TWI589990B - Photosensitive resin composition, method for producing cured film, cured film, organic EL display device, and liquid crystal display device - Google Patents

Description

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

The present invention relates to a photosensitive resin composition (hereinafter sometimes referred to simply as "the composition of the present invention"). In addition, 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, a protective film, or an interlayer insulating layer suitable for forming electronic components such as a liquid crystal display device, an organic electroluminescence (EL) display device, an integrated circuit device, and a solid-state imaging device. A photosensitive resin composition of a film and a method for producing a cured film using the same.

In an electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state imaging element, it is usually provided to insulate between wirings arranged in a layer shape. There is an interlayer insulating film. The material for forming the interlayer insulating film is preferably one in which the number of steps for obtaining the necessary pattern shape is small, and has sufficient flatness, so that the photosensitive property is widely used. Resin composition. Such a photosensitive resin composition is disclosed, for example, in Japanese Laid-Open Patent Publication No. 2011-209681.

On the other hand, a thermosetting resin composition having a copolymer derived from a constituent unit derived from a conjugated diene-based unsaturated compound is disclosed in Japanese Laid-Open Patent Publication No. Hei 6-157716.

In recent years, in the field of electronic materials, with the increase in integration, multi-functionality, and high performance, the capacitance of a circuit or a capacitor between wirings has increased, resulting in an increase in power consumption or delay time. Among them, the increase of the delay time is a major factor in the signal speed drop or crosstalk of the device, and the speed of the device is reduced in order to reduce the delay time, and the parasitic capacitance is required to be reduced. In order to reduce this parasitic capacitance, the demand for low dielectric constant of the interlayer insulating film is increased. Further, when the hygroscopicity is high, the physical properties are changed, and the insulating property may be inferior.

On the other hand, Japanese Laid-Open Patent Publication No. 2011-209681 and Japanese Patent Laid-Open No. Hei No. Hei No. Hei. In addition, the composition disclosed in Japanese Laid-Open Patent Publication No. H6-157716 is a thermosetting resin composition and cannot be used as a chemically amplified resist material.

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a photosensitive resin composition which can obtain a cured film which not only maintains high sensitivity but also has a low dielectric constant and low hygroscopicity. Further, an object of the invention is to provide a method for producing a cured film using the photosensitive resin composition, a cured film, an organic EL display device, and a liquid crystal. Display device.

Based on the above, the inventors of the present invention conducted active research and found that a polymer having a structural unit of a hydrocarbon having a low polarization and a low dielectric constant is contained as a main component in the photosensitive resin. In the composition, a cured film which not only maintains high sensitivity but also has a low dielectric constant and low hygroscopicity can be obtained, and the present invention has been completed.

Specifically, the above problem is preferably solved by <2> to <12> by the following means <1>.

<1> A photosensitive resin composition comprising: (A) a polymer component comprising a polymer satisfying at least one of the following (A1) and (A2): (A1) comprising (a1) having an acid group The constituent unit of the residue which is protected by the acid-decomposable group, and the polymer of (a4) the structural unit represented by the following general formula (S), (A2) includes (a1) a residue having an acid group protected by an acid-decomposable group a polymer of a constituent unit of a group, and a polymer comprising (a4) a constituent unit represented by the following formula (S); (B) a photoacid generator; and (C) a solvent,

(In the formula (S), R ¹ and R ² each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 3 carbon atoms or a perfluoroalkyl group having 1 to 3 carbon atoms).

The photosensitive resin composition as described in <1> which contains the component (A2) which has the bridge|crosslinking group.

<3> The photosensitive resin composition according to <1>, wherein the ratio of the above (a4) in the component (A) is from 5 mol% to 70 mol%.

<4> The photosensitive resin composition according to <3>, wherein the ratio of the above (a4) in the component (A) is from 15 mol% to 50 mol%.

The photosensitive resin composition as described in any one of <2> which has a crosslinkable group containing (a2) containing the epoxy group and the oxetanyl -NH-CH ₂ -OR (a group represented by a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and at least one constituent group of the ethylenically unsaturated group.

The photosensitive resin composition as described in any one of the above-mentioned (B) photoacid generator is the following general formula (B2), general formula (B3), and a general formula. An oxime sulfonate-based acid generator represented by any of (B4): general formula (B2)

(In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X may be the same Can also be different)

(In the formula (B3), R ⁴³ represents an alkyl group or an aryl group, and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, n4 An integer representing 0~5)

General formula (B4)

(In the formula (B4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group or a heteroaryl group; and R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom; 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-).

The photosensitive resin composition of any one of the following formula (a1-1-3) as the above-mentioned structural unit represented by the following General formula (a1-1-3). The constituent unit of the residue of the sex-based protection:

(In the formula (a1-1-3), 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 represent a hydrogen atom or a carbon number of 1 to 4; Alkyl).

(8) A method of producing a cured resin composition, comprising: (1) coating the photosensitive resin composition according to any one of <1> to <7> a step of depositing on the substrate; (2) a step of removing the solvent from the applied photosensitive resin composition; (3) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; and (5) a post-baking step of thermally curing the developed photosensitive resin composition.

<9> The method for producing a cured film according to <8>, wherein after the developing step, the step of performing the full exposure of the developed photosensitive resin composition is performed before the post-baking step.

<10> A cured film formed by the method for producing a cured film according to <8> or <9>.

<11> The cured film according to <10> which is an interlayer insulating film.

<12> An organic EL display device or a liquid crystal display device comprising the cured film according to <10> or <11>.

According to the present invention, it is possible to provide a photosensitive resin composition which can obtain a cured film which not only maintains high sensitivity but also has a low dielectric constant and low hygroscopicity.

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

18‧‧‧Contact hole

19‧‧‧Indium tin oxide transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

FIG. 1 is a conceptual diagram showing an example of an organic EL display device. Indicates the bottom A schematic cross-sectional view of a substrate in a light type organic EL display device includes a planarization film 4.

FIG. 2 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, including a cured film 17 as an interlayer insulating film.

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

Further, in the expression of the group (atomic group) in the present specification, the description that the substituted or unsubstituted is not described includes not only a substituent but also a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The photosensitive resin composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") contains: (A) a polymer component containing a polymer satisfying at least one of the following (A1) and (A2), (B) a photoacid generator, and (C) a solvent.

Hereinafter, preferred aspects of the composition of the present invention will be described in detail.

<(A) Polymer component>

The composition of the present invention contains at least the following (A1) and (A2) One of the polymers acts as a polymer component.

(A1) includes (a1) a constituent unit having a residue in which an acid group is protected by an acid-decomposable group, and (a4) a polymer having a constituent unit represented by the following formula (S); (A2) includes (a1) A polymer having a constituent unit of a residue in which an acid group is protected by an acid-decomposable group, and a polymer including (a4) a structural unit represented by the following formula (S).

(In the formula (S), R ¹ and R ² each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 3 carbon atoms or a perfluoroalkyl group having 1 to 3 carbon atoms.)

Further, the composition of the present invention may contain a polymer other than the above. Unless otherwise specified, the (A) polymer component (hereinafter referred to as "(A) component)" in the present invention means that, in addition to the above (A1) and/or (A2), other additives are added as needed. polymer.

The 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 an ester thereof, for example, a constituent unit derived from styrene or a constituent unit derived from a vinyl compound.

In addition, the "constituting unit derived from (meth)acrylic acid and/or its ester" may also be referred to as "acrylic constituent unit". In addition, "(meth)acrylic acid" means "methyl propyl acrylate" Oleic acid and / or acrylic acid.

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

Component A includes at least (a1) a constituent unit having a residue in which an acid group is protected by an acid-decomposable group. By including the constituent unit (a1) as the component (A), a photosensitive resin composition having an extremely high sensitivity can be obtained.

In the present invention, the "acid group which is protected by an acid-decomposable group" is a group which is known as an acid group and an acid-decomposable group, and is not particularly limited. Specific acid groups are preferably exemplified by a carboxyl group and a phenolic hydroxyl group. Further, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (A1), a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group can be used. An aldehyde functional group) or a group which is relatively difficult to decompose by an acid (for example, a tertiary alkyl carbonate group such as a tertiary butyl ester group or a tertiary butyl carbonate group such as a tertiary butyl carbonate group).

(a1) The constituent unit having a residue in which the acid group is protected by the acid-decomposable group is preferably a constituent unit having a protective carboxyl group protected by an acid-decomposable group or a protective phenolic hydroxyl group having an acid-decomposable group. unit.

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

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

The above constituent unit having a protected carboxyl group protected by an acid-decomposable group (a1-1) is a structural unit having a protective carboxyl group which is protected by an acid-decomposable group described below in detail.

The constituent unit having a carboxyl group which can be used in the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is not particularly limited, and a known constituent unit can be used. 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.

In the following, the constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, which is used as the constituent unit having a carboxyl group, will be described in order.

<<<<(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 constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, an unsaturated carboxylic acid as exemplified below can be used as the unsaturated carboxylic acid used in the present invention. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(methyl)acryloxyethyl succinic acid, and 2-(methyl group). 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 constituent unit having a carboxyl group may 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) group of a polyvalent carboxylic acid. Examples of the ester include succinic acid mono(2-propenyloxyethyl) ester, succinic acid mono(2-methylpropenyloxyethyl) ester, and phthalic acid mono(2-propene oxime). Oxyethyl)ester, mono(2-methylpropenyloxyethyl) phthalate, and the like. Further, the unsaturated polycarboxylic acid may 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, monoalkyl maleate, monoalkyl fumarate, 4- Carboxy styrene and the like.

In view of the developability, in order to form the structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, and 2 are preferably used. -(Meth)acryloxyethyl succinic acid, 2-(methyl)propenyloxyethylhexahydrophthalic acid, 2-(methyl)propenyloxyethyl-o-phenylene Formic acid or an acid anhydride of an unsaturated polycarboxylic acid, etc., more preferably acrylic acid, methacrylic acid or 2-(meth)acryloxyethyl hexahydrophthalic acid.

The constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule may be contained alone or in combination of two or more.

<<<<Acidolytic Groups Usable in Building Unit (a1-1)>>>>

As the acid-decomposable group which can be used in the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group, the acid-decomposable group can be used.

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, among the acid-decomposable groups, a carboxyl group is preferred. Protected carboxyl groups protected by the form of acetal. Further, in the acid-decomposable group, the carboxyl group is more preferably a protected carboxyl group 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 form of an acetal represented by the following general formula (a1-10), the entire protective carboxyl group is formed -(C=O)-O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ) structure.

(In the formula (a1-1), 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 And R ¹⁰³ can be linked to form a cyclic ether.)

In the above formula (a1-1), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, neither R ¹⁰¹ nor R ¹⁰² represents a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

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

The linear or branched alkyl group is preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and particularly preferably a carbon number of 1 to 4. Specific examples thereof include methyl group and ethyl group. N-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-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 above cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and particularly 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 the substituent may, for example, be a halogen atom, an aryl group or 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} aralkyl groups.

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 a carbon number of 6 to 12, and specifically, a phenyl group, an α-methylphenyl group, a naphthyl group or the like may be exemplified by an aryl group. The alkyl group as a whole, 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 1 to 4 carbon atoms, still more preferably a methoxy group or an ethoxy group.

Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group may be a linear or branched chain. In the case of an alkyl group, the substituent may have a cycloalkyl group having 3 to 12 carbon atoms.

These substituents may be further substituted by the above substituents.

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

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. R ¹⁰¹ and R ^102, the ring structure in the case of R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ bonded include, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantyl And tetrahydropyranyl and the like.

Further, in the above formula (a1-1), it is preferred that any of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

The radical polymerizable monomer for forming the structural unit having a protective carboxyl group represented by the above formula (a1-1) can be used commercially, or can be synthesized by a known method. For example, it can be synthesized by the synthesis method described in Paragraph No. 0037 to Paragraph No. 0040 of JP-A-2011-221494.

The first preferred aspect of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit represented by the following formula (a1-1-2).

General formula (a1-1-2)

(In the formula (a1-1-2), 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 , may be bonded to R ³ 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. In the case where 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.

A second preferred embodiment of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit of the following formula (a1-1-3).

General formula (a1-1-3)

(In the formula (a1-1-3), 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 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.

A preferred specific example of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is exemplified by the following constituent unit. Further, R represents a hydrogen atom or a methyl group.

<<<(a1-2) has a protective phenolic hydroxyl group protected by an acid-decomposable group Component unit>>>

The structural unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group, which is a structural unit having a phenolic hydroxyl group, has a protective phenolic hydroxyl group protected by an acid-decomposable group described in detail below. The constituent unit.

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

The constituent unit having a phenolic hydroxyl group may be a constituent unit of a hydroxystyrene-based constituent unit or a novolak-based resin, and among these constituent units, from the viewpoint of sensitivity, it is preferably derived from hydroxystyrene or A constituent unit of α-methylhydroxystyrene. In addition, from the viewpoint of the sensitivity, the constituent unit having a phenolic hydroxyl group is also preferably a constituent unit represented by the following formula (a1-2).

(In the formula (a1-2), 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 linear or branched chain alkyl having 1 to 5 carbon atoms. A, 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 or may be the same. )

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

Further, R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. Specific examples of the divalent linking group of R ²²¹ may be an alkylene group, and R ²²¹ is an alkylene group: methylene, ethyl, propyl, isopropyl, n-butyl, and isobutylene. Stretching the third butyl group, stretching the pentyl group, stretching the isoamyl group, stretching the neopentyl group, and stretching the hexyl group. Among them, R ^{221 is} preferably a single bond, a methylene group or an ethyl group. Further, the 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 the 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 neopentyl group. Base. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferred in terms of ease of production.

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

<<<<Acidolytic Groups Usable in Building Unit (a1-2)>>>>

The acid-decomposable group which can be used in the structural unit (a1-2) having a phenolic hydroxyl group which is protected by an acid-decomposable group, and the above-mentioned constituent unit having a protective carboxyl group protected by an acid-decomposable group (a1-1) The acid-decomposable group which can be used in the above is similarly used, and is not particularly limited. The acid-decomposable group preferably has an acetal from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity or the pattern shape, the storage stability of the photosensitive resin composition, and the contact hole formation property. A constituent unit that protects the phenolic hydroxyl group protected. Further, in the acid-decomposable group, the phenolic hydroxyl group is more preferably a protective phenolic hydroxyl group protected by the form of the acetal represented by the above formula (a1-1). Further, in the case where the phenolic hydroxyl group is a phenolic hydroxyl group protected by the form of the acetal represented by the above formula (a1-1), the overall formation of the phenolic hydroxyl group is protected - Ar-O-CR ¹⁰¹ R ¹⁰² The structure of (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 or R ¹⁰¹ = R ¹⁰² = methyl and R ¹⁰³ = benzyl.

In addition, the radically polymerizable monomer for forming a constituent unit having a phenolic hydroxyl group and a phenolic hydroxyl group, which is protected by a phenolic hydroxyl group, is described, for example, in Paragraph No. 0044 of JP-A-2011-215590. Monomers, etc.

Among these monomers, from the viewpoint of transparency, a 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl methacrylate or a tetrahydropyranyl group of 4-hydroxyphenyl methacrylate is preferred. Protector.

Specific examples of the acetal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl, 1-methoxyethyl, and 1-n-butoxyethyl. 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1- N-propoxyethyl, 1-cyclohexyloxyethyl, 1-(2-cyclohexylethoxy)ethyl, 1-benzyloxyethyl, etc., these groups may be used alone or in two The above combination is used.

The radical polymerizable monomer for forming the structural unit (a1-2) having the above-mentioned protective phenolic hydroxyl group protected by an acid-decomposable group can be used commercially, or can be synthesized by a known method. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The above synthesis allows a monomer having a phenolic hydroxyl group to be previously copolymerized with another monomer and then reacted with a vinyl ether in the presence of an acid catalyst.

A preferred specific example of the structural unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group is exemplified by the following constituent unit, but the present invention is not limited to the constituent units.

<<<The preferred aspect of the constituent unit (a1)>>>

In the case where the polymer containing the above-mentioned structural unit (a1) does not substantially contain the constituent unit (a2) described below, the constituent unit (a1) preferably contains 20 mol% to 100% of the polymer containing the constituent unit (a1). Molar%, more preferably 30% by mole to 90% by mole.

In the case where the polymer containing the above-mentioned structural unit (a1) contains the structural unit (a2), the constituent unit (in terms of sensitivity) of the polymer containing the structural unit (a1) and the structural unit (a2) A1) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%. Further, in particular, in the case where the acid-decomposable group which can be used in the above-mentioned structural unit (a1) is a constituent unit having a protective carboxyl group in which a carboxyl group is protected by an acetal form, it is preferably 20 mol% to 50 mol%. %.

The constituent unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group has a feature of rapid development as compared with the above-mentioned constituent unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group. . Therefore, in the case of rapid development, it is preferably a constituent unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group. On the contrary, in the case of slowing down the development, it is preferred to use the acid-decomposing base. A constituent unit (a1-2) for protecting a phenolic hydroxyl group.

<<(a2) constituent unit having a crosslinkable group>>

The component (A) preferably includes a constituent unit (a2) having 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. Preferred examples of the constituent unit having a crosslinkable group include an alkyl group selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The constituent unit of at least one of the group represented by the group and the ethylenically unsaturated group is preferably selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R). At least one of the groups represented by a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In the photosensitive resin composition of the present invention, the component (A) preferably contains at least one of an epoxy group and an oxetanyl group. More specifically, the following structural unit is mentioned.

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

The (A) copolymer preferably contains a structural unit (constituting unit (a2-1)) having an epoxy group and/or an oxetanyl group. The cyclic ether group of the 3-membered ring is also called an epoxy group, and the cyclic ether group of the 4-membered ring is also called an oxetanyl group.

The constituent unit (a2-1) having an epoxy group and/or an oxetanyl group may have at least one epoxy group or oxetanyl group in one constituent unit, and may have one or more members. The epoxy group and one or more oxetanyl groups, two or more epoxy groups, or two or more oxetanyl groups are not particularly limited, and preferably have a total of one to three Epoxy and/or oxetanyl, more preferably It is preferable to have one or two epoxy groups and/or oxetanyl groups, and it is especially preferable to have one epoxy group or oxetanyl 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-n-propyl group. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Hexylmethyl ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexylmethyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl Glycidyl ether, p-vinylbenzyl glycidyl ether, a compound containing an alicyclic epoxy skeleton described in Paragraph No. 0031 to Paragraph No. 0035 of Japanese Patent No. 4,184,843, and the like. In the manual.

Specific examples of the radically polymerizable monomer for forming a structural unit having an oxetanyl group include an oxygen heterocyclic ring described in Paragraph No. 0011 to Paragraph No. 0016 of JP-A-2001-330953. Butyl (meth) acrylates and the like, which are incorporated herein by reference.

A specific example of the radical polymerizable monomer for forming the above-mentioned structural unit (a2-1) having an epoxy group and/or an oxetanyl group is preferably a monomer having a methacrylate structure and containing an acrylate. The monomer of the structure.

Among these monomers, preferred are: glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxa) Cyclobutane-3-yl)methyl ester, and methacrylic acid (3-ethyloxetane-3- Base) methyl ester. These constituent units may be used alone or in combination of two or more.

A preferred specific example of the structural unit (a2-1) having an epoxy group and/or an oxetanyl group is exemplified by the following constituent unit. Further, 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) having a crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as "constituting unit (a2-2)"). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal group and having a carbon number of 3 to 16. The constituent unit of the side chain is particularly preferably a constituent unit having a side chain represented by the following formula (a2-2-1).

(In the formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * represents a constituent unit (a2) having a crosslinkable group. The part where the main chain is connected.)

R ³⁰¹ is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, a cycloalkenyl group, an extended aryl group or a group obtained by combining the groups, and may further contain an ester bond, an ether bond, or a guanamine bond. a bond such as a urethane bond. Further, the divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at any position. Specific examples of R ³⁰¹ include the following divalent linking groups.

The side chain represented by the above formula (a2-2-1) includes the divalent linking group represented by the above R ³⁰¹ , and is preferably an aliphatic side chain.

In addition, the constituent unit having an ethylenically unsaturated group (a2-2) can be referred to the description of Paragraph No. 0072 to Paragraph No. 0090 of JP-A-2011-215580, the contents of which are incorporated herein by reference. in.

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

The copolymer used in the present invention is also preferably a constituent unit (a2-3) having a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-3), the hardening reaction can be caused by a slow heat treatment, and a cured film excellent in characteristics 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, preferably a linear or branched alkyl group. The constituent unit (a2) is more preferably a constituent unit having a group represented by the following formula (a2-30).

(In the formula (a2-3), 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, particularly 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, 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 a n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

<<<The preferred aspect of the constituent unit (a2)>>>

In the case where the polymer containing the above structural unit (a2) does not substantially contain the above structural unit (a1), the polymer containing the structural unit (a2) The unit (a2) is preferably from 5 mol% to 90 mol%, more preferably from 20 mol% to 80 mol%.

In the case where the polymer containing the above-mentioned structural unit (a2) contains the above-mentioned structural unit (a1), the polymer containing the structural unit (a1) and the structural unit (a2) is chemically resistant. The constituent unit (a2) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%.

In the present invention, in any of the constituent elements of the component (A), it is preferable to contain a structural unit (a2) of 3 mol% to 70 mol%, more preferably 10 mol%. ~60% by mole.

When it is in the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.

<<(a4) Constituent unit of conjugated olefin>>

In the present invention, the component (A) includes a constituent unit of a hydrocarbon having a low polarization and a low dielectric constant, that is, a constituent unit (a4) represented by the following formula (S).

(In the formula (S), R ¹ and R ² each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 3 carbon atoms or a perfluoroalkyl group having 1 to 3 carbon atoms.)

The unsubstituted alkyl group having 1 to 3 carbon atoms can be exemplified by methyl group, ethyl group, and positive group. The propyl group and the isopropyl group are preferably a methyl group from the viewpoint of lowering the dielectric constant.

Examples of the perfluoroalkyl group having 1 to 3 carbon atoms include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ and -CFCF ₃ CF ₃ , and from the viewpoint of lowering the dielectric constant, it is preferably -CF ₃ .

The polymer including the constituent unit (a4) is not particularly limited, and for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3- can be used. Butadiene, 2-trifluoromethyl-1,3-butadiene, 2,3-bis(trifluoromethyl)-1,3-butadiene were obtained.

The constituent unit (a4) may include the above polymer component (A1) and/or polymer component (A2), but preferably contains a polymer component (A1). Further, for example, a polymer component including the above-described constituent unit (a1), the above-described constituent unit (a2), and a constituent unit (a3), and a polymer component including the above-described constituent unit (a3) and constituent unit (a4) may be used.

It is preferable that all the constituent units of the polymer component (A) contain 5 mol% to 70 mol% of the constituent unit (a4), more preferably 15 mol% to 50 mol%, and particularly preferably Contains 20% to 40% by mole. By including 5 mol% or more of the constituent unit (a4) in all the constituent units of the (A) polymer component, it is possible to provide a cured film which not only maintains high sensitivity but also has a lower dielectric constant and lower hygroscopicity. A photosensitive resin composition. In addition, when the constituent unit (a4) of 70 mol% or less is contained in all the constituent units of the polymer component (A), the cured film and the substrate when the photosensitive resin composition of the present invention is formed into a cured film can be improved. The connection between the two. (A) The structural unit (a4) in the polymer component may be used in combination of two or more kinds.

<<(a3) Other constituent units>>

In the present invention, the component (A) may include other constituent units (a3) other than the constituent units, in addition to the constituent unit (a1), the constituent unit (a2), and the constituent unit (a4). The constituent units may include the above polymer component (A1) and/or polymer component (A2). Further, in addition to the polymer component (A1) and/or the polymer component (A2), the constituent unit (a1), the constituent unit (a2), and the constituent unit (a4) may be substantially excluded, and the constituent unit may be included. The polymer component of (a3). In the case where the polymer component (a1), the constituent unit (a2), and the constituent unit (a4) are substantially excluded from the polymer component (A), and the polymer component including the constituent unit (a3) is included, all In the polymer component, the blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less.

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 aryl (meth)acrylate. , unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, Unsaturated dicarboxylic anhydride, other unsaturated compounds. Further, as will be described later, a constituent unit having an acid group may also be included. The monomers which are the constituent unit (a3) may be used singly or in combination of two or more.

Specifically, the constituent unit (a3) includes constituent units derived from the following compounds: styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated. Styrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy benzoyl Acid (3-methacryloxypropyl) ester, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (methyl) Isopropyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol Monoethyl acetate mono(meth) acrylate, and the like. In addition, the compound described in Paragraph No. 0021 to Paragraph No. 0024 of JP-A-2004-264623 is mentioned.

Further, from the viewpoint of electrical properties, the constituent unit (a3) is preferably a styrene group or a group having an aliphatic cyclic skeleton. Specific examples thereof include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, and (meth)acrylic acid ring. Hexyl ester, isobornyl (meth)acrylate, benzyl (meth)acrylate, and the like.

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

The constituent unit (a3) preferably contains an acid group. By containing an acid group, it is easy to be dissolved in an alkaline developing solution, and the effect of the present invention is more effectively exerted. The acid group in the present invention means a proton dissociative group having a pKa of less than 7. Usually, a monomer capable of forming an acid group is used as a constituent unit containing an acid group, and an acid group is incorporated 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 can be exemplified by those derived from a carboxylic acid group and derived from a sulfonium group. An amine group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonylamino group, a sulfonimide group, etc., preferably a carboxylic acid group and/or a source. Self-phenolic hydroxyl.

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.

Such a polymer is preferably a resin having a carboxyl group in a side chain. For example, Japanese Patent Publication No. Sho 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 A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, and a methacrylic acid described in each of the publications of Japanese Laid-Open Patent Publication No. 59-71048 An acid copolymer, a partially esterified maleic acid copolymer, or the like, an acidic cellulose derivative having a carboxyl group in a side chain, an acid anhydride added to a polymer having a hydroxyl group, and the like, and further, a side chain A polymer having a (meth)acryl fluorenyl group as a preferred one is preferred.

For example, benzyl (meth)acrylate / (meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic copolymer, Japanese patent 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate described in Kaiping No. 7-140654 Ester/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer , 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer.

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 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The content is incorporated into the specification of the present application.

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

These polymers can also be used commercially: SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above by 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 by 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.

The constituent unit containing an acid group is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, more preferably from 5 mol% to 40 mol% of the constituent units of all the polymer components. Ear %, particularly preferably 5 mole % to 30 mole %, optimally 5 mole % ~ 20 mole %.

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

(First embodiment)

The polymer component (A1) includes the constituent unit (a2) and the constituent unit (a3) in addition to the constituent unit (a1) and the constituent unit (a4).

(Second embodiment)

The first polymer including the constituent unit (a1), the constituent unit (a2), and the constituent unit (a3), and the second polymerization including the constituent unit (a2), the constituent unit (a3), and the constituent unit (a4) are used. The substance is used as the aspect of the polymer component (A2).

(Third embodiment)

The polymer component (A1) further includes one or two or more types of constituent units (a3).

(Fourth embodiment)

The polymer including the structural unit (a1) of the polymer component (A2) further includes one or two or more kinds of constituent units (a3).

(Fifth Embodiment)

The polymer including the structural unit (a2) of the polymer component (A2) further includes one or two or more kinds of constituent units (a3).

(Sixth embodiment)

In any of the first to fifth embodiments, a constituent unit including at least an acid group is included as a constituent unit (a3).

(Seventh embodiment)

In addition to the polymer component (A1) or the polymer component (A2), it further includes substantially no constituent unit (a1) and constituent unit (a2), but includes constituent units. The aspect of the polymer of (a3).

(Eighth embodiment)

The form of the combination of two or more types of the first embodiment to the seventh embodiment is included.

In all the constituent units of the polymer component (A), the constituent unit (a1) and the constituent unit (a2) (preferably comprising an epoxy group, an oxetanyl group, an -NH-CH ₂ -OR (R) a group represented by a hydrogen atom or an alkyl group having 1 to 20 carbon atoms and at least one of a group consisting of an ethylenically unsaturated group, a constituent unit (a3) (acid group), and a constituent unit The total amount of (a4) is preferably 95% by mole or more, more preferably 98% by mole or more.

<<(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 above numerical range, the 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>>

Further, a plurality of methods are also known for the synthesis method of the component (A), and if an example is used, at least the composition represented by the above (a1) and the above (a4) may be contained by using a radical polymerization initiator. The radically polymerizable monomer mixture of the radical polymerizable monomer of the unit is synthesized by polymerization in an organic solvent. Further, it can also be synthesized by a so-called polymer reaction.

<(B) Photoacid generator>

The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator (also referred to as "(B) component") 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 a wavelength of 300 nm to 450 nm, but Its chemical structure is not limited. In addition, the photoacid generator which does not directly induce the actinic ray 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 by using it together with a sensitizer. It can then be used in combination 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 2 or less. Acid photoacid generator.

Examples of the photoacid generator include trichloromethyl-s-triazines, phosphonium salts or phosphonium salts, quaternary ammonium salts, diazomethane compounds, sulfhydryl sulfonate compounds, and sulfonate compounds. . Among these compounds, 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. Specific examples of the trichloromethyl-s-triazine, the diarylsulfonium salt, the triarylsulfonium salt, the quaternary ammonium salt, and the diazomethane derivative can be exemplified by Japanese Patent Laid-Open Publication No. 2011-221494. The compounds described in paragraphs 0083 to 0088 are incorporated herein by reference.

The oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, is preferably a compound containing an oxime sulfonate structure represented by the following formula (B1).

General formula (B1)

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

Any group may be substituted, and the alkyl group in R ²¹ may be linear, may be branched, or may be cyclic. The permitted substituents will be described below.

The alkyl group of R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may be a bridged type such as an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including 7,7-dimethyl-2-oxonorbornyl group). An alicyclic group, preferably a bicycloalkyl group, is substituted.

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 with 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) is also preferably an oxime sulfonate compound represented by the following formula (B2).

(In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X may be the same It can be different.)

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

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

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

M4 is preferably 0 or 1. In 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-dimethyl group. a compound of 2-oxo norbornylmethyl or p-tolylmethyl.

The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B3).

(In the formula (B3), R ⁴³ has the same meaning as R ⁴² in the formula (B2), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cyano group. Or nitro, n4 represents an integer from 0 to 5.)

R ⁴³ in the above formula (B3) is preferably: methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro N-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.

X ^{1 is} preferably an alkoxy group having 1 to 5 carbon atoms, 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 (B3) include α-(methylsulfonyloxyimino)benzylcarbonitrile and α-(ethylsulfonyloxyimino)benzylcarbonitrile. --(n-propylsulfonyloxyimino)benzylcarbonitrile, α-(n-butylsulfonyloxyimino)benzylcarbonitrile, α-(4-toluenesulfonyloxyimino) Benzonitrile, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4-methoxybenzene Acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(n-butylsulfonyloxyimino)-4-methoxy Phenyl phenyl] acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile.

Specific examples of the preferred oxime sulfonate compound include the following compounds (i) to (viii), and the like, and may be used alone or in combination of two or more. The compound (i) to the compound (viii) can be obtained as a commercial product. Further, it can also be used in combination with other types of (B) photoacid generators.

The compound containing the oxime sulfonate structure represented by the above formula (B1) is also 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 sulfo group, a cyano group, or the like. 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 sulfo group or a cyano group. 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, and an alkyl group. Further, it is preferable to exemplify a state in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, from the viewpoint of sensitivity, it is preferred that all of R ¹²¹ to R ¹²⁴ are hydrogen atoms.

The functional groups described may each further have a substituent.

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

In the above formula (OS-2), R ¹⁰¹ , R ¹⁰² and R ¹²¹ to R ¹²⁴ have the same meanings as in the formula (OS-1), and preferred examples are also the same.

In these preferred embodiments, it is more preferred that the above formula (OS-1) and R ¹⁰¹ in the above formula (OS-2) are in the form of a cyano group or an aryl group, and it is most preferred from the above formula ( The aspect represented by OS-2) and R ¹⁰¹ is a cyano group, a phenyl group or a naphthyl group.

Further, the steric structure (E, Z, etc.) of the hydrazine or benzothiazole ring in the above sulfonate compound may be either a mixture or a mixture.

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 (exemplified compound b- 1 to the 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) is preferably a compound of the following formula (OS-3), the following formula (OS-4) or the following formula (OS). -5) The oxime sulfonate compound represented.

(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 n ¹ to n ³ each independently represent 1 or 2, and m ¹ to m ³ each independently represent an integer of 0 to 6.

In the above formula (OS-3) to formula (OS-5), the alkyl group, the aryl group or the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one ring which is a heteroaromatic ring, for example, a heteroaromatic ring and a benzene ring. Can also shrink the ring.

In the above formula (OS-3) to formula (OS-5), R ²³ , R ²⁶ and R ^{29 are} preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

In the above formula (OS-3) to formula (OS-5), two or more of R ²³ , R ²⁶ and R ²⁹ are present in the compound, and preferably one or two are alkyl groups, aryl groups or More preferably, one halogen atom is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group, and the balance is a hydrogen atom.

The alkyl group in R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having a total carbon number of 1 to 12 which may have a substituent, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.

The aryl group in R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), X ¹ to X ³ each independently represent O or S, and is preferably O.

In the above formula (OS-3) to formula (OS-5), the ring including X ¹ to X ³ as a ring member is a 5-membered ring or a 6-membered ring.

In the above formula (OS-3) to formula (OS-5), n ¹ to n ³ each independently represent 1 or 2, and when X ¹ to X ³ are 0, n ¹ to n ^{3 are} preferred. In order to be independently 1, respectively, and in the case where X ¹ to X ³ are S, n ¹ to n ^{3 are} preferably independently 2 each.

In the above formula (OS-3) to formula (OS-5), 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 Alkoxysulfonyl. Wherein R ²⁴ , R ²⁷ and R ³⁰ are each independently an alkyl group or an alkoxy group.

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

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkoxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkoxy group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), m ¹ to m ³ each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1. , especially good is 0.

Further, regarding the respective substituents of the above (OS-3) to (OS-5), The preferred range of the substituents of (OS-3) to (OS-5) described in Paragraph No. 0092 to Paragraph No. 0109 of JP-A-2011-221494 is preferably the same.

In addition, the compound containing the oxime sulfonate structure represented by the above formula (B1) is particularly preferably a compound represented by any one of the following formula (OS-6) to (OS-11).

(In the formula (OS-6)~(OS-11), R ³⁰¹ to R ³⁰⁶ represent an alkyl group, an aryl group or a heteroaryl group, and R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ and R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ³¹¹ and ^R314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.

The preferred range of the above formula (OS-6) to the formula (OS-11) and the paragraph number of the Japanese Patent Laid-Open No. 2011-221494, paragraph number 1010 to paragraph number 0112 The preferred ranges of (OS-6) to (OS-11) described above are the same.

Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include those described in paragraph No. 0114 to paragraph number 0120 of JP-A-2011-221494. A compound, but the invention is not limited to the compounds.

The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B4).

(In the formula (B4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group or a heteroaryl group; and R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group or a halogen 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 in the case where the alkyl group has a branched structure, it is preferably an alkyl group having 3 to 6 carbon atoms, and in the case of having a cyclic structure, It is preferably an alkyl group having a carbon number of 5 to 7.

The alkyl group may, for example, be propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, 1,1-dimethylpropane. The group, the hexyl group, the 2-ethylhexyl group, the cyclohexyl group, the octyl group and the like are preferably an isopropyl group, a tert-butyl group, a neopentyl group or a cyclohexyl group.

The carbon number of the aryl group is preferably from 6 to 12, more preferably from 6 to 8, and particularly 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, or an alkynyl group. , aryl, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, cyano, carboxyl, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, heterocyclooxy, Alkoxy group, amine group, nitro group, mercapto group, heterocyclic group and the like. In addition, it may be further substituted by these groups. A halogen atom or a methyl group is preferred.

In view of the transparency of the photosensitive resin composition of the present invention, R ^{1 is} preferably an alkyl group, and R ^{1 is} preferably a branch having a carbon number of 3 to 6 from the viewpoint of storage stability and sensitivity. The alkyl group of the structure, the 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 of 3 to 6 carbon atoms or an alkane having a cyclic structure of 5 to 7 carbon atoms base. By using such a large volume group (especially a large volume of alkyl group) as R ¹ , transparency can be further improved. Among the large-volume 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.

The aryl group is preferably an aryl group having 6 to 10 carbon atoms. 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 alkyl group represented by R ¹ and the substituent which the aryl group 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.

In 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 the ring preferably forms an alicyclic ring or an aromatic ring, more preferably a benzene 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 R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ^{6 are} bonded to each other. The benzene ring is 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 may be bonded to each other to form a benzene ring.

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

(Stage 1) At least two are hydrogen atoms.

(Section 2) The number of the alkyl group, the aryl group or the halogen atom 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.

(Stage 4) The aspect of the above-described aspect 1 and aspect 2 is satisfied, and/or the aspect of the above-described aspect 1 and aspect 3 is satisfied.

X represents -O- or -S-.

Specific examples of the above formula (B4) include the compounds described below, 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.

In the photosensitive resin composition of the present invention, it is preferred that (B) a photoacid generator is used in an amount of 100 parts by mass based on all the resin components (preferably a solid component, more preferably a total of the copolymer) in the photosensitive resin composition. It is more preferably used in an amount of from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 10 parts by mass. Two or more types may be used in combination.

<(C) Solvent>

The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared by dissolving an essential component of the present invention and further a component described below in (C) a solvent.

The solvent (C) used in the photosensitive resin composition of the present invention may be a known solvent, and examples thereof include ethylene glycol monoalkyl ethers and ethylene glycol dialkyl ethers. Ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, diethylene glycol monoalkane Ethyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. In addition, as a specific example of the (C) solvent used in the photosensitive resin composition of the present invention, the solvent described in Paragraph No. 0174 to Paragraph No. 0178 of JP-A-2011-221494 may be mentioned. Enter the application specification.

In addition, if necessary, it may be further added to the solvents: benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophor Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, carbonic acid Ether ethyl ester, propylene carbonate and other solvents. 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 or more, more preferably two kinds, and particularly preferably propylene glycol monoalkyl ether acetate or dialkyl ether or diacetate. It is used in combination with diethylene glycol dialkyl ethers or esters and butanediol alkyl ether acetate.

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

The solvent having a boiling point of 130 ° C or more 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).

The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ether (boiling point: 176 ° C), and 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), two Diol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C ), 1,3-butanediol diacetate (boiling point: 232 ° C).

The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably from 20 parts by mass to 95 parts by mass, particularly preferably from 30 parts by mass to 90%, per 100 parts by mass of all the components in the photosensitive resin composition. Parts by mass.

As described above, the photosensitive resin composition of the present invention contains a polymer component containing the above-mentioned polymer satisfying at least one of (A1) and (A2), (B) a photoacid generator, and (C) a solvent. . By using the photosensitive resin composition, it is possible to obtain a cured film which not only maintains sensitivity but also has a low dielectric constant and low hygroscopicity.

(E) alkoxydecane compound

The photosensitive resin composition of the present invention preferably contains an (E) 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 can be improved, or the film of the photosensitive resin composition of this invention can be adjusted. The (E) alkoxydecane compound which can be used in the photosensitive resin composition of the present invention is preferably an inorganic substance which is a base material, for example, an antimony compound such as cerium, cerium oxide or cerium nitride, which improves gold, copper, molybdenum, and the like. A compound having adhesion to a metal such as titanium or aluminum and an insulating film. Specifically, a known decane coupling agent or the like Also effective.

Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-glycidyloxy group. Propyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ-chloropropyl three Alkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. More preferably, these compounds are γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane, and particularly preferably γ-glycidoxypropyl III. The alkoxydecane is especially preferably 3-glycidoxypropyltrimethoxydecane. These compounds may be used alone or in combination of two or more.

Further, the following compounds can also be preferably used.

In the above, Ph is a phenyl group.

The (E) 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 (E) alkoxydecane compound in the photosensitive resin composition of the present invention is preferably from 0.1 part by mass to 30 parts by mass, more preferably 0.5, based on 100 parts by mass of all the solid components in the photosensitive composition. Parts by mass to 20 parts by mass.

(H) basic compound

The photosensitive resin composition of the present invention preferably contains a (H) basic compound. (H) The basic compound can be arbitrarily selected from the 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 such a compound include the compounds described in Paragraph No. 0204 to Paragraph No. 0207 of JP-A-2011-221494, the contents of which are incorporated herein by reference.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, and triethanolamine. Dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N-methyl. 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, Nicotinic acid, nicotinic acid decylamine, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, hydrazine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-diazabicyclo[4.3.0]-5-decene, 1,8-diaza Bicyclo [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, ammonium tetramethylbenzoate, tetra-n-butylammonium acetate, and tetra-n-butylbenzoic acid ammonium.

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 (H) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 part by mass to 3 parts by mass, more preferably 0.005 part by mass, based on 100 parts by mass of all the solid components in the photosensitive resin composition. ~2 parts by mass.

(I) surfactant

The photosensitive resin composition of the present invention preferably contains (I) a surfactant. (I) The surfactant may be any of an anionic, cationic, nonionic or amphoteric surfactant, and a preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, anthrone series, and fluorine interface. Active agent. In addition, the following product names are listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafac (DIC ) (manufacturing), Fluorad (manufactured by Sumitomo 3M), Asahi Guard, Surflon (made by Asahi Glass), PolyFox (made by OMNOVA), SH-8400 (Toray Dow Corning) (Toray Dow Corning Silicone)) and other series.

Further, the surfactant is preferably a copolymer comprising the constituent unit A represented by the following formula (I-1) and the constituent unit B, and using tetrahydrofuran (THF) as a solvent. The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography in the case of the measurement is 1,000 or more and 10,000 or less.

General formula (I-1)

(In the formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number of 1; In the above alkyl group, 4 or less, L represents 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 a numerical value of 10% by mass or more and 80% by mass or less, and q is 20. A numerical value of % 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 a branched alkyl group represented by the following formula (I-2). R ⁴⁰⁵ in the formula (I-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and preferably has a carbon number of 1 or more in terms of compatibility and wettability to a surface to be coated. An alkyl group of 3 or less is more preferably an alkyl group having 2 or 3 carbon atoms. The sum of p and q (p+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. Up, 5,000 or less.

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

The amount of the (I) surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass, based on 100 parts by mass of all the solid components in the photosensitive resin composition. 10 parts by mass, particularly preferably 0.01 parts by mass to 3 parts by mass.

<Other ingredients>

In addition to the above components, the photosensitive resin composition of the present invention may preferably contain a sensitizer, a crosslinking agent, and an antioxidant as needed. Further, an acid proliferating agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a tackifier, and an organic or inorganic precipitate may be added to the photosensitive resin composition of the present invention. A known additive such as a preventive agent.

Sensitizer

In combination with the (B) photoacid generator, the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer that is in an electronically excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, 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 at any wavelength in the wavelength region of 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, joints) Triphenyl, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropoxyfluorene), dibenzopyrazine Xanthene (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones ( Xanthone) (eg, xanthone, thioxanthone, dimethylthiazolone, dithionone), cyanine (eg, thiacarbocyanine) ), oxacarbocyanine, melocyanine (eg, merocyanine, carbomerocyanine), rhodacyanine, oxonol Thiazines (for example: thionine, methylene blue, toluidine blue), acridine (for example: acridine orange, Chloroflavin, acriflavine, acridone (eg acridone, 10-butyl-2-chloroacridone), anthraquinone (anthraquinone) For example, 蒽醌), squarylium (squarylium) : squaraine compound salt), styryl group, basic styryl group (for example: 2-[2-[4-(dimethylamino)phenyl]vinyl]benzoxazole), coumarin Coumarins (eg 7-diethylamino-4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl- 1H, 5H, 11H[1]benzopyrano[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.

The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably from 0 part by mass to 1000 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of the photoacid generator of the photosensitive resin composition. 500 parts by mass, particularly preferably 50 parts by mass to 200 parts 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 form 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 for component A). For example, a compound having two or more epoxy groups or oxetanyl groups, a crosslinking group containing an alkoxymethyl group, or a compound having at least one ethylenically unsaturated double bond in the molecule described below may be added. , blocked isocyanate compounds, etc.

The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass to 30 parts by mass per 100 parts by mass of all the solid components of the photosensitive resin composition. The mass part is preferably from 0.5 part by mass to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance is obtained. A plurality of crosslinking agents may be used in combination, and in this case, the total amount of the crosslinking agents is totaled to calculate the content.

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

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

These compounds are available as commercial products. For example, commercially available products such as JER157S70 and JER157S65 (manufactured by Mitsubishi Chemical Holdings), paragraph number 0189 of JP-A-2011-221494, and others, may also be mentioned: Denacol EX -611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Denacol EX-421, Denacol EX-313, Denacol EX -314, Denacol EX-321, Denacol EX-211, Denacol EX-212, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX -832, Denacol EX-841, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931, Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX -850L, Denacol DLC-201, Denacol DLC-203, Denacol DLC-204, Denacol DLC-205, Denacol DLC-206, Denacol DLC-301, Denacol DLC-402 (above manufactured by Nagase ChemteX), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above manufactured by Nippon Steel Chemical Co., Ltd.) .

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

Among these compounds, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and aliphatic epoxy resins, and particularly preferred are bisphenol A type epoxy resins. Resin.

Specific examples of the compound having two or more oxetanyl groups in the molecule can be used: Aron Oxetane OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.) .

Further, the compound containing an oxetanyl group is preferably used singly or in combination with a compound containing an epoxy group.

Further, the other crosslinking agent may preferably be an alkoxymethyl group-containing crosslinking agent described in Paragraph No. 0107 to Paragraph No. 0108 of JP-A-2012-8223, and having at least one ethylenic property. Compounds of unsaturated double bonds, etc., are incorporated herein by reference. The alkoxymethyl group-containing crosslinking agent is preferably an alkoxymethylated glycoluril.

<Block isocyanate compound>

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

Further, the term "block isocyanate group" in the present invention means a group which can form an isocyanate group by heat. For example, it is preferred to exemplify a reaction between a block agent and an isocyanate group to protect the difference. a group of cyanate groups. Further, the block isocyanate group is preferably a group which can form an isocyanate group by heat of from 90 ° C to 250 ° C.

Further, the skeleton of the blocked isocyanate compound is not particularly limited, and may be any of those having two isocyanato groups in one molecule, and may be an aliphatic, alicyclic or aromatic polyisocyanate, for example. Can be used as appropriate: 2,4-toluene diiso Cyanate ester, 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-diya 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 Isocyanate compounds such as diisocyanate, hydrogenated 1,3-benzenedimethyl diisocyanate, hydrogenated 1,4-benzyldimethyl diisocyanate, and prepolymer type skeleton derived from these compounds Thereof. Among these compounds, particularly preferred is tolylene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate. (isophorone diisocyanate, IPDI).

The parent structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention may be a biuret type, an isocyanurate type, an adduct type or a bifunctional type. Polymer type, etc.

Examples of the block forming the block structure of the above-mentioned blocked isocyanate compound include an anthracene 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. Compound a substance, a quinone imine compound or the like. Among these compounds, a block 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 above hydrazine compound include hydrazine and ketoxime, and specific examples thereof include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketoxime, cyclohexanone oxime, and benzophenone. Hey.

The above-mentioned indoleamine compound can be exemplified by ε-caprolactam, γ-butylide or the like.

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, and ethylenimine. Polyethylenimine and the like.

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

The above pyrazole compound can be exemplified by pyrazole, methylpyrazole, dimethylpyrazole and the like.

The above thiol compound can be exemplified by an alkylthiol, an arylthiol or the like.

The 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, Coronate 2515, Coronate 2507, Coronate can be preferably used. 2513, Coronate 2555, Millionate MS-50 (above manufactured by Nippon Polyurethane Industry), Takenate B-830, Takenate B-815N, Takenate B-820NSU, Takenate B-842N , Takenate B-846N, Takenate B-870N, Takenate B-874N, Takenate B-882N (above manufactured by Mitsui Chemicals Co., Ltd.), Duranate 17B-60PX, Duranate 17B-60P, Duranate TPA-B80X, Duranate TPA-B80E ,Duranate MF-B60X,Duranate MF-B60B,Duranate MF-K60X,Duranate MF-K60B,Duranate E402-B80B,Duranate SBN-70D,Duranate SBB-70P,Duranate K6000 (above manufactured by Asahi Kasei Chemicals Co., Ltd.), Desmodur BL1100, Desmodur BL1265 MPA/X, Desmodur BL3575/1, Desmodur BL3272MPA, BL3370MPA, Desmodur BL3475BA/SN, Desmodur BL5375MPA, Desmodur VPLS2078/2, Desmodur BL4265SN, Desmodur PL340, Desmodur PL350, Sumidur BL3175 (above by Baying Amine Sodium (Sumika Bayer Urethane) (manufactured by the company) and so on.

Antioxidants

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant can be contained. 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, and deterioration. Blood acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these compounds, a phenolic antioxidant, a guanamine antioxidant, a lanthanoid antioxidant, and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring and film thickness reduction of the cured film. These compounds may be used alone or in combination of two or more.

Commercial products of phenolic antioxidants include, for example, Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab AO- 50. Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A- 613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, Adekastab CDA-1, Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (above by ADEKA) Manufactured), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BASF) Share) manufacturing) and so on. Among them, Adekastab AO-60 and Adekastab AO-80 can be used. Irganox 1726, Irganox 1035, 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, even more preferably from 0.5% by mass to 4% by mass based on the total solid content of the photosensitive resin composition. By setting it as this range, the transparency of the formed film is acquired, and the sensitivity at the time of pattern formation also becomes favorable.

In addition, as the additive other than the antioxidant, various ultraviolet absorbers, metal passivators, and the like described in "New Development of Polymer Additives" (Nikkei Kogyo Co., Ltd.) may be added to the photosensitive resin of the present invention. In the composition.

[acid proliferator]

The photosensitive resin composition of the present invention can use an acid multiplier for the purpose of improving sensitivity.

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 is stably present in the absence of an acid. Since such a compound is increased by one or more acids by one reaction, the reaction proceeds with the progress of the reaction, but since the generated acid itself causes self-decomposition, the strength of the acid generated here is dissociated by acid. The constant and pKa are preferably 3 or less, and particularly preferably 2 or less.

Specific examples of the acid-proliferating agent include paragraph number 0203 to paragraph number 0223 of JP-A-10-1508, paragraph number 0016 to paragraph number 0055 of Japanese Patent Laid-Open No. Hei 10-282642, and Japanese Patent Special Table. The compounds described in Japanese Patent Publication No. Hei 9-512498, page 39, line 12 to page 47, line 2, are incorporated herein by reference.

The acid multiplying agent which can be used in the present invention is decomposed by using an acid generated by an acid generator to produce dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, or the like. A compound having an acid having a pKa of 3 or less.

Specifically, the following compounds are mentioned.

The content of the acid-proliferating agent in the photosensitive composition is preferably from 10 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the photo-acid generator, from the viewpoint of the dissolution ratio of the exposed portion and the unexposed portion. The optimum is set to 20 parts by mass to 500 parts by mass.

[development accelerator]

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

The development accelerator can be referred to the description of Paragraph No. 0171 to Paragraph No. 0172 of JP-A-2012-042837, which is incorporated herein by reference.

One type of the development accelerator may be used alone or two or more types may be used in combination.

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 all the solid components of the photosensitive composition. More preferably, it is 0.1 parts by mass~ 20 parts by mass, preferably 0.5 parts by mass to 10 parts by mass.

In addition, as the other additive, the thermal radical generating agent described in Paragraph No. 0120 to Paragraph No. 0121 of JP-A-2012-8223, the nitrogen-containing compound described in WO2011/136074A1, and a thermal acid generator may be used. These are incorporated in the specification of the present application.

<Method for Preparing Photosensitive Resin Composition>

The components are mixed at a predetermined ratio and by any method, and stirred and dissolved to prepare a photosensitive resin composition. For example, after the components are each dissolved in a solvent to prepare a solution, the solutions are mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared in the above manner can also be used after being filtered 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 onto a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; and (3) removing a solvent by an actinic ray pair a step of exposing the photosensitive resin composition; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; (5) post-baking for thermally curing the developed photosensitive resin composition Baking step Step.

Each step will be described in order below.

In the coating step of (1), it is preferred to apply the photosensitive resin composition of the present invention onto 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, the adhesion of the photosensitive resin composition to the substrate tends to be 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, a resin composite material, and the like.

Examples of the inorganic substrate include glass, quartz, anthrone, tantalum nitride, and a composite substrate on which molybdenum, titanium, aluminum, copper, or the like is deposited on the substrate as described above.

Examples of the resin include: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and poly Bismuth, polyether oxime, polyarylate, allyl diol carbonate, polyamine, polyimide, polyamidimide, polyether phthalimide, polybenzazole, polyphenylene Fluoroether, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, cross-linked anti-butyl A substrate of a synthetic resin such as an enedic acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound.

These substrates are rarely used as they are in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) element is usually formed by the form of the final product.

The method of applying 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 (slit) can be used. -and-spin method) and other methods. Further, a so-called pre-wet method described in Japanese Laid-Open Patent Publication No. 2009-145395 can also be applied.

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

In the solvent removal step of (2), a 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 in the solvent removal step is preferably from 70 ° C to 130 ° C and from about 30 seconds to about 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern is further improved, and the residue tends to be further reduced.

In the exposure step of (3), the substrate on which the coating film is provided is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. The acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid to form a carboxyl group or a phenolic hydroxyl group.

The exposure light source by actinic ray can be used: 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, etc., preferably used. G-ray (436 An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as nm), i-ray (365 nm), and h-ray (405 nm). Further, the illumination light may be adjusted by a long-wavelength cut filter, a short-wavelength cut filter, or a band pass filter such as a band pass filter as needed.

The exposure device can be used: a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, Various types of exposure machines such as lens scanners and laser exposure.

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. By PEB, it is possible to promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature in the case of performing PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and particularly preferably 50° C. or higher and 100° C. or lower.

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

In the developing step of (4), a polymer having a free carboxyl group or a phenolic hydroxyl group is developed using an alkaline developing solution. The resin composition has a carboxyl group or a phenolic hydroxyl group which is easily dissolved in the alkaline developing solution by removing the exposed portion region including the resin composition to form a positive image.

The developer used in the developing step preferably contains a basic compound. Alkali As the 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 hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate can be used. An aqueous solution of ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; or an aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution of an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the above-mentioned alkali as a developing solution.

A preferred developing solution is a 0.4% aqueous solution of tetraethylammonium hydroxide, a 0.5% aqueous solution, a 0.7% aqueous solution, and a 2.38% aqueous solution.

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.

The rinsing step can also be carried out after development. In the rinsing step, the developed substrate is cleaned by pure water or the like, and 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), the acid-decomposable group is thermally decomposed by heating the obtained positive image to form a carboxyl group or a phenolic hydroxyl group, and cross-linking with a crosslinkable group, a crosslinking agent, or the like. Thereby, a cured film can be formed. The heating is preferably performed by 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, it is carried out for 5 minutes to 90 minutes. Minutes, if it is an oven, it takes 30 minutes to 120 minutes. By performing such a crosslinking reaction, a protective film or an interlayer insulating film which is more excellent in heat resistance and hardness can be formed. Further, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

Before baking, it is also possible to perform post-baking after baking at a relatively low temperature (addition of the intermediate baking step). In the case of performing intermediate baking, it is preferred to perform post-baking at a high temperature of 200 ° C or higher after heating at 90 ° C to 150 ° C for 1 minute to 60 minutes. Further, the intermediate baking and the post-baking may be divided into three or more stages to perform heating. The taper angle of the pattern can be adjusted by the intermediate baking and post-baking operations as described above. A known heating method such as a hot plate, an oven, or an infrared heater can be used for the heating.

Further, after performing overall re-exposure (post-exposure) on the patterned substrate by actinic rays before post-baking, post-baking is performed, whereby acid is generated from the photo-acid generator present in the unexposed portion, It functions as a catalyst for promoting the crosslinking step, and promotes the hardening reaction of the film. The preferable exposure amount in the case of including the post-exposure step is preferably from 100 mJ/cm ² to 3,000 mJ/cm ² , particularly preferably from 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 an anti-dry etchant. In the case where the cured film obtained by heat-hardening by the post-baking step is used as an anti-dry etchant, the etching treatment may be subjected to dry etching treatment such as ashing, plasma etching, or ozone etching.

[hardened film]

The cured film of the present invention hardens the photosensitive resin composition of the present invention And the cured film obtained.

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 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 is obtained.

[display device]

The interlayer insulating film obtained by using the photosensitive resin composition of the present invention has high transparency and excellent physical properties of the cured film, and thus can be used for a display device (preferably a liquid crystal display device or an organic EL display device).

[Liquid Crystal Display Device]

The 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 can be cited.

Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-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, the liquid crystal driving method which the liquid crystal display device of the present invention can take is a twisted nematic (TN) method or a vertical alignment (Virtical). Alignment, VA), In-Place-Switching (IPS), Frings Field Switching (FFS), and Optical Compensated Bend (OCB).

In the panel structure, the cured film of the present invention can also be used in a color filter on Allay (COA) type liquid crystal display device, for example, as an organic insulating film of Japanese Laid-Open Patent Publication No. 2005-284291 ( 115) or an organic insulating film (212) of JP-A-2005-346054.

Moreover, the specific alignment of the liquid crystal alignment film which can be taken by the liquid crystal display device of the present invention is, for example, a rubbing alignment method or a photoalignment method. In addition, the polymer alignment support can be carried out 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 for various purposes. For example, in addition to the planarization film or the interlayer insulating film, a protective film suitable for a color filter or a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device fixed may be provided in the solid-state imaging element. Microlenses and the like on a color filter.

FIG. 2 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 provided with an element of the TFT 16, and the elements of the TFT 16 are disposed on two glass substrates 14 and a glass substrate 15 to which a polarizing film is attached. All pixels in between correspond. Formed on each element on the glass substrate, formed on the cured film In the contact hole 18 of 17, a indium tin oxide (ITO) transparent electrode 19 for forming a pixel electrode is wired. A layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are disposed on the indium tin oxide transparent electrode 19.

The light source of 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.

In addition, the liquid crystal display device can also be made into a three-dimensional (3D) (stereoscopic) type device or a touch panel type device. Further, it can be made into a flexible type, and can be used as the second interlayer insulating film (48) of JP-A-2011-145686 or the interlayer insulating film (520) of JP-A-2009-258758.

[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 by using the photosensitive resin composition of the present invention, and various known organic EL display devices having various structures or Liquid crystal display device.

Specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-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. 1 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, including a planarization film 4.

A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . 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 via the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in the step described later to the TFT 1.

Further, in order to planarize the unevenness due to 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 formed on the planarizing film 4 by being connected to the wiring 2 via the contact hole 7. 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, in FIG. 2, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by vapor deposition through a desired pattern mask, and then a second electrode including Al is formed on the entire upper surface of the substrate. An ultraviolet-curable epoxy resin is bonded to the glass plate for sealing and sealed, and an active matrix organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained.

The photosensitive resin composition of the present invention is characterized by hardenability and hardened film. Since it is excellent in the properties, a resist pattern formed using the photosensitive resin composition of the present invention is used as a structural member of a microelectromechanical system (MEMS) device, or is assembled as a part of a mechanically driven component. To use. Examples of such a MEMS device include a surface acoustic wave (SAW) filter, a bulk acoustic wave (BAW) filter, a gyro sensor, and a microshutter for display. , image sensor, electronic paper, inkjet head, biochip, sealant and other parts. More specific examples are exemplified in JP-A-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

The photosensitive resin composition of the present invention is excellent in flatness and transparency, and can be used, for example, in forming a bank layer (16) and planarization described in Fig. 2 of JP-A-2011-107476. The partition (12) and the flattening film (102) described in Fig. 4 (a) of the Japanese Patent Publication No. 2010-9793, and the description of Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 The deposition 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 flattening film (12) and the pixel separation insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638.

[Examples]

The present invention will be further specifically described below by way of examples. The materials, usage, ratio, processing contents, processing procedures, etc. shown in the following examples are only The present invention can be appropriately changed without departing from the gist of the present 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.

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

MATHF: 2-tetrahydrofuran methacrylate (synthetic)

MAEVE: 1-ethoxyethyl methacrylate (synthetic)

MACHOE: 1-(cyclohexyloxy)ethyl methacrylate (synthetic)

MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

PHSEVE: 4-(1-ethoxyethyloxy)styrene (synthetic)

PHSTHF: (synthetic)

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

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

NBMA: n-Butoxymethyl propylene decylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

MAA: Methacrylic acid (made by Wako Pure Chemical Industries, Ltd.)

MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

DCPM: Dicyclopentyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)

1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.)

2-trifluoromethyl-1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.)

2-methyl-1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.)

2,3-dimethyl-1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.)

2,3-diol-1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.)

V-601: 2,2'-azobis(2-methylpropionic acid) dimethyl ester (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)

<Synthesis of MATHF>

After methacrylic acid (86 g, 1 mol) was cooled to 15 ° C, 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 the mixture was extracted with ethyl acetate (500 mL), and dried over magnesium sulfate, and then filtered, and the insoluble materials were filtered, and concentrated under reduced pressure at 40 ° C or less to give a yellow residue. The oil was distilled under reduced pressure to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) of 54 ° C / 3.5 mmHg - 56 ° C / 3.5 mmHg as a colorless oil. (Yield 80%).

<Synthesis of MAEVE>

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

<Synthesis of PHSEVE>

PHSEVE was synthesized by changing the methacrylic acid of the MAEVE synthesis method to 4-hydroxystyrene.

<synthesis of MACHOE>

MACHOE was synthesized by changing 2-dihydrofuran to 2-dihydropyran in the synthesis of MATHF.

<Synthesis of PHSTHF>

The methacrylic acid of the MATHF synthesis method was changed to 4-hydroxystyrene to synthesize PHSTHF.

<Synthesis Example of Polymer P-1>

MEDG (89 g) was placed in a 3-neck flask, and the mixture was heated to 90 ° C under a nitrogen atmosphere. MAA (in an amount of 12 mol% of all monomer components), MATHF (amount of 28 mol% of all monomer components), and 1,3-butadiene (which became all monomer components) were dissolved in the solution. 60 mol%), V-65 (corresponding to 100 mol% of all the monomer components, and equivalent to 4 mol%), was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, the polymer P-1 was obtained.

The weight average molecular weight of the obtained polymer P-1 measured by gel permeation chromatography (GPC) was 15,000.

<Synthesis Example of Polymer P-2 to Polymer P-23, Polymer P'-1 to Polymer P'-8>

Other polymers were synthesized in the same manner as in the synthesis of the polymer P-1 except that the monomers used and the amounts thereof used were changed to those described in the following tables.

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

<Preparation of photosensitive resin composition>

The polymer, photoacid generator, alkoxydecane compound, basic compound, surfactant, and other components are dissolved and mixed in a solvent (MEDG) until solid as a solid component ratio shown in the following table. The concentration of the component was 40% by mass, and the mixture was filtered through a filter made of polytetrafluoroethylene having a diameter of 0.2 μm to obtain photosensitive resin compositions of various examples and comparative examples.

The details of the abbreviations indicating the respective compounds used in the examples and the comparative examples are as follows.

Polymer P-1~Polymer P-23, polymer P'-1~Polymer P'-8: polymer synthesized according to the above synthesis example

(photoacid generator)

B-1: a compound of the following structure (synthetic)

B-2: a compound of the following structure (synthetic)

(Ts represents toluenesulfonyl (p-toluenesulfonyl))

B-3: a compound of the following structure (synthesized according to the method described in paragraph 0108 of JP-A-2002-528451)

B-4: PAG-103 (structure shown below, manufactured by BASF)

B-5: GSID-26-1, triarylsulfonium salt (manufactured by BASF)

<Synthesis of B-1>

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C for 2 hours. 4N HCl aqueous solution (60 mL) was added to the reaction mixture under ice-cooling, and ethyl acetate (50 mL) was added to carry out liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour. Then, a 2N aqueous HCl solution (60 mL) was added and the mixture was separated, and the organic layer was concentrated, and then crystallized with diisopropyl ether (10 mL). Slurry, filtration, and drying to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated under reflux. After standing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain a hydrazine compound (2.4 g).

The obtained hydrazine compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and p-toluenesulfonium chloride (2.4 g) were added under ice cooling, and the temperature was raised. The reaction was allowed to reach room temperature for 1 hour. Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, and then re-slurryed with methanol (20 mL), filtered, and dried to obtain a compound (the above structure) (2.3 g) of B-1.

Further, the ¹ H-NMR spectrum of B-1 (300 MHz, CDCl ₃ ) was: δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B-2>

3.0 g of 2-amino-1-naphthol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.7 g of methyl 4,4-dimethyl-3-oxopentanoate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and p-toluene was added. 0.5 g of sulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was heated at 120 ° C for 2 hours under a nitrogen atmosphere. After standing to cool, the crude product was purified by column chromatography to afford 4.4 g of Intermediate B-2A.

B-2A (2.0 g) was mixed with p-xylene (10 mL), and 0.3 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated at 140 ° C for 6 hours. After standing to cool, water and ethyl acetate were added to the reaction mixture to carry out liquid separation, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to give crude B-2B.

THF (1.5 mL) was mixed with the total amount of crude B-2B, and 8.5 mL of 2M hydrochloric acid/THF solution was added dropwise thereto under ice-cooling, followed by dropwise addition of isoamyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (1.2 g), and the temperature was raised. Stir at room temperature for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture to carry out liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain intermediate crude B-2C.

Mix intermediate crude B-2C (1.0g) with acetone (10mL) on ice Triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (0.74 g) and p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.0 g) were added under cooling, and the mixture was heated to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture to carry out liquid separation, and the organic phase was dried over magnesium sulfate, followed by filtration and concentration to obtain a crude B-2. The crude B-2 was reslurryed with methanol, filtered, and dried to give B-2 (1.0 g).

(alkoxydecane compound)

E-1: γ-glycidoxypropyl trialkoxy decane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)

(alkaline compound)

H-1: a compound of the following structure

(surfactant)

I-1: a perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by Diane Health (DIC))

<Evaluation of relative dielectric constant>

Each of the photosensitive resin compositions was spin-coated on a bare wafer substrate (N-type low resistance) (manufactured by SUMCO Co., Ltd.), and then pre-baked on a hot plate at 90 ° C / 120 seconds to volatilize the solvent to form a film thickness. It is a photosensitive resin composition layer of 3.0 μm. Then, an ultrahigh pressure mercury lamp was used, and the total exposure amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and the substrate was heated in an oven at 230 ° C for 30 minutes, and further Heating was carried out in an oven at 230 ° C for 2 hours.

For the cured film, CVmap92A (manufactured by Four Dimensions Inc.) was used, and the relative dielectric constant was measured at a measurement frequency of 1 MHz. The results are shown in the following table. The smaller the value, the better, preferably A~C.

A: less than 3.0

B: 3.0 or more and less than 3.3

C: 3.3 or more and less than 3.7

D: 3.7 or more and less than 4.0

E: 4.0 or more

<Evaluation of hygroscopicity>

After each of the photosensitive resin compositions was spin-coated on a polyimide film, prebaking at 90 ° C for 120 seconds on a hot plate to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3.0 μm. . Then, an ultrahigh pressure mercury lamp was used, and the total exposure amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and the substrate was heated in an oven at 230° C. for 30 minutes, and further, Heating was carried out in an oven at 230 ° C for 2 hours.

For the cured film, the water vapor transmission rate was evaluated using a LYSSY water vapor permeability meter (manufactured by Systech Instruments Co., Ltd.).

The results are shown in the following table. It is preferably A to C.

A: less than 1g/m ² . Day

B: 1g/m ² . Above day and less than 5g/m ² . Day

C: 5g/m ² . Above day and less than 10g/m ² . Day

D: 10g/m ² . Above day and less than 50g/m ² . Day

E: 50g/m ² . More than day

<Evaluation of sensitivity>

A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated, and then heated on a heating plate. The solvent was volatilized by prebaking at 90 ° C / 120 seconds 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. Next, the exposed photosensitive resin composition layer was developed in an alkali developing solution (0.4% tetramethylammonium hydroxide aqueous solution) at 23° C. for 60 seconds, and then rinsed with ultrapure water for 20 seconds. The optimum i-ray exposure amount (Eopt) when the 5 μm hole was analyzed by these operations was taken as the sensitivity.

A: less than 20mJ/cm ²

B: 20 mJ/cm ² or more and less than 40 mJ/cm ²

C: 40 mJ/cm ² or more and less than 80 mJ/cm ²

D: 80 mJ/cm ² or more and less than 160 mJ/cm ²

E: 160mJ/cm ² or more

<hardened film adhesion>

After each photosensitive resin composition was spin-coated on a glass substrate on which a Mo (molybdenum) film was formed, it was prebaked on a hot plate at 90° C./120 seconds to volatilize the solvent to form a photosensitive film having a film thickness of 3.0 μm. A layer of a resin composition. Then, an ultrahigh pressure mercury lamp was used, and the total exposure amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and then the substrate was heated in an oven at 230 ° C for 30 minutes. A cured film is obtained.

Then, using a cutter, the slit was cut at intervals of 1 mm in the longitudinal and lateral directions on the cured film, and the tape peeling test was performed using Scotch tape (100 mass cross cut method): JIS5600). The adhesion between the cured film and the substrate was evaluated based on the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the value, the higher the adhesion to the base substrate, and A or B is a practical level.

A: The transferred area is less than 1%

B: The transferred area is 1% or more and less than 5%

C: The transferred area is 5% or more and less than 10%

D: The transferred area is 10% or more and less than 50%

E: The transferred area is 50% or more

As is apparent from the above results, by using the photosensitive resin composition of the present invention, it is possible to obtain a cured film which not only maintains high sensitivity but also has a low dielectric constant and low hygroscopicity. In addition, by including 40 mol% or less of the constituent unit (a4) in all the constituent units of the (A) polymer component of the photosensitive resin composition, the photosensitive resin composition of the present invention can be further improved. Adhesion between the cured film and the substrate when the film is cured.

<Example 32>

Example 32 is the same as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Co., Ltd. to FX-803M (gh-Line, stepper) manufactured by Nikon Co., Ltd. The way to proceed. The evaluation of the sensitivity was the same as that of Example 1.

<Example 33>

Example 33 was carried out in the same manner as in Example 1 except that the exposure machine was changed from a MPA 5500CF manufactured by Canon Co., Ltd. to a 355 nm laser exposure machine to perform 355 nm laser exposure. Here, the 355 nm laser exposure machine uses "AEGIS" (wavelength: 355 nm, pulse width: 6 nsec) manufactured by V-Technology Co., Ltd., and uses "PE10B-V2" manufactured by OPHIR to measure the exposure amount. .

The evaluation of the sensitivity was the same as that of Example 1.

<Example 34>

Active matrix type described in Fig. 1 of Japanese Patent No. 3321003 In the liquid crystal display device, the cured film 17 was formed as an interlayer insulating film in the following manner, and the liquid crystal display device of Example 34 was obtained. That is, the cured film 17 was used as the interlayer insulating film by using the photosensitive resin composition of Example 1.

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 paragraph 58 of Japanese Patent No. 3321003 and the interlayer insulating film 17. After the photosensitive resin composition of Example 1 was spin-coated, it was 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, using the MPA 5500CF (high-pressure mercury lamp) manufactured by Canon Co., Ltd., the resulting photosensitive light was obtained by a mask of a hole pattern of 10 μmφ at 40 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray). The resin composition layer was exposed. Next, the exposed photosensitive resin composition layer was subjected to liquid-coating development at 23 ° C / 60 seconds in an alkali developing solution (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds. Then, an ultrahigh pressure mercury lamp was used, and the total exposure amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and then the substrate was heated in an oven at 230 ° C for 30 minutes. A cured film is obtained.

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

When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited excellent display characteristics and high reliability.

<Example 35>

Compared with the embodiment 34, only the following processes were changed to obtain the same liquid crystal display. Display device. In other words, when the photosensitive resin composition of Example 1 is applied by hexamethyldiazepine (HMDS) treatment, which is a pretreatment of the substrate, the cured film obtained is also a defect or peeling in which no pattern is present. Good condition. Further, the performance as a liquid crystal display device was also good as in the case of Example 34. 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, it is also preferred to omit the step of pre-processing of the above substrate.

<Example 36>

The same process was changed as in the case of Example 34, and the same liquid crystal display device was obtained. That is, even after the pre-baking, the vacuum drying step (VCD) is introduced, and the obtained cured film is in a state in which no defects or peeling of the pattern are present. Further, the performance as a liquid crystal display device was also good as in the case of Example 34. From the viewpoint of suppressing coating unevenness depending on the solid content concentration or film thickness of the composition, it is also preferred to introduce a vacuum drying step.

<Example 37>

The same process was changed as in the case of Example 34, and the same liquid crystal display device was obtained. That is, even if the PEB step is introduced between the development steps after the mask exposure, the obtained cured film is in a good state in which no pattern defects or peeling are present. Further, the performance as a liquid crystal display device was also good as in the case of Example 34. From the standpoint of improving dimensional stability, it is also preferred to introduce the PEB step.

<Example 38>

The same process was changed as in the case of Example 34, and the same liquid crystal display device was obtained. That is, even if the alkali developer is changed from a 0.4% aqueous solution of tetramethylammonium hydroxide Further, a 2.38% aqueous solution of tetramethylammonium hydroxide was used, and the obtained cured film was also in a good state in which no pattern defects or peeling occurred. Further, the performance as a liquid crystal display device was also good as in the case of Example 34. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 39>

The same process was changed as in the case of Example 34, and the same liquid crystal display device was obtained. That is, even if the alkali development method is changed from the liquid-coating development to the shower development, the obtained cured film is in a state in which no defects or peeling of the pattern are present. Further, the performance as a liquid crystal display device was also good as in the case of Example 34. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 40>

The same process was changed as in the case of Example 34, and the same liquid crystal display device was obtained. That is, even if the alkali developing solution was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution, the obtained cured film was in a good state in which no pattern defects or peeling occurred. Further, the performance as a liquid crystal display device was also good as in the case of Example 34. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 41>

The same process was changed as in the case of Example 34, and the same liquid crystal display device was obtained. That is, the development is omitted. The step of full exposure after rinsing was carried out in an oven at 230 ° C for 30 minutes to obtain a cured film. The performance of the obtained liquid crystal display device was as good as that of Example 34. It is considered that the reason is that the composition of the present invention Excellent chemical resistance. In terms of improving productivity, it is also preferable to omit the step of full exposure.

<Example 42>

The same process was changed as in the case of Example 34, and the same liquid crystal display device was obtained. That is, a step of heating on a hot plate at 100 ° C for 3 minutes was added between the step of full exposure and the heating step of 230 ° C / 30 minutes in the oven. The performance of the obtained liquid crystal display device was as good as that of Example 34. From the viewpoint of aligning the shape of the hole pattern, it is preferable to add this step.

<Example 43>

The same process was changed as in the case of Example 34, and the same liquid crystal display device was obtained. That is, in development. Between the step of rinsing and the step of full exposure, a step of heating on a hot plate at 100 ° C for 3 minutes is added. The performance of the obtained liquid crystal display device was as good as that of Example 32. From the viewpoint of aligning the shape of the hole pattern, it is preferable to add this step.

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

A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . 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 via the contact hole is formed on the insulating film 3. This wiring 2 is for connecting the organic EL element formed in the TFT 1 or in the step described later to 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 planarizing film 4 is formed on the insulating film 3, and the photosensitive resin composition of the first embodiment is spin-coated on a substrate, prebaked on a hot plate (90 ° C / 120 seconds), and then self-masked. After irradiating an i-ray (365 nm) of 45 mJ/cm ² (energy intensity: 20 mW/cm ² ) with a high-pressure mercury lamp, development was carried out by using an aqueous alkali solution (0.4% aqueous solution of TMAH) to form a pattern, and an ultrahigh pressure mercury lamp was used for cumulative irradiation. The amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and overall exposure was performed, and heat treatment was performed at 230 ° C for 30 minutes.

When the photosensitive resin composition was applied, the coating property was good, and no occurrence of wrinkles or cracks was observed on 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 formed on the planarization film 4 via the contact hole 7 and connected to the wiring 2. Then, the resist is applied and prebaked, and exposed and developed through a mask of a desired pattern. This resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Then, 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 insulating film 8 was formed on the insulating film 8 by using the photosensitive resin composition of Example 1 in the same manner as described above. By providing the insulating film 8, the first electrode 5 can be prevented A short circuit between the second electrode formed in the subsequent step.

Further, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequentially depositing a mask in a vacuum vapor deposition apparatus with a desired pattern. Then, a second electrode containing Al is formed on the entire surface above the substrate. The obtained substrate was taken out from a vapor deposition machine, and sealed with an insulating glass plate using an ultraviolet curable epoxy resin.

In the above manner, an active matrix organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained. When a voltage was applied via a drive circuit, it was found that the organic EL display device exhibits excellent display characteristics and high reliability.

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

Claims (16)

A photosensitive resin composition comprising: (A) a polymer component comprising a polymer satisfying at least one of the following (A1) and (A2): (A1) comprising (a1) having an acid group decomposable by acid The constituent unit of the base-protected residue and the polymer of (a4) the structural unit represented by the following general formula (S), and (A2) includes (a1) a structure having a residue in which an acid group is protected by an acid-decomposable group. a polymer of the unit, and a polymer comprising (a4) a constituent unit represented by the following general formula (S); (B) a photoacid generator; and (C) a solvent, (In the formula (S), R ¹ and R ² each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 3 carbon atoms or a perfluoroalkyl group having 1 to 3 carbon atoms). The photosensitive resin composition according to the first aspect of the invention, wherein the component (A) contains (a2) a structural unit having a crosslinkable group. The photosensitive resin composition according to the above-mentioned item (1), wherein the ratio of the above (a4) is 5 mol% to 70 mol. ear%. The photosensitive resin composition according to claim 3, wherein in the component (A), the ratio of the above (a4) is from 15 mol% to 50 mol%. The photosensitive resin composition according to claim 2, wherein the structural unit having the crosslinkable group (a2) contains a component selected from the group consisting of epoxy groups, oxetanyl groups, and -NH-CH ₂ -OR. A constituent unit represented by at least one of a group represented by (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and an ethylenically unsaturated group. The photosensitive resin composition according to claim 3, wherein the structural unit having the crosslinkable group (a2) contains a component selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR. A constituent unit represented by at least one of a group represented by (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and an ethylenically unsaturated group. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photoacid generator is represented by the following formula (B2), formula (B3) and formula (B4) Any of the sulfonate-based acid generators represented by: (In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X may be the same Can also be different) (In the formula (B3), R ⁴³ represents an alkyl group or an aryl group, and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, n4 An integer representing 0~5) (In the formula (B4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group or a heteroaryl group; and R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom; 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-). The photosensitive resin composition according to claim 3, wherein the (B) photoacid generator is any one of the following formula (B2), formula (B3), and formula (B4). The oxime sulfonate acid generator represented: (In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X may be the same Can also be different) (In the formula (B3), R ⁴³ represents an alkyl group or an aryl group, and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, n4 An integer representing 0~5) (In the formula (B4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group or a heteroaryl group; and R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom; 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-). The photosensitive resin composition according to the first aspect or the second aspect of the invention, which has a structural unit represented by the following formula (a1-1-3) as the acid group-protected group having the acid group The constituent units of the residue: (In the formula (a1-1-3), 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 a carbon number of 1; ~4 alkyl). The photosensitive resin composition according to the third aspect of the invention, which has a structural unit represented by the following formula (a1-1-3) as a residue having an acid group-protected residue unit: (In the formula (a1-1-3), 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 a carbon number of 1; ~4 alkyl). A method for producing a cured film, comprising: (1) a step of applying a photosensitive resin composition according to any one of claims 1 to 10 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. The method for producing a cured film according to claim 11, wherein after the developing step, the post-baking step includes a step of performing total exposure on the developed photosensitive resin composition. A cured film formed by the method for producing a cured film according to claim 11 or 12. The cured film according to claim 13, which is an interlayer insulating film. An organic electroluminescence display device comprising the cured film according to claim 13 or claim 14. A liquid crystal display device comprising the cured film according to claim 13 or claim 14.