KR20130105420A - Positive type photosensitive resin composition, method for manufacturing cured film, cured film, organic el display device and liquid crystal display - Google Patents

Abstract

PURPOSE: A positive type photosensitive resin composition is suitable for a liquid crystal display device, organic EL display device, an IC diode, and a solid-photographing diode or for forming a protection film, and an insulating film. CONSTITUTION: A positive type photosensitive resin composition comprises a polymer component satisfying at least one of (1) and (2): (1) a polymer which has a structure unit having a residue in which an acid group is protected by an acid-decomposing group, a structure unit having a crosslinkable group, and a structure unit having a partial structure containing a fluorine atom in a branched chain, (2) a polymer which has a structure unit having a residue in which an acid group is protected by an acid-decomposing group, a structure unit having a partial structure containing a fluorine atom in a branched chain, and a structure unit having a crosslinkable group; a photoacid generator; and a solvent.

Description

POSITIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR MANUFACTURING CURED FILM, CURED FILM, ORGANIC EL DISPLAY DEVICE AND LIQUID CRYSTAL DISPLAY}

The present invention relates to a positive photosensitive resin composition. Moreover, it is related with the manufacturing method of the cured film using the said positive photosensitive resin composition, the cured film formed by hardening | curing a positive photosensitive composition, and the various image display apparatus using the said cured film.

More specifically, it relates to a positive type photosensitive resin composition suitable for the formation of planarization films, protective films or interlayer insulating films of electronic components such as liquid crystal display devices, organic EL display devices, integrated circuit devices, solid-state imaging devices, and a method for producing a cured film using the same. will be.

A patterned interlayer insulating film is formed in an organic EL display device, a liquid crystal display device, or the like. The photosensitive resin composition is widely used by the point that the number of processes for obtaining the required pattern shape is small, and sufficient flatness is obtained for formation of this interlayer insulation film.

The interlayer insulation film and planarization film which were pattern-formed using the positive type photosensitive resin composition as mentioned above are required for the photosensitive resin composition with high sensitivity from a viewpoint of reduction of manufacturing cost. In addition, in recent years, mobile displays such as smart phones have been widely used, and thus, a highly reliable cured film in a wide temperature environment has been particularly demanded.

An example using the photosensitive resin composition which improved storage stability, sensitivity, etc. is known (for example, refer Unexamined-Japanese-Patent No. 2011-221494). However, the photosensitive resin composition which is excellent in a sensitivity and chemical-resistance, and has a low dielectric constant is unknown. For this reason, dielectric constant and sensitivity (development) are considered to be in a trade-off relationship.

This invention solves the said subject, Comprising: It aims at providing the positive photosensitive resin composition which is high in sensitivity, excellent in chemical resistance, and low in dielectric constant.

As described above, the permittivity and sensitivity (development) are in a trade-off relationship. Therefore, when the dielectric constant is lowered, the sensitivity also decreases. As a result of earnest examination by this inventor about this point, it discovered that such a problem can be solved by mix | blending the structural unit containing a fluorine atom in a polymer component. In addition, although the fluorine atom is a component having a low solubility, the development rate is lowered. It was successful in reducing the dielectric constant while suppressing the decrease and maintaining the developability. In addition, it was surprisingly found that the chemical resistance could also be improved by this configuration, and thus the present invention was completed.

Specifically, the problem was solved by the following <1>, preferably by <2> to <18>.

<1> (A) the polymer component which satisfy | fills at least one of following (1) and (2),

(1) A polymer having (a1) a structural unit having a moiety in which an acid group is protected with an acid decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a structural unit having a partial structure containing a fluorine atom in the side chain:

(2) a polymer having a structural unit having a moiety in which the acid group (a1) has a moiety protected with an acid-decomposable group and (a3) a partial structure containing a fluorine atom in the side chain, and (a2) a structural unit having a crosslinkable group polymer,

(B) a photoacid generator,

(D) Positive photosensitive resin composition containing a solvent.

<2> The positive photosensitive resin composition according to <1>, wherein the partial structure containing the fluorine atom includes a hydrocarbon group substituted with a fluorine atom.

<3> The positive photosensitive resin composition according to <1>, wherein the partial structure containing a fluorine atom includes a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom.

<4> The positive photosensitive resin composition according to <1>, wherein the structural unit (a3) is a structure in which a group represented by the following general formula (1) or (2) is bonded directly to a main chain or through a linking group.

In general formula (1)

[In Formula (1), X represents -O- or -NH-, L <^1> represents a single bond or a bivalent coupling group, R <^12> represents the hydrocarbon group substituted by at least 1 or more by the fluorine atom.

General formula (2)

[In General Formula (2), Ar represents an aromatic ring group, Y represents a fluorine atom or -L ² -R ²² , R ²² represents a hydrocarbon group substituted with at least one or more by fluorine atoms, and L ² represents a single bond or 2 Shows a coupling group. n represents the integer of 1-5. When n is 2 or more, each Y may be the same or different.]

<5> Positive photosensitive resin composition as described in <1> whose said structural unit (a3) is a structural unit represented by following General formula (1 ') or (2').

In general formula (1 '),

[In General Formula (1 '), R ¹¹ represents hydrogen or a methyl group, X represents -O- or -NH-, L ¹ represents a single bond or a divalent linking group, and R ¹² represents at least one or more of fluorine atoms Substituted hydrocarbon group]

In general formula (2 '),

[In General Formula (2 '), R ²¹ represents hydrogen or a methyl group, Y represents a fluorine atom or -L ² -R ²² , R ²² represents a hydrocarbon group substituted with at least one or more by fluorine atoms, and L ² is a A bond or a divalent linking group. n represents the integer of 1-5. When n is 2 or more, each Y may be the same or different.]

<6> The crosslinkable group according to any one of <1> to <5>, wherein the crosslinkable group is selected from a group represented by an epoxy group, an oxetanyl group and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) Positive type photosensitive resin composition which is at least 1 sort.

<7> The positive photosensitive resin composition according to any one of <1> to <6>, wherein the acid decomposable group is a group having a structure protected in the form of acetal.

<8> Photosensitive resin composition in any one of <1>-<7> whose said structural unit (a1) is a structural unit represented with the following general formula (A2 ').

Formula (A2 ')

[Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group]

<9> Positive photosensitive resin composition in any one of <1>-<8> whose one of said (A) polymer components is a polymer which contains an acidic radical further.

<10> The positive photosensitive resin composition according to any one of <1> to <9>, wherein the photoacid generator (B) is an oxime sulfonate compound.

<11> The content of any one of <1> to <10>, in which 70 to 99.9 mass% of the polymer component (A) and 0.1 to 30 mass% of the (B) photoacid generator in terms of mass, based on the total solids of the composition. Positive photosensitive resin composition contained in the range of.

<12> Positive photosensitive composition in any one of <1>-<11> which further contains (C) crosslinking agent.

<13> The composition of <12>, which is 50 to 98% by mass of the polymer component (A), 0.1 to 10% by mass of the (B) photoacid generator, and (C) the crosslinking agent in terms of mass of the composition. Positive type photosensitive resin composition containing -40 mass%.

<14> (1) Process of applying the photosensitive resin composition in any one of <1>-<13> on a board | substrate,

(2) removing the solvent from the applied photosensitive resin composition,

(3) exposing to active radiation;

(4) developing with an aqueous developer; and

(5) The post-baking process of thermosetting is included, The manufacturing method of the cured film characterized by the above-mentioned.

<15> The method for forming a cured film according to <14>, comprising a step of exposing the whole surface after the developing step and before the post-baking step.

<16> Cured film formed by hardening | curing the photosensitive resin composition in any one of <1>-<13>.

<17> The cured film as described in <16> which is an interlayer insulation film.

<18> The liquid crystal display device or organic electroluminescence display which has a cured film as described in <16> or <17>.

(Effects of the Invention)

According to this invention, the photosensitive resin composition excellent in the sensitivity, dielectric constant, and chemical resistance can be provided.

1 shows a configuration conceptual diagram of an example of an organic EL display device. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4. As shown in FIG.
2 shows a configuration conceptual diagram of an example of a liquid crystal display device. Typical sectional drawing of the active-matrix board | substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. Although description of the element | module described below is made | formed based on typical embodiment of this invention, this invention is not limited to such embodiment. In addition, in this specification, "-" is used by the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have 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).

[Positive-type photosensitive resin composition]

The positive photosensitive resin composition (hereinafter may be simply referred to as "photosensitive resin composition") of the present invention is a polymer component that satisfies at least one of (A) the following (1) and (2) and (B) a photoacid generator And (D) a solvent.

(1) A polymer having (a1) a structural unit having a moiety in which an acid group is protected with an acid decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a structural unit having a partial structure containing a fluorine atom in the side chain:

(2) a polymer having a structural unit having a moiety in which the acid group (a1) has a moiety protected with an acid-decomposable group and (a3) a partial structure containing a fluorine atom in the side chain, and (a2) a structural unit having a crosslinkable group polymer

The photosensitive resin composition of this invention is a positive photosensitive resin composition. Moreover, it is preferable that the photosensitive resin composition of this invention is a chemically amplified positive photosensitive resin composition (chemical amplification positive photosensitive resin composition).

Best Mode for Carrying Out the Invention Preferred embodiments of the components of the photosensitive resin composition of the present invention will be described below in order.

&Lt; Component (A) >

The photosensitive resin composition of this invention contains the polymer which has a structural unit which has a structural unit which has the moiety which (a1) an acidic group has the residue protected by the acid-decomposable group as (A) component, and (a3) side chain contains a fluorine atom in a side chain. . Moreover, it has a structural unit which has a (a2) crosslinkable group as a structural unit of such a polymer, or as another polymer component. In the present invention, by combining the (a1) structural unit and the (a3) structural unit with the same polymer, it becomes possible to increase the solubility of the structural unit having a partial structure having a fluorine atom having inherently low solubility. Also, by including (a2), the resistance to the drug is dramatically improved.

It is preferable that (A) component is addition polymerization type resin, and it is more preferable that it is a polymer containing the structural unit derived from (meth) acrylic acid and / or its ester. Moreover, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.

As for the said (A) component, it is preferable to contain 50 mol% or more, and, as for the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units in a polymer, it is more preferable to contain 90 mol% or more. It is especially preferable that it is a polymer which consists only of the structural unit derived from (meth) acrylic acid and / or its ester.

In addition, "the structural unit derived from (meth) acrylic acid and / or its ester" is also called "acrylic structural unit." In addition, "(meth) acrylic acid" shall mean "methacrylic acid and / or acrylic acid."

The component (A) may contain other structural units in addition to the structural units (a1) to (a3).

It is preferable that (A) copolymer is alkali-insoluble, and it is preferable that it is resin which becomes alkali-soluble when the acid-decomposable group which a structural unit (a1) has decomposed. The acid decomposable group herein means a functional group capable of decomposing in the presence of an acid. That is, a structural unit having a protective carboxyl group in which a carboxyl group is protected with an acid decomposable group can generate a carboxyl group by decomposing a protecting group with an acid, and a structural unit having a protective phenolic hydroxyl group in which the phenolic hydroxyl group is protected with an acid decomposable group is an acid. The protecting group can be decomposed to form a phenolic hydroxyl group. Here, in the present invention, "alkali solubility" refers to 23 ° C of the coating film (thickness 3 µm) of the compound (resin) formed by applying a solution of the compound (resin) onto a substrate and heating at 90 ° C for 2 minutes. The dissolution rate in the 0.4% tetramethylammonium hydroxide aqueous solution in said solution is 0.01 micrometer / sec or more, and "alkali insoluble" is apply | coated the solution of the said compound (resin) on a board | substrate, and it heats at 90 degreeC for 2 minutes. The dissolution rate with respect to the 0.4% tetramethylammonium hydroxide aqueous solution in 23 degreeC of the coating film (3 micrometers in thickness) of the said compound (resin) formed is said to be less than 0.01 micrometer / sec.

The said (A) copolymer may have a carboxyl group mentioned later, the structure derived from carboxylic anhydride, and / or the other structural unit which has a phenolic hydroxyl group. However, when introducing an acidic group, it is preferable to introduce in the range which keeps the said (A) copolymer whole in alkali insoluble.

<< structural unit (a1) >>

Component A has at least a structural unit in which the acid group (a1) has a residue in which an acid-decomposable group is protected. When (A) component has a structural unit (a1), it can be set as the very highly sensitive photosensitive resin composition.

In the present invention, known residues may be used as the acid group and the acid decomposable group, and the residues in which the acid group is protected with the acid decomposable group are not particularly limited. As a specific acidic group, a carboxyl group and phenolic hydroxyl group are mentioned preferably. Moreover, as an acid-decomposable group, Acetal type, such as group which is comparatively easy to decompose | dissolve by an acid (for example, ester structure of group represented by Formula (A1) mentioned later, tetrahydropyranyl ester group, or tetrahydrofuranyl ester group) Functional groups) and groups (for example, tertiary alkyl carbonate groups such as t-butyl ester group, tertiary alkyl carbonate groups such as t-butyl carbonate group) which are relatively hard to decompose by an acid can be used.

(a1) It is preferable that the structural unit in which an acidic radical has the residue protected by the acid-decomposable group is a structural unit which has a protective carboxyl group protected by the acid-decomposable group, or a structural unit which has a protective phenolic hydroxyl group protected by the acid-decomposable group.

Hereinafter, the structural unit (a1-1) which has the protective carboxyl group protected by the acid-decomposable group, and the structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the acid-decomposable group are demonstrated in order, respectively.

<<< structural unit which has protective carboxyl group protected by (a1-1) acid-decomposable group >>>

The structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group is a structural unit which has the protective carboxyl group protected by the acid-decomposable group demonstrated in detail below.

As a structural unit which has the said carboxyl group which can be used for the structural unit (a1-1) which has a protective carboxyl group protected by the said acid-decomposable group, a well-known structural unit can be used without a restriction | limiting. For example, structural unit (a1-1-1) derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in molecules, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, etc., and ethylene The structural unit (a1-1-2) which has a structure derived from a unsaturated unsaturated group and an acid anhydride together is mentioned.

Hereinafter, the structural unit derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in (a1-1-1) molecule | numerator used as a structural unit which has the said carboxyl group, (a1-1-2) ethylenically unsaturated group and acid The structural unit which has the structure derived from anhydride together is demonstrated in order, respectively.

Structural unit >>>> derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in <<<< (a1-1-1) molecule | numerator

As an unsaturated carboxylic acid used by this invention as a structural unit (a1-1-1) derived from the unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the said molecule | numerator, what is enumerated below is used. That is, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Moreover, as unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to acquire the structural unit which has a carboxyl group. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester of polyhydric carboxylic acid, for example, succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryl). Monooxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. In addition, the unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the both terminal dicarboxy polymers, and for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. may be mentioned. have. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.

Especially, in order to form the structural unit (a1-1-1) derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the said molecule from a developable viewpoint, anhydride of acrylic acid, methacrylic acid, or unsaturated polyhydric carboxylic acid. It is preferable to use etc., and it is more preferable to use acrylic acid or methacrylic acid.

The structural unit (a1-1-1) derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the said molecule may be comprised individually by 1 type, and may be comprised by 2 or more types.

Structural unit >>>> which has a structure derived from <<<< (a1-1-2) ethylenically unsaturated group and acid anhydride

It is preferable that the structural unit (a1-1-2) which has a structure derived from an ethylenically unsaturated group and acid anhydride together is a unit derived from the monomer obtained by making the hydroxyl group and acid anhydride which exist in the structural unit which has an ethylenically unsaturated group react.

As said acid anhydride, a well-known thing can be used, Specifically, Dibasic acid anhydrides, such as maleic anhydride, succinic anhydride, itaconic acid anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, chloric anhydride; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. In these, phthalic anhydride, tetrahydro phthalic anhydride, or succinic anhydride is preferable from a developable viewpoint.

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

<<<< acid-decomposable group which can be used for structural unit (a1-1) >>>>

The acid-decomposable group described above can be used as the acid-decomposable group that can be used in the structural unit (a1-1) having a protective carboxyl group protected with the acid-decomposable group.

Among these acid decomposable groups, the carboxyl group is a protective carboxyl group protected in the form of acetal from the viewpoint of the basic physical properties of the photosensitive resin composition, in particular, the sensitivity and pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition. Moreover, it is more preferable from a viewpoint of a sensitivity that a carboxyl group is a protected carboxyl group protected by the form of the acetal represented by following General formula (a1-1) among acid-decomposable groups. In addition, when the carboxyl group is a protective carboxyl group protected in the form of acetal represented by the following general formula (a1-1), the whole of the protective carboxyl group has a structure of-(C = O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ). It is.

General formula (a1-1)

[Formula (a1-1) of R ¹⁰¹ and R ¹⁰² represents a hydrogen atom or an alkyl group, each independently, other than the R-stage ¹⁰¹ and, if R ¹⁰² is a hydrogen atom together. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² may be linked to R ¹⁰³ to form a cyclic ether.]

In said general formula (a1-1), R <^101> -R <^103> respectively independently represents a hydrogen atom or an alkyl group, and the said alkyl group may be any of linear, branched, and cyclic. Here, at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group without both of R ¹⁰¹ and R ¹⁰² representing hydrogen atoms.

In the general formula (a1-1), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.

As said linear or branched alkyl group, it is preferable that it is C1-C12, It is more preferable that it is C1-C6, It is further more preferable that it is C1-C4. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n-hexyl group , Texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As said cyclic alkyl group, it is preferable that it is C3-C12, It is more preferable that it is C4-C8, It is further more preferable that it is C4-C6. As said cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, isobonyl group etc. are mentioned, for example.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When a substituent having a halogen atom, R ^101, R ^102, R ¹⁰³ is a haloalkyl group, if having an aryl substituent as R ^101, R ^102, R ¹⁰³ is an aralkyl group.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated, Among these, a fluorine atom or a chlorine atom is preferable.

Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, (alpha) -methylphenyl group, a naphthyl group, etc. can be illustrated, and is substituted by the aryl group. As a whole alkyl group, ie, an aralkyl group, a benzyl group, (alpha)-methyl benzyl group, a phenethyl group, a naphthyl methyl group, etc. can be illustrated.

As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, A methoxy group or an ethoxy group is more preferable.

In addition, when the said alkyl group is a cycloalkyl group, the said cycloalkyl group may have a C1-C10 linear or branched alkyl group as a substituent, and when a alkyl group is a linear or branched alkyl group, it is C3-C12 as a substituent. May have two cycloalkyl groups.

These substituents may be further substituted by the above substituents.

In the general formula (a1-1), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group is preferably 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms may be preferably exemplified. As an aryl group, a phenyl group, a tolyl group, a silyl group, cumenyl group, 1-naphthyl group etc. can be illustrated, for example.

In addition, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring by becoming one with the carbon atom to which they are bonded. Examples of the ring structure in the case where R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ¹⁰³ combine, include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, tetrahydropyranyl group, and the like.

Also, R ¹⁰¹ and R ¹⁰² in the general formula (a1-1) It is preferable that either one is a hydrogen atom or a methyl group.

A commercially available radical may be used for the radically polymerizable monomer used in order to form the structural unit which has a protective carboxyl group represented by said general formula (a1-1), and what synthesize | combined by a well-known method can also be used. For example, Paragraph No. 0037 of Unexamined-Japanese-Patent No. 2011-221494-the synthesis method of 0040 can be synthesize | combined.

The 1st preferable embodiment of the structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group is a structural unit represented by Formula (A2 ').

Formula (A2 ')

[Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group]

When R <^1> and R <^2> is an alkyl group, a C1-C10 alkyl group is preferable. Phenyl groups are preferred when R ¹ and R ² are aryl groups. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R <^3> represents an alkyl group or an aryl group, a C1-C10 alkyl group is preferable and 1-6 alkyl group is more preferable.

X represents a single bond or an arylene group, and a single bond is preferable.

2nd preferable embodiment of the structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group is a structural unit of the following general formula.

[Wherein, R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]

R ¹²¹ is preferably a hydrogen atom or a methyl group.

L ¹ is preferably a carbonyl group.

R ¹²² to R ¹²⁸ are preferably hydrogen atoms.

The following structural unit can be illustrated as a preferable specific example of structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group. R represents a hydrogen atom or a methyl group.

<<< structural unit which has protective phenolic hydroxyl group protected by the (a1-2) acid-decomposable group >>>

The structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group is a structural unit which has the protective phenolic hydroxyl group protected by the acid-decomposable group which the structural unit which has a phenolic hydroxyl group is demonstrated in detail below.

Structural unit >>>> which has <<<< (a1-2-1) phenolic hydroxyl group

As a structural unit which has the said phenolic hydroxyl group, although the structural unit in a hydroxy styrene-type structural unit and novolak-type resin is mentioned, in these, the structural unit derived from hydroxy styrene or (alpha) -methylhydroxy styrene is transparency. It is preferable from a viewpoint. Among the structural units having a phenolic hydroxyl group, the structural units represented by the following general formula (a1-2) are preferable from the viewpoints of transparency and sensitivity.

General formula (a1-2)

[In general formula (a1-2), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, R ²²² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. a represents the integer of 1-5, b represents the integer of 0-4, and a + b is 5 or less. In addition, when two or more R <^222> exists, these R <^222> may mutually differ and may be the same.]

R ²²⁰ in the general formula (a1-2) represents a hydrogen atom or a methyl group, and is preferably a methyl group.

In addition, R ²²¹ represents a single bond or a divalent linking group. In the case of single-crystal combination, it is preferable since the sensitivity can be improved and the transparency of the cured film can be improved. Examples of the divalent linking group for R ²²¹ include an alkylene group, and specific examples in which R ²²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, Pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Especially, it is preferable that R <^221> is a single bond, a methylene group, and an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. In addition, although a shows the integer of 1-5, it is preferable that a is 1 or 2 from a viewpoint of the effect of this invention and manufacture, and it is more preferable that a is 1.

In addition, it is preferable that the coupling | bonding position of the hydroxyl group in a benzene ring couple | bonds in 4 positions, when the carbon atom couple | bonded with R <^221> is a reference | standard (1 position).

R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

Specifically, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned. Can be. Especially, since it is easy to manufacture, it is preferable that they are a chlorine atom, a bromine atom, a methyl group, or an ethyl group.

B represents 0 or an integer of 1 to 4;

<<<< acid-decomposable group used for structural unit (a1-2) >>>>

As said acid-decomposable group which can be used for the structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group, the said acid usable group can be used for the structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group. A well-known thing can be used similarly to an acid-decomposable group, and is not specifically limited. Among the acid decomposable groups, a structural unit having a protective phenolic hydroxyl group protected with acetal is preferable from the viewpoint of the basic physical properties of the photosensitive resin composition, in particular, the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, and the formability of the contact hole. Moreover, it is more preferable from a viewpoint of a sensitivity that a phenolic hydroxyl group is a protected phenolic hydroxyl group protected by the form of the acetal represented by said general formula (a1-1) among acid-decomposable groups. Further, in the phenolic hydroxyl groups when the above-mentioned general formula (a1-1) a protected phenolic hydroxyl date protection in the form of an acetal represented by as a whole of the protected phenolic hydroxyl group ^{-Ar-O-CR 101 R 102} (OR 103) It is structured. Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group include R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group and R ¹⁰¹ = R ¹⁰² = methyl group, and combinations of R ¹⁰³ = benzyl groups can be exemplified.

Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a protective phenolic hydroxyl group in which the phenolic hydroxyl group was protected by the form of acetal, it is what is described in Paragraph No. 0042 of Unexamined-Japanese-Patent No. 2011-215590, for example. Etc. can be mentioned.

Among these, the 1-alkoxyalkyl protecting body of 4-hydroxyphenyl methacrylate and the tetrahydropyranyl protecting body of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

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

The radically polymerizable monomer used in order to form the structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group may use a commercially available thing, and may use the thing synthesize | combined by a well-known method. For example, the compound having a phenolic hydroxyl group can be synthesized by reacting with vinyl ether in the presence of an acid catalyst. The said synthesis | combination may copolymerize previously the monomer which has a phenolic hydroxyl group with another monomer, and may make it react with vinyl ether in presence of an acid catalyst after that.

Although the following structural unit can be illustrated as a preferable specific example of structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group, this invention is not limited to these.

<<< preferred embodiment of a structural unit (a1) >>>

1-95 mol% is preferable with respect to the whole polymer from a viewpoint of a sensitivity, and, as for the content rate of the structural unit (a1) in the structural unit which comprises a copolymer (A), 10-80 mol% is more preferable, 20-70 mol % Is more preferable, and 20-50 mol% is especially preferable. Moreover, especially when the said structural unit (a1) is a structural unit which has a protective carboxyl group in which the carboxyl group was protected by the form of acetal, the content rate of the structural unit (a1) in the structural unit which comprises the polymer containing a structural unit (a1) is 20 70 mol% is more preferable, and 35-70 mol% is especially preferable.

In particular, when the structural unit (a2) is included in a polymer such as the structural units (a1) and (a3), 30 to 60 mol% is preferable, and 35 to 50 mol% is more preferable in the polymer.

On the other hand, when the structural unit (a2) is included in a polymer different from the structural units (a1) and (a3), 50 to 80 mol% is preferable and more preferably 60 to 70 mol% of the polymer containing the structural unit (a2). desirable.

The structural unit (a1-1) having a protective carboxyl group protected with the acid decomposable group has a feature that the development is faster than that of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid decomposable group. Therefore, when developing rapidly, the structural unit (a1-1) which has the protective carboxyl group protected by the acid-decomposable group is preferable. On the contrary, when it is desired to slow development, it is preferable to use a structural unit (a1-2) having a protective phenolic hydroxyl group protected with an acid decomposable group.

<< structural unit (a2) >>

(A) component has a structural unit (a2) which has a crosslinking group. The structural unit which has a crosslinkable group may be contained in the same polymer as a structural unit (a1) and a structural unit (a3), and may be contained in the other polymer.

The crosslinking group is not particularly limited as long as it is a group causing a curing reaction by heat treatment. By including a crosslinking group, the mechanical properties of the cured film are improved. As the embodiment of the constituent unit having a preferred cross-linking an epoxy group, an oxetanyl group, an ethylenically unsaturated group and the -NH-CH ₂ -OR at least one selected from a group represented by (R is an alkyl group having 1 to 20 carbon atoms) number, and an epoxy group, an oxetanyl group and the -NH-CH ₂ -OR is preferably at least one member selected from the groups represented by (R is an alkyl group having 1 to 20 carbon atoms), more preferably an epoxy group and / or oxetanyl . In particular, an epoxy group is preferable from the viewpoint of improving chemical resistance. On the other hand, an oxetanyl group is preferable from the viewpoint of decreasing the dielectric constant. In particular, in order to reduce dielectric constant, it is more preferable to include the structural unit which has an oxetanyl group, and the structural unit derived from styrene.

<< structural unit which has a (a2-1) epoxy group and / or oxetanyl group >>>

The said (A) copolymer can contain the structural unit (structural unit (a2-1)) which has an epoxy group and / or an oxetanyl group.

The structural unit (a2-1) which has the said epoxy group and / or oxetanyl group should just have at least 1 epoxy group or oxetanyl group in one structural unit, and at least 1 epoxy group and 1 or more oxetanyl group, 2 Although it may have the above epoxy group or two or more oxetanyl groups, although it does not specifically limit, it is preferable to have 1-3 epoxy groups and / or oxetanyl groups in total, and it has one or two epoxy groups and / or oxetanyl groups in total It is more preferable, and it is still more preferable to have one epoxy group or oxetanyl group.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycine (alpha)-n-propyl acrylate Dyl, α-n-butylacrylic acid glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4 -Epoxycyclohexylmethyl, alpha -ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Japanese Patent Paragraph number 0031 of Unexamined-Japanese-Patent No. 0031-the compound containing the alicyclic epoxy skeleton of 0035, etc. are mentioned.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an oxetanyl group, the (meth) acrylic acid ester which has the oxetanyl group of Paragraph No. 0011 of Unexamined-Japanese-Patent No. 2001-330953-0016, for example. Etc. can be mentioned.

As a specific example of the radically polymerizable monomer used in order to form the structural unit (a2-1) which has the said epoxy group and / or oxetanyl group, it is preferable that it is a monomer containing a methacrylic acid ester structure, and a monomer containing an acrylic ester structure. Do.

Among these monomers, compounds containing the alicyclic epoxy skeletons described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and oxetanyl groups described in paragraphs 0011 to 0016 of Japanese Patent Laid-Open No. 2001-330953 are more preferable. It is (meth) acrylic acid ester which has, and especially preferable is (meth) acrylic acid ester which has the oxetanyl group of Paragraph No. 0011 of Unexamined-Japanese-Patent No. 2001-330953-0016. Among these, preferred are methacrylic acid glycidyl, acrylic acid 3,4-epoxycyclohexylmethyl, methacrylic acid 3,4-epoxycyclohexylmethyl, acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl, most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

It is preferable that the structural unit (a2-1) which has the said epoxy group and / or oxetanyl group has a structure chosen from the group which consists of following formula (a2-1-1) and formula (a2-1-2).

The structural unit (a2-1) which has the said epoxy group and / or oxetanyl group has any one of the three structures represented by the said Formula (a2-1-1), and is represented by Formula (a2-1-1) It means having a group except one or more hydrogen atoms from the structure.

It is further more preferable that the structural unit (a2-1) which has the said epoxy group and / or oxetanyl group has a 3, 4- epoxycyclohexyl group, a 2, 3- epoxycyclohexyl group, and a 2, 3- epoxycyclopentyl group.

[In Formula (a2-1-2), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, and R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b , and R ^10b Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group]

R ^1b and R ^6b in the general formula (a2-1-2) 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 a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. It is more preferable that it is (hereinafter also referred to as "low speed 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 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 linear, branched or cyclic, and may have a substituent. The straight-chain or branched-chain alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and 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 straight chain and branched chain alkyl groups may be substituted with a cyclic alkyl group, and the cyclic alkyl group may be substituted with straight chain and / or branched chain alkyl groups.

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.

The said alkyl group and the aryl group may further have a substituent, As a substituent which the alkyl group may have, a halogen atom and an aryl group can be illustrated, As a substituent which an aryl group may have, a halogen atom and an alkyl group can be illustrated. Among these, R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a purple having 1 to 4 carbon atoms. It is more preferable that it is a fluoroalkyl group.

As the group having the structure represented by the general formula (a2-1-2), a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

The following structural unit can be illustrated as a preferable specific example of structural unit (a2-1) which has the said epoxy group and / or oxetanyl group. R represents a hydrogen atom or a methyl group.

<<< structural unit which has (a2-2) ethylenically unsaturated group >>>

The structural unit (a2-2) which has an ethylenically unsaturated group is mentioned as one of the structural units (a2) which have the said crosslinking group (henceforth "a structural unit (a2-2)"). As a structural unit (a2-2) which has the said ethylenically unsaturated group, the structural unit which has an ethylenically unsaturated group in a side chain is preferable, The structural unit which has an ethylenically unsaturated group at the terminal, and has a C3-C16 side chain, The structural unit which has a side chain shown by following General formula (a2-2-1) is more preferable.

General formula (a2-2-1)

[In Formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * is connected to the main chain of the structural unit (a2) having a crosslinking group. Indicates a site]

R ³⁰¹ is a C1-C13 divalent linking group, which includes an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and may include a bond such as an ester bond, an ether bond, an amide bond, a urethane bond, or the like. In addition, the divalent linking group may have substituents, such as a hydroxyl group and a carboxyl group, in arbitrary positions. Specific examples of R ³⁰¹ include the following divalent linking groups.

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

In addition, the ethylenically unsaturated group contained in the side chain represented by the said general formula (a2-2-1) is 150-2,000 g with respect to the sum total of the said polymer (A ') and a polymer (A "), or a copolymer (C). It is preferable to contain 1 mol with respect to, and it is more preferable that 1 mol is contained with respect to 200-1,300g.

In the present invention, the structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit represented by the following general formula (a2-2-2).

General formula (a2-2-2)

[R <^311> in general formula (a2-2-2) is synonymous with R < ³⁰¹ > in the said general formula (a2-2-1), and its preferable range is also the same. R ³¹² and R ³¹³ each independently represent a hydrogen atom or a methyl group.]

Although the method of obtaining the structural unit (a2-2) which has a side chain represented by the said general formula (a2-2-1) is not specifically limited, For example, the polymer which has a specific functional group by polymerization methods, such as radical polymerization previously, The structural unit (a2) which has a side chain represented by the said general formula (a2-2-1) by making and reacting the compound which has an ethylenically unsaturated group to the terminal and terminal which react with the specific functional group (henceforth a specific compound). It can be set as the copolymer which has -2).

As said specific functional group, a carboxyl group, an epoxy group, a hydroxyl group, the amino group which has active hydrogen, a phenolic hydroxyl group, an isocyanate group, etc. are mentioned here. The monomer which has a specific functional group for synthesize | combining the polymer which has a specific functional group is mentioned later.

As a combination of the group which reacts with the specific functional group and the specific functional group which the said specific compound has, a combination of a carboxyl group and an epoxy group, a combination of a carboxyl group and an oxetanyl group, a combination of a hydroxy group and an isocyanate group, a combination of a phenolic hydroxyl group and an epoxy group, a carboxyl group and an isocyanate Combinations of groups, combinations of amino groups and isocyanate groups, combinations of hydroxy groups and acid chlorides, and the like.

Moreover, as said specific compound, glycidyl methacrylate, glycidyl acrylate, 3, 4- epoxy cyclohexyl methyl methacrylate, 3, 4- epoxy cyclohexyl methyl acrylate, isocyanate ethyl methacrylate, isocyanate ethyl Acrylate, methacrylic acid chloride, acrylic acid chloride, methacrylic acid, acrylic acid and the like.

As a preferable combination of the said specific functional group and the said specific compound, the combination of the carboxyl group which is the said specific functional group, the glycidyl methacrylate which is the said specific compound, and the combination of the hydroxyl group which is the said specific functional group, and the isocyanate ethyl methacrylate which is the said specific compound are mentioned. have.

Although the specific example of the monomer which has the said specific functional group necessary for obtaining the polymer which has the said specific functional group is listed below, it is not limited to these.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono (2- (acryloyloxy) ethyl) phthalate, mono (2- (methacryloyloxy) ethyl) phthalate, and N-. (Carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, etc. are mentioned.

As a monomer which has the said epoxy group, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2- Epoxy-5-hexene, 1,7-octadiene monoepoxide, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like.

As a monomer which has the said hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acryl, for example. Latex, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, capro Lactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acrylic Royloxy-6-hydroxy norbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy norbornene-2-carboxylic-6-lactone, etc. are mentioned. .

As a monomer which has an amino group which has the said active hydrogen, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned.

As a monomer which has the said phenolic hydroxyl group, hydroxy styrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, etc. are mentioned, for example. have.

Moreover, as a monomer which has the said isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m- tetramethyl xylene isocyanate, etc. are mentioned, for example.

_{<<< (a2-3) -NH-CH 2} -OR configuration having a partial structure represented by (R is an alkyl group having 1 to 20 carbon atoms) unit >>>

The copolymer used in the present invention is a structural unit (a2-3) having a partial structure represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) (hereinafter referred to as "structural unit (a2-3) It is also referred to as "." By having a structural unit (a2-3), hardening reaction can be raise | generated by smooth heat processing and the cured film excellent in all the characteristics can be obtained. R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. Structural unit (a2-3), More preferably, it is a structural unit which has group represented by following General formula (1).

In general formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)

R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.

As a specific example of R <^2> , a methyl group, an ethyl group, n-butyl group, i-butyl group, a cyclohexyl group, and n-hexyl group are mentioned. Especially, i-butyl group, n-butyl group, and a methyl group are preferable.

<<< preferred embodiment of a structural unit (a2) >>>

1-95 mol% is preferable with respect to the whole polymer, as for the content rate of the structural unit (a2) in the structural unit which comprises a copolymer (A), 5-75% is more preferable, 10-50 mol% is still more preferable , 20-50 mol% is more preferable, and 30-50 mol% is especially preferable. If it exists in the range of the said numerical value, all the characteristics of the cured film obtained from the photosensitive resin composition will become favorable.

In particular, when the structural unit (a2) is included in a polymer such as the structural units (a1) and (a3), 30 to 50 mol% is preferable, and 35 to 45 mol% is more preferable in the polymer.

On the other hand, when structural unit (a2) is contained in a polymer different from structural unit (a1) and (a3), 40-80 mol% is preferable in the polymer containing said structural unit (a2), and 55-75 mol% is more preferable. desirable.

<< structural unit (a3) >>

The component (A) has a structural unit having a partial structure containing a fluorine atom in the side chain (a3). As a partial structure which has a fluorine atom in a side chain, the hydrocarbon group substituted by the fluorine atom is preferable, and it is more preferable that it is a C1-C20 hydrocarbon group substituted by the fluorine atom.

As a hydrocarbon group substituted by the fluorine atom, the alkyl group substituted with the linear or branched fluorine atom, or the aromatic ring group substituted with the fluorine atom is preferable. These groups may have a substituent and can illustrate an alkyl group and a hydroxyl group as a substituent. However, in this invention, it is more preferable not to have a substituent.

It is preferable that the structural unit (a3) has the partial structure containing a fluorine atom at least in a side chain terminal. For example, the carbon atom of the terminal which comprises a side chain is couple | bonded with a fluorine atom.

As for the side chain which has the partial structure which has a fluorine atom couple | bonded with the structural unit (a3), all the said side chains are a carbon atom and a fluorine atom as essential atoms, and the other constituent atoms are selected only from an oxygen atom, a hydrogen atom, and a nitrogen atom. It is preferable that it contains or does not contain at all, and it is more preferable that a carbon atom and a fluorine atom are essential, and the other constituent atoms contain only or are not selected at all from an oxygen atom and a hydrogen atom.

It is preferable that the group represented by the following general formula (1) or (2) couple | bonds the structural unit (a3) with the main chain directly or via a coupling group, and is represented by the following general formula (1) or general formula (2) It is more preferred that the losing group is bonded directly to the main chain.

In general formula (1)

[In Formula (1), X represents -O- or -NH-, L <^1> represents a single bond or a bivalent coupling group, R <^12> represents the hydrocarbon group substituted by at least 1 or more by the fluorine atom.

General formula (2)

[In General Formula (2), Ar represents an aromatic ring group, Y represents a fluorine atom or -L ² -R ²² , R ²² represents a hydrocarbon group substituted with at least one or more by fluorine atoms, and L ² represents a single bond or 2 Shows a coupling group. n represents the integer of 1-5. When n is 2 or more, each Y may be the same or different.]

In General Formula (1), X is preferably -O-.

L ¹ represents a single bond or a divalent linking group, and a single bond is preferable. As a bivalent coupling group, the divalent group which consists of an alkylene group (preferably C1-C3 alkylene group), -O-, -NH-, and these combination can be illustrated.

R ¹² represents a hydrocarbon group substituted with at least one or more fluorine atoms, preferably an alkyl group substituted with at least one or more fluorine atoms, and more preferably a linear or branched alkyl group substituted with at least one or more fluorine atoms. 1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, and 1-6 are more preferable. Moreover, it is preferable that more than half of the carbon atoms which comprise an alkyl group are substituted by at least 1 fluorine atom.

R ¹² is preferably has a -CF ₃ or -CHF _2, and more preferably having such a structure at an end of its side chain. By using such a structure, the effect of this invention is exhibited more effectively.

Ar in General formula (2) represents an aromatic ring group, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. Ar may have a substituent other than Y, but it is more preferable not to have a substituent other than Y.

Y represents a fluorine atom or -L ² -R ²² .

R ²² represents a hydrocarbon group substituted with at least one or more fluorine atoms, preferably an alkyl group substituted with at least one or more fluorine atoms, and more preferably a linear or branched alkyl group substituted with at least one or more fluorine atoms. 1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, and 1-6 are more preferable. Moreover, it is preferable that more than half of the carbon atoms which comprise an alkyl group are substituted by at least 1 fluorine atom.

L ² represents a single bond or a divalent linking group. As a bivalent coupling group, the bivalent group which consists of an alkylene group, -O-, -NH-, and a combination thereof can be illustrated. As an alkylene group, a C1-C5 alkylene group is preferable and a C1-C3 alkylene group is more preferable.

n represents the integer of 1-5. When n is two or more, each Y may be same or different. n is preferably 1 when Y represents -LR ²² .

It is preferable that a structural unit (a3) is a structural unit represented with the following general formula (1 ') or (2').

In general formula (1 '),

[In General Formula (1 '), R ¹¹ represents hydrogen or a methyl group, X represents -O- or -NH-, L ¹ represents a single bond or a divalent linking group, and R ¹² represents at least one or more of fluorine atoms Substituted hydrocarbon group]

In general formula (2 '),

[In General Formula (2 '), R ²¹ represents hydrogen or a methyl group, Y represents a fluorine atom or -L ² -R ²² , R ²² represents a hydrocarbon group substituted with at least one or more by fluorine atoms, and L ² is a A bond or a divalent linking group. n represents the integer of 1-5. When n is 2 or more, each Y may be the same or different.]

The formula (1 ') of the X, L ¹ and R ¹² are each X, L ¹ and R ¹² and agreed in the formula (1) according to a preferred range agrees. R ¹¹ is preferably a methyl group.

The formula (2 ') Y, R ²² and L ² are each Y, R ²² and L ² as agreed in the formula (2) in a preferred range agrees. R ²¹ is preferably a methyl group.

Although the example of the monomer which comprises the structural unit (a3) used preferably by this invention is shown below, it cannot be overemphasized that this invention is not limited to these.

<<< preferred embodiment of a structural unit (a3) >>>

5-50 mol% is preferable with respect to the whole polymer, and, as for the content rate of the structural unit (a3) in the structural unit which comprises a copolymer (A), 10-30 mol% is especially preferable. If it is in the said numerical range, all the characteristics of the cured film obtained from the photosensitive resin composition will become favorable.

In particular, when the structural unit (a2) is included in a polymer such as the structural units (a1) and (a3), 5 to 30 mol% is preferable, and 10 to 20 mol% is more preferable in the polymer.

On the other hand, when structural unit (a2) is contained in a polymer different from structural unit (a1) and (a3), 5-30 mol% is preferable in the polymer containing said structural unit (a2), and 10-20 mol% is more preferable desirable.

<< (a4) other structural unit >>

In the present invention, the component (A) may have other structural units (a4) other than these in addition to the structural units (a1), (a2) and (a3). There is no restriction | limiting in particular as a monomer used as other structural unit (a4).

For example, styrene, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic The compound, conjugated diene type compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic anhydride, and other unsaturated compound are mentioned. Moreover, you may have a structural unit which has an acidic radical as mentioned later.

Specifically, styrene, tert-butoxy styrene, methyl styrene, hydroxy styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chloro styrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy Benzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid 2 Structural units by -hydroxyethyl, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, etc. are mentioned. have. In addition, Paragraph No. 0021 of Unexamined-Japanese-Patent No. 2004-264623-the compound of 0024 can be mentioned.

Moreover, the group which has styrene and an alicyclic skeleton as other structural unit (a4) is preferable from a viewpoint of an electrical property. Specifically, styrene, tert-butoxy styrene, methyl styrene, hydroxy styrene, α-methyl styrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl ( Meth) acrylate, etc. are mentioned. In particular, when the styrene-derived structural unit is included, the dielectric constant tends to be low, which is preferable.

Moreover, (meth) acrylic-acid alkylester is preferable from a viewpoint of adhesiveness as other structural unit (a4). Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, etc. are mentioned, and methyl (meth) acrylate is more preferable.

The monomer used as the said other structural unit (a4) can be used individually or in combination of 2 or more types.

60 mol% or less is preferable, as for the content rate of a structural unit (a4) in the structural unit which comprises a copolymer (A), 50 mol% or less is more preferable, 40 mol% or less is more preferable. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, and can also be 5 mol% or more. If it is in the said numerical range, all the characteristics of the cured film obtained from the photosensitive resin composition will become favorable.

The component (A) used in the present invention preferably contains an acid group. By containing an acid group, it is easy to melt | dissolve in an alkaline developing solution, and the effect of this invention is exhibited more effectively. The acidic radical in this invention shows the proton dissociable group whose pKa is smaller than seven. An acidic radical is normally attached to resin as a structural unit containing an acidic radical using the monomer which can form an acidic radical. There exists a tendency for alkali solubility to become large by including the structural unit containing such an acidic radical in resin.

The acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfonamide groups, and alcohols. Ponylimide group etc. can be illustrated, It is preferable to originate from the thing derived from a carboxylic acid group, and / or a phenolic hydroxyl group.

It is more preferable that the structural unit containing the acid group used by this invention is a structural unit derived from the structural unit derived from styrene, the structural unit derived from a vinyl compound, (meth) acrylic acid, and / or its ester.

In this invention, it is especially preferable to contain the structural unit which has a carboxyl group, or the structural unit which has a phenolic hydroxyl group from a viewpoint of a sensitivity. As content, 1-50 mol% is preferable, It is more preferable that it is 2-30 mol%, It is further more preferable that it is 5-20 mol%, It is especially preferable that it is 5-15 mol%. As a structural unit which has a carboxyl group or phenolic hydroxyl group, the monomer which has a well-known acidic group is mentioned, Especially, hydroxy styrene, (meth) acrylic acid, and the following length chain carboxylic acid are preferable.

As a structural unit which has a long-chain carboxylic acid, the structural unit represented by a following formula is preferable.

[In formula, R <^1> is a hydrogen atom or a methyl group, R <^2> is an organic group of n + 1 value, and n is an integer of 1-4.

R ² is preferably an organic group having 2 to 15 carbon atoms and 0 to 6 hetero atoms (more preferably 1 to 6 hetero atoms).

As for the structural unit which has a long-chain carboxylic acid, the structural unit represented by a following formula is more preferable.

[Wherein R ¹ is a hydrogen atom or a methyl group, R ³ is an alkylene group having 1 to 10 carbon atoms, and R ⁴ is an alkylene group having 1 to 10 carbon atoms]

R <^3> and R <^4> may be any of linear, branched or cyclic, respectively. R <^3> and R <^4> has preferable C2-C8 alkylene group, respectively, and its 4-8 alkylene group is more preferable.

As for the structural unit containing an acidic radical, 1-80 mol% of the structural unit of all the resin components is preferable, 1-50 mol% is more preferable, 5-40 mol% is still more preferable, 5-30 mol% is especially It is preferable and 5-20 mol% is especially preferable.

<< molecular weight of (A) copolymer >>

The molecular weight of the copolymer (A) is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000, in terms of polystyrene reduced weight average molecular weight. All the characteristics are good if it is in the said numerical range. The ratio of the number average molecular weight to the weight average molecular weight (dispersion degree) is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< The manufacturing method of (A) copolymer >>

Moreover, although various methods are known also about the synthesis | combining method of (A) component, For example, radically polymerizable including the radically polymerizable monomer used in order to form the structural unit represented by said (a1) and said (a3) at least. A monomer mixture can be synthesize | combined by superposing | polymerizing using the radical polymerization initiator in the organic solvent. Moreover, it can also synthesize | combine by what is called a polymer reaction.

Moreover, it is also preferable that (A) component has a carboxyl group at the terminal.

[Synthesis method of resin which has a carboxyl group at the terminal]

Resin which has a carboxyl group at the terminal can be manufactured by copolymerizing a corresponding monomer by radical polymerization, anion polymerization, group transfer polymerization (GTP), etc. Although the manufacturing method of resin which has a carboxyl group at the terminal of this invention is not specifically limited, For example, Paragraph No. 0099 of Unexamined-Japanese-Patent No. 2005-122035-the method of (01) of (0117) are mentioned. .

Especially, the method of (a) and (b) is preferable.

(A) As a method of using the polymerization initiator which has a carboxyl group, the polymerization initiator which has a carboxyl group is used as an initiator at the time of superposition | polymerization.

Although widely used as a polymerization initiator which has a carboxyl group, VA-057 (made by Wako Pure Chemical Industries, Ltd.) and V-501 (made by Wako Pure Chemical Industries, Ltd.) are mentioned as an example.

It is preferable that it is 0.05-10 mol% with respect to 100 mol of polymeric monomers, and, as for such a polymerization initiator, it is more preferable that it is 0.1-5 mol%.

It is preferable that it is 50-100 degreeC, and, as for the reaction temperature of a copolymerization reaction, it is more preferable that it is 60-100 degreeC.

(B) In the method of using the chain transfer agent which has a carboxyl group at the time of superposition | polymerization, the thiol compound which has at least 1 carboxyl group is used together at the time of superposition | polymerization. Examples of the thiol compound having at least one carboxyl group include the following examples.

It is preferable to mix | blend a chain transfer agent in the ratio of 1 / 100-2 / 3 mol with respect to an initiator amount, and it is more preferable to mix | blend in the ratio of 1 / 20-1 / 3 mol.

Although molecular weight is adjusted according to the sum total of the initiator amount and the chain transfer agent, it is preferable that it is 0.05-10 mol% with respect to the total mole of all monomers, and it is more preferable that it is 0.1-5 mol%.

It is preferable that it is 50-100 degreeC, and, as for the reaction temperature of a copolymerization reaction, it is more preferable that it is 60-95 degreeC.

It is preferable to contain (A) component in the ratio of 50-99.9 mass% with respect to all solid content, and, as for the photosensitive resin composition of this invention, it is more preferable to contain in the ratio of 70-98 mass%.

<(B) Mine Generator>

The photosensitive resin composition of this invention contains the (B) photo-acid generator. As a photo-acid generator (also called "(B) component") used by this invention, the compound which generate | occur | produces an acid in response to actinic light of wavelength 300nm or more, Preferably wavelength 300-450nm is preferable, but the chemical structure It is not limited. Also, for 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 in response to an actinic ray having a wavelength of 300 nm or more by being used 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 for generating an acid having a pKa of 4 or less is preferable, a photoacid generator for generating an acid having a pKa of 3 or less is more preferable, and a photoacid generator for generating an acid having a value of 2 or less is most preferred. .

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds. Among these, it is preferable to use an onium salt compound and an oxime sulfonate compound from an insulating viewpoint, and an oxime sulfonate compound is still more preferable. These photo-acid generators can be used individually by 1 type or in combination of 2 or more types. Specific examples of the trichloromethyl-s-triazines, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives are described in paragraphs 0083 to 0088 of JP2011-221494A. Compounds can be exemplified.

As an oxime sulfonate compound, ie, a compound which has an oxime sulfonate structure, the compound containing the oxime sulfonate structure represented by following General formula (B1) can be illustrated preferably.

General formula (B1)

[In General Formula (B1), R ²¹ represents an alkyl group or an aryl group. Dashed lines indicate bonding with other groups]

Either group may be substituted and the alkyl group in R ²¹ may be linear, branched, or cyclic. Acceptable substituents are described below.

As an alkyl group of R <^21> , a C1-C10 linear or branched alkyl group is preferable. The alkyl group of R ^{21 preferably} includes a bicyclic alkyl group such as a C 6 -C 11 aryl group, a C 1 -C 10 alkoxy group or a cycloalkyl group (7,7-dimethyl-2-oxo nobornyl group, etc.). ) May be substituted.

As an aryl group of R <^21> , a C6-C11 aryl group is preferable and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a slow alkyl group, an alkoxy group or a halogen atom.

It is preferable that the said compound containing the oxime sulfonate structure represented by said general formula (B1) is also an oxime sulfonate compound represented with the following general formula (B2).

[In formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m 4 represents an integer of 0 to 3, and when m 4 is 2 or 3, a plurality of X may be the same. May be different]

As a preferable range of R <^{42>, it} is the same as the preferable range of said R <^21> .

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

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

The halogen atom as X is preferably a chlorine atom or a fluorine atom.

m4 is preferably 0 or 1.

In said general formula (B2), m4 is 1, X is a methyl group, a substitution position of X is an ortho position, R <^42> is a C1-C10 linear alkyl group, 7,7- dimethyl- 2-oxo nobornyl methyl group Or a compound that is a p-toluyl group.

It is more preferable that the compound containing the oxime sulfonate structure represented by said general formula (B1) is an oxime sulfonate compound represented with the following general formula (B3).

[In Formula (B3), R ⁴³ is synonymous with R ⁴² in Formula (b1), and X ¹ is a halogen atom, a hydroxyl group, a C 1-4 alkyl group, a C 1-4 alkoxy group, a cyano group, or a nitro group N4 represents an integer of 0 to 5].

As R ⁴³ in the general formula (B3), a methyl group, an ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is especially preferable.

As X <^{1>, a} C1-C5 alkoxy group is preferable and a methoxy group is more preferable.

As n4, 0-2 are preferable and 0-1 are especially preferable.

Specific examples of the compound represented by the general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzylcyanide, α- (n-propylsulfonyloxyimino) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl ] Acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[( n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile and (alpha)-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

As a specific example of a preferable oxime sulfonate compound, following compound (i)-(i) etc. are mentioned, It can use individually by 1 type, or can use two or more types together. Compound (i)-(iv) can be obtained as a commercial item. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

It is preferable that it is also a compound represented with the following general formula (OS-1) as a compound containing the oxime sulfonate structure represented by said general formula (B1).

R ¹⁰¹ in formula (OS-1) represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. . R ¹⁰² represents an alkyl group or an aryl group.

X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, and R ¹⁰⁵ to R ¹⁰⁷ represent an alkyl group or aryl Group.

R ¹²¹ to R ¹²⁴ 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 ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

As R ¹²¹ to R ¹²⁴ , a hydrogen atom, a halogen atom and an alkyl group are preferable, and embodiments in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group are also preferable. Especially, the form whose R <^121> -R <^124> is all hydrogen atoms is preferable from a viewpoint of a sensitivity.

All of the said functional groups may have a substituent further.

As for the compound represented by the said general formula (OS-1), it is more preferable that it is a compound represented with the following general formula (OS-2).

In said general formula (OS-2), R <^101> , R <^102> , R <^121> -R <^124> are synonymous with the thing in Formula (OS-1), respectively, and a preferable example is also the same.

Among these, the embodiment in which R ^{101 in} General Formula (OS-1) and General Formula (OS-2) is a cyano group or an aryl group is more preferable, represented by General Formula (OS-2), and R ^{The embodiment where 101} is a cyano group, a phenyl group, or a naphthyl group is the most preferable.

In addition, in the said oxime sulfonate compound, the stereo structure (E, Z etc.) of an oxime and a benzothiazole ring may be respectively any one, or a mixture may be sufficient as it.

As a specific example of the compound represented by the said general formula (OS-1) which can be used suitably for this invention, Paragraph No. 0128 of Unexamined-Japanese-Patent No. 2011-221494-the compound of 0232 (example compound b-1-b-34) ), But the present invention is not limited to this.

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

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

The alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ in General Formulas (OS-3) to (OS-5) may have a substituent.

It is preferable that it is a C1-C30 alkyl group which may have a substituent as an alkyl group in R <^22> , R <^25> and R <^28> in said Formula (OS-3)-(OS-5).

Moreover, as an aryl group in R <^22> , R <^25> and R <^28> in the said general formula (OS-3)-(OS-5), the C6-C30 aryl group which may have a substituent is preferable.

Moreover, as a heteroaryl group in R <^1> in said general formula (OS-3)-(OS-5), the heteroaryl group of 4-30 total carbons which may have a substituent is preferable.

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

In General Formulas (OS-3) to (OS-5), R ²³ , R ^26, and R ²⁹ are each preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.

It is preferable that one or two of R ²³ , R ²⁶ and R ²⁹ present in two or more of the compounds in the general formulas (OS-3) to (OS-5) are alkyl groups, aryl groups or halogen atoms, and one is an alkyl group. It is more preferable that it is an aryl group or a halogen atom, It is especially preferable that one is an alkyl group and the remainder is a hydrogen atom.

As an alkyl group in R <^23> , R <^26> and R <^29> , it is preferable that it is a C1-C12 alkyl group which may have a substituent, and it is more preferable that it is a C1-C6 alkyl group which may have a substituent.

As an aryl group in R <^23> , R <^26> and R <^29> , it is preferable that they are a C6-C30 aryl group which may have a substituent.

In General Formulas (OS-3) to (OS-5), X ¹ to X ³ each independently represent O or S, and are preferably O.

In General Formulas (OS-3) to (OS-5), the ring containing X ¹ to X ³ as a reduction is a 5- or 6-membered ring.

N ¹ to n ³ in General Formulas (OS-3) to (OS-5) each independently represent 1 or 2, and when X ¹ to X ³ are O, n ¹ to n ³ are each independently 1; It is preferable that n ¹ to n ³ are each independently 2 when X ¹ to X ³ are S.

R ²⁴ , R ²⁷ and R ³⁰ in the general formulas (OS-3) to (OS-5) each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Especially, it is preferable that R <^24> , R <^27> and R <^30> are respectively independently an alkyl group or an alkyloxy group.

The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.

As said alkyl group in R <^24> , R <^27> and R <^30> in the said general formula (OS-3)-(OS-5), it is preferable that it is the alkyl group of 1-30 total carbons which may have a substituent.

As said alkyloxy group in R <^24> , R <^27> and R <^30> in the said general formula (OS-3)-(OS-5), it is preferable that it is the alkyloxy group of 1-30 total carbons which may have a substituent.

In addition, m <^1> -m <^3> in the said general formula (OS-3)-(OS-5) respectively independently represents the integer of 0-6, It is preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1 And it is especially preferable that it is zero.

Moreover, about each substituent of said (OS-3)-(OS-5), the substituents of (OS-3)-(OS-5) of Paragraph No. 0092-0109 of Unexamined-Japanese-Patent No. 2011-221494 Preferred ranges are likewise preferred.

Moreover, it is especially preferable that the compound containing the oxime sulfonate structure represented by said general formula (B1) is an oxime sulfonate compound represented by either of the following general formula (OS-6)-(OS-11). .

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

The preferable range in said general formula (OS-6)-(OS-11) is the preferable range of (OS-6)-(OS-11) as described in Paragraph No. 0110 of Unexamined-Japanese-Patent No. 2011-221494-0112. Same as

Although the compound of Paragraph No. 0114 of Unexamined-Japanese-Patent No. 2011-221494-0120 is mentioned as a specific example of the oxime sulfonate compound represented by the said General Formula (OS-3)-the said General Formula (OS-5), The invention is not limited to these.

In the photosensitive resin composition of this invention, it is preferable to use 0.1-10 mass parts of (B) photo-acid generators with respect to 100 mass parts of all the resin components (preferably solid content, more preferably the sum total of a copolymer) in the photosensitive resin composition. It is preferable and it is more preferable to use 0.5-10 mass parts. You may use 2 or more types together.

<(D) solvent>

The photosensitive resin composition of this invention contains the (D) solvent. The photosensitive resin composition of this invention is prepared as a solution which melt | dissolved the above-mentioned (C)-(D) component which is an essential component, (E)-(I) component mentioned later which is a preferable component, and the arbitrary components mentioned later further in the (D) solvent. It is preferable to be.

A well-known solvent can be used as (D) solvent used for the photosensitive resin composition of this invention, Ethylene glycol monoalkyl ether, Ethylene glycol dialkyl ether, Ethylene glycol monoalkyl ether acetate, Propylene glycol monoalkyl ether , 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, di Propylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like can be exemplified. Moreover, as a specific example of the (D) solvent used for the photosensitive resin composition of this invention, Paragraph No. 0174 of Unexamined-Japanese-Patent No. 2011-221494-the solvent of 078 can also be mentioned.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, and 1-octa, as necessary for these solvents. Solvents such as phenol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may be further added. These solvents can be used individually by 1 type or in mixture of 2 or more types. It is preferable to use together single 1 type or 2 types of solvents which can be used for this invention, It is more preferable to use 2 types together together, Propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates, and diethylene It is more preferable to use glycol dialkyl ether or ester and butylene glycol alkyl ether acetate together.

Moreover, as component D, it is preferable that they are a boiling point of 130 degreeC or more, a solvent below 160 degreeC, a solvent with a boiling point of 160 degreeC or more, or a mixture thereof, a solvent with a boiling point of 130 degreeC or more and less than 160 degreeC, a solvent with a boiling point of 160 degreeC or more and 200 degrees C or less, or these It is more preferable that it is a mixture of, and it is still more preferable that it is a mixture of the boiling point of 130 degreeC or more and the solvent below 160 degreeC, and the solvent of boiling point 160 degreeC or more and 200 degrees C or less.

As a solvent of boiling point 130 degreeC or more and less than 160 degreeC, propylene glycol monomethyl ether acetate (boiling point 146 degreeC), propylene glycol monoethyl ether acetate (boiling point 158 degreeC), propylene glycol methyl- n-butyl ether (boiling point 155 degreeC), propylene glycol Methyl-n-propyl ether (boiling point of 131 degreeC) can be illustrated.

As a solvent of boiling point 160 degreeC or more, 3-ethoxy propionate ethyl (boiling point 170 degreeC), diethylene glycol methyl ethyl ether (boiling point 176 degreeC), propylene glycol monomethyl ether propionate (boiling point 160 degreeC), dipropylene glycol methyl ether acetate (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C ), Diethylene glycol monoethyl ether acetate (boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.) can be exemplified.

It is preferable that content of the (D) solvent in the photosensitive resin composition of this invention is 50-3,000 mass parts per 100 mass parts of all resin components (preferably solid content, more preferably said (C) copolymer) in the photosensitive resin composition. It is more preferable that it is 100-2,000 mass parts, and it is still more preferable that it is 150-1,500 mass parts.

<Other ingredients>

To the positive photosensitive resin composition of the present invention, (E) sensitizer, (F) crosslinking agent, (G) adhesion improving agent, (H) basic compound, and (I) surfactant may be preferably added in addition to the above components. Can be. Moreover, well-known additives, such as a plasticizer, a thermal radical generator, antioxidant, a thermal acid generator, a ultraviolet absorber, a thickener, a development promoter, and an organic or inorganic precipitation inhibitor, can be added to the positive photosensitive resin composition of this invention.

(E) sensitizer

It is preferable that the photosensitive resin composition of this invention contains a sensitizer in order to accelerate the decomposition | disassembly in combination with (B) photo-acid generator. A sensitizer will absorb actinic light or a radiation and will be in an electron excited state. A sensitizer which has become an electron excited state comes into contact with a photoacid generator to generate an electron transfer, energy transfer, and heat generation. As a result, the photoacid generator causes a chemical change to decompose to produce an acid. As a preferable example of a sensitizer, the compound which belongs to the following compounds, and has an absorption wavelength in either of 350 nm-450 nm of wavelength ranges is mentioned.

Polynuclear aromatics (e.g., pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxy Anthracene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (e.g., xanthone, thioxanthone, dimethyl thioxanthone, diethylthioke) Santon), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), rhodayanine, oxonol, thia Bindus (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavin), acridones (eg acridon, 10-butyl-2-chloroacridone), anthraquinones (eg anthraquinones), squaryliums (eg squarylium), styryls, bays Styryls (eg 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (eg 7-diethylamino4-methylcoumarin, 7-hydride) Oxy4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolidine-11-non).

Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Among the polynuclear aromatics, anthracene derivatives are most preferred.

It is preferable that the addition amount of the sensitizer in the photosensitive resin composition of this invention is 0-1000 weight part with respect to 100 weight part of photo-acid generators of the photosensitive resin composition, It is more preferable that it is 10-500 weight part, It is 50-200 weight part More preferred.

You may use 2 or more types together.

(F) crosslinking agent

It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of this invention can be made a stronger film.

There is no restriction | limiting as long as a crosslinking agent generate | occur | produces a crosslinking reaction by heat (except component A). For example, the compound which has a 2 or more epoxy group or an oxetanyl group, the alkoxy methyl group containing crosslinking agent, or the compound which has at least 1 ethylenically unsaturated double bond can be added in the molecule | numerator demonstrated below.

Among these crosslinking agents, compounds having two or more epoxy groups or oxetanyl groups in the molecule are preferred, and epoxy resins are particularly preferred.

It is preferable that the addition amount of the crosslinking agent in the photosensitive resin composition of this invention is 0.01-50 weight part with respect to 100 weight part of total solids of the photosensitive resin composition, It is more preferable that it is 0.5-30 weight part, It is more preferable that it is 2-10 weight part. desirable. By adding in this range, the cured film excellent in mechanical strength and solvent resistance is obtained. A crosslinking agent can also use plurality together, and in that case, adds all the crosslinking agents, and calculates content.

<Compounds having two or more epoxy groups or oxetanyl groups in the molecule>

As a specific example of the compound which has two or more epoxy groups in a molecule | numerator, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

These are available as commercial products. For example, the commercial item of Paragraph No. 0189 of Unexamined-Japanese-Patent No. 2011-221494, such as JER150S70 (made by JAPAN EPOXY RESINS CO., Ltd.), etc. are mentioned.

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, made by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, made by ADEKA CORPORATION), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX -313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841 , EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC -205, DLC-206, DLC-301, DLC-402 (above, manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, Nippon Steel Chemical Co., Ltd.) etc. are mentioned.

These may be used alone or in combination of two or more.

Among these, bisphenol-A epoxy resin, bisphenol-F epoxy resin, a phenol novolak-type epoxy resin, an aliphatic epoxy, and an aliphatic epoxy resin are mentioned more preferable, A bisphenol-A epoxy resin is especially preferable.

As a specific example of a compound which has two or more oxetanyl groups in a molecule | numerator, Aaronoxetane OXT-121, OXT-221, OX-SQ, PNOX (above, TOAGOSEI CO., LTD.) Can be used.

In addition, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

Moreover, as another crosslinking agent, Paragraph No. 0107 of Unexamined-Japanese-Patent No. 2012-8223-the crosslinking agent of 0108 and the compound which has at least 1 ethylenically unsaturated double bond, etc. can also be used preferably.

(G) adhesion improver

The photosensitive resin composition of this invention may contain the (G) adhesion improving agent. The (G) adhesion improving agent used in the photosensitive resin composition of this invention improves the adhesiveness of the insulating material, for example, silicon compounds, such as a silicon, silicon oxide, and silicon nitride, metal, such as gold, copper, aluminum, and an insulating film. Compound. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as a (G) adhesion improving agent used by this invention aims at the modification of an interface, A well-known thing can be used without a restriction | limiting in particular.

As a preferable silane coupling agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyltrialkoxysilane, (gamma)-glycidoxy propyl dialkoxysilane, (gamma)-meta, Cryoxypropyl trialkoxysilane, (gamma)-methacryloxypropyl dialkoxysilane, (gamma)-chloropropyl trialkoxysilane, (gamma)-mercaptopropyl trialkoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrialkoxysilane, Vinyltrialkoxysilane. Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane Even more preferred. These may be used alone or in combination of two or more. They are effective for improving the adhesiveness with a board | substrate and also for adjusting the taper angle with a board | substrate.

0.1-30 mass parts is preferable with respect to 100 mass parts of total solids in the photosensitive resin composition, and, as for content of the (G) adhesion improving agent in the photosensitive resin composition of this invention, 0.5-10 mass parts is more preferable.

(H) basic compounds

The photosensitive resin composition of this invention may contain the (H) basic compound. (H) It can be used selecting arbitrarily as a basic compound from what is used by chemically amplified resist. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, quaternary ammonium salt of carboxylic acid, etc. are mentioned. As these specific examples, Paragraph No. 0204 of Unexamined-Japanese-Patent No. 2011-221494-the compound of 0207 are mentioned.

Although the basic compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types together, It is preferable to use 2 or more types together, It is more preferable to use 2 types together, It uses two types of heterocyclic amines together More preferably.

It is preferable that it is 0.001-1 mass part with respect to 100 mass parts of total solids in the photosensitive resin composition, and, as for content of the (H) basic compound in the photosensitive resin composition of this invention, it is more preferable that it is 0.005-0.2 mass part.

(I) surfactant

The photosensitive resin composition of this invention may contain surfactant (I). As the (I) surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but the preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone and fluorine-based surfactants. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflo (manufactured by Tokyoeisha Chemical Co., Ltd.), F-top (manufactured by Japan Electronic Monetary Claim Organization), and Mega Pack (manufactured by DIC Corporation) are referred to below. , Fluoride (manufactured by Sumitomo 3M Limited), Asahi Guard, Safron (manufactured by ASAHI GLASS CO., LTD.), PolyFox (manufactured by OMNOVA Solutions Inc.), SH-8400 (Dow Corning Toray Co., Ltd.) Each series is mentioned.

Moreover, the weight average of the polystyrene conversion measured by the gel permeation chromatography in which the structural unit A and structural unit B which are represented by following General formula (1) as a surfactant is made into tetrahydrofuran (THF) as a solvent is included. The copolymer whose molecular weight (Mw) is 1,000 or more and 10,000 or less is mentioned as a preferable example.

In general formula (1)

[In formula (1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a straight chain alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or 1 or more carbon 4 Or less alkyl group, L represents a C3 or more and 6 or less alkylene group, p and q are the weight percentages which show a polymerization ratio, p represents the numerical value of 10 mass% or more and 80 mass% or less, q Represents a numerical value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less]

It is preferable that said L is a branched alkylene group represented by following General formula (2). R ⁴⁰⁵ in the general formula (2) represents an alkyl group having 1 to 4 carbon atoms, and in view of compatibility and wettability to the surface to be coated, an alkyl group having 1 to 3 carbon atoms is preferable, and has 2 or more carbon atoms. Three alkyl groups are more preferable. It is preferable that sum (p + q) of p and q is p + q = 100, ie, 100 mass%.

General formula (2)

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.

It is preferable that it is 10 mass parts or less with respect to 100 mass parts of total solids in the photosensitive resin composition, and, as for the addition amount of (I) surfactant in the photosensitive resin composition of this invention, it is more preferable that it is 0.001-50 mass parts, and it is 0.01-10 mass More preferably denial.

[Antioxidant]

The photosensitive resin composition of this invention may contain antioxidant. As antioxidant, a well-known antioxidant can be contained. By adding antioxidant, coloring of a cured film can be prevented, the film thickness reduction by decomposition can be reduced, and there exists an advantage that it is excellent in heat resistance transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite salts, sulfites, thiosulfates, hydroxylamines And derivatives thereof. Among these, a phenolic antioxidant is especially preferable from a viewpoint of coloring of a cured film and reduction of a film thickness. These may be used individually by 1 type and may mix and use 2 or more types.

As a commercial item of a phenolic antioxidant, For example, adecastaob-A-20, adecastab-AO-30, adecastab-AO-40, adecastab-AO-50 made by ADEKA CORPORATION, adecastab-AO-60, Adecastabe AO-70, Adecastabe AO-80, Adecastabe AO-330, Sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizerBBM-S, sumilizerWX-R, sumilizerGA-80, Ciba Japan KRG IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425WL, IRGANOX1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IOXANOX295, IRGBOXOX95 , Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 and the like.

Among them, adecastabu AO-60, adecastabu AO-80 (above, made by ADEKA CORPORATION) and Irganox 1098 (manufactured by Ciba Japan K.K.) are preferable.

It is preferable that content of antioxidant is 0.1-10 mass% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 0.2-5 mass%, It is especially preferable that it is 0.5-4 mass%. By setting it as this range, sufficient transparency of the formed film is obtained and the sensitivity at the time of pattern formation also becomes favorable.

Moreover, you may add the various ultraviolet absorbers, metal inactivating agents, etc. which were described in "New development of polymer additives" (Daily Industrial News, Inc.) as additives other than antioxidant to the photosensitive resin composition of this invention.

Moreover, in this invention, it is also preferable to use the sulfonic acid ester which generate | occur | produces an acid by heat, without generating an acid substantially by irradiation of exposure light.

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

It is preferable that it is 230-1,000, and, as for the molecular weight of sulfonic acid ester, it is more preferable that it is 230-800.

The sulfonic acid ester which can be used for this invention may use a commercially available thing, and may use the thing synthesize | combined by a well-known method. The sulfonic acid esters can be synthesized, for example, by reacting sulfonylchloride or sulfonic anhydride with the corresponding polyhydric alcohol under basic conditions.

When content of the thermal acid generator to the photosensitive resin composition makes the total content of (C) component 100 weight part, 0.5-20 weight part is preferable and 1-15 weight part is more preferable.

[Acid multipliers]

The photosensitive resin composition of this invention can use an acid increasing agent for the purpose of a sensitivity improvement.

The acid propagation agent used in the present invention is a compound capable of further generating an acid by an acid catalyzed reaction to increase the acid concentration in the reaction system, and is a compound which is stably present in the absence of acid. Since one or more acids are increased in one reaction, the compound accelerates as the reaction proceeds. However, since the generated acid itself is self-analyzed, the strength of the acid generated here is acid dissociation constant, pKa. It is preferable that it is 3 or less, and it is especially preferable that it is 2 or less.

As an example of an acid increasing agent, Paragraph No. 0203 of Unexamined-Japanese-Patent No. 10-1508-0223, Paragraph No. 0016 of Unexamined-Japanese-Patent No. 10-282642, 0016-0055, and Japanese Patent Publication No. 9-512498, page 39 The compound of 12th line-47th page 2nd line is mentioned.

As the acid multiplying agent used in the present invention, it is decomposed by an acid generated from an acid generator to generate an acid having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid. The compound to make is mentioned.

Specifically,

And the like.

It is preferable to set it as 10-1,000 weight part with respect to 100 weight part of photo-acid generators, and, as for content of an acid increasing agent to the photosensitive resin composition, it is more preferable to set it as 20-500 weight part. .

[Improvement accelerator]

The photosensitive resin composition of this invention can contain a development accelerator.

Arbitrary compounds having an image development promoting effect can be used as the development accelerator, but are preferably compounds having at least one structure selected from the group of carboxyl groups, phenolic hydroxyl groups and alkyleneoxy groups, and compounds having carboxyl groups or phenolic hydroxyl groups. This is more preferable and the compound which has a phenolic hydroxyl group is the most preferable.

Moreover, as a molecular weight of (M) image development promoter, 100-2000 are preferable, 100-1000 are more preferable, and it is 100-800 optimally.

Examples of the development promoter include polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester and poly Butylene glycol, polyethylene glycol bisphenol A ether, polypropylene glycol bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, the compound described in JP-A-9-222724, etc. are mentioned. .

Examples of the carboxyl group include maleic acid, fumaric acid, acetylenecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, sericinic acid, adipic acid, citric acid and malic acid. In addition, the compound of Unexamined-Japanese-Patent No. 2000-66406, Unexamined-Japanese-Patent No. 9-6001, Unexamined-Japanese-Patent No. 10-20501, Unexamined-Japanese-Patent No. 11-338150, etc. are mentioned.

As having a phenolic hydroxyl group, Unexamined-Japanese-Patent No. 2005-346024, Unexamined-Japanese-Patent No. 10-133366, Unexamined-Japanese-Patent No. 9-194415, Unexamined-Japanese-Patent No. 9-222724, Unexamined-Japanese-Patent No. The compound of 11-171810, Unexamined-Japanese-Patent No. 2007-121766, Unexamined-Japanese-Patent No. 9-297396, Unexamined-Japanese-Patent No. 2003-43679, etc. are mentioned. Among these, the phenol compound of 2-10 benzene rings is suitable, and the phenol compound of 2-5 benzene rings is more suitable. As a particularly preferable thing, the phenolic compound disclosed as a dissolution promoter in Unexamined-Japanese-Patent No. 10-133366 is mentioned.

The image development promoter may be used individually by 1 type, and can also use 2 or more types together.

When the addition amount of the development accelerator in the photosensitive resin composition of this invention makes 100 mass parts of (A) components from a viewpoint of a sensitivity and a residual film ratio, 0-30 mass parts is preferable, 0.1-20 mass parts is more preferable, 0.5- Most preferably, it is 10 mass parts.

Moreover, as another additive, the thermal radical generator and thermal acid generator as described in Paragraph No. 0120 of Unexamined-Japanese-Patent No. 2012-8223-0121 can also be used.

[Production method of hardened film]

Next, the manufacturing method of the cured film of this invention is demonstrated.

It is preferable that the manufacturing method of the cured film of this invention includes the process of the following (1)-(5).

(1) Process of applying positive type photosensitive resin composition of this invention on board | substrate;

(2) removing the solvent from the applied positive photosensitive resin composition;

(3) exposing with actinic light;

(4) developing with an aqueous developer;

(5) Post-baking step of thermosetting.

Each step will be described below in order.

In the application process of (1), it is preferable to apply the positive photosensitive resin composition of this invention on a board | substrate, and to set it as the wet film containing a solvent.

In the solvent removal process of (2), a solvent is removed from the said film | membrane applied by decompression (vacuum) and / or heating, and a dry coating film is formed on a board | substrate.

In the exposure process of (3), actinic light of wavelength 300nm or more and 450nm or less is irradiated to the obtained coating film. In this step, the (B) photoacid generator is decomposed to generate acid. The acid decomposable group contained in the polymer component (A) is hydrolyzed by the generated acid catalysis to produce a carboxyl group or a phenolic hydroxyl group.

Post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as &quot; PEB &quot;) is performed in order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote the production of carboxyl groups or phenolic hydroxyl groups from acid-decomposable groups. It is preferable that the temperature at the time of PEB is 30 degreeC or more and 130 degrees C or less, 40 degreeC or more and 110 degrees C or less are more preferable, 50 degreeC or more and 100 degrees C or less are especially preferable.

The acid-decomposable group in the structural unit represented by the formula (a1-1) in the present invention has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from an acid generator by exposure, and represents a carboxyl group or a phenolic hydroxyl group. Although it is possible to form a positive image by development without necessarily performing PEB, in the manufacturing method of the cured film of this invention, the cured film obtained by performing the post-baking process of (5) using the photosensitive resin composition of this invention is a heat flow. Can be less. Therefore, even when the cured film obtained by the manufacturing method of the cured film of this invention is used for a board | substrate as a resist, even if the cured film of the board | substrate this invention was heated, the resolution of a pattern does not deteriorate for the most part. In addition, in this specification, the term "heat flow" is deformed when the cross-sectional shape of the pattern cured film formed by the exposure and development processes is heated when the cured film is heated (preferably 180 ° C or more, more preferably 200 ° C to 240 ° C). , Taper angle, etc. are deteriorated.

In the developing process of (4), the copolymer which has a free carboxyl group or phenolic hydroxyl group is developed using alkaline developing solution. A positive image is formed by removing the exposure part area | region containing the resin composition which has a carboxyl group or phenolic hydroxyl group which is easy to melt | dissolve in an alkaline developing solution.

By heating the positive image obtained in the post-baking process of (5), the acid-decomposable group in a structural unit (a1) is thermally decomposed, a carboxyl group or a phenolic hydroxyl group is produced, and a cured film is crosslinked by crosslinking group, crosslinking agent, etc. of structural unit (a3). Can be formed. It is preferable to heat this heating at 150 degreeC or more high temperature, It is more preferable to heat at 180-250 degreeC, It is especially preferable to heat at 200-240 degreeC. The heating time can be appropriately set depending on the heating temperature and the like, but it is preferably within a range of 10 to 120 minutes.

By adding a step of totally irradiating actinic light, preferably ultraviolet rays, to the developing pattern before the post-baking process, the crosslinking reaction can be promoted by the acid generated by actinic light irradiation.

Moreover, the cured film obtained from the photosensitive resin composition of this invention can also be used as a dry etching resist.

When using the cured film obtained by thermosetting by the post-baking process of (5) as a dry etching resist, as an etching process, dry etching processes, such as ashing, plasma etching, and ozone etching, can be performed.

Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Preparation method of the photosensitive resin composition>

(A) component and (B) component which are essential components are mixed by a predetermined ratio, by arbitrary methods, and are stirred and dissolved, and the photosensitive resin composition is prepared. For example, after making the component used by this invention into the solution which melt | dissolved in the (D) solvent previously, respectively, these can also be mixed in a predetermined ratio, and the resin composition can also be prepared. The composition solution prepared as mentioned above can also be used for use, after filtering using a filter etc. of 0.2 micrometer of pore diameters.

<Application process and solvent removal process>

The desired dry coating film can be formed by applying a photosensitive resin composition to a predetermined board | substrate, and removing a solvent by pressure reduction and / or heating (prebaking). As said board | substrate, the glass plate etc. which further formed the polarizing plate, the black matrix layer, the color filter layer as needed, and formed the transparent conductive circuit layer can be illustrated, for example in manufacture of a liquid crystal display element. Although there is no restriction | limiting in particular as a method of applying a photosensitive resin composition to a board | substrate, Especially, in this invention, it is preferable to apply | coat a photosensitive resin composition to a board | substrate. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coating method, and a spin coating method, can be used. Among them, the slit coat method is preferable from the viewpoint of being suitable for large substrates. It is preferable to manufacture on a large board | substrate because of high productivity. Here, a large board | substrate means the board | substrate of the magnitude | size of each side 1 m or more and 5 m or less.

In addition, the heating conditions of (2) solvent removal process are the ranges in which an acid-decomposable group decomposes | disassembles in the structural unit (a1) in an unexposed part, and does not make (A) component soluble in an alkaline developing solution, and the kind and compounding ratio of each component Although it depends also on, Preferably it is about 30 to 120 second at 80-130 degreeC.

<Exposure process and development process (pattern forming method)>

In an exposure process, actinic light is irradiated to the board | substrate which formed the coating film through the mask which has a predetermined | prescribed pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in the developing step, the exposure area is removed using an alkaline developer to form an image pattern.

Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, chemical lamps, LED light sources, excimer laser generators and the like can be used for exposure to active light, and g-rays (436 nm), i-rays (365 nm), and h-rays (405 nm). Actinic rays having a wavelength of 300 nm or more and 450 nm or less, such as), can be preferably used. Moreover, irradiation light can also be adjusted through spectroscopic filters, such as a long wavelength cutoff filter, a short wavelength cutoff filter, and a bandpass filter, as needed.

It is preferable that a basic compound is contained in the developing solution used at the image development process. As a basic compound, For example, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, 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; Aqueous solutions, such as sodium silicate and sodium metasilicate, can be used. Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the aqueous solution of the said alkalis can also be used as a developing solution.

As a preferable developing solution, 0.4 weight% aqueous solution of tetraethylammonium hydroxide, 0.5 mass% aqueous solution, and 2.38% aqueous solution are mentioned.

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 puddle method and a dipping method. After development, flowing water can be washed for 30 to 90 seconds to form a desired pattern.

A rinse process may be performed after image development. In the rinsing step, the developer is removed and the developer residue is removed by washing the substrate after development with pure water or the like. The rinse method can use a well-known method. For example, shower rinse, dipping rinse, etc. are mentioned.

<Post Baking Process (Crosslinking Process)>

For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 for a hot plate phase. In the case of an oven, a protective film and an interlayer insulating film excellent in heat resistance, hardness, etc. can be formed by advancing a crosslinking reaction by heat-processing for 30 to 120 minutes. In addition, when performing heat processing, transparency can also be improved by performing in nitrogen atmosphere.

Post-baking may be performed after baking at a relatively low temperature before post-baking (addition of middle baking process). When performing middle baking, it is preferable to heat at 90-150 degreeC for 1 to 60 minutes, and to post-bak at high temperature 200 degreeC or more. In addition, the middle baking and the post-baking may be divided into three or more multi-steps and heated. The taper angle of a pattern can be adjusted by the study of such a middle baking and post-baking. These heatings can use well-known heating methods, such as a hotplate, oven, and an infrared heater.

In addition, after the re-exposure to actinic rays on the substrate on which the pattern is formed prior to the heat treatment, post-baking (re-exposure / post-baking) is performed to generate an acid from the component (B) present in the unexposed portion, thereby accelerating the crosslinking process. It is preferable to function as a catalyst.

That is, it is preferable that the formation method of the cured film of this invention includes the re-exposure process which re-exposes by actinic light between a developing process and a post-baking process. Although exposure in a re-exposure process may be performed by the same means as the said exposure process, in the said re-exposure process, it is preferable to perform whole surface exposure to the side in which the film | membrane was formed by the photosensitive resin composition of this invention of a board | substrate.

As a preferable exposure amount of a re-exposure process, it is 100-1,000mJ / cm <2>.

[Curing film]

The cured film of this invention is a cured film obtained by hardening | curing the photosensitive resin composition of this invention.

The cured film of this invention can be used suitably as an interlayer insulation film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.

By the photosensitive resin composition of this invention, the interlayer insulation film which is excellent in insulation and has high transparency also when baked at high temperature is obtained. The interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency and is excellent in physical properties of a cured film, and thus is useful for an organic EL display device and a liquid crystal display device.

[Organic EL Display, Liquid Crystal Display]

The organic electroluminescence display and liquid crystal display of this invention are equipped with the cured film of this invention, It is characterized by the above-mentioned.

The organic EL display device or liquid crystal display device of the present invention is not particularly limited except having a planarization film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices having various structures. And a liquid crystal display device.

For example, amorphous silicon TFT, low temperature polysilicon TFT, oxide semiconductor TFT etc. are mentioned as a specific example of TFT (Thin-Film Transistor) with which the organic electroluminescence display and liquid crystal display of this invention are equipped.

Since the cured film of this invention is excellent in an electrical property, it can be used conveniently in combination with these TFT.

In addition, the liquid crystal display device of the present invention may be a twisted nematic (TN) method, a vertical alignment (VA) method, an in-place-switching (IPS) method, a frings field switching (FFS) method, or an OCB. (Optical Compensated Bend) method.

Moreover, the rubbing orientation method, the photo-alignment method, etc. are mentioned as a specific orientation system of the alignment film which the liquid crystal display device of this invention can take. Furthermore, the polymer orientation may be supported by the PSA (Polymer Sustained Alignment) technique described in Japanese Patent Laid-Open No. 2003-149647 and Japanese Patent Laid-Open No. 2011-257734.

In addition, the photosensitive resin composition of this invention and the cured film of this invention can be used for various uses, without being limited to the said use. For example, in addition to the planarization film and the interlayer insulation film, spacers for maintaining the thickness of the protective film of the color filter or the liquid crystal layer in the liquid crystal display device or microlenses formed on the color filter in the solid-state image sensor may be suitably used. Can be.

1 shows a configuration conceptual diagram of an example of an organic EL display device. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4. As shown in FIG.

It may form a bottom-gate type TFT (1), and comprising a state covering the TFT (1) to the Si ₃ N ₄ insulation film 3 is formed on the glass substrate 6. After forming a contact hole (not shown) in the insulating film 3, a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state of filling the unevenness of the wiring 2.

On the planarization film 4, the bottom emission type organic electroluminescent element is formed. That is, on the planarization film 4, the 1st electrode 5 which consists of ITO is connected to the wiring 2 through the contact hole 7, and is formed. In addition, the 1st electrode 5 is corresponded to the anode of organic electroluminescent element.

The insulating film 8 of the shape which covers the periphery of the 1st electrode 5 is formed, and forming this insulating film 8 prevents the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process. can do.

In addition, although not shown in FIG. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially formed through a desired pattern mask, and then a second electrode made of Al is formed on the entire surface above the substrate, and the sealing glass plate is formed. And an ultraviolet-curable epoxy resin are attached and sealed, and the active matrix type organic electroluminescent display apparatus by which the TFT 1 for driving this is connected to each organic electroluminescent element is obtained.

2 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back side, the liquid crystal panel corresponding to all pixels disposed between two glass substrates 14 and 15 with a polarizing film attached thereto. The element of 16 is arrange | positioned. In each element formed on the glass substrate, the ITO transparent electrode 19 which forms a pixel electrode through the contact hole 18 formed in the cured film 17 is wired. On the ITO transparent electrode 19, the RGB color filter 22 which has arrange | positioned the layer of the liquid crystal 20 and a black matrix is formed.

It does not specifically limit as a light source of a backlight, A well-known light source can be used. For example, a white LED, multicolor LEDs, such as blue, red, green, a fluorescent lamp (cold cathode tube), an organic EL, etc. are mentioned.

In addition, the liquid crystal display device may be a 3D (three-dimensional) type or a touch panel type.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, the amounts used, the ratios, the treatment contents, the treatment sequences, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In addition, "part" and "%" are mass references | standards unless there is particular notice.

In the following synthesis examples, the following codes | symbols represent the following compounds, respectively.

MAEVE: Methacrylic acid 1-ethoxyethyl

MATHF: Methacrylic acid tetrahydro-2H-furan-2-yl

Oxe-30: methacrylic acid (3-ethyloxetan-3-yl) methyl (made by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)

GMA: glycidyl methacrylate

NBMA: n-butoxymethylacrylamide (NBMA, Tokyo Chemical Industry Co., Ltd. product)

MMA: Methyl methacrylate

PHS: p-hydroxystyrene

V-3FM: 2,2,2-trifluoromethylethyl methacrylate (OSAKA ORGANIC CHEMICAL INDUSTRY LTD)

V-8FM: 1H, 1H, 5H-octafluoropentyl methacrylate (OSAKA ORGANIC CHEMICAL INDUSTRY LTD)

HFIP-A: Hexafluoro-2-propyl acrylate (manufactured by Central Glass Co., Ltd)

PFSt: Pentafluorostyrene (manufactured by Wako Pure Chemical Industries, Ltd.)

MAA: methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

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

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

DCPM: Dicyclopentanyl methacrylate

St: Styrene

<Mathf Synthesis>

Methacrylic acid (86g, 1 mol) was cooled to 15 degreeC, and camphor sulfonic acid (4.6g, 0.02 mol) was added. 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was dripped at this solution. After stirring for 1 hour, saturated sodium hydrogen chloride (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, the insolubles were filtered and concentrated under reduced pressure to 40 ° C. or lower, and the yellow oily residue was distilled under reduced pressure. Thus, 125 g of methacrylic acid tetrahydro-2H-furan-2-yl (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg fraction was obtained as a colorless oil (yield 80%).

Synthesis of Polymer A-1

PGMEA (84 g) was put into a three neck flask, and it heated in 90 degreeC under nitrogen atmosphere. The solution contained MAA (5.72 g, equivalent to 9.5 mol% of shearing component), MATHF (44.28 g, equivalent to 37.5 mol%), V-3FM (14.27 g, equivalent to 12.5 mol%), OXE-30 (48.30 g, equivalent to 37.5 mol%) and V-601 (4.83 g, 3 mol% based on 100 mol% of the total amount of the shearing component) were dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours to terminate the reaction. This obtained the polymer A-1.

The monomer type and the like were changed as shown in the following table to synthesize other polymers.

In the said Tables 1-4, the numerical value which does not attach a unit in particular in a table | surface makes mole% a unit. The numerical value of a polymerization initiator is mol% when making a monomer component 100 mol%. Solid content concentration is shown as monomer weight / (monomer weight + solvent weight) x 100 (unit weight%). When using V-601 as a polymerization initiator, reaction temperature made 70 degreeC reaction temperature, when 90 degreeC and V-65 were used.

<Adjustment of the photosensitive resin composition>

A polymer (component A), a photoacid generator (component B), a sensitizer, an additive (component C), a basic compound (component D), and a surfactant are dissolved and mixed in a solvent so as to have a solid content as shown in the following table. It filtered with the filter made from polytetrafluoroethylene, and obtained the photosensitive resin composition of various Examples and a comparative example.

The detail of the symbol which shows each compound used for the Example and the comparative example is as follows.

(Photo acid generator)

P-1: Oxime sulfonate (composite) of the following structure

P-2: Oxime sulfonate of the following structure (made by PAI-101, Midori Kagaku Co., Ltd.)

P-3: Sulfonium sulfonate (composite) of the following structure

NQD: TAS-200 (made by Toyo Gosei CO.Ltd.)

(Sensitizer)

S-1: dibutoxy anthracene of the following structure (manufactured by KAWASAKI KASEI CHEMICALS LTD.)

(Crosslinking agent)

JER: JER150S70 (Epoxy crosslinking agent, JAPAN EPOXY RESINS CO., Ltd. product)

(Basic compound)

G-1: 2,4,5-triphenylimidazole (made by Tokyo Chemical Industry Co., Ltd.)

G-2: 1,5-diazabicyclo [4.3.0] -5-nonene (made by Wako Pure Chemical Industries, Ltd.)

(Surfactants)

W-1: Perfluoroalkyl group containing nonionic surfactant represented by the following structural formula (F-554, DIC Corporation make)

W-2: Silicone Surfactant SH-8400 (Dow Corning Toray Co., Ltd.)

(solvent)

PGMEA: methoxypropyl acetate (manufactured by Showa Denko K.K.)

HS-EDM: High Solve EDM (manufactured by TOHO Chemical Industry Co., Ltd.)

<Transparency Evaluation>

A coating film having a film thickness of 3.0 µm was formed on the glass substrate. Subsequently, it exposed through the predetermined | prescribed mask using i line | wire stepper (FPA-3000i5 + by Canon Inc.). After puddle development at 23 ° C. for 65 seconds with an alkaline developer (2.38 wt% tetramethylammonium hydroxide aqueous solution), the mixture was rinsed with ultrapure water for 1 minute. The coating film after image development was irradiated with 300mJ / cm <2> light in wavelength 365nm using the ultrahigh pressure mercury lamp, and it heated for 45 minutes at 220 degreeC in oven. The transmittance | permeability of this cured film was measured at the wavelength of 400 nm using the spectrophotometer (U-3000: Hitachi, Ltd. make). The lowest transmittance is shown in the table (Fresh transparency).

In addition, it heated at 230 degreeC in oven for 2 hours. The transmittance | permeability of this cured film was similarly measured (heat resistance transparency).

<Evaluation of sensitivity>

After slit coating each photosensitive resin composition on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning Incorporated)), prebaking was carried out on a 95 ° C / 140 second hotplate to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 4.0 µm. Formed.

Subsequently, the obtained photosensitive resin composition layer was exposed through the predetermined mask using the PLA-501F exposure machine (ultra high pressure mercury lamp) by Canon Inc. And after developing the photosensitive resin composition layer after exposure for 23 degreeC / 60 second with alkaline developing solution (0.4 weight% of tetramethylammonium hydroxide aqueous solution), it rinsed with ultrapure water for 20 second.

The optimal i line | wire exposure amount (Eopt) when resolving a 9 micrometer line and space by 1: 1 by these operation was made into the sensitivity.

<Evaluation of chemical resistance>

After slit coating each photosensitive resin composition on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning Incorporated)), the photosensitive resin composition having a film thickness of 3.0 μm was removed by heating on a hot plate at 90 ° C./120 sec. Formed a layer.

The board | substrate with which the obtained photosensitive resin composition layer was formed was exposed by the Inc. PLA-501F exposure machine (ultra-high pressure mercury lamp) so that accumulated irradiation amount might be set to 300 mJ / cm <2> (roughness: 20 mW / cm <2>, i line | wire), and this board | substrate is then exposed to an oven Heated at 230 ° C. for 1 hour to obtain a cured film.

This cured film was immersed in NMP80 degreeC for 10 minutes, and the change rate of the film thickness before and after that was measured. The rate of change when the film thickness before immersion was t0 and the film thickness after immersion was t1 was made into t1 / t0.

<Measurement of comparative permittivity>

After spin-coating apply | coating the photosensitive resin composition on a bare wafer (N type low resistance) (made by SUMCO Corporation), it prebaked at 90 degreeC for 2 minutes, and formed the photosensitive resin composition layer of 0.35 micrometer in film thickness. The obtained photosensitive resin composition layer was exposed to a cumulative irradiation amount of 300 mJ / cm 2 (roughness: 20 mW / cm 2) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Inc., and the substrate was heated at 220 ° C. for 1 hour in an oven. A cured film was obtained. About this cured film, the comparative dielectric constant was measured at the measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). The results are shown in the following table. When this value is 3.4 or less, the relative dielectric constant of the cured film is good.

In addition, the rotation speed depends on the viscosity of the photosensitive resin composition. In order to adjust a film thickness to 0.35 micrometer, rotation speed was changed and performed in each.

&Lt; Example 40 >

Example 40 was similarly performed in Example 1 except having changed the exposure machine into the Nikon Corporation FX-803M (gh-Line stepper) from the Canon Inc. PLA-501F exposure machine. Evaluation of the sensitivity was the same level as Example 1.

&Lt; Example 41 >

Example 41 was similarly performed in Example 1 except having changed the exposure machine into the 355 nm laser exposure machine from Canon Inc. PLA-501F exposure machine, and performed 355 nm laser exposure. As the 355 nm laser exposure machine, "AEGIS" made by V-Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using "PE10B-V2" made by Ophir Optronics Solutions Ltd. did.

Evaluation of the sensitivity was the same level as Example 1.

&Lt; Example 42 >

Example 42 was similarly performed in Example 1 except having changed the exposure machine into the UV-LED light source exposure machine from Canon Inc. PLA-501F exposure machine. Evaluation of the sensitivity was the same level as Example 1.

As mentioned above, it turned out that the photosensitive resin composition of an Example shows the outstanding sensitivity irrespective of a board | substrate and an exposure machine, and also the shape of the formed pattern was also excellent.

&Lt; Example 43 >

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

A glass substrate 6, the insulating film 3 made of Si ₃ N ₄ forming a TFT (1) of the bottom gate type on, and in a state covering the TFT (1) was formed. Subsequently, a contact hole (not shown here) was formed in the insulating film 3, and then a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact hole was formed on the insulating film 3. This wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization film 4 was formed on the insulating film 3 in a state where the unevenness by the wiring 2 was filled up. Formation of the planarization film 4 onto the insulating film 3 was performed by spin-coating the photosensitive resin composition of Example 16 on a substrate, prebaking (90 占 폚 x 2 minutes) on a hot plate, and then applying a high pressure mercury lamp from the mask. After irradiating i line | wire (365 nm) to 45mJ / cm <2> (roughness 20mW / cm <2>), it developed in alkaline aqueous solution, the pattern was formed, and the heat processing for 60 minutes was performed at 230 degreeC.

The applicability | paintability at the time of apply | coating the photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle and a crack was not recognized in the cured film obtained after exposure, image development, and baking. Moreover, the film thickness of the planarization film 4 which produced 500 nm of average level | step differences of the wiring 2 was 2,000 nm.

Subsequently, a bottom emission type organic EL device was formed on the obtained planarization film 4. First, on the planarization film 4, the 1st electrode 5 which consists of ITO was connected to the wiring 2 through the contact hole 7, and was formed. Then, the resist was apply | coated and prebaked, and it exposed and developed through the mask of a desired pattern. Patterning was carried out by wet etching using ITO etchant using this resist pattern as a mask. Then, the said resist pattern was peeled at 50 degreeC using the resist stripping liquid (Remover 100, a product made from AZELECTRONIC MATERIALS Co Ltd.). The 1st electrode 5 obtained in this way is corresponded to the anode of organic electroluminescent element.

Next, the insulating film 8 of the shape which covers the periphery of the 1st electrode 5 was formed. The insulating film 8 was formed in the insulating film 8 using the photosensitive resin composition of Example 25 by the method similar to the above. By forming this insulating film 8, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process can be prevented.

Furthermore, the hole transport layer, the organic light emitting layer, and the electron transport layer were sequentially deposited in a vacuum deposition apparatus through a desired pattern mask. Next, the 2nd electrode which consists of Al was formed in the whole surface above a board | substrate. The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by sticking using the sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix organic EL display device obtained by connecting the TFT 1 for driving this to each organic EL element is obtained. As a result of applying a voltage through the driving circuit, it was found that the display device exhibited good display characteristics and was a highly reliable organic EL display device.

&Lt; Example 44 >

In the active-matrix liquid crystal display device of FIG. 1 of Unexamined-Japanese-Patent No. 3321003, the cured film 17 was formed as an interlayer insulation film as follows, and the liquid crystal display device of Example 44 was obtained.

That is, using the photosensitive resin composition of Example 25, the cured film 17 was formed as an interlayer insulation film in the same way as the formation method of the planarization film 4 of the organic electroluminescence display in Example 43.

As a result of applying a drive voltage to the obtained liquid crystal display device, it showed favorable display characteristics, and it turned out that it is a highly reliable liquid crystal display device.

1: TFT (Thin Film Transistor) 2: Wiring
3: insulating film 4: planarization film
5: first electrode 6: glass substrate
7: contact hole 8: insulating film
10: liquid crystal display device 12: backlight unit
14,15: glass substrate 16: TFT
17: cured film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: color filter

Claims (20)

(A) a polymer component that satisfies at least one of the following (1) and (2);
(1) a polymer having a structural unit having a moiety in which the acid group (a1) is protected with an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a side structure containing a fluorine atom in the side chain,
(2) a polymer having a structural unit having a moiety in which the acid group (a1) has a moiety protected with an acid-decomposable group and (a3) a partial structure containing a fluorine atom in the side chain, and (a2) a structural unit having a crosslinkable group polymer,
(B) a photoacid generator;
(D) A positive photosensitive resin composition containing a solvent. The method of claim 1,
The partial structure containing the said fluorine atom contains the hydrocarbon group substituted by the fluorine atom, The positive type photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The partial structure containing the said fluorine atom contains the C1-C20 hydrocarbon group substituted by the fluorine atom, The positive type photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
Said (a3) structural unit is a structure in which the group represented by following General formula (1) or (2) has the structure which couple | bonded with the main chain directly or via a linking group, Positive type photosensitive resin composition characterized by the above-mentioned.
In general formula (1)

[In Formula (1), X represents -O- or -NH-, L <^1> represents a single bond or a bivalent coupling group, R <^12> represents the hydrocarbon group substituted by at least 1 or more by the fluorine atom.
In general formula (2)

[In General Formula (2), Ar represents an aromatic ring group, Y represents a fluorine atom or -L ² -R ²² , R ²² represents a hydrocarbon group substituted with at least one or more by fluorine atoms, and L ² represents a single bond or 2 Shows a coupling group. n represents the integer of 1-5. When n is 2 or more, each Y may be the same or different.] The method of claim 1,
The said structural unit (a3) is a structural unit represented by following General formula (1 ') or (2'), The positive photosensitive resin composition characterized by the above-mentioned.
In general formula (1 '),

[In General Formula (1 '), R ¹¹ represents hydrogen or a methyl group, X represents -O- or -NH-, L ¹ represents a single bond or a divalent linking group, and R ¹² represents at least one or more of fluorine atoms Substituted hydrocarbon group]
In general formula (2 '),

[In General Formula (2 '), R ²¹ represents hydrogen or a methyl group, Y represents a fluorine atom or -L ² -R ²² , R ²² represents a hydrocarbon group substituted with at least one or more by fluorine atoms, and L ² is a A bond or a divalent linking group. n represents the integer of 1-5. When n is 2 or more, each Y may be the same or different.] 3. The method according to claim 1 or 2,
Wherein the crosslinking group is an epoxy group, an oxetanyl group and the -NH-CH ₂ -OR a positive photosensitive resin composition, characterized in that at least one selected from the groups represented by (R is an alkyl group having 1 to 20 carbon atoms). 3. The method according to claim 1 or 2,
The acid-decomposable group is a group having a structure protected in the form of acetal. 3. The method according to claim 1 or 2,
Said structural unit (a1) is a structural unit represented with the following general formula (A2 '), The photosensitive resin composition characterized by the above-mentioned.
Formula (A2 ')

[Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group] 3. The method according to claim 1 or 2,
The positive photosensitive resin composition, wherein any one of the (A) polymer components is a polymer further containing an acid group. 3. The method according to claim 1 or 2,
Said photo-acid generator (B) is an oxime sulfonate compound, The positive type photosensitive resin composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
Positive type photosensitive resin composition containing 70 to 99.9 mass% of (A) polymer components, and (B) photoacid generator in the range of 0.1-30 mass% with respect to the total solid of the said composition. 3. The method according to claim 1 or 2,
(C) The positive type photosensitive resin composition containing a crosslinking agent further. 3. The method according to claim 1 or 2,
The crosslinkable group is at least one selected from an epoxy group, an oxetanyl group and a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms), and the acid decomposable group is protected in the form of acetal. Positive type photosensitive resin composition characterized by the above-mentioned group. 3. The method according to claim 1 or 2,
The crosslinkable group is at least one selected from the group represented by an epoxy group, an oxetanyl group and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms), and the structural unit (a1) is represented by the following general formula ( It is a structural unit represented by A2 '), The positive photosensitive resin composition characterized by the above-mentioned.
Formula (A2 ')

[Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group] 3. The method according to claim 1 or 2,
The crosslinkable group is at least one selected from the group represented by an epoxy group, an oxetanyl group and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms), and any one of the polymer components (A) is an acid group. Positive type photosensitive resin composition characterized by the above-mentioned. (1) Process of applying the positive photosensitive resin composition of Claim 1 or 2 on a board | substrate,
(2) removing the solvent from the applied positive photosensitive resin composition,
(3) exposing to active radiation;
(4) developing with an aqueous developer; and
(5) A method for producing a cured film, comprising a post-baking step of thermal curing. 17. The method of claim 16,
And a step of exposing the whole surface after the developing step and before the post-baking step. The cured film formed by hardening | curing the positive photosensitive resin composition of Claim 1 or 2. The method of claim 18,
An interlayer insulating film, The cured film characterized by the above-mentioned. It has a cured film of Claim 18, The liquid crystal display device or organic electroluminescence display characterized by the above-mentioned.

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