TW201500846A - Photo-sensitive resin composition, method for manufacturing cured film, cured film, liquid crystal display device, and organic EL display device - Google Patents

Abstract

A photo-sensitive resin composition is provided, which includes: a polymer component (A) containing a polymer satisfying at least one of the following (1) and the following (2), wherein (1) is a polymer having a structural unit (a1) containing a group in which an acidic group is protected by an acid-decomposable group and a structural unit (a2) containing a crosslinking group, (2) is a polymer having the structural unit (a1) and a polymer having the structural unit (a2); a photo-acid generator (B); and a solvent (C). In the polymer component (A), at least one structural unit (a4) having a lactone structure is included, or at least one polymercontaining the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2) is included.

Description

Photosensitive resin composition, method for producing cured film, cured film, Liquid crystal display device and organic EL display device

The present invention relates to a photosensitive resin composition (hereinafter sometimes referred to simply as "the composition of the present invention"). Further, the present invention relates to a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing a photosensitive composition, and various image display devices using the cured film.

More specifically, the present invention relates to a planarizing film and protection for an electronic component suitable for forming a liquid crystal display device, an organic electroluminescence (organic EL) display device, an integrated circuit device, a solid-state imaging device, and the like. A photosensitive resin composition of a film or an interlayer insulating film, and a method of producing a cured film using the same.

In an electronic component such as a thin film transistor (hereinafter referred to as a "TFT (Thin Film Transistor)" type liquid crystal display device, a magnetic head element, an integrated circuit element, or a solid-state imaging device, it is usually arranged between layers of wiring. Insulated with inter-layer Insulating film. The material for forming the interlayer insulating film is preferably a material having a small number of steps for obtaining a desired pattern shape and having sufficient flatness. Therefore, a photosensitive resin composition is widely used (for example, refer to Patent Document 1 to Patent Literature). 4).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-221494

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-220360

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-46206

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-46098

In recent years, a photosensitive resin composition capable of maintaining high sensitivity and improving chemical resistance and further reducing the relative dielectric constant has been demanded.

As a result of the investigation conducted by the inventors of the present invention, it is considered that the photosensitive resin composition having a group in which the acid group is protected by an acid-decomposable group and a crosslinkable group in the composition is increased in sensitivity in order to make the sensitivity higher than before. The ratio of the acid-decomposable group or the acid group to be blended in the resin composition is known, but in this case, the chemical resistance is lowered. Further, it has been found that when the ratio of the crosslinking group is increased to compensate for the chemical resistance, the relative dielectric constant is too high.

An object of the present invention is to solve the above problems, and an object of the invention is to provide a photosensitive resin composition which can maintain a high sensitivity and which is excellent in chemical resistance and further reduce a relative dielectric constant.

As a result of research conducted by the inventors of the present invention, it has been found that a constituent unit containing a group having an acid group-protected group containing an acid group, a constituent unit containing a crosslinkable group, and a content are contained in the photosensitive resin composition. The constituent unit of the lactone structure can make the chemical resistance good and also reduce the relative dielectric constant. Further, it has been found that high sensitivity can also be maintained, and the present invention has been completed.

The reason for this is that it is estimated that a constituent unit containing a group having an acid group protected by an acid-decomposable group and a constituent unit containing a crosslinkable group are blended in the photosensitive resin composition, and a lactone-containing structure is prepared. In the constituent unit, the deterioration of the chemical resistance caused by the developable group can be suppressed while maintaining the high sensitivity, and as a result, the chemical resistance can be improved and the relative dielectric constant can be further lowered.

Specifically, the above problem is solved by <2> to <15> by the following means <1>.

<1> A photosensitive resin composition comprising: (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2), (1) having (a1) an acid group a constituent unit of a group protected by an acid-decomposable group, and (a2) a polymer having a structural unit containing a crosslinkable group, or (2) a polymer having the above-mentioned structural unit (a1) and having the above-mentioned structural unit (a2) (B) a photoacid generator; and (C) a solvent; comprising at least one (a4) lactone-containing ester in the above (A) polymer component The constituent unit of the structure or at least one type of (3) polymer containing the above-mentioned structural unit (a4) and not including the above-mentioned structural unit (a1) and the above-mentioned structural unit (a2).

<2> The photosensitive resin composition according to the above-mentioned item, wherein the constituent unit containing the lactone structure contains a group represented by the following formula (1).

(In the formula (1), R ^A1 represents a substituent, and n ₁ R ^A1 are each independently and may be the same or different. Z ¹ represents a monocyclic structure or a polycyclic structure containing -OC(=O)-. ₁ means an integer greater than 0)

The photosensitive resin composition as described in <1>, wherein the structural unit (a4) containing the lactone structure is represented by the following general formula (2).

General formula (2) [Chemical 2]

(In the formula (2), RX ¹ represents a hydrogen atom or an alkyl group. R ^A2 represents a substituent, and n ₂ R ^A2 are each independently and may be the same or different. A ¹ represents a single bond or a divalent linking group. Z ² represents a monocyclic structure or a polycyclic structure containing a group represented by -OC(=O)-. n ₂ represents an integer of 0 or more)

The photosensitive resin composition according to any one of the above-mentioned, wherein the structural unit (a4) containing the lactone structure is represented by the following general formula (3).

(In the formula (3), RX ₂ represents a hydrogen atom or an alkyl group. R ^A3 represents a substituent, and n ₃ R ^A3 are each independently the same or different. A ² represents a single bond or a divalent linking group. Z ³ represents a monocyclic structure or a polycyclic structure containing a group represented by -OC(=O)-. n ₃ represents an integer of 0 or more. X ¹ represents an oxygen atom or -NR"-. R" represents a hydrogen atom or alkyl)

The photosensitive resin composition according to any one of <1> to <4> wherein the lactone structure is a lactone structure which forms a 5-membered ring or a 6-membered ring.

The photosensitive resin composition of any one of the above-mentioned structural unit (a1) is a structural unit containing the group whose carboxyl group is protected by the acetal form.

The photosensitive resin composition of any one of the above-mentioned structural unit (a1) is a structural unit represented by the following General formula (1-11).

(In the formula (1-11), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group. , R ¹ or R ² and R ³ may be bonded to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an extended aryl group)

The photosensitive resin composition according to any one of <1> to <7> wherein the crosslinkable group is selected from the group consisting of an epoxy group, an oxetane group, and -NH-CH ₂ - At least one of OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).

The photosensitive resin composition according to any one of the above aspects, wherein the (B) photoacid generator is an oxime sulfonate compound or an onium salt compound.

The photosensitive resin composition according to any one of the above-mentioned <1> to <9>, wherein the structural unit (a4) containing the lactone structure is represented by the following general formula (4) to (7) Said.

The photosensitive resin composition as described in any one of the above-mentioned <1>, wherein the structural unit (a4) containing the lactone structure is represented by the following general formula (4).

General formula (4) [Chemical 6]

<12> A method for producing a cured film, comprising: (1) a step of applying the photosensitive resin composition according to any one of <1> to <11> to a substrate; a step of removing a solvent in the applied photosensitive resin composition; (3) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4) using an aqueous developing solution to expose the photosensitive resin a step of developing the composition; and (5) a post-baking step of thermally curing the developed photosensitive resin composition.

<13> A cured film which is formed by curing the photosensitive resin composition according to any one of <1> to <11> or by a method for producing a cured film according to <12>. form.

<14> The cured film according to <13> which is an interlayer insulating film.

<15> A liquid crystal display device or an organic electroluminescence display device comprising the cured film according to <13> or <14>.

According to the present invention, it is possible to provide a high sensitivity and chemical resistance The photosensitive resin composition which is excellent in properties and further reduces the relative dielectric constant.

1,16‧‧‧TFT

2‧‧‧Wiring

3,8‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7, 18‧‧‧ contact holes

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

17‧‧‧ hardened film

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

FIG. 1 is a conceptual diagram showing an example of a liquid crystal display device. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, and having a cured film 17 as an interlayer insulating film.

FIG. 2 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and having a planarization film 4.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, in the specification of the present application, "~" is used in the meaning of including the numerical values described before and after the lower limit and the upper limit.

In addition, in the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The composition of the present invention includes: (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2) below, (1) A polymer having (a1) a structural unit containing a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit containing a crosslinkable group, or (2) having the above-mentioned structural unit (a1) a polymer and a polymer having the above structural unit (a2); (B) a photoacid generator; and (C) a solvent; wherein the polymer component (A) contains at least one (a4) lactone-containing structure. The constituent unit or at least one type of (3) polymer containing the above-mentioned structural unit (a4) and not including the above-mentioned structural unit (a1) and the above-mentioned structural unit (a2).

According to the present invention, it is possible to provide a photosensitive resin composition which can maintain high sensitivity and which is excellent in chemical resistance and further reduce the relative dielectric constant.

Here, as the form of the structural unit containing at least one (a4) lactone structure in the (A) polymer component, the following (1) to (5) are exemplified.

(1): (A) The polymer component contains at least one of the following polymers (hereinafter also referred to as polymer (A2)), and the polymer has at least one (a1) acid group-containing acid group-protected group The structural unit of the base, (a2) a structural unit containing a crosslinkable group, and (a4) a structural unit containing a lactone structure.

(2): (A) The polymer component contains the following polymer (hereinafter also referred to as polymer (A2a)) and a polymer (hereinafter also referred to as polymer (A2b)), and the above polymer (A2a) contains (a1) a structural unit containing a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit containing a crosslinkable group, wherein the polymer (A2b) contains (a4) The constituent unit containing a lactone structure does not contain (a1) a structural unit containing a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit containing a crosslinkable group.

(3): (A) The polymer component contains the following polymer (hereinafter also referred to as polymer (A2c)) and a polymer (hereinafter also referred to as polymer (A2d)), and the above polymer (A2c) contains (a1) a structural unit containing a group in which an acid group is protected by an acid-decomposable group, and (a4) a structural unit containing a lactone structure, wherein the polymer (A2d) contains (a2) a structural unit containing a crosslinkable group.

(4): (A) The polymer component contains the following polymer (hereinafter also referred to as polymer (A2e)) and a polymer (hereinafter also referred to as polymer (A2f)), and the above polymer (A2e) contains (a1) A structural unit containing a group in which an acid group is protected by an acid-decomposable group, and the polymer (A2f) includes (a2) a structural unit containing a crosslinkable group and (a4) a structural unit containing a lactone structure.

(5): (A) The polymer component contains the following polymer (hereinafter also referred to as polymer (A2g)) and polymer (hereinafter also referred to as polymer (A2h)), and polymer (hereinafter also The polymer (A2i), the polymer (A2g) contains (a1) a constituent unit containing a group in which an acid group is protected by an acid-decomposable group, and the polymer (A2h) contains (a2) a crosslinkable group. In the constituent unit, the polymer (A2i) contains (a4) a constituent unit having a lactone structure.

The lactone structure in the present invention means a cyclic ester containing a -COO- group in the ring. Further, the constituent unit containing a lactone structure in the present invention means a constituent unit containing the above-described lactone structure, and for example, it means that a single ring structure is formed, or another ring structure is formed in a lactone structure to form a condensed ring. Ring structure. In addition, in the present invention In the constituent unit containing a lactone structure used in the lactone structure, the lactone structure may be directly bonded to the main chain.

Further, in the present invention, a constituent unit containing a group having an acid group protected by an acid-decomposable group, a constituent unit containing a crosslinkable group, and a constituent unit having a lactone structure are formulated in the photosensitive resin composition. When a high concentration alkaline developing solution (for example, 2.0% by mass or more of an aqueous solution of Tetramethyl Ammonium Hydroxide (TMAH)) is used, the developability can be further improved. Although the reason is estimated, it is estimated that when the composition of the present invention is developed using a high-concentration alkaline developing solution, the lactone structure is opened to generate a carboxylic acid, and as a result, the composition of the present invention is applied to an alkaline developing solution. The solubility is further improved.

<(A) Polymer component>

The polymer component (A) is preferably an addition polymerization type resin, and more preferably a polymer containing a constituent unit derived from (meth)acrylic acid and/or an ester thereof. Further, it may have a constituent unit other than the constituent unit derived from (meth)acrylic acid and/or its ester, and may have, for example, a constituent unit derived from styrene or a constituent unit derived from a vinyl compound. In addition, "a structural unit derived from (meth)acrylic acid and/or its ester" is also referred to as "(meth)acrylic structural unit". (A) The polymer component becomes a main component of a component other than the solvent of the composition of the present invention, and preferably accounts for 60% by mass or more of the total solid content.

<<(a1) A constituent unit of a group having an acid group protected by an acid-decomposable group>>

(A) The polymer component has at least a structural unit (a1) containing a group in which an acid group is protected by an acid-decomposable group. By (A) the polymer component has a constituent unit (a1) A photosensitive resin composition having an extremely high sensitivity is prepared.

In the present invention, the "acid group which is protected by an acid-decomposable group" can be used as a group known as an acid group or an acid-decomposable group, and is not particularly limited.

As a specific acid group, a carboxyl group and a phenolic hydroxyl group are preferable.

Further, as the specific acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure such as an ester structure, a tetrahydropyranyl ester group, or an acetal functional group such as a tetrahydrofuran ester group) which is described later may be used, or it may be difficult to use. a group decomposed by an acid (for example, a tertiary alkyl carbonate group such as a tertiary alkyl group such as a third butyl ester group or a third butyl carbonate group such as a third butyl carbonate group).

The constituent unit (a1) is preferably a constituent unit containing a protective carboxyl group protected by an acid-decomposable group or a constituent unit containing a protective phenolic hydroxyl group protected by an acid-decomposable group.

Hereinafter, the constituent unit (a1-1) containing a protective carboxyl group protected by an acid-decomposable group and the constituent unit (a1-2) containing a protective phenolic hydroxyl group protected by an acid-decomposable group will be sequentially described.

<<<(a1-1) A constituent unit containing a protected carboxyl group protected by an acid-decomposable group>>>

The structural unit (a1-1) is a structural unit having a protective carboxyl group protected by an acid-decomposable group of a carboxyl group-containing constituent unit.

As the constituent unit having a carboxyl group which can be used in the above-mentioned structural unit (a1-1), a known constituent unit can be used without particular limitation. For example, a constituent unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid can be mentioned.

Hereinafter, the constituent unit (a1-1-1) which can be used as the constituent unit having the above carboxyl group will be described.

<<<<(a1-1-1) is derived from a constituent unit of an unsaturated carboxylic acid having at least one carboxyl group in a molecule>>>>

As the unsaturated carboxylic acid used in the present invention, those listed below can be used.

That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloyloxyethyl-succinic acid, and 2-( Methyl) propylene methoxyethyl hexahydrophthalic acid, 2-(meth) propylene methoxyethyl phthalic acid, and the like.

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

Further, the unsaturated polycarboxylic acid used to obtain a structural unit containing a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and butyl Di(2-methylpropenyloxyethyl) diester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate ) esters, etc. Further, the unsaturated polycarboxylic acid may also be a mono(meth)acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethyl group. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4 may be used. - Carboxystyrene and the like.

Among them, from the viewpoint of developability, in order to form the above-mentioned structural unit (a1-1-1), it is preferred to use acrylic acid, methacrylic acid, 2-(meth)acryloxyethyl-succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acrylomethoxyethyl-phthalic acid, or an anhydride of an unsaturated polycarboxylic acid, etc., more preferably Acrylic acid, methacrylic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid was used.

The constituent unit (a1-1-1) may be contained alone or in combination of two or more.

<<<< can be used to form the acid-decomposable group of unit (a1-1) >>>>

As the acid-decomposable group which can be used for the structural unit (a1-1), the above-mentioned acid-decomposable group can be used.

Among these acid-decomposable groups, a group having a structure in which an acid-decomposable group is protected by an acetal is preferred. For example, from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition, it is preferred that the carboxyl group be protected by an acetal form. Protect the carboxyl group. Further, from the viewpoint of sensitivity, the carboxyl group is more preferably a protected carboxyl group which is protected by the form of an acetal represented by the following formula (a1-10). Further, in the case where the carboxyl group is a protected carboxyl group protected by the acetal form represented by the following formula (a1-10), the entire protected carboxyl group becomes -(C=O)-O-CR ¹⁰¹ R ¹⁰² The structure of (OR ¹⁰³ ).

General formula (a1-10) [Chemical 7]

(In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, wherein R ¹⁰¹ and R ¹⁰² are each a hydrogen atom. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² Can be linked to R ¹⁰³ to form a cyclic ether)

In the above formula (a1-10), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain. Here, in the case where both R ¹⁰¹ and R ¹⁰² represent a hydrogen atom, at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2,3-Dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.

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

The above alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When a halogen atom is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ^{103 are} a halogenated alkyl group, and when an aryl group is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ^{103 are} an aralkyl group.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these halogen atoms, a fluorine atom or a chlorine atom is preferred.

Further, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, and a naphthalene group. The base or the like, as the aryl group substituted with an aryl group, that is, an aralkyl group, may, for example, be a benzyl group, an α-methylbenzyl group, a phenethyl group or a naphthylmethyl group.

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

Further, when the above alkyl group is a cycloalkyl group, the above cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and when the alkyl group is linear or branched The alkyl group may have a cycloalkyl group having a carbon number of 3 to 12 as a substituent.

These substituents may also be further substituted by the above substituents.

In the above formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The above aryl group may have a substituent, and as the above substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. The aryl group may, for example, be a phenyl group, a tolyl group, a decyl group, a cumenyl group or a 1-naphthyl group.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other and form a ring together with the bonded carbon atoms. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ^{103 are} bonded to each other include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and an adamantyl group. And tetrahydropyranyl and the like.

Further, in the above formula (a1-10), it is preferred that one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

A radically polymerizable monomer for forming a constituent unit containing a protective carboxyl group represented by the above formula (a1-10) may be a commercially available radical polymerizable monomer, or may be synthesized by a known method. A radical polymerizable monomer. For example, it can be synthesized by the synthesis method described in Paragraph No. 0037 to Paragraph No. 0040 of JP-A-2011-221494, and the content can be incorporated into the specification of the present application.

The first preferred embodiment of the above-mentioned structural unit (a1-1) is a structural unit represented by the following general formula (1-11).

(In the formula (1-11), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² represents an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group. R ¹ or R ² and R ³ may be bonded to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an extended aryl group)

When R ¹ and R ² are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R ¹ and R ² are an aryl group, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

X represents a single bond or an extended aryl group, preferably a single bond.

The second preferred embodiment of the above constituent unit (a1-1) is a constituent unit represented by the following general formula (1-12).

(In the formula (1-12), R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenyl group, and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or have a carbon number of 1 ~4 alkyl)

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 a hydrogen atom.

As a preferable specific example of the said structural unit (a1-1), the following structural unit is illustrated. Further, in the constituent units described below, R represents a hydrogen atom or a methyl group.

<<<(a1-2) A constituent unit containing a protective phenolic hydroxyl group protected by an acid-decomposable group>>>

The constituent unit (a1-2) is a constituent unit (a1-2-1) having a phenolic hydroxyl group-containing constituent unit having a phenolic hydroxyl group protected by an acid-decomposable group, which will be described in detail below.

<<<<(a1-2-1) constitutive unit containing phenolic hydroxyl group>>>>

The constituent unit containing the phenolic hydroxyl group may be a constituent unit of a hydroxystyrene-based constituent unit or a novolac-based resin, and among these constituent units, from the viewpoint of sensitivity, it is preferably derived from hydroxybenzene. A constituent unit of ethylene or α-methylhydroxystyrene. In addition, as a constituent unit containing a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.

General formula (a1-20)

(In the formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a straight or branched chain having a carbon number of 1 to 5. The alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a+b is 5 or less. Further, when two or more R ²²² are present, the R ²²² may be different from each other. the same)

In the above formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

Further, R ²²¹ represents a single bond or a divalent linking group. When R ²²¹ is a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. R ²²¹ is a divalent linking group, may be exemplified alkylene group, specific examples of R ²²¹ is alkylene include: methylene, stretching ethyl, propyl stretching, stretch isopropyl, n-butyl extending , stretching isobutyl, stretching tert-butyl, stretching pentyl, stretching isoamyl, stretching neopentyl, stretching hexyl and the like. Among them, R ^{221 is} preferably a single bond, a methylene group or an ethyl group. Further, the above-mentioned divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group and the like. Further, a represents an integer of 1 to 5. However, from the viewpoint of the effects of the present invention or the ease of production, a is preferably 1 or 2, and more preferably a is 1.

Further, when a carbon atom bonded to R ²²¹ is used as a reference (1 position), the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4 position.

R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a new one. Amyl and so on. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferred from the viewpoint of easy production.

In addition, b represents an integer of 0 or 1 to 4.

<<<< can be used to form the acid-decomposable group of unit (a1-2) >>>>

As the acid-decomposable group which can be used for the above-mentioned structural unit (a1-2), similarly to the acid-decomposable group which can be used for the above-mentioned structural unit (a1-1), a known acid-decomposable group can be used, and it is not particularly limited. . Among the acid-decomposable groups, the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact pores are preferred. An aldehyde-protected constituent unit that protects a phenolic hydroxyl group. Further, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably a phenolic hydroxyl group protected by the acetal form represented by the above formula (a1-10) from the viewpoint of sensitivity. Further, in the case where the phenolic hydroxyl group is a protective phenolic hydroxyl group protected by the acetal form represented by the above formula (a1-10), the entirety of the protective phenolic hydroxyl group becomes -Ar-O-CR ¹⁰¹ R Structure of ¹⁰² (OR ¹⁰³ ). Further, Ar represents an aryl group.

A preferred example of the acetal ester structure of the phenolic hydroxyl group is exemplified by a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, or R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

In addition, as a radically polymerizable monomer which forms a structural unit which protects a phenolic hydroxyl group which has a phenolic hydroxyl group and is protected by the acetal, it is set, for example, in the paragraph 0042 of Unexamined-Japanese-Patent No. 2011-215590. A radical polymerizable monomer or the like described.

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

Specific examples of the acetal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl group, 1-methoxyethyl group, and 1-n-butoxyethyl group. , 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxyethyl, 1-cyclohexyl An oxyethyl group, a 1-(2-cyclohexylethoxy)ethyl group, a 1-benzyloxyethyl group, etc. may be used alone or in combination of two or more.

A commercially available radical polymerizable monomer can be used as the radical polymerizable monomer for forming the above-mentioned structural unit (a1-2), and a radical polymerizable monomer synthesized by a known method can also be used. For example, it can be synthesized by reacting a compound containing a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be copolymerized with another monomer in advance, and then reacted with a vinyl ether in the presence of an acid catalyst.

As a preferable specific example of the above-mentioned structural unit (a1-2), the following structural unit can be exemplified, but the present invention is not limited to these constituent units.

The above-described constituent unit (a1-1) has a feature of faster development than the above-described constituent unit (a1-2). Therefore, in the case of rapid development, it is preferable to constitute the unit (a1-1). Conversely, in the case where the development is to be slowed down, it is preferable to use the constituent unit (a1-2).

<<(a2) Component unit containing a crosslinkable group>>

(A) The polymer component has a structural unit (a2) containing a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which undergoes a curing reaction by heat treatment.

The form of the preferable structural unit containing a crosslinkable group is selected from the group consisting of an epoxy group, an oxetane group, and -NH-CH ₂ -OR (R is a hydrogen atom or a carbon number of 1~) The constituent unit of at least one of the group represented by the alkyl group of 20 and the ethylenically unsaturated group is preferably selected from the group consisting of an epoxy group, an oxetanyl group, and an -NH group. At least one of -CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). In the photosensitive resin composition of the present invention, the polymer component (A-1) preferably contains at least one of an epoxy group and an oxetanyl group, and more preferably contains an epoxy group. The constituent unit of the base. More specifically, the following are mentioned.

<<<(a2-1) constituent unit having an epoxy group and/or an oxetane group>>>

The polymer component (A) preferably contains a constituent unit having an epoxy group and/or an oxetanyl group (hereinafter also referred to as a constituent unit (a2-1)).

The constituent unit (a2-1) may have at least one epoxy group or oxetanyl group in one constituent unit, and may have one or more epoxy groups and one or more oxetane groups. The group or two or more epoxy groups or two or more oxetanyl groups are not particularly limited, but preferably have a total of one to three epoxy groups and/or oxetane groups. The alkyl group is more preferably an epoxy group and/or an oxetanyl group having a total of one or two, and still more preferably one epoxy group or oxetane group.

Specific examples of the radical polymerizable monomer for forming a constituent unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-positive propylene. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Cyclohexyl methyl ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexyl methyl ester, o-vinylbenzyl glycidyl ether, m-vinyl benzyl a glycidyl ether, a p-vinylbenzyl glycidyl ether, a compound containing an alicyclic epoxy group described in Paragraph No. 0031 to Paragraph No. 0035 of Japanese Patent No. 4,184,443, etc. It is incorporated into the specification of this application.

Specific examples of the radically polymerizable monomer for forming a structural unit having an oxetane group include, for example, those described in paragraphs 0011 to 0016 of JP-A-2001-330953. The (meth) acrylate of the oxetane group, or the compound described in Paragraph No. 0027 of JP-A-2012-088459, the contents of which are incorporated herein by reference.

As a constituent unit for forming the above epoxy group and/or oxetane group Specific examples of the radical polymerizable monomer of (a1-2-1) are preferably a monomer having a methacrylate structure or a monomer having an acrylate structure.

Among these, from the viewpoints of enhancing copolymerization reactivity and various properties of the cured film, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and methacrylic acid 3,4- are preferred. Epoxycyclohexylmethyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, acrylic acid (3-ethyloxetane-3-yl) Methyl ester, and (3-ethyloxetane-3-yl)methyl methacrylate. These constituent units may be used alone or in combination of two or more.

As a preferable specific example of the said structural unit (a2-1), the following structural unit is illustrated. Further, in the constituent units described below, R represents a hydrogen atom or a methyl group.

<<<(a2-2) constituent unit having an ethylenically unsaturated group>>>

One type of the structural unit (a2) containing the crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group. The structural unit (a2-2) is preferably a structural unit having an ethylenically unsaturated group in a side chain, more preferably a terminal having an ethylenically unsaturated group and having a side chain having a carbon number of 3 to 16. unit.

In addition, the constituent unit (a2-2) is described in paragraphs 0072 to 0090 of JP-A-2011-215580, and paragraph number 0013 to paragraph 0031 of JP-A-2008-256974. The compounds and the like are preferred examples, and the contents can be incorporated into the specification of the present application.

<<<(a2-3) A constituent unit having a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>>

The polymer component (A) used in the present invention preferably contains a constituent unit (a2) having a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). -3). By containing the constituent unit (a2-3), a hardening reaction can be generated by a gentle heat treatment, and a cured film excellent in various properties can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The constituent unit (a2-3) is more preferably a constituent unit having a group represented by the following formula (a2-30).

(In the formula (a2-30), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)

R ^{2 is} preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.

Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and an n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

<<(a4) Constituent unit containing lactone structure>>

The composition of the present invention contains at least one (a4) structural unit containing a lactone structure, or at least one type containing the above structural unit (a4), and does not contain the above constituent unit (a1). And the polymer of the above constituent unit (a2).

By formulating (a4) a constituent unit containing a lactone structure to the composition of the present invention, it is possible to provide a photosensitive property which can maintain high sensitivity, improve chemical resistance, and further reduce relative dielectric constant. Resin composition.

The lactone structure in the constituent unit containing a lactone structure is not particularly limited, and a lactone structure of any structure can be used. In particular, as the lactone structure used in the present invention, a lactone structure which forms a 5-membered ring to a 7-membered ring is preferable, and a lactone structure which forms a 5-membered ring or a 6-membered ring is more preferable.

Further, as a constituent unit containing a lactone structure used in the present invention, in the lactone structure in which a 5-membered ring to a 7-membered ring is formed, other ring structures may be condensed in a lactone structure to form a polycyclic structure. However, it is preferred that the other ring structure is not in the lactone structure. Shrink the ring. When the other ring structure is condensed in a lactone structure forming a 5-membered ring to a 7-membered ring, it is preferred that the other ring structure is condensed in the form of a bicyclic structure or a spiro structure. Examples of the other ring structure include a cyclic hydrocarbon group having 3 to 20 carbon atoms and a heterocyclic group having 3 to 20 carbon atoms. The heterocyclic group is not particularly limited, and one or more of the atoms constituting the ring may have a hetero atom or an aromatic heterocyclic group. Further, the heterocyclic group is preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 5-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.

When the other ring structure is condensed in a lactone structure to form a polycyclic structure in a constituent unit containing a lactone structure, the number of other ring structures condensed in the lactone structure is preferably from 1 to 5, More preferably 1~3.

Further, the lactone structure used in the present invention may have a substituent or may have no substituent, but preferably has no substituent. The substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a carbon number of 2 to 2. An alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group or the like. More preferably, it is an alkyl group or a cyano group having a carbon number of 1 to 4.

The alkyl group is preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, more preferably A linear alkyl group having 1 to 3 carbon atoms.

When the lactone structure has a substituent, the number of the substituent is not particularly limited, but is preferably from 1 to 4, more preferably 1 or 2. When the lactone structure used in the present invention has When a plurality of substituents are used, the plurality of substituents may be the same or different from each other. Further, when other ring structures are condensed in a lactone structure, the other ring structures may have a substituent.

The constituent unit containing a lactone structure used in the present invention preferably contains a group represented by the following formula (1).

(In the formula (1), R ^A1 represents a substituent, and n ₁ R ^A1 are each independently and may be the same or different. Z ¹ represents a monocyclic structure or a polycyclic structure containing -OC(=O)-. ₁ means an integer greater than 0)

In the formula (1), R ^A1 represents a substituent, and n ₁ R ^A1 are each independently and may be the same or different. The meaning of R ^{A1 is} the same as the substituent which the above lactone structure may have, and the preferred range is also the same.

In the formula (1), Z ¹ represents a monocyclic structure or a polycyclic structure containing -OC(=O)-, and preferably represents a monocyclic structure. When Z ¹ represents a monocyclic structure, as a monocyclic structure, a lactone structure of a 5-membered ring to a 7-membered ring is preferably formed, and a lactone structure of a 5-membered ring or a 6-membered ring is more preferable. When Z ¹ represents a polycyclic structure, as the polycyclic structure, it is preferred that the other ring structure is condensed in the lactone structure in the form of a bicyclic structure or a spiro structure. As other ring structures, the meanings are the same as those of the other ring structures described above, and the preferred ranges are also the same.

In the formula (1), n ₁ represents an integer of 0 or more, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0. When n ₁ is an integer of 2 or more, a plurality of substituents may be the same or different from each other. Further, a plurality of substituents may be bonded to each other to form a ring, but it is preferred that they are not bonded to each other to form a ring.

Further, the above structural unit (a4) is preferably represented by the following general formula (2).

(In the formula (2), RX ¹ represents a hydrogen atom or an alkyl group. R ^A2 represents a substituent, and n ₂ R ^A2 are each independently and may be the same or different. A ¹ represents a single bond or a divalent linking group. Z ² represents a monocyclic structure or a polycyclic structure containing a group represented by -OC(=O)-. n ₂ represents an integer of 0 or more)

In the formula (2), RX ¹ represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. The alkyl group may have a substituent. As the substituent, a hydroxyl group or a halogen atom (particularly a fluorine atom) is preferred.

In the formula (2), R ^A2 represents a substituent, and n ₂ R ^A2 are each independently and may be the same or different. The meaning of R ^{A2 is} the same as the substituent which the above lactone structure may have, and the preferred range is also the same.

In the formula (2), A ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include a linear, branched or cyclic alkyl group, an extended aryl group, -O-, -COO-, -S-, -NR"-, -CO-, a NR "CO-, -SO ₂ - or the like divalent group, or a combination comprising the groups. Here, R" represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. As a divalent linking group, -O-, -COO-, -S-, -NH- are preferable. And at least one of -CO- or including the group and -(CH ₂ ) _m - (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4) The basis of the combination.

In the formula (2), Z ² represents a monocyclic structure or a polycyclic structure containing a group represented by -OC(=O)-, and the meaning thereof is the same as Z ¹ in the formula (1), and a preferred range The same is true.

In the formula (2), n ₂ represents an integer of 0 or more, and the meaning thereof is the same as n ₁ in the formula (1), and the preferred range is also the same.

Further, the above constituent unit (a4) is preferably represented by the following general formula (3).

General formula (3) [Chem. 19]

(In the formula (3), RX ₂ represents a hydrogen atom or an alkyl group. R ^A3 represents a substituent, and n ₃ R ^A3 are each independently the same or different. A ² represents a single bond or a divalent linking group. Z ³ represents a monocyclic structure or a polycyclic structure containing a group represented by -OC(=O)-. n ₃ represents an integer of 0 or more. X ¹ represents an oxygen atom or -NR"-. R" represents a hydrogen atom or alkyl)

In the formula (3), R ^A3 represents a substituent, and n ₃ R ^A3 are each independently the same, and may be the same or different. The meaning of R ^{A3 is} the same as the substituent which the above lactone structure may have, and the preferred range is also the same.

In the formula (3), A ² represents a single bond or a divalent linking group. The divalent linking group has the same meaning as in the case where A ¹ in the formula (2) represents a divalent linking group. The preferred divalent linking group is preferably at least one of -COO- or -CO-, or includes the group and -(CH ₂ ) _m - (m is an integer of 1 to 10, preferably A combination of an integer of 1 to 6 and more preferably an integer of 1 to 4. In particular, as A ² in the formula (3), a single bond is preferred.

In the formula (3), Z ³ represents a monocyclic structure or a polycyclic structure containing a group represented by -OC(=O)-, and the meaning thereof is the same as Z ¹ in the formula (1), and a preferred range The same is true.

In the formula (3), n ₃ represents an integer of 0 or more, and the meaning thereof is the same as n ₁ in the formula (1), and the preferred range is also the same.

In the formula (3), X ¹ represents an oxygen atom or -NR"-, preferably an oxygen atom. R" represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

The structural unit (a4) preferably contains a structure represented by any one of the following general formulae (LC1-1) to (LC1-21) as the structure represented by the above formula (1).

More preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), particularly preferred The structures are (LC1-1), (LC1-4), (LC1-17). By including such a structure in the above-mentioned structural unit (a4), the chemical resistance of the composition of the present invention can be improved, and the relative dielectric constant can be further lowered.

[Chemistry 20]

In the structure represented by the above formula (LC1-1) to formula (LC1-21), (Rb ₂ ) represents a substituent, and may have (Rb ₂ ) or may not have (Rb ₂ ), but is preferably. It is not (Rb ₂ ) (that is, n4 is 0 in the above formula (LC1-1) to formula (LC1-21). The preferred substituent (Rb ₂ ) has the same meaning as the substituent which the above lactone structure may have, and the preferred range is also the same.

Further, in the structure represented by the above formula (LC1-1) to formula (LC1-21), n4 has the same meaning as n ₁ in the above formula (1), and the preferred range is also the same.

The constituent unit containing a lactone structure usually has an optical isomer and can be used. Any optical isomer. Further, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, its optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.

Specific examples of the constituent unit containing a lactone structure which can be used in the present invention are shown below, but the present invention is not limited thereto.

[化22]

[化23]

In particular, the constituent unit (a4) having a lactone structure which can be used in the present invention is preferably represented by the following formula (4) to formula (7), and more preferably represented by the following formula (4).

The composition of the present invention may be used in combination of two or more constituent units containing a lactone structure. When two or more constituent units containing a lactone structure are used in combination, the total amount thereof is preferably a numerical range of the constituent unit (a4) to be described later.

<<(a3) Other constituent units>>

In the present invention, the polymer component (A) may have other constituent units (a3) other than the constituent unit (a1), the constituent unit (a2), and the constituent unit (a4). The above polymer (1) and/or polymer (2) may contain a constituent unit (a3). Further, in addition to the above polymer (1) or polymer (2), a polymer containing substantially no constituent unit (a1) and a constituent unit (a2) and containing another constituent unit (a3) may be contained.

The monomer to be a constituent unit (a3) is not particularly limited, and examples thereof include styrene, alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, and (meth)acrylic acid. Base ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid Acid, unsaturated dicarboxylic anhydride, other unsaturated compounds. Further, as will be described later, it may have a constituent unit containing an acid group. The monomers which are other constituent units (a3) may be used singly or in combination of two or more kinds.

Specifically, the constituent unit (a3) includes constituent units formed of the following compounds: styrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, and methoxybenzene. Ethylene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid (3-methacrylic acid) 醯oxypropyl)ester, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (A) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) propylene morpholine, N-ring Hexyl maleimide, acrylonitrile, ethylene glycol monoacetic acid monoester (meth) acrylate. In addition, the compound described in Paragraph No. 0021 to Paragraph No. 0024 of JP-A-2004-264623 is mentioned.

Further, as the other structural unit (a3), from the viewpoint of electrical properties, a styrene type or a group having an aliphatic cyclic skeleton is preferable. Specific examples thereof include styrene, methyl styrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylic acid. Isobornyl ester, benzyl (meth) acrylate, and the like.

Further, as the other structural unit (a3), from the viewpoint of adhesion, an alkyl (meth)acrylate is preferred. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. .

It is preferred to contain a repeating unit containing an acid group as another constituent unit (a3). The effect of the present invention can be more effectively exhibited by containing an acid group and easily dissolving in an alkaline developing solution. Usually, a monomer capable of forming an acid group is used as a constituent unit containing an acid group, and an acid group is introduced into the polymer. When such a structural unit containing an acid group is contained in a polymer, it tends to be easily dissolved in an alkaline developing solution.

The acid group used in the present invention may, for example, be an acid group derived from a carboxylic acid group, an acid group derived from a sulfonylamino group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, or a source. The acid group derived from a phenolic hydroxyl group, a sulfonylamino group, a sulfonyl sulfoximine group, or the like is preferably an acid group derived from a carboxylic acid group and/or an acid group derived from a phenolic hydroxyl group.

The constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth)acrylic acid and/or an ester thereof. For example, a compound described in Paragraph No. 0021 to Paragraph No. 0023 and Paragraph No. 0029 to Paragraph No. 0044 of JP-A-2012-88459 can be used, and the content can be incorporated into the specification of the present application. Among them, a constituent unit derived from p-hydroxystyrene, (meth)acrylic acid, maleic acid, or maleic anhydride is preferred.

As such a polymer, a resin having a carboxyl group in a side chain is preferred. For example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836 A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification as described in each of Japanese Laid-Open Patent Publication No. 59-71048 An acid-based cellulose derivative having a carboxyl group in a side chain, an acid anhydride derivative added to a polymer having a hydroxyl group, and the like, and a (meth) propylene having a side chain A mercapto-based polymer is preferred as the polymer.

For example, benzyl (meth)acrylate/(meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymerization 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, acrylic acid, as described in Japanese Laid-Open Patent Publication No. Hei. 7-145. 2-Hydroxy-3-phenoxypropyl ester/polymethyl methacrylate macromer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer Molecular/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.

In addition, Japanese Patent Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. Hei 8-259876, Japanese Patent Laid-Open No. Hei 10-300922, Japanese Patent Laid-Open No. Hei 11-140144, and Japanese Patent No. A known polymer compound described in JP-A-H07-174224, JP-A-2000-56118, JP-A-2003-233179, and JP-A-2009-52020, etc. The content can be incorporated into the specification of the application.

These polymers may be contained alone or in combination of two or more.

As such polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by East Asia Synthetic Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, BASF) (BASF) manufacturing) and so on.

In the present invention, from the viewpoint of sensitivity, a structural unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group is particularly preferable. For example, a compound described in Paragraph No. 0021 to Paragraph No. 0023 and Paragraph No. 0029 to Paragraph No. 0044 of JP-A-2012-88459 can be used, and the content can be incorporated into the specification of the present application.

The constituent unit containing an acid group is preferably 1 mol% to 80 mol%, more preferably 1 mol% to 50 mol%, and even more preferably 5 mol% to 40% of all constituent units of the polymer component. Moer%, especially preferably 5 mol%~30 mol%, especially preferably 5 mol%~25 mol%.

Hereinafter, preferred embodiments of the polymer component (A) of the present invention are listed, but the present invention is not limited to the embodiments.

(First embodiment)

(A) The polymer component contains one or more types of polymers (A2).

In all the constituent units of the polymer component (polymer (A2)), the content of the constituent unit (a1) is preferably from 3 mol% to 70 mol%. In all the constituent units of the polymer (A2), the content of the constituent unit (a2) is preferably from 3 mol% to 70 mol%. In all the constituent units of the polymer (A2), the content of the constituent unit (a4) is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, and even more preferably 3 mol%. Ear %~20% of the ear.

The polymer (A2) may contain the above constituent unit (a3). When the polymer (A2) contains the above structural unit (a3), the content of the constituent unit (a3) in all the constituent units of the polymer (A2) is preferably from 1 mol% to 50 mol%.

In the (A) polymer component, the content of the polymer other than the polymer (A2) is preferably 10% by mass or less based on the (A) polymer component.

(Second embodiment)

(A) The polymer component comprises a polymer (A2a) and a polymer (A2b). Further, the polymer (A2a) usually does not contain (a4) a constituent unit having a lactone structure. Further, the polymer (A2b) usually does not contain the constituent unit (a1) and the constituent unit (a2).

In all the constituent units of the polymer component (polymer (A2a) and polymer (A2b)), the content of the constituent unit (a1) is preferably from 3 mol% to 70 mol%. In all the constituent units of the polymer (A2a) and the polymer (A2b), the content of the constituent unit (a2) is preferably from 3 mol% to 70 mol%.

In all the constituent units of the polymer (A2a) and the polymer (A2b), the content of the constituent unit (a4) is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, More preferably, it is 3 mol% to 20 mol%.

The polymer (A2a) and/or the polymer (A2b) may further contain the above constituent unit (a3). In all the constituent units of the polymer component (polymer (A2a) and polymer (A2b)), the content of the constituent unit (a3) is preferably from 1 mol% to 50 mol%.

When the polymer (A2a) contains the above-mentioned structural unit (a3), the total of the constituent unit (a1), the constituent unit (a2), and the constituent unit (a3) in the polymer (A2a) is 100 mol%.

When the polymer (A2b) contains the above structural unit (a3), the total of the constituent unit (a3) and the constituent unit (a4) in the polymer (A2b) is 100 mol%.

(A) Group of polymer (A2a) and polymer (A2b) in the polymer component The ratio is preferably (polymer (A2a) / polymer (A2b)) = 1 to 20, more preferably 2 to 10 by mass ratio.

Further, in the polymer component (A), the content of the polymer other than the polymer (A2a) and the polymer (A2b) is preferably 10% by mass or less based on the (A) polymer component.

In all the constituent units in the polymer (A2a), the content of the constituent unit (a1) in the polymer (A2a) is preferably from 3 mol% to 90 mol%, more preferably from 10 mol% to 80 mol%. %. In all the constituent units in the polymer (A2a), the content of the constituent unit (a2) in the polymer (A2a) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%. %. When the polymer (A2a) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2a) is preferably from 3 mol% to 70 in all the constituent units in the polymer (A2a). Molar%, more preferably 10% by mole to 50% by mole.

In all the constituent units in the polymer (A2b), the content of the constituent unit (a4) in the polymer (A2b) is preferably from 2 mol% to 95 mol%, more preferably from 3 mol% to 90 mol%. %, and more preferably 5 mol% to 85 mol%. When the polymer (A2b) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2b) is preferably from 3 mol% to 70 in all the constituent units in the polymer (A2b). Molar%, more preferably 10% by mole to 50% by mole.

(Third embodiment)

(A) The polymer component comprises a polymer (A2c) and a polymer (A2d). Further, the polymer (A2c) usually does not contain the constituent unit (a2). In addition, the polymer (A2d) pass The constituent units containing the lactone structure of the constituent units (a1) and (a4) are usually not contained.

In all the constituent units of the polymer component (polymer (A2c) and polymer (A2d)), the content of the constituent unit (a1) is preferably from 3 mol% to 70 mol%. In all the constituent units of the polymer component (A), the content of the constituent unit (a2) is preferably from 3 mol% to 70 mol%. In all the constituent units of the polymer component (A), the content of the constituent unit (a4) is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, and still more preferably 3 Mole%~20% by mole.

In the (A) polymer component, the content of the polymer other than the polymer (A2c) and the polymer (A2d) is preferably 10% by mass or less based on the (A) polymer component.

The polymer (A2c) and/or the polymer (A2d) may further contain the above constituent unit (a3). In all the constituent units of the polymer component (polymer (A2c) and polymer (A2d)), the content of the constituent unit (a3) is preferably from 1 mol% to 50 mol%.

When the polymer (A2c) contains the above structural unit (a3), the total of the constituent unit (a1), the constituent unit (a3) and the constituent unit (a4) in the polymer (A2c) is 100 mol%.

Further, when the polymer (A2d) contains the above structural unit (a3), the total of the constituent unit (a2) and the constituent unit (a3) in the polymer (A2d) is 100 mol%.

In the polymer component (A), the composition ratio of the polymer (A2c) to the polymer (A2d) is preferably (polymer (A2c) / polymer (A2d)) = 0.5 to 5, more preferably 0.8. ~2.5.

Further, among all the constituent units in the polymer (A2c), the content of the constituent unit (a1) in the polymer (A2c) is preferably from 3 mol% to 90 mol%, more preferably from 10 mol% to 80%. Moer%. Further, among all the constituent units in the polymer (A2c), the content of the constituent unit (a4) in the polymer (A2c) is preferably from 2 mol% to 95 mol%, more preferably from 3 mol% to 90%. Molar%, and more preferably 5 mol% to 85 mol%. When the polymer (A2c) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2c) is preferably from 3 mol% to 70 in all the constituent units in the polymer (A2c). Molar%, more preferably 10% by mole to 50% by mole.

Further, among all the constituent units in the polymer (A2d), the content of the constituent unit (a2) in the polymer (A2d) is preferably from 1 mol% to 90 mol%, more preferably from 40 mol% to 80%. Moer%. When the polymer (A2d) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2d) is preferably from 3 mol% to 70 in all the constituent units in the polymer (A2d). Molar%, more preferably 10% by mole to 50% by mole.

(Fourth embodiment)

(A) The polymer component comprises a polymer (A2e) and a polymer (A2f). Further, the polymer (A2e) usually does not contain the constituent unit (a2) and the constituent unit (a4) having a lactone structure. Further, the polymer (A2f) usually does not contain the constituent unit (a1).

In all the constituent units of the polymer component (polymer (A2e) and polymer (A2f)), the content of the constituent unit (a1) is preferably from 3 mol% to 70 mol%. In all the constituent units of the polymer (A2e) and the polymer (A2f), the content of the constituent unit (a2) is preferably from 3 mol% to 70 mol%. Polymer (A2e) and polymer (A2f) In all the constituent units, the content of the constituent unit (a4) is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, and even more preferably from 3 mol% to 20 mol. ear%.

In the (A) polymer component, the content of the polymer other than the polymer (A2e) and the polymer (A2f) is preferably 10% by mass or less based on the (A) polymer component.

The polymer (A2e) and/or the polymer (A2f) may further contain the above constituent unit (a3). In all the constituent units of the polymer component (polymer (A2e) and polymer (A2f)), the content of the constituent unit (a3) is preferably from 1 mol% to 50 mol%.

When the polymer (A2e) contains the above structural unit (a3), the total of the constituent unit (a1) and the constituent unit (a3) in the polymer (A2e) is 100 mol%.

When the polymer (A2f) contains the above structural unit (a3), the total of the constituent unit (a2), the constituent unit (a3) and the constituent unit (a4) in the polymer (A2f) is 100 mol%.

In the polymer component (A), the composition ratio of the polymer (A2e) to the polymer (A2f) is preferably (polymer (A2e) / polymer (A2f)) = 0.5 to 5, more preferably 0.8. ~2.5.

Further, among all the constituent units in the polymer (A2e), the content of the constituent unit (a1) in the polymer (A2e) is preferably from 3 mol% to 90 mol%, more preferably from 10 mol% to 80%. Moer%. When the polymer (A2e) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2e) is preferably from 3 mol% to 70 in all the constituent units in the polymer (A2e). Mole%, more preferably 10 m %~50% by mole.

Further, among all the constituent units in the polymer (A2f), the content of the constituent unit (a2) in the polymer (A2f) is preferably from 1 mol% to 90 mol%, more preferably from 40 mol% to 80%. Moer%. Further, among all the constituent units in the polymer (A2f), the content of the constituent unit (a4) in the polymer (A2f) is preferably from 2 mol% to 95 mol%, more preferably from 3 mol% to 90%. Molar%, and more preferably 5 mol% to 85 mol%. When the polymer (A2f) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2f) is preferably from 1 mol% to 70 in all the constituent units in the polymer (A2f). Moer%, more preferably 3 mol% to 50 mol%.

(Fifth Embodiment)

(A) The polymer component comprises a polymer (A2g) and a polymer (A2h) and a polymer (A2i). Further, the polymer (A2g) usually does not contain constituent units containing the lactone structure of the constituent units (a2) and (a4). Further, the polymer (A2h) usually does not contain constituent units containing the lactone structure of the constituent units (a1) and (a4). Further, the polymer (A2i) usually does not contain the constituent unit (a1) and the constituent unit (a2).

In all the constituent units of the polymer component (polymer (A2g), polymer (A2h), and polymer (A2i)), the content of the constituent unit (a1) is preferably from 3 mol% to 70 mol%. . In all the constituent units of the polymer (A2g), the polymer (A2h) and the polymer (A2i), the content of the constituent unit (a2) is preferably from 3 mol% to 70 mol%. In all the constituent units of the polymer (A2g), the polymer (A2h) and the polymer (A2i), the content of the constituent unit (a4) is preferably from 1 mol% to 80 mol%, more preferably 1 mol%. ~50% by mole, and more preferably 3% by mole to 20% by mole.

Further, in the polymer component (A), the content of the polymer other than the polymer (A2g), the polymer (A2h) and the polymer (A2i) is preferably 10% by mass or less based on the (A) polymer component.

At least one of the polymer (A2g), the polymer (A2h), and the polymer (A2i) may further contain the above structural unit (a3). In all the constituent units of the polymer component (polymer (A2g), polymer (A2h), and polymer (A2i)), the content of the constituent unit (a3) is preferably from 1 mol% to 50 mol%. .

When the polymer (A2g) contains the above structural unit (a3), the total of the constituent unit (a1) and the constituent unit (a3) in the polymer (A2g) is 100 mol%.

When the polymer (A2h) contains the above structural unit (a3), the total of the constituent unit (a2) and the constituent unit (a3) in the polymer (A2h) is 100 mol%.

When the polymer (A2i) contains the above structural unit (a3), the total of the constituent unit (a3) and the constituent unit (a4) in the polymer (A2i) is 100 mol%.

The composition ratio of the total amount of the polymer (A2g) to the polymer (A2h) to the polymer (A2i) is preferably ((polymer (A2g) + polymer (A2h)) / polymer (A2i)) by mass ratio) =1~20, more preferably 2~10. Further, the composition ratio of the polymer (A2g) to the polymer (A2h) is preferably (polymer (A2g) / polymer (A2h)) = 0.5 to 5, more preferably 0.8 to 2.5 by mass ratio.

Further, among all the constituent units in the polymer (A2g), the content of the constituent unit (a1) in the polymer (A2g) is preferably from 3 mol% to 90 mol%, more preferably from 10 mol% to 80%. Moer%. When the polymer (A2g) further contains the constituent unit (a3), in all the constituent units in the polymer (A2g), the structure in the polymer (A2g) The content of the unit (a3) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 50 mol%.

Further, in all the constituent units in the polymer (A2h), the content of the constituent unit (a2) in the polymer (A2h) is preferably from 1 mol% to 90 mol%, more preferably from 40 mol% to 80%. Moer%. When the polymer (A2h) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2h) is preferably from 3 mol% to 70 in all the constituent units in the polymer (A2h). Molar%, more preferably 10% by mole to 50% by mole.

Further, among all the constituent units in the polymer (A2i), the content of the constituent unit (a4) in the polymer (A2i) is preferably from 2 mol% to 95 mol%, more preferably from 3 mol% to 90%. Molar%, and more preferably 5 mol% to 85 mol%. When the polymer (A2i) further contains the constituent unit (a3), the content of the constituent unit (a3) in the polymer (A2i) is preferably from 3 mol% to 70 in all the constituent units in the polymer (A2i). Molar%, more preferably 10% by mole to 50% by mole.

<<(A) Molecular Weight of Polymer>>

The molecular weight of the (A) polymer is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight. If it is within the range of the above numerical values, various characteristics are good. The ratio (dispersion) of the number average molecular weight to the weight average molecular weight is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.

<<(A) Method for producing polymer component>>

Further, various methods are also known for the synthesis method of the (A) polymer component, and if an example is used, at least the content may be used by using a radical polymerization initiator. The radical polymerizable monomer mixture forming the radical polymerizable monomer of the structural unit represented by the above (a1) and the above (a2) is synthesized by polymerization in an organic solvent. Further, it can also be synthesized by a so-called polymer reaction.

The polymer component (A) preferably contains 50 mol% or more of a constituent unit derived from (meth)acrylic acid and/or an ester thereof, and more preferably contains 80 mol% or more.

<(B) Photoacid generator>

The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator used in the present invention is preferably a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but is not limited by its chemical structure. In addition, a photoacid generator that does not directly induce actinic rays having a wavelength of 300 nm or more is a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more with an sensitizer. It can also be preferably used after being combined with a sensitizer. The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, more preferably a photoacid generator which produces an acid having a pKa of 3 or less, and preferably has a pKa of A photoacid generator of 2 or less acids.

Examples of the photoacid generator include trichloromethyl-s-triazines, phosphonium salts or phosphonium salts, quaternary ammonium salts, diazomethane compounds, sulfhydryl sulfonate compounds, and sulfonic acid. Ester compound and the like. Among these photoacid generators, an oxime sulfonate compound is preferably used from the viewpoint of insulating properties. These photoacid generators may be used alone or in combination of two or more. As trichloromethyl-s-triazines, diaryl Specific examples of the sulfonium salt, the triaryl sulfonium salt, the quaternary ammonium salt, and the diazomethane derivative can be exemplified in Paragraph No. 0083 to Paragraph No. 0088 of JP-A-2011-221494. Compounds, the contents of which can be incorporated into the specification of the present application.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following formula (B1-1) can be preferably exemplified.

(In the formula (B1-1), R ²¹ represents an alkyl group or an aryl group. The wavy line indicates a bond with another group)

In the formula (B1-1), any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. The substituents allowed are explained below.

The alkyl group of R ²¹ is preferably a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may be a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (containing 7,7-dimethyl-2-oxorolide) The group is a bridged cyclic alicyclic group, preferably a bicycloalkyl group or the like.

The aryl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted by a lower alkyl group, an alkoxy group or a halogen atom.

The above compound containing the oxime sulfonate structure represented by the above formula (B1-1) is preferably an oxime sulfonate compound represented by the following formula (B1-2).

(In the formula (B1-2), R ⁴² represents an alkyl group or an aryl group which may be substituted, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents an integer of 0 to 3, and when m4 is 2 or 3 , multiple Xs can be the same or different)

The preferred range of R ⁴² is the same as the preferred range of the above R ²¹ .

The alkyl group as X is preferably a linear alkyl group or a branched alkyl group having 1 to 4 carbon atoms. Further, the alkoxy group as X is preferably a linear alkoxy group having a carbon number of 1 to 4 or a branched alkoxy group. Further, the halogen atom as X is preferably a chlorine atom or a fluorine atom.

M4 is preferably 0 or 1. In the above formula (B2), it is particularly preferred that m4 is 1, X is a methyl group, the substitution position of X is an ortho position, and R ⁴² is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethylene. A compound of the group -2-oxo norbornylmethyl or p-tolylmethyl.

The compound containing the oxime sulfonate structure represented by the above formula (B1-1) is preferably an oxime sulfonate compound represented by the following formula (B1-3).

(In the formula (B1-3), R ^{43 has} the same meaning as R ⁴² in the formula (B1-2), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and a carbon number of 1 to 4; Alkoxy, cyano or nitro, n4 represents an integer from 0 to 5)

R ⁴³ in the above formula (B1-3) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl or perfluoro-n-propyl. Base, perfluoro-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.

X ^{1 is} preferably an alkoxy group having a carbon number of 1 to 5, more preferably a methoxy group.

N4 is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the above formula (B1-3) and specific examples of the preferred oxime sulfonate compound can be referred to Japanese Patent Laid-Open No. 2012-163937. The description of Paragraph No. 0080 to Paragraph No. 0082 of the Gazette can be incorporated into the specification of the present application.

The compound containing the oxime sulfonate structure represented by the above formula (B1-1) is preferably a compound represented by the following formula (OS-1).

In the above formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfonic acid group or a cyano group. , aryl, or heteroaryl. 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 an aromatic group. base.

R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfonic acid group or a cyanogen group. Base, or aryl. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

R ¹²¹ to R ^{124 are} preferably a hydrogen atom, a halogen atom or an alkyl group, and a form in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Among them, from the viewpoint of sensitivity, it is preferred that R ¹²¹ to R ¹²⁴ are each a hydrogen atom.

The functional groups described may each further have a substituent.

The compound represented by the above formula (OS-1) is preferably a compound represented by the formula (OS-2) as described in Paragraph No. 0087 to Paragraph No. 0089 of JP-A-2012-163937. This content can be incorporated into the specification of the present application.

Specific examples of the compound represented by the above formula (OS-1) which can be suitably used in the present invention include the compounds described in Paragraph No. 0128 to Paragraph No. 0132 of JP-A-2011-221494. (Illustrative compound b-1 to exemplified compound b-34), but the present invention is not limited thereto.

In the present invention, the compound containing the oxime sulfonate structure represented by the above formula (B1-1) is preferably represented by the following formula (OS-3) or the following formula (OS-4). Or an oxime sulfonate compound represented by the following formula (OS-5).

[化29]

(In the general formula (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are each independently The ground represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonate. The thiol group, X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, and n1 to n3 each independently represent 1 or 2, and m1 to m3 each independently represent an integer of 0 to 6)

For the above-described general formula (OS-3) to the general formula (OS-5), for example, the description of Paragraph No. 0098 to Paragraph No. 0115 of Japanese Patent Laid-Open No. 2012-163937 can be incorporated into the present application. In the manual.

In addition, the compound containing the oxime sulfonate structure represented by the above formula (B1-1) is particularly preferably a formula (OS-6) as described in paragraph 0117 of JP-A-2012-163937. The compound represented by any of the formula (OS-11) can be incorporated into the specification of the present application.

The preferred range of the above-mentioned general formula (OS-6) to the general formula (OS-11) is (OS-6) as described in Paragraph No. 0110 to Paragraph No. 0112 of JP-A-2011-221494. The preferred scope of (OS-11) is the same, and the content can be incorporated into the specification of the present application.

Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include paragraph number 0114 to paragraph 0120 of JP-A-2011-221494. The compounds described in this specification can be incorporated into the specification of the present application. The invention is not limited to these compounds.

The compound containing the oxime sulfonate structure represented by the above formula (B1-1) is preferably an oxime sulfonate compound represented by the following formula (B1-4).

(In the formula (B1-4), R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group, an aryl group or a heteroaryl group. R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen. An atom wherein R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form an alicyclic or aromatic ring. X represents -O- or -S-)

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having a branched structure or an alkyl group having a cyclic structure.

The alkyl group preferably has a carbon number of from 3 to 10. Particularly, when the alkyl group has a branched structure, it is preferably an alkyl group having a carbon number of 3 to 6, and when it has a cyclic structure, it preferably has a carbon number of 5 to 7. Alkyl.

Examples of the alkyl group include propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and 1,1-dimethyl Preference is given to propyl, hexyl, 2-ethylhexyl, cyclohexyl, octyl and the like, preferably isopropyl, tert-butyl, neopentyl or cyclohexyl.

The carbon number of the aryl group is preferably from 6 to 12, more preferably from 6 to 8, more preferably from 6 to 7. The aryl group may, for example, be a phenyl group or a naphthyl group, and is preferably a phenyl group.

The alkyl group and the aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear, branched or cyclic alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, and the like. Alkynyl, aryl, decyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, cyano, carboxy, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, heteroepoxy Base, decyloxy, amine, nitro, fluorenyl, heterocyclic, and the like. In addition, these groups may be further substituted. A halogen atom or a methyl group is preferred.

The photosensitive resin composition of the present invention in terms of the viewpoint of transparency, R ¹ is preferably an alkyl group, and causes the storage stability viewpoint of sensitivity exist, R ¹ preferably having a carbon number of 3 to 6 An alkyl group having a branched structure, an alkyl group having a cyclic structure of 5 to 7 carbon atoms, or a phenyl group, more preferably an alkyl group having a branched structure having a carbon number of 3 to 6, or a ring having a carbon number of 5 to 7. An alkyl group of a structure. The transparency can be further improved by using such a bulky group (especially a bulky alkyl group) as R ¹ .

Among the bulky substituents, preferred are isopropyl, tert-butyl, neopentyl, cyclohexyl, and more preferred are tert-butyl or cyclohexyl.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ² is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group or a cyclohexyl group, and is preferably a methyl group.

As the aryl group, an aryl group having 6 to 10 carbon atoms is preferred. Examples of the aryl group include a phenyl group, a naphthyl group, a p-tolylmethyl group (p-methylphenyl group), and the like, and a phenyl group and a p-tolylmethyl group are preferable.

Examples of the heteroaryl group include a pyrrolyl group, a fluorenyl group, a carbazolyl group, a furyl group, a thienyl group and the like.

The alkyl group, the aryl group, and the heteroaryl group represented by R ² may have a substituent. The substituent has the same meaning as the substituent which the alkyl group and the aryl group represented by R ¹ may have.

R ^{2 is} preferably an alkyl group or an aryl group, more preferably an aryl group, and even more preferably a phenyl group. The substituent of the phenyl group is preferably a methyl group.

R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). The alkyl group represented by R ³ to R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. Further, the aryl group represented by R ³ to R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.

Among R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form a ring, and as the ring, an alicyclic or aromatic ring is preferred, and benzene is more preferred. ring.

R ³ to R ^{6 are} preferably a hydrogen atom, an alkyl group, a halogen atom (a fluorine atom, a chlorine atom or a bromine atom), or a combination of R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ . The benzene ring, more preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a bromine atom or R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ^{6 are} bonded to each other to form a benzene ring.

Preferred forms of R ³ to R ⁶ are as follows.

(Form 1) At least two are hydrogen atoms.

(Form 2) The number of alkyl groups, aryl groups or halogen atoms is one or less.

(Form 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ^{6 are} bonded to each other to form a benzene ring.

(Form 4) A form that satisfies the above-described Form 1 and Form 2, and/or a form that satisfies the above Form 1 and Form 3.

X represents -O- or -S-.

Specific examples of the above formula (B1-4) include the following compounds, but the invention is not particularly limited thereto. Further, in the exemplified compound, Ts represents a toluenesulfonyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

[化31]

As the quinone sulfinate compound, a compound represented by the following formula (B1-5) can be preferably used.

(In the formula (B1-5), R ⁷ independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. The base n represents an integer from 0 to 4. X represents an integer from 1 to 20, Y represents an integer from 0 to 20, Z represents 0 to 20, and W represents an integer from 0 to 5.

As a specific example of the sulfhydryl sulfonate compound, the compound described in paragraph 0084 of JP-A-2012-155115 can be exemplified, and the content can be incorporated into the specification of the present application.

In the photosensitive resin composition of the present invention, the amount of the photoacid generator added is preferably from 0.1% by mass to 10% by mass, more preferably from the total solid content of the photosensitive resin composition of the present invention. It is set to 0.5 mass% to 10 mass%. Two or more kinds of photoacid generators may be used in combination. When two or more kinds of photoacid generators are used in combination, the total amount thereof is preferably in the above numerical range.

<(C) Solvent>

The photosensitive resin composition of the present invention contains a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving an essential component of the present invention and an optional component described later in a solvent. As the solvent used for the preparation of the composition of the present invention, those which uniformly dissolve the essential components and optional components and do not react with the respective components can be used.

As the solvent to be used in the photosensitive resin composition of the present invention, a known solvent can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl ether acetate. Esters, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol Monoalkyl ethers, dipropylene glycol dialkyl ethers, two Propylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. In addition, as a specific example of the solvent used in the photosensitive resin composition of the present invention, a solvent described in paragraphs 0174 to 0178 of JP-A-2011-221494, Japanese Patent Laid-Open No. 2011-221494 The solvent described in paragraphs 0167 to 0168 of the 2012-194290 publication, the contents of which are incorporated herein by reference.

In addition, benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone may be further added to the solvents as needed. , caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethyl carbonate, A solvent such as propyl carbonate. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably used singly or in combination of two, more preferably two, and more preferably propylene glycol monoalkyl ether acetate or dialkyl ether or diacetate. And diethylene glycol dialkyl ethers, or esters and butanediol alkyl ether acetates.

Further, the solvent is preferably a solvent having a boiling point of 130 ° C or higher and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture thereof.

The solvent having a boiling point of 130 ° C or higher and less than 160 ° C can be exemplified by propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol monoethyl ether acetate (boiling point: 158 ° C), propylene glycol methyl-n-butyl Ether (boiling point 155 ° C), propylene glycol methyl-n-propyl ether (boiling point 131 ° C).

As a solvent having a boiling point of 160 ° C or more, ethyl 3-ethoxypropionate (boiling) can be exemplified Point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetic acid Ester (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butanediol diacetate (boiling point 232 ° C).

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, more preferably 60 parts by mass to 90 parts by mass, per 100 parts by mass of all the components in the photosensitive resin composition.

<Other ingredients>

In addition to the above components, the photosensitive resin composition of the present invention may preferably contain a sensitizer, a crosslinking agent, an alkoxydecane compound, a basic compound, a surfactant, and an antioxidant. Further, in the photosensitive resin composition of the present invention, an acid multiplier, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, a UV absorber, a tackifier, and an organic or inorganic additive may be added. A known additive such as an anti-precipitation agent. Further, as such a compound, for example, a compound described in Paragraph No. 0201 to Paragraph No. 0224 of JP-A-2012-88459 can be used, and the contents of these can be incorporated into the specification of the present application.

Sensitizer

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with a photoacid generator to promote decomposition of the photoacid generator. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. Sensitizer and photoacid that become electronically excited The generator contacts, and generates electron movement, energy movement, heat generation and the like. Thereby, the photoacid generator generates a chemical change to decompose and generate an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of wavelength regions of 350 nm to 450 nm.

Polynuclear aromatics (eg, ruthenium, osmium, tert-triphenyl, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Dipropoxy fluorene), xanthene (such as fluorescein, blush, erythrosine, Rhodamine B, Rose Bengal) ), xanthone (such as xanthone, thioxanthone, dimethylthiazinone, diethyl thianonanone), cyanine (such as thiacarbocyanine, oxacarbonyl) Cyanine), merocyanines (eg, merocyanine, carbonyl cyclamate), rhodamines, oxaphthalocyanines, thiazides (eg, thiazide, methylene blue, toluidine blue), acridine (eg acridine orange, chloroflavin, acriflavine), acridone (eg acridone, 10-butyl-2-chloroacridone), anthraquinone (eg hydrazine), squaraine Intrinsic salts (eg, squaric acid ylide), styryls, basic styryls (eg 2-[2-[4-(dimethylamino)phenyl]vinyl]benzoxazole) ), coumarins (eg 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl -1H, 5H, 11H[1] benzo Pyrano[6,7,8-ij]quinolizin-11-one).

Among these sensitizers, polynuclear aromatics, acridones, styrenes, basic styrenes, and coumarins are preferred, and polynuclear aromatics are more preferred. Among the polynuclear aromatics, the most preferred is an anthracene derivative.

With respect to the total solid content in the photosensitive resin composition of the present invention, The amount of the sensitizer added to the photosensitive resin composition of the invention is preferably from 0% by mass to 100% by mass, more preferably from 0.1% by mass to 50% by mass, even more preferably from 0.5% by mass to 20% by mass. Two or more types of sensitizers may be used in combination.

Crosslinker

The photosensitive resin composition of the present invention preferably contains a crosslinking agent as needed. The cured film obtained from the photosensitive resin composition of the present invention can be made into a stronger film by adding a crosslinking agent.

The crosslinking agent is not limited as long as it is a crosslinking reaction by heat (except component A). For example, a compound having two or more epoxy groups or oxetane groups in the molecule, a crosslinking agent containing an alkoxymethyl group, or at least one ethylenically unsaturated double bond may be added as described below. a compound, a blocked isocyanate compound, or the like.

The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably 0.01% by mass to 50% by mass, and more preferably 0.1% by mass, based on the total solid content of the photosensitive resin composition of the present invention. 30% by mass, and more preferably 0.5% by mass to 20% by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination, and in this case, the total content of all the crosslinking agents is calculated.

<Compound having two or more epoxy groups or oxetane groups in the molecule>

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

These compounds are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc., and the commercial products described in Paragraph No. 0189 of JP-A-2011-221494 Etc. Other than this, 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 Kasei), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, Nippon Steel Chemicals) Manufacturing) and so on. These may be used alone or in combination of two or more.

Among these, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and an aliphatic epoxy resin can be more preferably mentioned, and a bisphenol A type ring can be especially mentioned. Oxygen resin.

Specific examples of the compound having two or more oxetanyl groups in the molecule include ARONE OXETANE OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.).

Further, the oxetane group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.

Further, as the other crosslinking agent, an alkoxymethyl group-containing crosslinking agent described in paragraphs 0107 to 0108 of JP-A-2012-8223, and having at least 1 may be preferably used. Compounds of ethylenically unsaturated double bonds, etc., may be incorporated into the specification of the present application. As the crosslinking agent containing an alkoxymethyl group, an alkoxymethylated glycoluril is preferred.

<Blocked isocyanate compound>

In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also preferably be used as the crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group. From the viewpoint of curability, a compound having two or more blocked isocyanate groups in one molecule is preferred.

In addition, the blocked isocyanate group in the present invention means a group which can form an isocyanate group by heat, and for example, a group which blocks a blocking agent and an isocyanate group to protect an isocyanate group can be preferably exemplified. Further, the blocked isocyanate group is preferably a group capable of forming an isocyanate group by heat of from 90 ° C to 250 ° C.

Further, the blocked isocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups in one molecule, and may be any compound, and may be an aliphatic, alicyclic or aromatic polyisocyanate, for example. It can be suitably used: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1 , 4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene Diisocyanate, 1,10-Tia Methyl diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, P-xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5- Naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane An isocyanate compound such as diisocyanate, hydrogenated 1,3-benzyldimethylisocyanate or hydrogenated 1,4-benzyldimethylisocyanate, and a compound of a prepolymer type skeleton derived from the compounds. Among them, particularly preferred is Tolylene Diisocyanate (TDI) or Diphenyl Methane Diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Isophorone II. Isocyanate Diisocyanate (IPDI).

The parent structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention may, for example, be a biuret type, an isomeric cyanurate type, an adduct type or a difunctional prepolymer type.

Examples of the blocking agent for forming the closed structure of the blocked isocyanate compound include a ruthenium compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, and an imidazole system. a compound, a quinone imine compound, or the like. Among these, a blocking agent selected from the group consisting of an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.

Examples of the hydrazine compound include hydrazine and ketoxime. Specific examples thereof include acetone oxime, formaldehyde oxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, diphenyl ketone oxime, and acetone. Hey.

The above-mentioned indoleamine compound may, for example, be ε-caprolactam or γ-butylidene.

The phenol compound may, for example, be phenol, naphthol, cresol, xylenol or halogen-substituted phenol.

The alcohol compound may, for example, be methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether or alkyl lactate.

Examples of the amine compound include a primary amine and a secondary amine, and may be any of an aromatic amine, an aliphatic amine, and an alicyclic amine, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine. Wait.

The active methylene compound may, for example, be diethyl malonate, dimethyl malonate, ethyl acetate or ethyl acetate.

The pyrazole compound may, for example, be pyrazole, methylpyrazole or dimethylpyrazole.

The thiol compound may, for example, be an alkyl mercaptan or an aryl thiol.

A blocked isocyanate compound which can be used in the photosensitive resin composition of the present invention can be obtained as a commercial product, and for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (for example) can be preferably used. Above, manufactured by Nippon Polyurethane Industry (shares), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above , Mitsui Chemicals (stock) manufacturing), Duranate17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, Asahi Kasei Chemicals) (Asahi Kasei Chemicals) (manufactured by shares), Desmodur BL1100, BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, Sustain Sumika Bayer Urethane (manufactured by the company) and so on.

Alkoxydecane compound

The photosensitive resin composition of the present invention may contain an alkoxydecane compound. When an alkoxy decane compound is used, the adhesiveness of the film formed from the photosensitive resin composition of this invention and a board|substrate, or the film of the photosensitive resin composition of this invention can be adjusted. The alkoxydecane compound which can be used in the photosensitive resin composition of the present invention is preferably an inorganic substance which is promoted as a substrate (for example, a ruthenium compound such as ruthenium, iridium oxide or tantalum nitride, or a metal such as gold, copper, molybdenum, titanium or aluminum). A compound having adhesion to an insulating film. Specifically, a known decane coupling agent or the like is also effective.

Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-glycidol. Oxypropyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl dialkoxy decane, γ-chloropropyl trialkoxide Basear, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. More preferably, it is γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane, and further Preferably, it is γ-glycidoxypropyltrialkoxydecane, and more preferably 3-glycidoxypropyltrimethoxydecane. These may be used alone or in combination of two or more.

Further, a compound represented by the following formula can also be preferably used.

(R ¹ ) _4-n -Si-(OR ² ) _n

In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms which does not have a reactive group, R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 1 to 3.

Specific examples thereof include the following compounds.

[化33]

[化34]

In the above, Ph is a phenyl group.

The alkoxydecane compound in the photosensitive resin composition of the present invention is not particularly limited to these compounds, and a known compound can be used.

The content of the alkoxydecane compound in the photosensitive resin composition of the present invention is preferably from 0.1% by mass to 30% by mass, more preferably 0.5% by mass, based on the total solid content of the photosensitive resin composition of the present invention. ~20% by mass.

Basic compound

The photosensitive resin composition of the present invention may contain a basic compound. As the basic compound, it can be arbitrarily selected from the basic compounds used in the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned. Specific examples of the above are described in paragraphs 0204 to 0207 of JP-A-2011-221494. The compounds, the contents of which can be incorporated into the specification of the present application.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, and trisole. Ethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N- Methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine , nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, anthracene, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N -cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo [5.3.0]-7-undecene and the like.

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

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

The basic compound which can be used in the present invention may be used alone or in combination of two or more.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001% by mass to 3% by mass, and more preferably 0.005% by mass to 1%, based on the total solid content of the photosensitive resin composition of the present invention. quality%.

Surfactant

The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant may be used, but a preferred surfactant is a nonionic surfactant. As the surfactant to be used in the composition of the present invention, for example, the surfactant described in Paragraph No. 0201 to Paragraph No. 0205 of JP-A-2012-88459, or Japanese Patent Laid-Open No. 2011-215580 can be used. The surfactants described in Paragraph No. 0185 to Paragraph No. 0188 of the Japanese Patent Publication are incorporated herein by reference.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene diols, anthrones, and fluorines. Surfactant. In addition, the following product names are listed: KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), and Eftop (Mitsubishi material) Kasei) company), Megafac (made by Diane (DIC) (share)), Fluorad, Novec FC-4430 (manufactured by Sumitomo 3M (share)), Surflon S-242 (manufactured by AGC SEIMI CHEMICAL) , PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning silicone), Ftergent FTX-218G (manufactured by Neos), etc. series.

In addition, as a surfactant, the copolymer containing the structural unit A and the structural unit B represented by the following general formula (I-1-1), and tetrahydrofuran (THF) is mentioned as a preferable example. As a solvent, measured by gel permeation chromatography The weight average molecular weight (Mw) in terms of polystyrene is 1,000 or more and 10,000 or less.

(In the formula (I-1-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having a carbon number of 1 or more and 4 or less, and R ⁴⁰⁴ represents a hydrogen atom or An alkyl group having 1 or more and 4 or less carbon atoms, L is an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, and p is 10% by mass or more and 80% by mass or less. Numerical value, q represents a numerical value of 20% by mass or more and 90% by 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. The above L is preferably represented by the following formula (I-1) -2) The branched alkyl group represented. R ⁴⁰⁵ in the formula (I-1-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and is preferably a carbon number from the viewpoint of compatibility and wettability to a surface to be coated. The alkyl group is 1 or more and 3 or less, and more preferably an alkyl group having 2 or 3 carbon atoms. The sum (p+q) of p and q is preferably p+q=100, that is, 100% by mass.

The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

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

The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10% by mass or less, and more preferably 0.001% by mass to 10% by mass based on the total solid content of the photosensitive resin composition of the present invention. Further, it is more preferably 0.01% by mass to 3% by mass.

Antioxidants

The photosensitive resin composition of the present invention may contain an antioxidant. A known antioxidant can be contained as an antioxidant. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or reduction in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.

Examples of such an antioxidant include phosphorus-based antioxidants, guanamines, guanidines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, sugars, and nitrites. , sulfite, thiosulfate, hydroxylamine derivatives, and the like. Among these antioxidants, the coloration and film thickness of the cured film are reduced. In view of the above, a phenol-based antioxidant, a guanamine-based antioxidant, a lanthanide-based antioxidant, and a sulfur-based antioxidant are particularly preferred, and a phenol-based antioxidant is preferred. These antioxidants may be used alone or in combination of two or more.

Specific examples thereof include the compounds described in Paragraph No. 0026 to Paragraph No. 0031 of JP-A-2005-29515, the contents of which are incorporated herein by reference.

Preferred examples of the commercially available product include Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, and Irganox 1098.

The content of the antioxidant is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 5% by mass, particularly preferably from 0.5% by mass to 4%, based on the total solid content of the photosensitive resin composition of the present invention. quality%. By setting it as this range, the film formed can obtain sufficient transparency, and the sensitivity at the time of pattern formation also becomes favorable.

[acid proliferator]

In order to enhance the sensitivity, an acid proliferating agent can be used as the photosensitive resin composition of the present invention.

The acid multiplying agent which can be used in the present invention is a compound which can further generate an acid by an acid catalyst reaction and raise the acid concentration in the reaction system, and is a compound which stably exists in the absence of an acid.

Specific examples of such an acid-proliferating agent include the acid-proliferating agent described in Paragraph No. 0226 to Paragraph No. 0228 of JP-A-2011-221494, which is incorporated herein by reference.

[development accelerator]

The photosensitive resin composition of the present invention may contain a development accelerator.

As the development accelerator, those described in Paragraph No. 0171 to Paragraph No. 0172 of JP-A-2012-042837 can be incorporated into the specification of the present application.

The development accelerator may be used alone or in combination of two or more.

From the viewpoint of the sensitivity and the residual film ratio, the amount of the development accelerator added to the photosensitive resin composition of the present invention is preferably from 0 to 30 mass% per 100 parts by mass of the total solid content of the photosensitive composition. The portion is more preferably 0.1 part by mass to 20 parts by mass, most preferably 0.5 part by mass to 10 parts by mass.

Further, as the other additive, the thermal radical generating agent described in paragraph 0120 to paragraph 0121 of JP-A-2012-8223, and the nitrogen-containing compound and thermal acid described in WO2011/136074 A1 can be used. The generating agent, the contents of which can be incorporated into the specification of the present application.

<Method for Preparing Photosensitive Resin Composition>

The components are mixed at a predetermined ratio and in an arbitrary manner, and then stirred and dissolved to prepare a photosensitive resin composition. For example, the components may be prepared by dissolving the components in a solvent in advance to prepare a solution, and then mixing the solutions at a predetermined ratio to prepare a resin composition. The composition solution prepared in the above manner can also be used after being filtered, for example, using a filter having a pore size of 0.2 μm or the like.

[Method for producing cured film]

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

The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).

(1) a step of applying the photosensitive resin composition of the present invention to a substrate; (2) a step of removing a solvent from the photosensitive resin composition to be applied; and (3) using a actinic ray to remove a solvent a step of exposing the resin composition; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; and (5) a post-baking for thermally curing the developed photosensitive resin composition step.

Each step will be described in order below.

In the application step of (1), it is preferred to apply (preferably, apply) the photosensitive resin composition of the present invention to a substrate to form a wet film containing a solvent. It is preferred to perform cleaning of the substrate such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition onto the substrate, and it is more preferable to treat the surface of the substrate with hexamethyldiaziridine after the substrate is cleaned. By performing this treatment, there is a tendency that the adhesion of the photosensitive resin composition to the substrate is improved. The method of treating the surface of the substrate with hexamethyldioxane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldioxane vapor in advance.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material.

Examples of the inorganic substrate include glass, quartz, anthrone, tantalum nitride, and a composite substrate obtained by vapor-depositing molybdenum, titanium, aluminum, copper, or the like on the substrate.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, and polycarbonate. Ester, polyfluorene, polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimine, polyamidimide, polyether phthalimide, polybenzoxazole, poly Fluororesin such as phenyl sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, cross-linking A synthetic resin such as a butylene diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound.

These substrates are used as they are in the above-described form, and a multilayered structure such as a TFT element is usually formed depending on the form of the final product.

The application method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, a slit and a spin method, and the like can be used. method.

The wet film thickness at the time of application is not particularly limited, and it can be applied in a film thickness corresponding to the application, but is usually used in the range of 0.5 μm to 10 μm.

Further, a so-called prewet method as described in JP-A-2009-145395 may be applied before the composition used in the present invention is applied onto a substrate.

In the solvent removal step of (2), the solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating condition of the solvent removal step is preferably from 70 ° C to 130 ° C for about 30 seconds to 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern is further improved, and the tendency of the residue can be further reduced.

In the exposure step of (3), the substrate on which the coating film is provided is irradiated Pattern of actinic rays. In this step, the photoacid generator decomposes and produces an acid. The acid generated by the acid-decomposable gene contained in the coating component is hydrolyzed by a catalytic action to form a carboxyl group or a phenolic hydroxyl group.

As the exposure light source using the actinic ray, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, or the like can be used, and can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm). Further, the illumination light may be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed. The exposure amount is preferably from 1 mJ/cm ² to 500 mJ/cm ² .

As an exposure device, it can be used in various ways such as mirror projection aligner, stepper, scanner, proximity, contact, microlens array, lens scanner, and laser exposure. machine.

In the region where the acid catalyst is formed, in order to accelerate the hydrolysis reaction, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") may be performed. The formation of a carboxyl group or a phenolic hydroxyl group derived from an acid-decomposable group can be promoted by PEB. The temperature at the time of PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and particularly preferably 50° C. or higher and 100° C. or lower.

However, the acid-decomposable group in the present invention has a low activation energy due to acid decomposition, is easily decomposed by an acid derived from an acid generator generated by exposure, and generates a carboxyl group or a phenolic hydroxyl group, so that it is not necessary to carry out PEB. A positive image can be formed by development.

In the developing step of (4), a copolymer having a free carboxyl group or a phenolic hydroxyl group is developed using an alkaline developing solution. The exposed portion region containing the resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in the alkaline developing solution is removed, whereby a positive image is formed.

It is preferred that the developer used in the developing step contains a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; or an alkali metal such as sodium bicarbonate or potassium bicarbonate can be used. Bicarbonate; ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above-mentioned alkali may be used as the developing solution.

As a preferable developing solution, an aqueous solution of 0.4% by mass to 2.5% by mass of tetramethylammonium hydroxide can be mentioned.

The pH of the developer is preferably from 10.0 to 14.0.

The development time is preferably from 30 seconds to 500 seconds, and the development method may be any one of a puddle method, a shower method, and a dipping method.

After the development, a rinsing step can also be performed. In the elution step, the developed substrate is washed with pure water or the like, whereby the adhered developer is removed, and the development residue is removed. A known method can be used for the rinsing method. For example, spray rinsing, immersion rinsing, etc. are mentioned.

In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to form a carboxyl group or a phenolic hydroxyl group, and A crosslinkable group, a crosslinking agent, or the like is crosslinked to form a cured film. The heating is preferably performed by using a heating means such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C to 250 ° C, for a predetermined period of time, for example, if it is a hot plate, heat treatment is performed for 5 minutes to 90 minutes. In the case of an oven, heat treatment is performed for 30 minutes to 120 minutes. By performing the crosslinking reaction as described above, it is possible to form a protective film or an interlayer insulating film which is more excellent in heat resistance and hardness. Further, when the heat treatment is performed, it can also be carried out under a nitrogen atmosphere, thereby further improving the transparency.

It is also possible to perform intermediate baking after baking at a relatively low temperature before post-baking (addition of the intermediate baking step). When the intermediate baking is performed, it is preferably heated at 90 ° C to 150 ° C for 1 minute to 60 minutes, and then post-baked at a high temperature of 200 ° C or higher. Further, the intermediate baking and the post-baking may be divided into three or more stages to perform heating. With this intermediate baking and post-baking design, the taper angle of the pattern can be adjusted. A known heating method such as a hot plate, an oven, or an infrared heater can be used for the heating.

Furthermore, the patterned substrate can be fully re-exposed (post-exposure) with actinic radiation before post-baking, and then post-baked, thereby being present in the photoacid generator present in the unexposed portion. The acid is generated and functions as a catalyst for promoting the crosslinking step, thereby promoting the hardening reaction of the film. The preferred exposure amount in the case of including the post-exposure step is preferably 100 mJ/cm ² to 3,000 mJ/cm ² , particularly preferably 100 mJ/cm ² to 500 mJ/cm ² .

Further, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. When going through the post-baking step When the cured film obtained by thermal curing is used as a dry etching resist, dry etching treatment such as ashing, plasma etching, or ozone etching may be performed as an etching treatment.

[hardened film]

The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention.

The cured film of the present invention can be suitably used as an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the above-described method for forming a cured film of the present invention.

According to the photosensitive resin composition of the present invention, an interlayer insulating film which is excellent in insulating properties and has high transparency even when baked at a high temperature can be obtained. The interlayer insulating film which is obtained by 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 use in a liquid crystal display device or an organic EL display device.

[Liquid Crystal Display Device]

A liquid crystal display device of the present invention is characterized by comprising the cured film of the present invention.

The liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and a known liquid crystal display device having various structures is exemplified.

Specific examples of the TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

Further, examples of the liquid crystal driving method which can be employed in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and a coplanar switching (In-Plane-Switching). IPS) mode, Fringe Field Switching (FFS) mode, Optically Compensated Bend (OCB) mode, etc.

In the panel configuration, even a color filter on Array (COA) liquid crystal display device can use the cured film of the present invention, for example, as an organic insulating film of JP-A-2005-284291. (115), or an organic insulating film (212) of JP-A-2005-346054. In addition, as a specific alignment method of the liquid crystal alignment film which can be used for the liquid crystal display device of the present invention, a rubbing alignment method, a photoalignment method, and the like can be given. Further, the polymer alignment support can be obtained by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used in various applications. For example, in addition to the planarization film or the interlayer insulating film, a protective film which is suitably used for a color filter, or a spacer for maintaining the thickness of the liquid crystal layer in the liquid crystal display device to be fixed, or a solid-state imaging element A microlens or the like disposed on a color filter.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is disposed with two glass substrates 14 disposed on a polarizing film. All of the pixels between the glass substrates 15 correspond to the elements of the TFT 16. Among the elements formed on the glass substrate, an ITO transparent electrode 19 on which a pixel electrode is formed is wired by a contact hole 18 formed in the cured film 17. A layer of the liquid crystal 20 and an RGB color filter 22 in which a black matrix is disposed are provided on the ITO transparent electrode 19.

The light source as the backlight is not particularly limited, and a known light source can be used. For example, white LED, blue. red. Multicolor LEDs such as green, fluorescent lamps (cold cathode tubes), organic EL, etc.

Further, the liquid crystal display device can also be a 3D (stereoscopic) type device or a touch panel type device. Further, it can be set to a flexible type, and can be used as the second interlayer insulating film (48) described in Japanese Laid-Open Patent Publication No. 2011-145686, or as described in Japanese Laid-Open Patent Publication No. 2009-258758. Interlayer insulating film (520).

[Organic EL display device]

The organic EL display device of the present invention is characterized by comprising the cured film of the present invention.

The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic EL displays having various structures can be used. Device or liquid crystal display device.

Specific examples of the TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

FIG. 2 is a conceptual diagram showing an example of an organic EL display device. Indicates bottom illumination A schematic cross-sectional view of a substrate in a type of organic EL display device, and having a planarization film 4.

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. The wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and the TFT 1.

Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried.

A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 including ITO is connected to the wiring 2 via the contact hole 7 to be formed on the planarization film 4. Further, the first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, although not shown in FIG. 2, vapor deposition is sequentially performed through a desired pattern mask to provide a hole transport layer, an organic light-emitting layer, and an electron transport layer, and then, the entire surface is formed on the upper surface of the substrate. The second electrode of Al is sealed by bonding with a glass plate for sealing by using an ultraviolet curable epoxy resin, and an active matrix obtained by connecting TFT1 for driving the organic EL elements to be driven is obtained. Type organic EL display device.

The photosensitive resin composition of the present invention has curability and cured film properties Excellent, the resist pattern formed using the photosensitive resin composition of the present invention is used as a partition wall as a structural member of an element for micro electro mechanical systems (MEMS), or as a part of a mechanically driven part. Used after assembly. Examples of such a MEMS element include a surface acoustic wave (SAW) filter, a Bulk Acoustic Wave (BAW) filter, a gyro sensor, and a micro shutter for display. Image sensor, electronic paper, inkjet head, biochip, sealant and other parts. More specific examples are exemplified in Japanese Patent Laid-Open Publication No. 2007-522531, Japanese Patent Laid-Open Publication No. 2008-250200, and Japanese Patent Laid-Open No. 2009-263544.

The photosensitive resin composition of the present invention is excellent in flatness and transparency, and can be used to form a buildup layer (16) and a planarization film (57) as shown in Fig. 2 of JP-A-2011-107476. The partition wall (12) and the flattening film (102) described in Fig. 4 (a) of Japanese Patent Laid-Open Publication No. 2010-9793, and the stacking shown in Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 The layer (221) and the third interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4(a) of JP-A-2009-128577 The planarizing film (12) and the pixel separation insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638. In addition to this, it can be suitably used for the spacer for maintaining the thickness of the liquid crystal layer in the liquid crystal display device, or the imaging of the on-chip color filter of a facsimile machine, an electronic photocopier, a solid-state imaging element, or the like. Microlens for optical systems or fiber optic connectors.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.

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

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

MEDG (diethylene glycol ethyl methyl ether): Hisolve EDM (manufactured by Toho Chemical Industry Co., Ltd.)

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

ANON (cyclohexanone): (manufactured by Tokyo Chemical Industry Co., Ltd.)

[A component]

(the raw material of the constituent unit (a1))

<Synthesis of MAEVE>

To 144.2 parts (2 moles equivalent) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts of methacrylic acid (1 molar equivalent) was added dropwise to the reaction system while cooling to 10 ° C or less. Stir at temperature (25 ° C) for 4 hours. After 5.0 parts of pyridinium p-toluenesulfonate was added, the mixture was stirred at room temperature for 2 hours and then allowed to stand at room temperature overnight. 5 parts of sodium hydrogencarbonate and 5 parts of sodium sulfate were added to the reaction liquid, and the mixture was stirred at room temperature for 1 hour, and the insoluble matter was filtered, and concentrated under reduced pressure at 40 ° C or less, and the residue was evaporated under reduced pressure. Further, 134.0 parts of 1-ethoxyethyl methacrylate having a boiling point (bp.) of 43 ° C / 7 mmHg to 45 ° C / 7 mmHg as a colorless oil was obtained.

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was first cooled to 15 ° C, then camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution was added dropwise 2-dihydrofuran (71 g, 1 mol, 1.0 eq.). After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added, and extracted with ethyl acetate (500 mL). After drying over magnesium sulfate, the insolubles were filtered, and then concentrated under reduced pressure at 40 ° C or less. The yellow oil was distilled under reduced pressure to obtain tetrahydro-2H-furan-2-yl methacrylate as a colorless oil (bp.) 54 ° C / 3.5 mmHg - 56 ° C / 3.5 mmHg fraction. MATHF) 125 g (yield 80%).

(Material of constituent unit (a4))

Lactone (1): 2-oxooxacyclo-3-yl = methacrylate

[化37]

Lactone (2): 5-oxooxacyclo-3-yl = methacrylate

Lactone (3): 6-cyano-5-oxo-4-oxatricyclo[4.2.1.0 ^3.7 ]decane-2-yl=methacrylate

Lactone (4): condensed lactone monomer A

<Synthesis of condensed lactone monomer A (lactone (4)) >

The method is synthesized according to the method (synthesis example 1) described in paragraphs 0256 to 0259 of JP-A-2006-146143.

Lactone (5): 5,5-dimethyl-2-oxooxacyclo-3-yl=methacrylate

<<5,5-Dimethyl-2-oxooxol-3-yl=Methyl acrylate (lactone (5)) synthesis>>

Acetonitrile (500 mL), pantolactone (manufactured by Tokyo Chemical Industry Co., Ltd., 130 g) and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., 101 g) were dissolved in a three-necked flask, and cooled to 0 ° C by an ice bath. Thereafter, methacrylic acid ruthenium chloride (manufactured by Tokyo Chemical Industry, 104 g) was added dropwise. The temperature was raised to room temperature and stirred for 2 hours. Water and ethyl acetate were added, and the organic layer was extracted, dried over magnesium sulfate, and concentrated. The concentrate was subjected to silica gel column chromatography to thereby obtain a target (160 g, 81%).

(the raw material of the constituent unit (a3))

N-cyclohexylmethyleneimine

4-hydroxyphenyl methacrylate

[Component B]

B-1: a compound of the following structure

[化44]

B-2: a compound of the following structure

B-3: a compound of the following structure

B-4: IRGACURE PAG-103

B-7: a compound of the following structure

<Example of Polymerization of Polymer A-1>

(Example of introduction of gamma-butyrolactone Methacrylate (GBLMA))

MEDG (41 g) was introduced into a three-necked flask, and the mixture was stirred at 70 rpm at 70 rpm under a nitrogen atmosphere (N ₂ flow rate: 50 ml/min). MATHF (40 mol%, 24.99 g), MAA (10 mol%, 3.44 g), MMA (10 mol%, 4.00 g), GMA (30 mol%, 17.06 g) were slowly added to the solution at room temperature over 2 hours. GBLMA (10 mol%, 6.81 g) and V-65 (4 mol%, 3.97 g with respect to the monomer) were dissolved in MEDG (41 g). The post reaction was carried out at 70 ° C and stirred for 4 hours, whereby Polymer A-1 was obtained.

Further, a polymer solution having a solid concentration of 40% by mass was prepared. The solid content concentration was defined as monomer mass / (monomer mass + solvent mass) × 100 (単 position: mass %).

<Synthesis Example of Polymer A-2 to Polymer A-50>

The other polymer A-2 to polymer A-50 were synthesized by changing the monomer type and the like as shown in the following table. The solid content concentration of the polymer was 40% by mass.

<Polymerization Example of Polymer A'-1>

MEDG (40 g) was introduced into a three-necked flask, and the mixture was stirred at 70 rpm at 70 rpm under a nitrogen atmosphere (N ₂ flow rate: 50 ml/min). MATHF (40 mol%, 24.99 g), MAA (10 mol%, 3.44 g), MMA (10 mol%, 4.00 g), GMA (30 mol%, 17.06 g) were slowly added to the solution at room temperature over 2 hours. HEMA (10 mol%, 5.21 g) and V-65 (4 mol%, 3.97 g with respect to the monomer) were dissolved in MEDG (40 g). The post reaction was carried out at 70 ° C and stirred for 4 hours, whereby A'-1 was obtained.

<Polymer Example of Polymer A'-2~Polymer A'-18>

The other polymer A'-2 to polymer A'-18 were synthesized by changing the monomer type and the like as shown in the following table. The solid content concentration of the polymer A'-2 to the polymer A'-18 was 40% by mass.

In the above Tables 3 to 7, the values of the units not particularly added in the table are expressed in mol%. The numerical value of the polymerization initiator and the additive is mol% when the monomer component is 100 mol%. The solid content concentration is expressed as a monomer mass / (monomer mass + solvent mass) × 100 (unit: mass %). When V-601 was used as the polymerization initiator, the reaction temperature was set to 90 ° C, and when V-65 was used as the polymerization initiator, the reaction temperature was set to 70 ° C.

<Preparation of photosensitive resin composition>

A polymer, a photoacid generator, a sensitizer, a basic compound, a crosslinking agent, an antioxidant, an alkoxydecane compound, and interfacial activity were formed so as to have a solid content ratio shown in Tables 8 to 12 below. The solvent and other components were dissolved and mixed in a solvent (MEDG) until the solid content concentration became 25% by mass, and then filtered using a filter made of polytetrafluoroethylene having a diameter of 0.2 μm to obtain photosensitivity of various examples and comparative examples. Resin composition.

<Evaluation of sensitivity>

The glass substrate (EAGLEXG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated at 90 ° C. The hot plate was prebaked for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3.0 μm.

Then, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by Canon. Then, the exposed photosensitive resin composition layer was developed at 23 ° C for 60 seconds using an alkaline developer (2.38% aqueous solution of tetramethylammonium hydroxide), and then ultrapure water was used. Rinse for 20 seconds. The optimum i-ray exposure amount (Eopt) when the 10 μm hole was analyzed by these operations was set as the sensitivity.

A: less than 100mJ/cm ²

B: 100 mJ/cm ² or more, less than 200 mJ/cm ²

C: 200 mJ/cm ² or more, less than 300 mJ/cm ²

D: 300 mJ/cm ² or more, less than 400 mJ/cm ²

E: 400mJ/cm ² or more

<Evaluation of chemical resistance>

The glass substrate was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C for 120 seconds. The solvent was volatilized to form a photosensitive resin composition layer having a film thickness of 3.0 μm. Then, the ultrahigh pressure mercury lamp was used for exposure so that the total irradiation amount became 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and the substrate was heated at 230 ° C for 30 minutes in an oven.

The film thickness (T1) of the obtained cured film was measured. Further, the substrate on which the cured film was formed was immersed in a solution of dimethyl hydrazine: monoethanolamine = 3:7 having a temperature controlled at 60 ° C for 3 minutes, and then the film thickness (t1) of the cured film after immersion was measured. The film thickness change rate {| t1-T1 |/T1} × 100 [%] caused by the immersion was calculated. The results are shown in the following table.

The smaller the better, the above C is practically no problem.

A: less than 2%

B: 2% or more, less than 3%

C: 3% or more and less than 4%

D: 4% or more, less than 6%

E: 6% or more

<Evaluation of relative dielectric constant>

Each photosensitive resin composition was spin-coated on a bare wafer substrate (N-type low resistance) (manufactured by Mitsubishi Sumitomo (SUMCO) Co., Ltd.), and then pre-baked on a hot plate at 90 ° C for 120 seconds to volatilize the solvent. On the other hand, a photosensitive resin composition layer having a film thickness of 3.0 μm was formed. Then, the ultrahigh pressure mercury lamp was used for exposure so that the total irradiation amount became 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and the substrate was heated at 230 ° C for 30 minutes in an oven.

CVmap92A (manufactured by Four Dimensions Inc.) was used for the cured film, and the relative dielectric constant was measured at a measurement frequency of 1 MHz.

A: Less than 3.6

B: 3.6 or more, less than 3.8

C: 3.8 or more, less than 4.0

D: 4.0 or more, less than 4.2

E: 4.2 or more

The values in Tables 8 to 12 below are based on "% by mass".

As is clear from the above results, it is understood that the composition of the present invention contains at least one (a4) constituent unit having a lactone structure in the (A) polymer component, or at least one containing the above constituent unit ( A4) does not contain (a1) a structural unit containing a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit containing a crosslinkable group, and can maintain high sensitivity and chemical resistance The properties become good and the relative dielectric constant is further lowered.

<Example 127>

In the same manner as in Example 16, except that the exposure machine was changed from MPA 5500CF manufactured by Canon (share) to FX-803M (gh-Line stepper) manufactured by Nikon Co., Ltd., the same procedure was carried out. 127. The sensitivity was evaluated to the same level as in Example 1.

<Example 128>

In Example 1, Example 128 was carried out in the same manner except that the exposure machine was changed from a MPA 5500CF manufactured by Canon (Stock) to a 355 nm laser exposure machine to perform laser exposure at 355 nm. Here, "AEGIS" (wavelength: 355 nm, pulse width: 6 nsec) manufactured by V-Technology Co., Ltd. was used as a 355 nm laser exposure machine, and "PE10B" manufactured by OPHIR (OPHIR) was used. -V2" to measure the exposure amount.

The sensitivity was evaluated to the same level as in Example 1.

<Example 129>

In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, the cured film 17 is formed as an interlayer insulating film as follows. The liquid crystal display device of Example 55 was obtained. That is, using the photosensitive resin composition of Example 1, the cured film 17 was formed as an interlayer insulating film.

In other words, the substrate is exposed to hexamethyldioxane (HMDS) vapor for 30 seconds as a pretreatment for improving the wettability of the substrate of the 58th paragraph of Japanese Patent No. 3321003 and the interlayer insulating film 17. Thereafter, the photosensitive resin composition of Example 1 was spin-coated, and then prebaked on a hot plate at 90 ° C for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, the obtained photosensitive resin composition layer was exposed to 80 mJ/cm ² through a mask of a hole pattern of 10 μmφ, using MPA 5500CF (high-pressure mercury lamp) manufactured by Canon Co., Ltd. Then, the exposed photosensitive resin composition layer was subjected to liquid-coating development at 23 ° C for 60 seconds using an alkaline developer (2.38% aqueous solution of tetramethylammonium hydroxide), and then subjected to ultrapure water for 20 seconds. wash. Then, the ultra-high pressure mercury lamp was used to perform total exposure so that the cumulative irradiation amount became 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and thereafter, the substrate was heated at 230 ° C for 30 minutes in an oven. A cured film is obtained.

The coating property when the photosensitive resin composition was applied was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and firing.

As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited high display characteristics and high reliability.

<Example 130>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, even if the pretreatment of hexamethyldioxane (HMDS) as a substrate is omitted In the case of applying the photosensitive resin composition of Example 1, the cured film obtained was also in a good state in which no pattern was missing or peeled off. Further, the performance as a liquid crystal display device was also good as in Example 129. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate. From the viewpoint of improving productivity, the step of omitting the pretreatment of the above substrate is also preferable.

<Example 131>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, even after the pre-baking, a vacuum drying step (Vacuum Dry (VCD)) is introduced, the obtained cured film is in a good state in which no pattern is missing or peeled off. Further, the performance as a liquid crystal display device was also good as in Example 129. From the viewpoint of suppressing coating unevenness in accordance with the solid content concentration or film thickness of the composition, it is also preferable to introduce a vacuum drying step.

<Example 132>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, even if the PEB step is introduced during the period from the mask exposure to the development step, the obtained cured film is in a good state in which no pattern is missing or peeled off. Further, the performance as a liquid crystal display device was also good as in Example 129. The introduction of the PEB step is also preferable from the viewpoint of improving the dimensional stability.

<Example 133>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, even if the alkaline developing solution was changed from a 2.38% aqueous solution of tetramethylammonium hydroxide to a 0.4% aqueous solution of tetramethylammonium hydroxide, the obtained cured film was also unpatterned. A good state of missing or flaking. Further, the performance as a liquid crystal display device was also good as in Example 129. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 134>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, even if the alkali development method is changed from the development of the coating liquid to the shower development, the obtained cured film is in a good state in which no pattern is missing or peeled off. Further, the performance as a liquid crystal display device was also good as in Example 129. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 135>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, even if the alkaline developing solution was changed from a 2.38% aqueous solution of tetramethylammonium hydroxide to a 0.04% aqueous KOH solution, the obtained cured film was in a state in which no pattern was missing or peeled off. Further, the performance as a liquid crystal display device was also good as in Example 129. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 136>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, the development is omitted. The step of total exposure after rinsing was carried out by heating at 230 ° C for 30 minutes in an oven to obtain a cured film. The performance of the obtained liquid crystal display device was also good as in Example 129. The reason for this is considered to be that the composition of the present invention is excellent in chemical resistance. In terms of improving productivity, omission of full exposure The steps are also preferred.

<Example 137>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, between the step of full exposure and the step of heating at 230 ° C for 30 minutes in an oven, a step of heating at 100 ° C for 3 minutes on a hot plate was added. The performance of the obtained liquid crystal display device was also good as in Example 129. It is also preferable to add this step from the viewpoint of making the shape of the hole pattern uniform.

<Example 138>

The same liquid crystal display device as that of Example 129 was obtained by changing only the following processes. That is, in development. Between the step of rinsing and the step of full exposure, a step of heating at 100 ° C for 3 minutes on a hot plate was added. The performance of the obtained liquid crystal display device was also good as in Example 129. It is also preferable to add this step from the viewpoint of making the shape of the hole pattern uniform.

An organic EL display device using TFTs was produced by the following method (see FIG. 2).

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. Then, after the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. This wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and the TFT 1.

Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The planarization film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 1 on a substrate, and pre-baking (90 ° C / 120 seconds) on a hot plate, using a high-pressure mercury lamp. The mask was irradiated with i-rays (365 nm) of 80 mJ/cm ² (energy intensity of 20 mW/cm ² ), and then developed with an alkaline aqueous solution (2.38% of TMAH aqueous solution) to form a pattern, and an ultrahigh pressure mercury lamp was used to accumulate the amount of irradiation. The whole exposure was carried out in such a manner as to become 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and then heat treatment was performed at 230 ° C for 30 minutes.

When the photosensitive resin composition was applied, the coating property was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the thickness of the produced planarizing film 4 was 2,000 nm.

Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 containing ITO is connected to the wiring 2 via the contact hole 7 to be formed on the planarization film 4. Thereafter, the resist is applied, pre-baked, exposed through a mask of a desired pattern, and then developed. This resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was peeled off at 50 ° C using a resist stripper (Remover 100, manufactured by AZ Electronic Materials Co., Ltd.). The first electrode 5 obtained in the above manner corresponds to the anode of the organic EL element.

Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The photosensitive resin composition of Example 1 was used for the insulating film 8, and the insulating film 8 was formed in the same manner as described above. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, in the vacuum vapor deposition apparatus, vapor deposition is sequentially performed through a desired pattern mask to provide a hole transport layer, an organic light-emitting layer, and an electron transport layer. Then, a second electrode containing Al is formed on the entire upper surface of the substrate. The obtained substrate was taken out from the vapor deposition machine and sealed by bonding with an ultraviolet curable epoxy resin and a sealing glass plate.

As described above, an active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained. As a result of applying a voltage via a driving circuit, it is understood that the organic EL display device exhibits excellent display characteristics and high reliability.

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

18‧‧‧Contact hole

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

Claims (17)

A photosensitive resin composition comprising: (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2), (1) having (a1) an acid group-containing acid group decomposed a constituent unit of the group that protects the group, and (a2) a polymer having a constituent unit of a crosslinkable group, or (2) a polymer having the structural unit (a1) and a constituent unit (a2) a polymer; (B) a photoacid generator; and (C) a solvent; wherein the (A) polymer component comprises at least one (a4) constituent unit having a lactone structure, or at least one (3) a polymer containing the constituent unit (a4) and not including the constituent unit (a1) and the constituent unit (a2). The photosensitive resin composition according to the first aspect of the invention, wherein the constituent unit containing a lactone structure contains a group represented by the following formula (1). In the formula (1), R ^A1 represents a substituent, and n ₁ R ^A1 are each independently different, and may be the same or different; Z ¹ represents a monocyclic structure or a polycyclic structure containing -OC(=O)-; n ₁ An integer representing 0 or more. The photosensitive resin composition according to the first or second aspect of the invention, wherein the constituent unit (a4) having a lactone structure is represented by the following formula (2), In the formula (2), RX ¹ represents a hydrogen atom or an alkyl group; R ^A2 represents a substituent, and n ₂ R ^A2 are each independently the same or different; A ¹ represents a single bond or a divalent linking group; ² represents a monocyclic structure or a polycyclic structure containing a group represented by -OC(=O)-; n ₂ represents an integer of 0 or more. The photosensitive resin composition according to the first or second aspect of the invention, wherein the constituent unit (a4) having a lactone structure is represented by the following general formula (3), and the general formula (3) 3] In the formula (3), RX ₂ represents a hydrogen atom or an alkyl group; R ^A3 represents a substituent, and n ₃ R ^A3 are each independently the same or different; A ² represents a single bond or a divalent linking group; ³ represents a monocyclic structure or a polycyclic structure containing a group represented by -OC(=O)-; n ₃ represents an integer of 0 or more; X ¹ represents an oxygen atom or -NR"-;R" represents a hydrogen atom or an alkane base. The photosensitive resin composition according to claim 1 or 2, wherein the lactone structure is a lactone structure which forms a 5-membered ring or a 6-membered ring. The photosensitive resin composition according to the first or second aspect of the invention, wherein the structural unit (a1) is a constituent unit containing a group in which a carboxyl group is protected by an acetal form. The photosensitive resin composition according to claim 1 or 2, wherein the constituent unit (a1) is a constituent unit represented by the following general formula (1-11), and the general formula (1) 11) [Chemical 4] In the formula (8), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, and R ¹ Or R ² and R ³ may be bonded to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an extended aryl group. The photosensitive resin composition according to claim 1 or 2, wherein the crosslinkable group is selected from the group consisting of an epoxy group, an oxetane group, and a -NH-CH ₂ -OR. At least one kind, and R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photoacid generator is an oxime sulfonate compound or a phosphonium salt compound. The photosensitive resin composition according to the first or second aspect of the invention, wherein the constituent unit (a4) having a lactone structure is represented by the following general formula (4) to formula (7). Formula (4) Formula (5) Formula (6) Formula (7) [Chemical 5] The photosensitive resin composition according to the first or second aspect of the invention, wherein the constituent unit (a4) having a lactone structure is represented by the following formula (4), A method for producing a cured film, comprising: (1) a step of applying a photosensitive resin composition according to any one of items 1 to 11 to a substrate; (2) a step of removing a solvent in the applied photosensitive resin composition; (3) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4) using an aqueous developing solution to expose the photosensitive resin Composition for development And (5) a post-baking step of thermally hardening the developed photosensitive resin composition. A cured film formed by curing the photosensitive resin composition according to any one of the first to eleventh aspects of the invention. A cured film formed by the method for producing a cured film according to claim 12 of the patent application. The cured film according to claim 13, which is an interlayer insulating film. A liquid crystal display device comprising the cured film according to claim 13 or claim 14. An organic electroluminescence display device comprising the cured film according to claim 13 or claim 14.