to produce a carboxyl group and a phenolic hydroxyl group, and an epoxy group and / or an oxetanyl group (A cyclic ether residue of a 3-membered ring and / or a cyclic ether residue of a 4-membered ring), whereby a cured film can be formed. This heating is preferably performed at a high temperature of 150 ° C or higher, more preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 250 ° C. The heating time can be appropriately set according to the heating temperature and the like, but it is preferably within a range of 10 to 90 minutes.

When a step of irradiating an entire surface of the development pattern with an actinic ray, preferably ultraviolet light, is carried out before the post-baking step, the cross-linking reaction can be promoted by an acid generated by actinic light irradiation.

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

&Lt; Method of producing photosensitive resin composition >

(A) to (C) are mixed in an arbitrary manner at a predetermined ratio, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which the component (A) or (B) is dissolved in advance in the solvent (C), and then mix them in a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered using a filter having a pore diameter of 0.2 mu m or the like.

<Coating Process and Solvent Removal Process>

A desired dry film can be formed by applying the resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate, a glass plate provided with a black matrix layer, a color filter layer and a transparent electroconductive circuit layer as required can be exemplified. 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. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, a large substrate refers to a substrate having a size of 1 m or more on each side.

The heating condition of the solvent removal step (2) is such that the acid decomposable group decomposes in the monomer unit (1) and the monomer unit (2) in the component (A) in the unexposed portion and the component (A) And it varies depending on the kind of each component and blending ratio, and is preferably about 80 to 130 DEG C for about 30 to 120 seconds.

&Lt; Exposure step and development step (pattern formation method) >

In the exposure step, an active ray is irradiated onto a substrate provided with a coating film through a mask having a predetermined pattern. After the exposure process, a heating process (PEB) is carried out if necessary, and in the development process, an exposed area is removed by using an alkaline developer to form an image pattern.

(436 nm), i-line (365 nm), h-line (405 nm), and the like can be used for the exposure by the active light beam, and a low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, chemical lamp, LED light source, Of an active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. If necessary, the irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

A basic compound is used for the developing solution used in the developing process. Examples of the basic compound 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 and a dipping method. After the development, a desired pattern can be formed by conducting water washing for 30 to 90 seconds.

&Lt; Post baking step (crosslinking step) >

For example, at a predetermined temperature, for example, 180 to 250 DEG C, for a predetermined time, for example, in a hot plate state, by using a heating apparatus such as a hot plate or an oven to a pattern corresponding to the unexposed region, (A) by decomposing the acid-decomposable group in the component (A) to generate a carboxyl group and a phenolic hydroxyl group by heating the mixture for 60 minutes and 60 minutes in an oven for 30 to 90 minutes to obtain an epoxy group and / A protective film or an interlayer insulating film excellent in heat resistance and hardness can be formed by reacting with the crosslinkable group and crosslinking. In addition, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

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

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

The exposure in the re-exposure step may be performed by the same means as in the exposure step, but in the re-exposure step, it is preferable to perform the whole exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention.

A preferable exposure amount of the re-exposure step is 100 to 1,000 mJ / cm &lt; ^{2 &} gt ;.

By the photosensitive resin composition of the present invention, an interlayer insulating film having excellent transparency can be obtained even when it is baked at a high temperature with excellent insulating properties. The interlayer insulating film formed using the photosensitive resin composition of the present invention is useful for an organic EL display device and a liquid crystal display device because it has high transparency and excellent physical properties of a cured film.

The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that they have a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention and may be various known organic EL displays Device or a liquid crystal display device.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned use, and can be used for various purposes. For example, in addition to a planarizing film and an interlayer insulating film, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, and a microlens provided on the color filter in the solid-state image pickup device can be used.

1 is a conceptual diagram showing an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

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

The planarization layer 4 is formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 2.

On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarization film 4 by being connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

An insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing this insulating film, a short circuit is formed between the first electrode 5 and the second electrode formed in the subsequent steps .

Although not shown in Fig. 1, a hole transport layer, an organic luminescent layer, and an electron transport layer are sequentially deposited by a desired pattern mask, then a second electrode made of Al is formed on the entire upper surface of the substrate, And an ultraviolet curing type epoxy resin are used to form an organic EL display device in which an active matrix type organic EL display device in which a TFT 1 for driving each organic EL element is connected to each organic EL element is sealed.

2 is a conceptual cross-sectional view showing an example of the liquid crystal display device 10 of the active matrix type. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel is a liquid crystal display panel in which all of the liquid crystal display panel 10 is disposed between two glass substrates 14, Elements of the TFT 16 corresponding to the pixel are disposed. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are arranged is provided.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

(Synthesis Example)

<Synthesis of phenol 1 (4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester]

20 ml of N, N-dimethylacetamide was added to a solution of 21 g of 4-hydroxybenzoic acid (2-hydroxyethyl) ester in 100 ml of acetonitrile while stirring, and 20 g of methacrylic chloride was further added. The reaction mixture was poured into ice water and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to obtain 4-hydroxybenzoic acid (2-methacryloyl Chloroyloxyethyl) ester.

<Synthesis of phenol 2 (4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester]

To a solution of 23 g of 4-hydroxybenzoic acid (3-hydroxypropyl) ester in 100 ml of acetonitrile was added 20 ml of N-methylpyrrolidone with stirring, and 16 g of methacrylic chloride was further added. The reaction mixture was poured into ice water, and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to obtain 4-hydroxybenzoic acid (3-methacryloyloxypropyl ) &Lt; / RTI &gt; ester.

<Synthesis of phenol 3 (4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester]

100 g of p-hydroxybenzoic acid, 100 g of glycidyl methacrylate and 9.7 g of tetrabutylammonium bromide were added to 250 ml of N-methylpyrrolidone and reacted with stirring at 90 DEG C for 6 hours, The crystals precipitated were collected by filtration and recrystallized from ethyl acetate / n-hexane to obtain 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester.

&Lt; Synthesis of protected phenol >

The phenol 1, 2, and 3 thus obtained and the phenol 4 described below were allowed to react with ethyl vinyl ether under an acid catalyst to obtain an ethyl acetal protective agent of a phenolic hydroxyl group (protected phenol 1, 2, 3, and 4 ).

In addition, the phenolic hydroxyl group of phenol 3 (4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester) is protected with tert-butyl by a well- Butyl protected product (protected phenol 3 ').

&Lt; Synthesis of protected carboxylic acid 1 >

Methacrylic acid was reacted with ethyl vinyl ether under acid catalysis to obtain 1-ethoxyethyl methacrylate (protected carboxylic acid 1).

&Lt; Synthesis of protected carboxylic acid 2: Synthesis of tetrahydrofuran-2-yl methacrylate (MATHF)

Methacrylic acid (86 g, 1 mole) was cooled to 15 占 폚 and camphorsulfonic acid (4.6 g, 0.02 mole) was added. 2,3-dihydrofuran (71 g, 1 mole, 1.0 equivalent) was added dropwise to the solution. After stirring for 1 hour, a saturated aqueous solution of sodium hydrogencarbonate (500 ml) was added, extracted with ethyl acetate (500 ml) and dried over magnesium sulfate. The insoluble material was filtered off and concentrated under reduced pressure at 40 ° C or lower to obtain a residue The yellow oily matter was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg as a colorless oil (Yield: 80%).

<Other Monomers>

Other monomers used for the copolymerization of the component (A) are exemplified below.

Phenol 4: 4-hydroxyphenyl methacrylate (manufactured by Showa Kobunshi Co., Ltd.)

t-BuMA: tert-butyl methacrylate

GMA: glycidyl methacrylate

M100: 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd.)

OXE-30: 3- (methacryloyloxymethyl) -3-ethyloxetane (Osaka Yuki Kagaku Kogyo Co., Ltd.)

MAA: methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

MMA: methyl methacrylate

St: Styrene

&Lt; Synthesis Example 1 (Synthesis of Resin 1) >

As the monomer component, protected phenol 1 (64.47 g, 0.2 mol), protected carboxylic acid 1 (31.64 g, 0.2 mol), GMA (56.86 g, 0.4 mol), MAA (8.61 g, 0.1 mol) and HEMA , 0.1 mole), V-601 (dimethyl-2,2'-azobis (2-methylpropionate), Wako Pure Chemical Industries, Ltd., 7.50 g) was used as a radical polymerization initiator, These were polymerized in a solvent PGMEA (propylene glycol monomethyl ether acetate, 407.38 g) for 6 hours to obtain a PGMEA solution (solid concentration: 30% by weight) of the resin 1. The polymerization temperature was adjusted to 70 ° C.

The weight average molecular weight of the obtained Resin 1 as measured by GPC was 15,000.

Synthesis Examples 2 to 8 and 10 to 15 (Synthesis of Resins 2 to 8 and Resins 10 to 15)

Synthesis was carried out by the same method as in Synthesis Example 1 at the monomer species and the addition amount shown in Tables 1 and 2 as monomer components. The weight-average molecular weight of the obtained resin was measured by GPC and is shown in Table 1 and Table 2. [

&Lt; Synthesis Example 9 (Synthesis of Resin 9) >

Synthesis was carried out in the same manner as in Synthesis Example 1 except that a radical polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 2.50 g) was used as the monomer component and the addition amount as shown in Table 1 as a monomer component . The weight average molecular weight of Resin 9 thus obtained was 32,000.

(Example 1)

&Lt; Preparation of Photosensitive Resin Composition >

The following composition was dissolved and mixed, and the mixture was filtered through a 0.2 占 퐉 polytetrafluoroethylene filter to obtain a photosensitive resin composition of Example 1.

· [(A) resin] as

The PGMEA solution (100.0 parts by solid content) of the resin 1 obtained by the above-

· [(B) photoacid generator]

B-12.5 part

· As [Others]

Adhesion improver (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., the following structure) 0.5 part

0.02 part of a surfactant (PolyFoxPF-6320, manufactured by OMNOVA)

(2.0 parts of an antioxidant (ADEKA STOP AO-60, manufactured by ADEKA, the following structure)

(Cross-linking agent E-1 (MX-270, manufactured by Sanwa Chemical Co., Ltd., 2.0 parts)

(5.0 parts of cross-linking agent E-2 (JER157S65, manufactured by Japan Epoxy Resin Co., Ltd.)

(Basic compound G-1: 1,8-diazabicyclo [5.4.0] undecene-7, manufactured by Tokyo Chemical Industry Co., Ltd.)

(Examples 2 to 49 and Comparative Examples 1 to 3)

The photosensitive resin compositions of Examples 2 to 18 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the respective component amounts of Example 1 were changed as shown in Table 1 below.

For Example 15, a photosensitive resin composition was prepared in the same manner as in Example 8 except that the surfactant was changed to W-3 (the following structure).

For Examples 16 and 17, antioxidant and crosslinking agent E-1 in parentheses described in the preparation of the photosensitive resin composition of Example 1 were also added as shown in Table 1 to prepare a photosensitive resin composition.

For Examples 5 to 17 and 45 and Comparative Example 1, B-2 was used instead of the photo acid generator B-1 as shown in Tables 1 and 2.

For Example 18, B-3 was used in place of the photoacid generator B-1, and B-4 as the sensitizer was added in the same amount as in Example B-3, as shown in Table 1.

For Examples 19 to 31, 46 and 48, B-5 was used in place of photoacid generator B-1, and B-4 as a sensitizer was further added in the same amount as B-5 as shown in Table 2 .

For Examples 32 to 44, 47 and 49, B-6 was used in place of the photo acid generator B-1 as shown in Table 2.

For Examples 19 to 49, as shown in Table 2, the basic compound G-1 in the parentheses described in the preparation of the photosensitive resin composition of Example 1 and, if necessary, the crosslinking agent E-2 were also added, A composition was prepared.

In Comparative Examples 2 and 3, the photosensitive resin compositions described in Example 1 of Patent Documents 1 and 2 were prepared and evaluated.

The respective materials used were as follows.

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

B-2: CGI-1397 (manufactured by Ciba Specialty Chemicals)

B-3: PAI-1001 (manufactured by Midori Kagaku Co., Ltd.)

B-4: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Chemical Industry Co., Ltd.)

B-5: Compound of the following structure

B-6: Compound of the following structure

(Synthesis Example 10: Synthesis of Photoacid generator B-5)

1-1. Synthesis of Synthetic Intermediate B-5A

(25 占 폚) in 100 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 31.3 g of 2-aminobenzenethiol (manufactured by Tokyo Chemical Industry Co., Ltd.). Subsequently, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was reacted by stirring at room temperature for 1 hour and then at 100 ° C for 2 hours. 500 mL of water was added to the obtained reaction solution to dissolve the precipitated salt, the toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B-5A.

1-2. Synthesis of B-5

2.25 g of the thus-obtained synthetic intermediate B-5A was mixed with 10 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and then immersed in an ice bath to cool the reaction solution to 5 ° C or less. Next, 4.37 g of tetramethylammonium hydroxide (25% by weight methanol solution, manufactured by Alfa Acer Co.) was added dropwise, and the mixture was reacted with stirring for 0.5 hour in an ice bath. Further, 7.03 g of isopentyl nitrite was added dropwise while keeping the internal temperature at 20 캜 or lower. After completion of dropwise addition, the reaction solution was heated to room temperature and stirred for 1 hour.

Subsequently, the reaction solution was cooled to 5 캜 or lower, p-toluenesulfonyl chloride (1.9 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred for 1 hour while maintaining the temperature at 10 캜 or lower. Then, 80 mL of water was added, and the mixture was stirred at 0 ° C for 1 hour. The resultant precipitate was filtered, and 60 mL of isopropyl alcohol (IPA) was added thereto. The mixture was heated to 50 占 폚 and stirred for 1 hour, filtered, and dried to obtain 1.8 g of (B-5: the above structure) .

The resulting ¹ H-NMR spectrum (300 MHz, DMSO ((D ₃ C) ₂ S = O) of the obtained B-5 was δ = 8.2-8.17 (m, 1H), 8.03-8.00 (M, 2H), 7.6-7.45 (m, 9H), 2.45 (s, 3H).

From the ¹ H-NMR measurement results, it is estimated that the obtained B-5 is a single geometric isomer.

(Synthesis Example 11: Synthesis of B-6)

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

Acetic acid (7.3 g) and a 50 wt% aqueous solution of hydroxyamine (8.0 g) were added to the suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After cooling, 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 and then slurry was rinsed with methanol (20 mL), followed by filtration and drying to obtain B-6 (2.3 g).

In addition, ¹ H-NMR spectrum of _{B-6 (300MHz, 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 (q,

[Table 1]

[Table 2]

(evaluation)

Evaluation of Stability (Liquid Storage Properties)

The viscosity (initial viscosity) of the photosensitive resin composition immediately after preparation and the viscosity (viscosity at the time of storage) of the photosensitive resin composition after storage at 30 ° C for 2 weeks were measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) 3 &quot;, a case where the viscosity change is less than 10% and 5% or more is &quot; 2 &quot;, and a case where the viscosity change is less than 5% is referred to as &quot; 1 &quot;.

&Lt; Evaluation of sensitivity &

Each of the photosensitive resin compositions was coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) using a spinner and then pre-baked on a hot plate at 100 캜 for 60 seconds to volatilize the solvent. Of the photosensitive resin composition layer.

Next, exposure was performed through a predetermined mask using a PLA-501F exposure device (a high-pressure mercury lamp (365 nm (i line), 405 nm (h line), 436 nm (g line) mixed line) manufactured by Canon Inc. . Then, the resist film was developed with an alkaline developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 DEG C for 60 seconds, and then rinsed with ultrapure water for 20 seconds. By these operations, the optimum i-line exposure amount (Eopt) at the time of resolving the line-and-space of 10 mu m at a ratio of 1: 1 was taken as the sensitivity. The evaluation criteria are as follows.

1: Less than 40 mJ / cm ²

^2: 40mJ / cm 2 or more and less than 60mJ / cm ²

3: 60 mJ / cm ² or more

<Evaluation of transparency>

Each of the photosensitive resin compositions was coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) using a spinner and then pre-baked on a hot plate at 100 캜 for one minute to volatilize the solvent. Of the photosensitive resin composition layer.

The thus-obtained photosensitive resin composition layer was exposed with a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation dose was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) Was heated in an oven at 230 DEG C for 1 hour to obtain a cured film.

The light transmittance of the glass substrate having the cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer &quot; 150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.). Evaluation of the lowest light transmittance at that time is shown in Tables 3 and 4. The evaluation criteria are as follows.

1: 95% or more

2: 92% or more and less than 95%

3: 90% or more and less than 92%

4: 88% or more and less than 90%

5: Less than 88%

&Lt; Evaluation of solvent resistance &

A cured film was formed on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) as in the evaluation of the transparency.

The film thickness (T ¹ ) of the obtained cured film was measured. Then, the substrate on which the cured film was formed was immersed in a dimethylsulfoxide controlled at a temperature of 70 캜 for 20 minutes, and then the film thickness t ^{1 of the} cured film was measured, and the film thickness change rate {| t ¹ -T ¹ | / T ¹ } × 100 [%] was calculated. The results are shown in Tables 3 and 4. When this value is less than 3%, the solvent resistance of the cured film can be said to be good.

Less than 1: 1%

2: 1% to less than 2%

3: Less than 2% and less than 3%

4: 3% or more

&Lt; Evaluation of tolerance of solvent removal process >

Each of the photosensitive resin compositions was coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) using a spinner, and then dried at 90 ° C, 100 ° C, 110 ° C for 60 seconds, And the heated solvent was removed on a hot plate for a second time to form a photosensitive resin composition layer having a film thickness of 3.0 mu m. The obtained photosensitive resin composition layer was removed with a heating solvent at 100 占 폚 for 60 seconds using a PLA-501F exposure device (ultra-high pressure mercury lamp) manufactured by Canon Inc., through a mask having a pattern opening of 10 占 퐉, and then 0.4% tetramethylammonium Exposure was performed at an exposure dose (illumination: 20 mW / cm ² , i-line) at which contact hole patterns of 10 탆 square were obtained after development for 60 seconds at 23 캜 using a hydroxide aqueous solution as a developer. The exposed substrate was subjected to paddle development at 23 DEG C for 60 seconds using 0.4% tetramethylammonium hydroxide aqueous solution as a developer. When the difference between the contact diameter at this time and the difference of 10 mu m is less than 0.5 mu m, the tolerance of the solvent removing step of the photosensitive resin composition can be said to be good.

1: less than 0.3 탆

2: 0.3 탆 or more and less than 0.5 탆

3: 0.5 탆 or more

The results are shown in Tables 3 and 4.

[Table 3]

[Table 4]

(Example 50)

Using the photosensitive resin composition of Example 38, the same evaluation as in Example 38 was carried out using a UV-LED light source exposing device instead of an ultra high pressure mercury lamp. As a result, the same results as in Example 38 were obtained.

(Example 51)

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

A TFT 1 of a bottom gate type was formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 did. This wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

The planarization layer 4 was formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 2. The planarizing film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 8 on a substrate, pre-baking it on a hot plate (at 100 캜 for 1 minute), and then using a high- Irradiated at 40 mJ / cm ² (illuminance of 20 mW / cm ² , i-line), developed with an alkali aqueous solution to form a pattern, and subjected to heat treatment at 230 캜 for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Next, an organic EL device of a bottom emission type was formed on the obtained planarization film (4). First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, the resist was applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film, the insulating film 8 was formed using the photosensitive resin composition of Example 8 in the same manner as described above. By providing this insulating film, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in a subsequent step.

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

As described above, an active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements are connected to each organic EL element was obtained. When the voltage was applied through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was highly reliable.

(Example 52)

An organic EL device was prepared in the same manner as in Example 51 except that the photosensitive resin composition of Example 8 was changed to the photosensitive resin composition of Example 48. [ The organic EL display device exhibits good display characteristics and is highly reliable.

(Example 53)

An organic EL device was prepared in the same manner as in Example 46 except that the photosensitive resin composition of Example 8 was changed to the photosensitive resin composition of Example 49. [ The organic EL display device exhibits good display characteristics and is highly reliable.

(Example 54)

In the active matrix type liquid crystal display device shown in Fig. 1 of Japanese Patent No. 3321003, a liquid crystal display device of Example 54 was obtained by forming a cured film 17 as an interlayer insulating film as follows.

That is, the photosensitive resin composition of Example 17 was used to form a cured film 17 as an interlayer insulating film in the same manner as in the method of forming the planarization film 4 of the organic EL display device in Example 51 above.

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

(Example 55)

A liquid crystal display device was manufactured in the same manner as in Example 54 except that the photosensitive resin composition of Example 8 was changed to the photosensitive resin composition of Example 48. [ The liquid crystal display device exhibits good display characteristics and is highly reliable.

(Example 56)

A liquid crystal display device was manufactured in the same manner as in Example 54 except that the photosensitive resin composition of Example 8 was changed to the photosensitive resin composition of Example 49. The liquid crystal display device exhibits good display characteristics and is highly reliable.

1: TFT (thin film transistor)
2: Wiring
3: Insulating film
4: Planarizing film
5: First electrode
6: glass substrate
7: Contact hole
8: Insulating film
10: Liquid crystal display
12: Backlight unit
14, 15: glass substrate
16: TFT
17:
18: Contact hole
19: ITO transparent electrode
20: liquid crystal
22: Color filter

Claims (17)

(A) a monomer unit (1) having a carboxyl group protected by an acid-decomposable group, a monomer unit (2) having a phenolic hydroxyl group protected by an acid-decomposable group, a cyclic ether residue of 3-membered ring, And a monomer unit (3) having at least any one of an ether residue and an ether residue,
(B) a photoacid generator, and
(C) a solvent.
Sensitive resin composition. The method according to claim 1,
Wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition. 3. The method according to claim 1 or 2,
Wherein the monomer unit (1) is a monomer unit having at least one residue selected from the group consisting of a residue in which a carboxyl group is protected with a tertiary alkyl group, a residue in which a carboxyl group is protected with an acetal, and a residue in which a carboxyl group is protected with a ketal , The monomer unit (2) is at least one selected from the group consisting of a residue in which the phenolic hydroxyl group is protected with a tertiary alkyl group, a residue in which the phenolic hydroxyl group is protected with an acetal, and a residue in which the phenolic hydroxyl group is ketal protected Wherein the monomer unit is a monomer unit having a moiety of at least one kind selected from the group consisting of 3. The method according to claim 1 or 2,
Wherein the monomer unit (1) has at least one of a residue in which the carboxyl group is protected with a tertiary alkyl group represented by the following formula (a) and an acetal or ketal-protected residue in which the carboxyl group is represented by the following formula (b) , Wherein the monomer unit (2) is a residue in which the phenolic hydroxyl group is protected with a tertiary alkyl group represented by the following formula (a) and a residue in which the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the following formula (b) Wherein the photosensitive resin composition has at least one of the following properties.

In formula (a), R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring.

In the formula (b), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, but R ⁴ and R ⁵ do not form a hydrogen atom together, R ⁶ represents an alkyl group, and R ⁴ or R ⁵ and R &lt; ⁶ &gt; may be connected to form a cyclic ether. 3. The method according to claim 1 or 2,
Wherein the monomer unit (3) has a residue selected from the group consisting of the following formulas (3a) and (3b).

R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represents a hydrogen atom or an alkyl group, and R ^1b and R ^6b independently represent a hydrogen atom or an alkyl group, An atom, a halogen atom, an alkyl group, or an aryl group. 3. The method according to claim 1 or 2,
(B) a photosensitive resin composition, wherein the photoacid generator is a compound which generates an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more and 450 nm or less. 3. The method according to claim 1 or 2,
(B) the photoacid generator is a compound having an oxime sulfonate residue represented by the following formula (4).

In the formula (4), R ⁵ represents an alkyl group or an aryl group. 3. The method according to claim 1 or 2,
Wherein the photo acid generator (B) photoacid generator is a compound represented by formula (OS-3), formula (OS-4) or formula (OS-5).

Expression (OS-3) ~ formula (OS-5) of, R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ² are, each independently, a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ Each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, In the formula (OS-4), m represents an integer of 0 to 6, and in the formula (OS-5), m represents an integer of 0 to 4. 3. The method according to claim 1 or 2,
(B) the photoacid generator is a compound represented by the following formula (5).

Equation (5) of, R ⁵ is, represents an alkyl group or an aryl group, X is an alkyl group, an alkoxy group, or a halogen atom, m is, as an integer of 0~3, m is 2 or 3, The plural Xs may be the same or different. 3. The method according to claim 1 or 2,
(D) an antioxidant. 3. The method according to claim 1 or 2,
(E) a crosslinking agent. A cured film formed by applying at least one of light and heat to the photosensitive resin composition according to claim 1 or 2. (1) a coating step of applying the photosensitive resin composition according to any one of claims 1 to 3 on a substrate,
(2) a solvent removing step of removing the solvent from the applied photosensitive resin composition,
(3) an exposure process for exposing with an active light beam,
(4) a developing step of developing with an aqueous developing solution, and
(5) a post-baking step of thermally curing
Method of forming a cured film. A cured film formed by the method according to claim 13. 13. The method of claim 12,
A cured film which is an interlayer insulating film. An organic EL display device comprising the cured film according to claim 12. A liquid crystal display device comprising the cured film according to claim 12.

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