TW201520695A - Photo-sensitive resin composition, method for manufacturing cured film, cured film, liquid crystal display device and organic EL display device - Google Patents

Abstract

A photo-sensitive resin composition, a method for manufacturing cured film, a cured film, a liquid crystal display device, and an organic El display device are provided. The photo-sensitive resin composition includes: (A-1) a polymer component including a polymer which satisfies at least one of the following (1) and (2), (1) a polymer which has (a1) a constituent unit having a group wherein an acid group is protected with a acid-decomposable group and (a2) a constituent unit having a crosslinkable group, (2) a polymer which has (a1) a constituent unit having a group wherein an acid group is protected with a acid-decomposable group and a polymer which has (a2) a constituent unit having a crosslinkable group; (S) a compound represented by the following general formula (1) and/or general formula (2); (B-1) a photoacid generator; and (C-1) a solvent.

Description

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

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

More specifically, the present invention relates to a planarizing film and a protective film suitable for forming electronic components such as a liquid crystal display device, an organic electroluminescence (organic luminescence) display device, an integrated circuit device, and a solid-state imaging device. Or a photosensitive resin composition of an interlayer insulating film, and a method of producing a cured film using the same.

A patterned interlayer insulating film is provided in an organic EL display device, a liquid crystal display device, or the like. In the formation of the interlayer insulating film, since the number of steps for obtaining a necessary pattern shape is small and sufficient flatness can be obtained, a photosensitive resin composition is widely used.

Insulation and solvent resistance for the interlayer insulating film in the display device High transparency is also desired in addition to the physical properties of the cured film such as heat resistance, heat resistance, hardness, and excellent indium tin oxide (ITO) sputtering compatibility. Therefore, an acrylic resin excellent in transparency has been tried as a film forming component. For example, those described in Patent Document 1 to Patent Document 3 are known.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-209681

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-221471

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-150494

However, the photosensitive resin composition described in Patent Document 1 and Patent Document 2 has a problem in that, in the lithography step of forming the interlayer insulating film, when the photosensitive resin composition layer is exposed and then developed, When the photosensitive resin composition layer is peeled off from the substrate side when exposed to the developer, the yield of the liquid crystal display device is lowered.

On the other hand, in Patent Document 3, the adhesion of the substrate to the photosensitive resin composition layer is improved by adding a decane coupling agent to the photosensitive resin composition. However, in the alkoxyalkylene group in the decane coupling agent described in Patent Document 3, the OH group at the interface between the Si-OH and the substrate is hydrogen-bonded by hydrolysis of the alkoxide group, and then it is carried out at the time of baking. Dehydration condensation reaction to achieve surface modification. However, in Patent Document 3, there is a problem in that hydrogen bonding due to the interface with the substrate is insufficient, so that The alkane coupling agent cannot exist in the vicinity of the interface, and the substrate and the film are not uniformly spread over the entire surface, and unevenness occurs between the surface-modified surface and the surface which is not surface-modified. In addition, since the decane coupling agent described in the literature 3 is a low molecular component, the film of the photosensitive resin composition is softened, and the taper angle is reduced by the overheating, and the pore diameter is enlarged, resulting in a problem of high resolution.

The present invention has been made in view of the above problems, and an object of the invention is to provide an adhesive which is excellent in adhesion between a photosensitive resin composition layer and a base substrate in a developing step, and which is not thermally melted in a baking step. A photosensitive resin composition having a high angle, a method for producing a cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, and an organic EL display device.

The inventors of the present invention conducted research based on the above-mentioned conditions, and found that the compound ((S) component) having an alkoxyalkyl group and a predetermined hydrogen bonding group can be prepared by disposing a photosensitive resin composition. The subject.

Specifically, the above problem is solved by the following solution <1>, preferably by means <2> to resolution <17>.

<1> A photosensitive resin composition comprising: (A-1) a polymer component containing at least one polymer satisfying the following (1) and (2), and (1) containing (a1-1) having an acid a structural unit of a group protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group, (2) containing (a1-1) having an acid group protected by an acid-decomposable group a polymer of a structural unit of a group, and a polymer containing (a1-2) a structural unit having a crosslinkable group; (S) a compound represented by the formula (1) and/or a formula (2) a compound represented; (B-1) a photoacid generator; and (C-1) a solvent; a formula (1)

In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ¹ represents a single bond or a divalent linking group; and X ¹ represents -S. -or-NH-, R ³ represents a monovalent organic group; formula (2)

In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ² represents a single bond or a divalent linking group; and X ² represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom.

<2> A photosensitive resin composition comprising: (A-2) a polymer component containing a polymer satisfying at least one of the following (1) and (2), and (1) containing (a2-1) having an acid a structural unit of a group, and a polymer of (a2-2) a structural unit having a crosslinkable group, (2) a polymer containing (a2-1) a structural unit having an acid group, and containing (a2-2) having a polymer of a structural unit of a crosslinkable group; (B-2) a quinonediazide compound; and (S) a compound represented by the formula (1) and/or a compound represented by the formula (2); (C) -2) solvent; general formula (1)

In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ¹ represents a single bond or a divalent linking group; and X ¹ represents -S. -or-NH-, R ³ represents a monovalent organic group; formula (2)

In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ² represents a single bond or a divalent linking group; and X ² represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom.

<3> A photosensitive resin composition comprising: (A-3) a polymerizable monomer; (B-3) a photopolymerization initiator; (A-4) comprising the following (1) and (2); a polymer component of at least one polymer, (1) a polymer comprising (a4-1) a structural unit having an acid group, and (a4-2) a structural unit having a crosslinkable group, and (2) containing (a4) -1) a polymer having a structural unit having an acid group, and a polymer containing (a4-2) a structural unit having a crosslinkable group; (S) a compound represented by the formula (1) and/or a formula ( 2) the compound represented; and (C-3) solvent; formula (1)

In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ¹ represents a single bond or a divalent linking group; and X ¹ represents -S. -or-NH-, R ³ represents a monovalent organic group; formula (2)

In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ² represents a single bond or a divalent linking group; and X ² represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom.

The photosensitive resin composition of any one of the above-mentioned <1>, and the compound of the formula (1) and / / (S) with respect to the solid component of the photosensitive resin composition. The compounding amount of the compound represented by the formula (2) is from 0.1% by mass to 20% by mass.

<5><1> to <4> described in any one of photosensitive resin composition, wherein the general formula R (1) ³ represents alkyl having 1 to 10 carbon atoms or 6 to 20 Aryl.

<6> The <1> to <5> described in any one of photosensitive resin composition, wherein the general formula R (2) represents a ^4-pyridyl or thiazolyl.

<7> The <1> to <6> The photosensitive resin composition according to any one of claims, wherein the carbon number of L ² respectively Formula ¹ or Formula L (2) (1) 2 to 8 alkylene.

The photosensitive resin composition of any one of the above-mentioned (1), and (S) the compound represented by General formula (1) and / or the compound represented by General formula (2). The molecular weights are each 1000 or less.

The photosensitive resin composition as described in any one of <1> to <8>, wherein the crosslinkable group is selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR ( R is at least one of a group represented by a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

The photosensitive resin composition as described in any one of <1>, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal.

The photosensitive resin composition as described in any one of the above-mentioned (1), and the compound represented by the formula (1) and/or the compound represented by the formula (2) are Any of the compounds represented by the following (S-1) to (S-2), (S-9), and (S-14) to (S-16); wherein, Me represents a methyl group, and Et represents Ethyl;

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

<13> The method for producing a cured film according to <12>, which comprises, after the developing step and before the post-baking step, a step of (6) performing a full-surface exposure of the developed photosensitive resin composition.

<14> The method for producing a cured film according to <13>, which comprises the step of dry etching a substrate having a cured film obtained by thermal curing using a post-baking step.

<15> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <11>, or by any one of <12> to <14> It is formed by the manufacturing method of the hardened film described.

<16> The cured film according to <15>, which is an interlayer insulating film.

<17> An organic EL display device or a liquid crystal display device comprising the cured film according to <15> or <16>.

According to the present invention, it is possible to provide a photosensitive resin which is excellent in adhesion between the photosensitive resin composition layer and the base substrate in the developing step, and which does not thermally melt the photosensitive resin composition layer in the baking step and has a high taper angle. A composition, a method for producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device.

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‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

100‧‧‧Substrate

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

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

Fig. 3 is a schematic view showing an example of a speculative mechanism of the present invention.

Fig. 4 is a schematic view showing another example of the estimation mechanism of the present invention.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be carried out in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the specification of the present application, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

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

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene oxime. And methacryl oxime.

The photosensitive resin composition of the present invention contains a polymer component, a component (S) to be described later, and a solvent, and for example, a photosensitive resin composition can be applied to a substrate. The solvent is removed, exposed to actinic rays, developed with an aqueous developing solution (preferably an alkali developing solution), and thermally cured to form a cured film.

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in adhesion between a photosensitive resin composition layer and a substrate during development and which has a tapered shape after baking.

Although the mechanism is speculative, it is considered as follows.

In the present invention, when the component (S) is a compound represented by the formula (1), as shown in the example shown in FIG. 3, since the thiourea portion has a high basicity, it is easy to form an OH group with the substrate 100. Hydrogen bonds are formed. That is, the sulfur atom at the thiourea site is hydrogen-bonded to the hydrogen atom of the OH group of the substrate, and the -NH-R ³ moiety forms a hydrogen bond with the oxygen atom of the OH group of the substrate, and as a result, the (S) component can be densely present. On the interface.

On the other hand, when the (S) component is a compound represented by the formula (2), as shown in the example shown in FIG. 4, the oxygen atom of the -C(=O)- group forms hydrogen with the OH group of the substrate. The bond, and the hetero atom of the hetero ring represented by R ⁴ (a nitrogen atom in FIG. 4) forms a hydrogen bond with the hydrogen atom of the OH group of the substrate 100, and as a result, the (S) component can be densely present at the interface.

Further, it is considered that the hydrocarbyl group of the alkoxyalkylalkyl group in the general formula (1) and the general formula (2) is hydrolyzed to form a hydrogen bond between the Si-OH and the OH group at the interface of the substrate, and then dehydrated and condensed at the time of baking. The reaction is fixed on the surface, so that the adhesion is improved. Thereby, since the hydrogen bonding of the OH group at the interface of Si-OH and the substrate is sufficient, it is considered that the surface modification can be performed uniformly without unevenness.

Further, it is considered that the thiourea moiety in the general formula (1) and the urea moiety in the general formula (2) are alkaline and act to harden the cross-linking group, thereby promoting hardening. Speed and prevent the reduction of the taper angle caused by overheating. As a result of investigation, the inventors have found that the crosslinkable group in (A-1) reacts easily with the carboxylic acid in the presence of the compound having a high basicity, and the crosslinking density is improved.

Hereinafter, the composition of the present invention will be described in the order of the first aspect to the third aspect. The first aspect and the second aspect of the composition of the present invention can be preferably used as a positive photosensitive resin composition. The third aspect of the composition of the present invention can be preferably used as a negative photosensitive resin composition.

[First aspect of the invention]

The photosensitive composition of the first aspect of the present invention is characterized in that (A-1) contains a polymer component which satisfies at least one of the following (1) and (2), and (1) contains (a1) a structural unit having a group protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, and (2) containing (a1) having an acid group protected by an acid-decomposable group a polymer of a structural unit of a group, and a polymer containing (a2) a structural unit having a crosslinkable group; (S) a compound represented by the formula (1) and/or the formula (2); (B- 1) a photoacid generator; and (C-1) a solvent.

General formula (1) [Chemical 8]

General formula (2)

(In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. L ¹ represents a single bond or a divalent linking group. X ¹ represents - S- or -NH-, R ³ represents a monovalent organic group.

In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. L ² represents a single bond or a divalent linking group. X ² represents -S- or -NH-, and A represents a hetero ring containing a carbon atom and a nitrogen atom. )

Hereinafter, the first aspect of the composition of the present invention will be described in detail.

<(A-1) polymer component>

The composition of the present invention contains at least one of the following polymers as a polymer component: a structural unit containing (a1-1) a group having an acid group which is protected by an acid-decomposable group and (a1-2) having a crosslinkable group Polymer (1) of structural unit, and contains (a1-1) A polymer having a structural unit of a group having an acid group protected by an acid-decomposable group and a polymer (2) containing (a1-2) a structural unit having a crosslinkable group. Further, a polymer other than these may be contained. The polymer component (A-1) of the present invention means that other polymer added as needed, in addition to the polymer (1) and/or the polymer (2), unless otherwise specified.

In the case of a polymer comprising (2) a structural unit containing (a1-1) a structural group having an acid group-protected group, and a polymer containing (a1-2) a structural unit having a crosslinkable group The ratio of the polymer containing (a1-1) a structural unit having a group having an acid group which is protected by an acid-decomposable group to the polymer containing (a1-2) a structural unit having a crosslinkable group is preferably 95: 5~5:95, better 80:20~20:80, and then 70:30~30:70.

The polymer component (A-1) is preferably an addition polymerization type resin, more preferably a polymer containing a structural unit derived from (meth)acrylic acid and/or an ester thereof. Further, a structural unit other than the structural unit derived from (meth)acrylic acid and/or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound may be contained. Further, the "structural unit derived from (meth)acrylic acid and/or its ester" is also referred to as "acrylic structural unit".

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

(A-1) The polymer component contains at least a structural unit (a1-1) having a group in which an acid group is protected by an acid-decomposable group. By containing the structural unit (a1-1) in the polymer component (A-1), a photosensitive resin composition having an extremely high sensitivity can be obtained.

In the present invention, the "acid group-protected group which is protected by an acid-decomposable group" is not particularly limited as long as it is a group known as an acid group and an acid-decomposable group.

Specific acid groups are preferably exemplified by a carboxyl group and a phenolic hydroxyl group.

Further, as the specific acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure, an acetal functional group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group described later), or A group which is relatively difficult to decompose by acid (for example, a tertiary alkyl group such as a tert-butyl group such as a tert-butyl group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).

The structural unit (a1-1) is preferably a structural unit having a carboxyl group protected by an acid-decomposable group or a structural unit having a phenolic hydroxyl group protected by an acid-decomposable group.

Hereinafter, the structural unit (a1-1-1) having a protective carboxyl group protected by an acid-decomposable group and the structural unit (a1-1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group are respectively sequentially Explain.

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

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

The structural unit having the carboxyl group usable in the structural unit (a1-1-1) is not particularly limited, and a known structural unit can be used. For example, a structural unit (a1-1-1-1) 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 may be mentioned.

Hereinafter, a structural unit used as the structural unit having a carboxyl group is used. (a1-1-1-1) is explained.

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

As the unsaturated carboxylic acid used in the present invention, an unsaturated carboxylic acid as exemplified below can be used.

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

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

Further, the unsaturated polycarboxylic acid used to obtain a structural unit having a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and succinic acid. Mono(2-methylpropenyloxyethyl)ester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate Wait. 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. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4-carboxystyrene, etc. may be used. .

Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1-1), acrylic acid, methacrylic acid, 2-(meth)acryloyloxyethyl-amber is preferably used. More preferably, acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl-phthalic acid or an anhydride of an unsaturated polycarboxylic acid, etc. To use acrylic acid, methacrylic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid.

The structural unit (a1-1-1-1) may be composed of a single type or two or more types.

<<<< Acid decomposable group available for structural unit (a1-1-1)>>>>

The acid-decomposable group which can be used for the structural unit (a1-1-1) can use the acid-decomposable group described above.

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

General formula (a1-10) [10]

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

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

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 more preferably a carbon number of 1 to 4. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2,3 - dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.

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

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

The cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and further preferably has 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, an isobornyl group, and the like.

The 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, 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, an aryl group-substituted alkane such as a phenyl group, an α-methylphenyl group or a naphthyl group. The base group, that is, the aralkyl group can be exemplified by a benzyl group, an α-methylbenzyl group, a phenethyl group, a naphthylmethyl group or the like.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and 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 linear. Or a branched alkyl group, or a cycloalkyl group having 3 to 12 carbon atoms As a substituent.

These substituents may also be further substituted via the substituents.

In the above formula (a1-10), 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 substituent may preferably be an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a 1-naphthyl group and the like.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other and form a ring together with the carbon atoms bonded thereto. R ¹⁰¹ and R ^102, R ¹⁰² of the case ^103, or R ¹⁰³ and R ¹⁰¹ bonded ring structures such as R include: cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantyl and Tetrahydropyranyl and the like.

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

A commercially available product may be used as the radical polymerizable monomer for forming a structural unit containing the protective carboxyl group represented by the above formula (a1-10), or may 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, and the content thereof is incorporated into the specification of the present application.

The first preferred aspect of the structural unit (a1-1-1) is a structural unit represented by the following general formula (A2').

[11]

(In the formula (A2'), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² represents an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may also be bonded to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an extended aryl group)

When R ¹ and R ² are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. 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.

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

General formula (1-12) [Chemical 12]

(In the formula (1-12), R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenyl group, and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or a carbon number of 1 to 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 (a1-1-1) can exemplify the following structural unit. Further, in the following structural unit, R represents a hydrogen atom or a methyl group.

<<<(a1-1-2) Structural unit having a phenolic hydroxyl group protected by an acid-decomposable group>>>

The structural unit (a1-1-2) is a structural unit (a1-1-2-1) having a phenolic hydroxyl group protected by a structural unit having a phenolic hydroxyl group by an acid-decomposable group described in detail below. .

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

The structural unit having a phenolic hydroxyl group may be a structural unit in a hydroxystyrene structural unit or a novolak-based resin, and among these, from the viewpoint of sensitivity, it is preferably derived from hydroxystyrene or α-A. A structural unit of a hydroxystyrene. Further, from the viewpoint of sensitivity, the structural unit having a phenolic hydroxyl group is also preferably a structural unit represented by the following formula (a1-20).

General formula (a1-20)

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

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

Further, R ²²¹ represents a single bond or a divalent linking group. 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, and a is preferably 1 or 2, and more preferably a is 1 in terms of the effect of the present invention or the ease of production.

Further, when the bonding position of the hydroxyl group on the benzene ring is based on the carbon atom bonded to R ²²¹ (1 position), it 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 t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like. . 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.

<<<< Acid decomposable group available for structural unit (a1-1-2)>>>>

The acid-decomposable group which can be used for the structural unit (a1-1-2) can be used in the same manner as the acid-decomposable group which can be used for the structural unit (a1-1-1), and Specially limited. In the acid-decomposable group, it is preferred to have an acetal from the viewpoint of basic physical properties of the photosensitive resin composition, particularly sensitivity or pattern shape, storage stability of the photosensitive resin composition, and formation of contact pores. Protected structural unit that protects phenolic hydroxyl groups. Further, in the acid-decomposable group, it is more preferable to protect the phenolic hydroxyl group from the phenolic hydroxyl group in the form of the acetal represented by the above formula (a1-10) from the viewpoint of sensitivity. Further, in the case of protecting the phenolic hydroxyl group in the form of the acetal represented by the above formula (a1-10), the protective phenolic hydroxyl group is generally -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 structural unit having a phenolic hydroxyl group which protects a phenolic hydroxyl group in the form of an acetal is described, for example, in Paragraph No. 0044 of JP-A-2011-215590.

Among these, 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-cyclohexyloxy Ethyl ethyl, 1-(2-cyclohexylethoxy)ethyl, 1-benzyl Ethoxyethyl or the like, these may be used alone or in combination of two or more.

A commercially available product may be used as the radical polymerizable monomer for forming the structural unit (a1-1-2), or may be synthesized by a known method. For example, the synthesis can be carried out by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The synthesis may also cause a monomer having a phenolic hydroxyl group to be copolymerized with another monomer in advance, and then reacted with a vinyl ether in the presence of an acid catalyst.

The preferred specific examples of the structural unit (a1-1-2) may exemplify the following structural units, but the present invention is not limited to the structural units.

[Chemistry 16]

<<<The preferred aspect of structural unit (a1-1)>>>

In the case where the polymer containing the structural unit (a1-1) is substantially free of the structural unit (a1-2), the content of the structural unit (a1-1) in the polymer is preferably 20 mol% (Mo The percentage of the ear is ~100 mol%, more preferably 30 mol% to 90 mol%.

In the case where the polymer containing the structural unit (a1-1) contains the structural unit (a1-2), the content of the structural unit (a1-1) is preferably in the polymer from the viewpoint of sensitivity. 3 mol% to 70 mol%, more preferably 10 mol% to 60 mol%. Further, in particular, in the case where the acid-decomposable group which can be used for the structural unit (a1) has a structural unit protecting a carboxyl group in the form of an acetal, it is preferably 20 mol%. ~50mol%.

The structural unit (a1-1-1) has a feature of faster development than the structural unit (a1-1-2). Therefore, in the case of rapid development, the structural unit (a1-1-1) is preferred. On the other hand, in the case where the development is to be slow, it is preferable to use the structural unit (a1-1-2).

<<(a1-2) Structural unit having a crosslinkable group>>

(A-1) The polymer component contains a structural unit (a1-2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which causes a curing reaction by heat treatment. Preferred examples of the structural 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 a carbon number of 1 to 20). The structural 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 polymer component (A-1) preferably contains a structural unit having at least one of an epoxy group and an oxetanyl group. More specifically, the following structural unit is mentioned.

<<<(a1-2-1) structural unit having an epoxy group and/or oxetanyl group>>>

The (A-1) polymer component preferably contains a structural unit having an epoxy group and/or an oxetanyl group (hereinafter also referred to as a structural unit (a1-2-1)).

The structural unit (a1-2-1) may have at least one of an epoxy group or an oxetanyl group in one structural unit, and may have one or more epoxy groups and one The above oxetanyl group, 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 groups and/or oxygen. The heterocyclic butyl group preferably has one or two epoxy groups and/or oxetanyl groups in total, and further preferably has one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer for forming a structural unit having an epoxy group include, for example, 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-epoxycyclohexyl acrylate Ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexylmethyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidol Ether, p-vinylbenzyl glycidyl ether, the alicyclic epoxy skeleton-containing compound described in Paragraph No. 0031 to Paragraph No. 0035 of Japanese Patent No. 4,184,843, etc., which are incorporated herein by reference. in.

Specific examples of the radical 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. The butyl (meth) acrylate or the compound described in Paragraph No. 0027 of JP-A-2012-088459 is incorporated herein by reference.

A specific example of the radical polymerizable monomer for forming the structural unit (a1-2-1) having an epoxy group and/or an oxetanyl group is preferably a monomer having a methacrylate structure, A monomer containing an acrylate structure.

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

A preferred specific example of the structural unit (a1-2-1) can exemplify the following structural unit. Further, in the following structural unit, R represents a hydrogen atom or a methyl group.

<<<(a1-2-2) Structural unit having an ethylenically unsaturated group>>>

One of the structural units (a1-2) having a crosslinkable group may be a structural unit (a1-2-2) having an ethylenically unsaturated group. The structural unit (a1-2-2) is preferably a structural unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal, and having a side chain having a carbon number of 3 to 16. Structural unit.

In addition, as for the structural unit (a1-2-2), the description and date of paragraph number 0072 to paragraph number 0090 of JP-A-2011-215580 can be cited. The compounds described in Paragraph No. 0013 to Paragraph No. 0031 of JP-A-2008-256974 are preferred, and the contents are incorporated into the specification of the present application.

<<<(a1-2-3) Structural 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 (A-1) polymer component used in the present invention is also preferably a structural unit having a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) (a1) -2-3). By containing the structural unit (a1-2-3), a hardening reaction can be caused by a slow heat treatment, and a cured film excellent in various 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 structural unit (a1-2-3) is more preferably a structural unit having a group represented by the following formula (a2-30).

General formula (a2-30)

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

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

<<<Preferred aspect of structural unit (a1-2) having crosslinkable group>>>

In the case where the polymer containing the structural unit (a1-2) is substantially free of the structural unit (a1-1), the content of the structural unit (a1-2) is preferably from 5 mol% to 90 mol in the polymer. %, more preferably 20 mol% to 80 mol%.

In the case where the polymer containing the structural unit (a1-2) contains the structural unit (a1-1), in the polymer, from the viewpoint of chemical resistance, the structural unit (a1-2) The content is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%.

In the present invention, in any of the structural units of the (A-1) polymer component, the content of the structural unit (a1-2) is preferably from 3 mol% to 70 mol%, more preferably 10 mol%. ~60mol%.

By setting it as the said numerical value, the hardening film which is excellent in various characteristics can be formed.

<<(a1-3) Other structural units>>

In the present invention, the polymer component (A-1) may contain other structural units other than the structural unit (a1-1) and/or the structural unit (a1-2). (a1-3). The structural unit (a1-3) may also be contained in the polymer (1) and/or the polymer (2). Further, it may be different from the polymer (1) or the polymer (2) and further contain substantially no structural unit (a1-1) and structural unit (a1-2) and contain other structural units (a1- 3) polymer.

The monomer forming the other structural unit (a1-3) is not particularly limited, and examples thereof include styrene, alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, and (meth)acrylic acid. Aryl ester, 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 described later, a structural unit having an acid group may also be contained. The monomers forming the other structural unit (a1-3) may be used alone or in combination of two or more.

Specifically, the structural unit (a1-3) may be exemplified by structural units derived from styrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, methoxy group. Styrene, ethoxystyrene, chlorostyrene, methyl benzoate, ethyl vinyl benzoate, 4-hydroxypropenyl propyl 4-hydroxybenzoate, (methyl) Acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) ) 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isodecyl (meth) acrylate, (meth) propylene hydrazino, N-cyclohexyl maleimide, acrylonitrile, ethylene Alcohol monoacetic acid 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 characteristics, the other structural unit (a1-3) is preferably a styrene group or a group having an aliphatic cyclic skeleton. Specific examples thereof include styrene, methyl styrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isodecyl (meth)acrylate. , benzyl (meth) acrylate and the like.

Further, from the viewpoint of adhesion, the other structural unit (a1-3) is 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.

As the other structural unit (a1-3), it is preferred to contain a repeating unit containing an acid group. The effect of the present invention can be more effectively exhibited by containing an acid group and easily dissolving in an alkaline developing solution. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer in the form of a structural unit containing an acid group using a monomer capable of forming an acid group. By containing such a structural unit containing an acid group 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 an acid group derived from a carboxylic acid group, an acid group derived from a sulfonylamino group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, and a phenol derived from a phenol group. The acid group of the hydroxyl group, the sulfonylamino group, the sulfonyl fluorenylene group or the like is preferably an acid group derived from a carboxylic acid group and/or an acid group derived from a phenolic hydroxyl group.

The acid group-containing structural unit used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth)acrylic acid and/or an ester thereof. For example, Japanese Patent Laid-Open No. 2012-88459 can be used. The compounds described in paragraph number 0021 to paragraph number 0023 and paragraph number 0029 to paragraph number 0044 are incorporated in the specification of the present application. Among them, a structural unit derived from p-hydroxystyrene, (meth)acrylic acid, maleic acid or maleic anhydride is preferred.

The introduction method of the repeating unit containing an acid group can be introduced into the same polymer as (a1-1) structural unit and/or (a1-2) structural unit, and can also be combined with (a1-1) structural unit and (a1-2) Form introduction of structural units of polymers having different structural units.

Such a polymer is preferably a resin having a carboxyl group in a side chain. For example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836 A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, a maleic acid copolymer, or a partially esterified horse as described in each of the publications of Japanese Laid-Open Patent Publication No. SHO 59-71048 An acid-based 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 having a (meth)acryl fluorenyl group in a side chain. The polymer is preferred.

For example, benzyl (meth)acrylate/(meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, Japanese patent 2-Hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-benzene acrylate described in JP-A-7-140654 Oxypropyl propyl ester / polymethyl methacrylate macromonomer / methacrylic acid Benzyl ester/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polyphenylene Ethylene 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, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. 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 with commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above is Cray Valley), and ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above is manufactured by East Asia Synthetic Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, BASF) and the like.

In the present invention, in particular, from the viewpoint of sensitivity, a structural unit containing a carboxyl group or a structural unit containing a phenolic hydroxyl group is preferable. For example, the compounds described in Paragraph No. 0021 to Paragraph No. 0023 and Paragraph No. 0029 to Paragraph No. 0044 of JP-A-2012-88459 can be used, and the contents thereof are incorporated in the present application. In the case description.

The structural unit containing an acid group is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, even more preferably from 5 mol% to 40 mol%, even more preferably from 5 mol% to 30 mol%, of the structural unit of all the polymer components. It is particularly preferably from 5 mol% to 25 mol%.

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

(First embodiment)

The polymer (1) further contains one or two or more kinds of other structural units (a1-3).

(Second embodiment)

The polymer containing (a1-1) a structural unit having a group having an acid group which is protected by an acid-decomposable group in the polymer (2) further contains one or more kinds of other structural units (a1-3). kind.

(Third embodiment)

The polymer containing (a1-2) a structural unit having a crosslinkable group in the polymer (2) further contains one or two or more kinds of other structural units (a1-3).

(Fourth embodiment)

In any of the first to third embodiments, at least the structural unit containing an acid group is included as the other structural unit (a1-3).

(Fifth Embodiment)

Different from the polymer (1) or the polymer (2), it further contains substantially no structural unit (a1-1) and structural unit (a1-2) and contains other structural units (a1-3). The aspect of the polymer.

(Sixth embodiment)

A form including two or more combinations of the first embodiment to the fifth embodiment.

In the aspect containing a polymer substantially containing no (a1-1) and (a1-2) and containing other structural unit (a1-3), (a1-1) and/or (a1-2) are contained. The weight ratio of the total amount of the polymer to the total amount of the polymer substantially not containing (a1-1) and (a1-2) and containing the other structural unit (a1-3) is preferably 99:1 to 5: 95, preferably 97:3~30:70, and then 95:5~50:50.

The composition of the first aspect of the present invention preferably contains (A-1) a polymer component in a proportion of 70% by mass or more of the solid content of the composition.

<<(A-1) Molecular Weight of Polymer Composition>>

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

(A-1) The weight average molecular weight and the degree of dispersion of the polymer component are defined as polystyrene-converted values measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer component can be, for example, by using HLC-8120 (manufactured by Tosoh Corporation), using TSK gel Multipore HXL-M (Dongcao) ), manufactured, 7.8mm ID × 30.0cm) as a column and using tetrahydrofuran (Tetrahydrofuran, THF) was obtained as a washing liquid.

<<(A-1) Method for Producing Polymer Component>>

Further, various methods are also known for the synthesis method of the (A-1) polymer component. When an example is given, the synthesis can be carried out by using a radical polymerization initiator in an organic solvent to at least The radically polymerizable monomer mixture containing the radical polymerizable monomer for forming the structural unit represented by the above (a1-1) and the above (a1-3) is polymerized. Further, it is also possible to carry out the synthesis by a so-called polymer reaction.

Further, for example, a molecular weight modifier such as pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate) or α-methylstyrene dimer may be used.

The polymer (A-1) preferably contains 50 mol% or more of a structural unit derived from (meth)acrylic acid and/or an ester thereof, and more preferably contains 80 mol% or more of a (meth)-based (meth) group. a structural unit of acrylic acid and/or its ester.

<(B-1) Photoacid generator>

The photosensitive resin composition of the present invention contains (B-1) a photoacid generator. The photoacid generator used in the present invention is preferably a compound which generates an acid by an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and its chemical structure is not limited. In addition, the photoacid generator which does not directly induce actinic rays having a wavelength of 300 nm or more can be combined with a sensitizer by using an actinic ray having a wavelength of 300 nm or more and a compound which generates an acid by using it together with a sensitizer. It is preferably used. 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 produces 2 The following acid photoacid generator.

Examples of the photoacid generator include trichloromethyls-triazines, phosphonium salts or phosphonium salts, quaternary ammonium salts, diazomethane compounds, sulfhydryl sulfonate compounds, and sulfonate compounds. Among these, from the viewpoint of insulating properties, an oxime sulfonate compound and a quinone sulfinate compound are preferably used, and an oxime sulfonate compound is more preferably used. These photoacid generators may be used alone or in combination of two or more.

Specific examples of trichloromethyl-s-triazines, diarylsulfonium salts, triarylsulfonium salts (for example, the following compounds), quaternary ammonium salts, and diazomethane derivatives can be exemplified by Japanese Patent Laid-Open No. 2011- The compound described in Paragraph No. 0083 to Paragraph No. 0088 of 221494 is 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 (B1-1).

General formula (B1-1)

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

In the general formula (B1-1), any of the groups may be substituted, and the alkyl group of R ²¹ may be linear or branched or cyclic. The permissible 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 halogen atom, 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). The bridged alicyclic group, preferably a bicycloalkyl group, etc., 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 compound containing the oxime sulfonate structure represented by the above formula (B1-1) is also preferably an oxime sulfonate compound represented by the following formula (B1-2).

General formula (B1-2) [Chem. 22]

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

The preferred range of R ^{42 is} the same as the preferred range of R ²¹ .

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

M4 is preferably 0 or 1. In the above formula (B1-2), 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, 7, 7 a compound of dimethyl-2-oxo norbornylmethyl or p-tolylmethylhydrazine.

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

General formula (B1-3)

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

R ⁴³ in the formula (B1-3) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, Perfluoro-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, especially 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 (B1-3) and specific examples of the preferred oxime sulfonate compound can be referred to the description of paragraph number 0080 to paragraph number 0082 of JP-A-2012-163937. The contents thereof are incorporated into the specification of the present application.

The compound containing the oxime sulfonate structure represented by the above formula (B1-1) 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 or a cyano group. , aryl or heteroaryl. R ¹⁰² represents an alkyl group or an aryl group.

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

R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an 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 or an alkyl group, and further preferably, a form 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 group may further have a substituent.

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

Specific examples of the compound represented by the above formula (OS-1) which can be preferably used in the present invention include the compounds described in Paragraph No. 0128 to Paragraph No. 0132 of JP-A-2011-221494. The 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 (B1-1) is preferably a compound of the following formula (OS-3), the following formula (OS-4) or the following An oxime sulfonate compound represented by the formula (OS-5).

(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)

For the general formula (OS-3) to the general formula (OS-5), for example, the description of Paragraph No. 0098 to Paragraph No. 0115 of JP-A-2012-163937 can be referred to, and the contents thereof are incorporated in the present application. In the case description.

In addition, the compound containing the oxime sulfonate structure represented by the above formula (B1-1) is, for example, preferably the formula (OS-6) described in Paragraph No. 0117 of JP-A-2012-163937. A compound represented by any one of the formula (OS-11), the contents of which are incorporated in the specification of the present application.

The preferred range of the general formula (OS-6) to the general formula (OS-11) and the (OS-6) described in paragraphs 0110 to 0112 of JP-A-2011-221494 The preferred ranges of ~(OS-11) are the same, and the contents thereof are incorporated into the specification of the present application.

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

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

General formula (B1-4)

(In the formula (B1-4), R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group, an aryl group or a heteroaryl group. R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom. Wherein R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ⁶ may also 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. Especially in the case where the alkyl group has a branched structure In the case of having a cyclic structure, an alkyl group having 3 to 6 carbon atoms is preferred, and an alkyl group having 5 to 7 carbon atoms is preferred.

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 further preferably from 6 to 7. The aryl group may, for example, be a phenyl group or a naphthyl group, and is preferably a phenyl group.

The alkyl group and the aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear, branched or cyclic alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, and 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.

The photosensitive resin composition of the present invention in terms of the viewpoint of transparency, R ¹ is preferably an alkyl group, on both the storage stability and in terms of sense, R ¹ is preferably branched having a carbon number of 3 to 6 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, and ring. The hexyl group is more preferably a tributyl group or a cyclohexyl group.

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 substituent which the alkyl group and the aryl group represented by R ¹ may have.

R ^{2 is} preferably an alkyl group or an aryl group, more preferably an aryl group, and further 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 or 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 to form a benzene ring. More preferably, it is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ^{6 are} bonded to each other to form a benzene ring.

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

(Stage 1) At least two are hydrogen atoms.

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

(Stage 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 aspect 1 and the aspect 2 is satisfied and/or the aspect of the aspect 1 and the aspect 3 is satisfied.

X represents -O- or -S-.

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

[化27]

As the liminium sulfonate compound to be used as the photoacid generator, a ruthenium sulfonate compound having a structure represented by the following formula (B1-5) can be preferably used.

[化28]

(In the formula (B1-5), R ²⁰⁰ represents a monovalent organic group having 16 or less carbon atoms. The wave line indicates a bond with another group)

R ²⁰⁰ represents a monovalent organic group having 16 or less carbon atoms. R ²⁰⁰ preferably contains only C, H, O, F. Examples of R ²⁰⁰ include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a toluenesulfonyl group.

A preferred aspect of the compound containing the structure represented by the formula (B1-5) is an oximine sulfonate compound represented by the following formula (I).

In the formula (I), R ¹ and R ² each represent a group represented by the following formula (A) or a hydrogen atom. R ³ represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted by any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group; any one which may pass through a halogen atom, an alkylthio group, an alkyl group and a fluorenyl group More than one substituted aryl group having 6 to 20 carbon atoms; an aralkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom and/or an alkylthio group; 10-camphoric group or represented by the following formula (B) base.

In the formula (A), X ¹ represents an oxygen atom or a sulfur atom, Y ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, and R ⁵ represents a carbon number of 1 to 2. The alkyl group of 4, R ⁶ represents a hydrogen atom, a branched alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a heterocyclic group or a hydroxyl group. n represents an integer of 0 to 5, and when n is 2 to 5, a plurality of R ^{5 's} may be the same or different.

In the formula, X ¹ represents an oxygen atom or a sulfur atom, Y ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, R ¹¹ represents a hydrocarbon group having 1 to 12 carbon atoms, and R ¹² represents an alkane having 2 to 4 carbon atoms. Further, R ¹³ represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a heterocyclic group which may have a branch, m represents 0 to 5, and m is 2 to 5 In the meantime, a plurality of R ^{12 's} may be the same or different.

In the formula (B), Y ² represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ⁷ represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkyl group having 2 to 6 carbon atoms, and a carbon number of 6 ~20 of an aryl group or a halogenated aryl group having a carbon number of 6 to 20, R ⁸ represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkyl group having 2 to 6 carbon atoms, and a carbon number of 6 to 20 An aryl group or a halogenated aryl group having 6 to 20 carbon atoms, R ⁹ represents a branchable alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms, and a carbon number of 6 to 20 An aryl group, a halogenated aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a halogenated aralkyl group having 7 to 20 carbon atoms. a and b each independently represent 0 or 1, and at least one of a and b is 1.

For the general formula (I), for example, the description of Paragraph No. 0019 to Paragraph No. 0063 of International Publication WO11/087011 can be referred to, and the contents thereof are incorporated in the present specification. The compound represented by the formula (I) can, for example, be exemplified by the following compounds. Further, in addition to the compounds exemplified below, the description of Paragraph No. 0065 to Paragraph No. 0075 of International Publication WO11/087011 can be referred to, and the contents thereof are incorporated in the present specification.

In the photosensitive resin composition of the present invention, the content of the (B-1) photoacid generator is preferably from 0.1 part by mass to 20 parts by mass, more preferably 100 parts by mass based on the total solid content of the photosensitive resin composition. It is 0.5 parts by mass to 10 parts by mass, and more preferably 0.5 parts by mass to 5 parts by mass. The photoacid generator may be used singly or in combination of two or more.

<(C-1) solvent>

The photosensitive resin composition of the present invention contains (C-1) a solvent. The photosensitive resin composition of the present invention is preferably prepared by dissolving an essential component of the present invention and further optional components described later in a solvent. As the solvent for preparing the composition of the present invention, a solvent which uniformly dissolves an essential component and an optional component and does not react with each component can be used.

A known solvent can be used as the solvent to be used in the photosensitive resin composition of the present invention, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl ether acetates. Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl groups Ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. Further, a specific example of the solvent to be used in the photosensitive resin composition of the present invention is a solvent described in Paragraph No. 0174 to Paragraph No. 0178 of JP-A-2011-221494, and JP-A-2012-194290. The solvent described in paragraph number 0167 to paragraph number 0168 is incorporated into the specification of the present application.

Further, among these solvents, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and different Buddha may be further added as needed. Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethyl carbonate , a solvent such as propylene carbonate. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably one alone or two, more preferably two, and it is preferred to use propylene glycol monoalkyl ether acetate or dialkyl ether, diacetate and diethyl Diol dialkyl ethers, or esters and butanediol alkyl ether acetates.

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 ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160) °C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene Alcohol 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 in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, more preferably 60 parts by mass to 90 parts by mass, per 100 parts by mass of all the components in the photosensitive resin composition. The solvent may be used singly or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof becomes the above range.

<(S) a compound represented by the formula (1) and/or a compound represented by the formula (2)>

The composition of the present invention contains a compound represented by the formula (1) and/or the following formula (2) (also referred to as a component (S)).

General formula (1)

(In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. L ¹ represents a single bond or a divalent linking group. X ¹ represents - S- or -NH-, R ³ represents a monovalent organic group)

R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. R ¹ and R ² preferably represent the same group.

n represents an integer of 0 to 2, preferably an integer of 0 or 1, more preferably 0.

L ¹ represents a single bond or a divalent linking group, and is preferably a divalent linking group. Examples of the divalent linking group include an alkylene group and an extended aryl group, and an alkylene group is preferred.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 3 to 5 carbon atoms. The alkylene group may have a substituent, but is preferably unsubstituted. Specific examples of the alkylene group include: methylene, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, thiol, decyl Wait.

As the aryl group, a aryl group having a carbon number of 6 to 20 is preferred, and an aryl group having a carbon number of 6 to 10 is more preferred. Specifically, a phenyl group, a naphthyl group, etc. are mentioned.

Further, the alkylene group and the extended aryl group may contain an ether oxygen atom to form an alkyleneoxy group and an extended aryloxy group.

X ¹ represents -S- or -NH-, preferably -NH-.

R ³ represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy group. Among them, an alkyl group or an aryl group is preferred.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group and the like.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group and the like.

The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms. Specifically, a methoxy group, an ethoxy group, a propoxy group, and an isopropyl group are mentioned. Oxyl, butoxy, tert-butoxy, pentyloxy and the like.

The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms. Specific examples thereof include a phenoxy group, a 2-methylphenoxy group, a 4-tert-butylphenoxy group, a 3-nitrophenoxy group, a 2-tetradecylaminophenoxy group, and the like.

The decyloxy group is preferably a methoxycarbonyl group, an alkylcarbonyloxy group having 2 to 30 carbon atoms, or an arylcarbonyloxy group having 6 to 30 carbon atoms. Specific examples thereof include an ethoxycarbonyl group, a trimethylacetoxy group, a hard methoxy group, a phenyl decyloxy group, a p-methoxyphenylcarbonyloxy group, and the like.

The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 30 carbon atoms. Specific examples thereof include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.

The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 30 carbon atoms. Specific examples thereof include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a p-hexadecaneoxyphenoxycarbonyloxy group, and the like.

The monovalent organic group represented by R ³ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear, branched or cyclic alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, and 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.

General formula (2) [34]

(In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. L ² represents a single bond or a divalent linking group. X ² represents - S- or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom)

R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, and have the same meanings as R ¹ and R ² in the formula (1), and the preferred ranges are also the same.

n represents an integer of 0 to 2, and has the same meaning as n in the general formula (1), and the preferred range is also the same.

L ² represents a single bond or a divalent linking group, and has the same meaning as L ¹ in the formula (1), and the preferred range is also the same.

X ² represents -S- or -NH- and has the same meaning as X ¹ in the formula (1), and the preferred range is also the same.

A represents a hetero ring containing a carbon atom and a nitrogen atom. The hetero ring containing a carbon atom and a nitrogen atom may be aromatic or non-aromatic, and is usually an aromatic hetero ring. The hetero ring containing a carbon atom and a nitrogen atom may further contain a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom in addition to the nitrogen atom. Further, the heterocyclic ring may be either a monocyclic ring or a condensed ring, but is preferably a single ring. The heterocyclic ring is preferably a 3-membered ring to a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring.

Specific examples thereof include a pyridyl group, a thiazolyl group, and a 2-furyl group. A thienyl group, a pyrimidinyl group, a benzothiazolyl group, a morpholinyl group, a pyrrolyl group, a fluorenyl group, a carbazolyl group, a furan group, a thiophene group, and the like.

The hetero ring containing a carbon atom and a nitrogen atom represented by A may have a substituent. The substituent has the same meaning as the substituent which R ³ in the formula (1) may have.

The exemplified compounds of the component (S) used in the present invention are shown below, but the present invention is of course not limited to these compounds. In the formula, Me represents a methyl group and Et represents an ethyl group.

Among these, it is preferably (S-1) to (S-24), more preferably (S-1) to (S-8), and further preferably (S-1) to (S-2).

The compound represented by the formula (1) and/or the compound represented by the formula (2) are more preferably a compound represented by the formula (2).

The molecular weight of the compound represented by the formula (1) and/or the compound represented by the formula (2) is preferably 1,000 or less, more preferably 500 or less, still more preferably 400 or less. The lower limit is not particularly limited and is 100 or more. By setting it as the said range, the effect of this invention is exerted more effectively.

The photosensitive resin composition of the present invention preferably contains the component (S) in an amount of 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass based on the total solid content of the photosensitive resin composition. The ratio (S) is preferably contained in the proportion of (S), and the (S) component is preferably contained in a ratio of from 1% by mass to 10% by mass, and particularly preferably (S) in an amount of from 2% by mass to 5% by mass. The (S) component may be one type or two or more types. When the (S) component is two or more, it is preferred that the total amount is the above range.

<Other ingredients>

In the photosensitive resin composition of the present invention, a sensitizer, a crosslinking agent, a basic compound, a surfactant, and an antioxidant may be preferably added in addition to the above components. Further, in the photosensitive resin composition of the present invention, an acid growth agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, a UV absorber, a thickener, and an organic or inorganic agent may be added. A known additive such as an anti-precipitant. Further, as the compounds, for example, the compounds described in Paragraph No. 0201 to Paragraph No. 0224 of JP-A-2012-88459 can be used, and the contents are incorporated in the specification of the present application. In addition, a decane coupling agent other than the component (S) may be contained, and the amount of the decane coupling agent other than the component (S) may be set to be less than 0.1% by mass of the solid content of the composition of the present invention. These components may be used alone or in combination of two or more.

<<sensitizer>>

The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof when combined with a photoacid generator. Sensitizer absorbs actinic rays and becomes electron excited Status. The sensitizer that is in an electronically excited state is in contact with the photoacid generator, and functions to move electrons, move energy, and generate heat. Thereby, the photoacid generator chemically changes and decomposes to form an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength at any of the wavelength ranges of 350 nm to 450 nm.

Polynuclear aromatics (eg, ruthenium, osmium, triphenylene, ruthenium, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropoxyfluorene), xanthones (eg luciferin, eosin, red algae, rhodamine B, bengal rose), xanthones (eg xanthones, Xanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanines (eg, thiocarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, Carbonyl cyanine), rhodacyanine, oxindole, thiazide (eg thiopurine, methylene blue, toluidine blue), acridine (eg acridine orange, chloroflavin, acridine flavin) ), acridone (such as acridone, 10-butyl-2-chloroacridone), anthraquinones (such as hydrazine), squaric acid guanidines (such as squaric acid ylide), styryl Classes, basic styryl groups (eg 2-[2-[4-(dimethylamino)phenyl]vinyl]benzoxazole), coumarins (eg 7-diethylamino) 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[1]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.

When the photosensitive resin composition of the present invention contains a sensitizer, the phase The amount of the sensitizer added is preferably from 0.001 part by mass to 100 parts by mass, more preferably from 0.1 part by mass to 50 parts by mass, even more preferably from 0.5 part by mass to 100 parts by mass of the total solid content in the photosensitive resin composition. 20 parts by mass. The sensitizer may be used in combination of two or more.

<<Crosslinker>>

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

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

In the case where the photosensitive resin composition of the present invention contains a crosslinking agent, the amount of the crosslinking agent added is preferably from 0.01 part by mass to 50% by mass based on 100 parts by mass of the total of the (A-1) polymer component. The portion is more preferably 0.1 part by mass to 30 parts by mass, and further preferably 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 can be 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.

<<<Compounds 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 a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenol novolak type epoxy resin. A cresol novolac type epoxy resin, an aliphatic epoxy resin, or the like.

These can be obtained as a commercial item. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc., and the commercial products described in Paragraph No. 0189 of JP-A-2011-221494 Etc. In addition, there are also: Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Dina 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, Dinaco Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX- 841, Denacol EX-911, Denacol EX-941, Denacol E X-920, Denacol EX-931, Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Dina Denacol EX-321L, Denacol EX-850L, Denacol DLC-201, Denacol DLC-203, Denacol DLC -204, Denarcourt (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 is Nippon Steel Chemical Manufacturing). These commercially available products may be used alone or in combination of two or more.

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

Specific examples of the compound having two or more oxetanyl groups in the molecule include: 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 oxetanyl group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.

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 into the specification of the present application. The alkoxymethyl group-containing crosslinking agent is preferably an alkoxymethylated glycoluril.

<<<Seal blocked isocyanate compound>>>

In the photosensitive resin composition of the present invention, it is also preferred to use blocked isocyanic acid. An ester compound is used as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound other than the compound represented by the above formula (S1) and has a blocked isocyanate group. From the viewpoint of curability, it is preferably two or more in one molecule. A compound that blocks an isocyanate group.

Further, the skeleton of the blocked isocyanate compound is not particularly limited, and may be any compound as long as it has two isocyanate groups in one molecule, and may be an aliphatic, alicyclic or aromatic polyisocyanate, and can be preferably used, for example. : 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetra Methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1 , 10-methylene 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'- Isocyanate compounds such as phenyl ether diisocyanate, tetrachlorobenzene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylene diisocyanate, hydrogenated 1,4-xylene diisocyanate, and prepolymers derived from the compounds a type of skeleton compound. Among these, it is especially preferably toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI).

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

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

The hydrazine compound may be exemplified by hydrazine and ketoxime, and specific examples thereof include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, Acetone oxime and the like.

The 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.

The amine compound may be exemplified by 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, ethylenimine, and polyethylene. Imine and the like.

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

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

The thiol compound can be exemplified by an alkyl thiol, an aryl thiol 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 commercially available product, and for example, Coronate AP stable M, Croonate can be preferably used. 2503, Coronate 2515, Coronate 2507, Coronate 2513, Coronate 2555, Millionate MS-50 (above Made by Japan Polyurethane Industry Co., Ltd., 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 Mitsui Chemical (manufacturing), Duranate 17B-60PX, Duranate 17B-60P, Duranate TPA-B80X, Duranate TPA-B80E , Duranate MF-B60X, Duranate MF-B60B, Duranate MF-K60X, Duranate MF-K60B, Durantite Duranate) E402-B80B, Duranate SBN-70D Duranate SBB-70P, Duranate K6000 (above is manufactured by Asahi Kasei Chemicals Co., Ltd.), Desmodule BL1100, Desmodule BL1265 MPA/X, Germany Desmodule BL3575/1, Desmodule BL3272MPA, Desmodule BL3370MPA, Desmodule BL3475BA/SN, Desmo (Desmodule) BL5375MPA, Desmodule VPLS2078/2, Desmodule BL4265SN, Desmodule PL340, Desmodule PL350, Sumidule BL3175 (above) Manufactured by Bayeramine (manufacturing) and the like.

<<Alkaline compound>>

The photosensitive resin composition of the present invention may also contain a basic compound. The basic compound can be arbitrarily selected from those 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, triethanolamine, and dicyclohexylamine. , dicyclohexylmethylamine, and the like.

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

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

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, benzyltrimethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetrahydric hydroxide. N-hexyl ammonium and the like.

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

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

When the photosensitive resin composition of the present invention contains a basic compound, the content of the basic compound is preferably 0.001 parts by mass to 3 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition. Preferably, it is 0.005 parts by mass to 1 part by mass.

<<Interfacial active agent>>

The photosensitive resin composition of the present invention may also contain a surfactant. The surfactant may be any of an anionic, cationic, nonionic or amphoteric, but a preferred surfactant is a nonionic surfactant. The surfactant used in the composition of the present invention can be, for example, those described in paragraph number 0201 to paragraph number 0205 of JP-A-2012-88459, or paragraph number 0185 of JP-A-2011-215580. The ones described in paragraph number 0188 are incorporated into the specification of the present application.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylidene higher alkylphenyl ethers, and higher fatty acid esters of polyoxyethylene glycol. An ester, an anthrone or a fluorine-based surfactant. In addition, it can be listed by the following product names: KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), Ai Eftop (manufactured by Mitsubishi Materials Chemical Co., Ltd.), Megafac (made by DiCai (DIC) Co., Ltd.), and Fluorad Novec FC-4430 (Sumitomo 3M (share) manufacturing) ), Surflon S-242 (made by AGC Seimi Chemicals), PolyFox PF-6320 (made by OMNOVA), SH-8400 (East) Toray-Dow corning silicone, Ftergent FTX-218G (manufactured by Neos), and the like.

In addition, the gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent is exemplified. A copolymer having a weight average molecular weight (Mw) in terms of polystyrene of 1,000 or more and 10,000 or less is preferably used.

General formula (I-1-1)

(In the formula (I-1-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon. An alkyl group having 1 or more and 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, q A numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.

The L is preferably a branched alkyl group represented by the following formula (I-1-2). R ⁴⁰⁵ in the formula (I-1-2) 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. Further, 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.

General formula (I-1-2)

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

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

When the photosensitive resin composition of the present invention contains a surfactant, the phase The amount of the surfactant added is preferably 10 parts by mass or less, more preferably 0.001 parts by mass to 10 parts by mass, even more preferably 0.01 parts by mass to 3 parts by mass per 100 parts by mass of the total solid content of the photosensitive resin composition. .

<<Antioxidants>>

The photosensitive resin composition of the present invention may also contain an antioxidant. The antioxidant may contain a well-known antioxidant. By adding an antioxidant, it is possible to prevent the coloration of the cured film, or to reduce the film thickness reduction by decomposition, and to have excellent heat-resistant transparency.

Examples of such an antioxidant include phosphorus-based antioxidants, guanamines, guanidines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, saccharides, nitrites, and sub- Sulfate, thiosulfate, hydroxylamine derivative, and the like. Among these, from the viewpoint of coloring and thinning of the cured film, a phenolic antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, a guanamine antioxidant, and a lanthanide antioxidant are particularly preferable. A sulfur-based antioxidant, preferably a phenolic antioxidant. These antioxidants may be used alone or in combination of two or more.

Specific examples include the compound described in Paragraph No. 0026 to Paragraph No. 0031 of JP-A-2005-29515, and the compound described in Paragraph No. 0106 to Paragraph No. 0116 of JP-A-2011-227106. This content is incorporated into the specification of the present application.

Preferred commercial products include: Adekastab AO-60, Adekastab AO-20, Adekastab AO-80, Eddie Costap (Adekastab) LA-52, Eddie Costabo (Adekastab) LA-81, Adekastab AO-412S, Adekastab PEP-36, Irganox 1035, Irganox 1098, Di Nubin (Tinuvin) 144.

In the case where the photosensitive resin composition of the present invention contains an antioxidant, the content of the antioxidant is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 100 parts by mass of the total solid content of the photosensitive resin composition. 0.2 parts by mass to 5 parts by mass, particularly preferably 0.5 parts by mass to 4 parts by mass. By setting it as this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation also becomes favorable.

<<acid proliferator>>

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

The acid-proliferating 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.

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

<<Developing accelerator>>

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

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

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

When the photosensitive resin composition of the present invention contains a development accelerator, the amount of the development accelerator is preferably added to 100 parts by mass of the total solid content of the photosensitive composition from the viewpoint of sensitivity and residual film ratio. It is 0 parts by mass to 30 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass, most 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, and the nitrogen-containing compound and the thermal acid generator described in WO2011/136074A1 may be used. These are incorporated into the specification of the present application.

[Second aspect of the invention]

Hereinafter, the second aspect of the composition of the present invention will be described.

The composition of the present invention is characterized by comprising (A-2) a polymer component containing a polymer satisfying at least one of the following (1) and (2), and (1) containing (a2-1) having an acid group. a structural unit, and (a2-2) a polymer having a structural unit having a crosslinkable group, (2) a polymer containing (a2-1) a structural unit having an acid group, and having (a2-2) a crosslinked group a polymer of a structural unit; (B-2) a quinonediazide compound; (S) a compound represented by the formula (1) and/or a compound represented by the formula (2); and (C-2) ) Solvent.

<(A-2) polymer component>

The (A-2) polymer component used in the present invention contains at least one of the following polymers: a polymer containing (a2-1) a structural unit having an acid group and (a2-2) a structural unit having a crosslinkable group. And a polymer containing (a2-1) a structural unit having an acid group and a polymer containing (a2-2) a structural unit having a crosslinkable group. Further, the (A-2) polymer component may contain a polymer other than the above.

<<(a2-1) Structural unit having an acid group>>

By containing (a2-1) a structural unit having an acid group in the polymer component (A-2), it is easily dissolved in an alkaline developing solution, and the effect of the present invention can be more effectively exhibited. The acid group is usually incorporated into the polymer in the form of a structural unit having an acid group using a monomer capable of forming an acid group. When such a structural unit having 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 an acid group derived from a carboxylic acid group, an acid group derived from a sulfonylamino group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, and a phenol derived from a phenol group. The acid group of the hydroxyl group, the sulfonylamino group, the sulfonyl fluorenylene group or the like is preferably an acid group derived from a carboxylic acid group and/or an acid group derived from a phenolic hydroxyl group. The acid group-containing structural unit used in the present invention is particularly preferably a structural unit containing a carboxyl group and/or a phenolic hydroxyl group.

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

From the viewpoint of sensitivity, in the present invention, it is particularly preferred to contain a repeating unit containing a carboxyl group or a repeating unit having a phenolic hydroxyl group. For example, the compounds described in Paragraph No. 0021 to Paragraph No. 0023 and Paragraph No. 0029 to Paragraph No. 0044 of JP-A-2012-88459 can be used, and the contents thereof are incorporated into the specification of the present application.

<<(a2-2) Structural unit having a crosslinkable group>>

Further, the structural unit having a crosslinkable group (a2-2) preferably contains a group selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R is a hydrogen atom or a carbon number of 1 to 20). A structural unit of at least one of a group consisting of a group represented by an alkyl group and an ethylenically unsaturated group.

(a2-2) The structural unit having a crosslinkable group has the same meaning as the structural unit having a crosslinkable group of (a1-2) in the (A-1) polymer described above, except for the blending amount. The range is also the same.

<<(a2-3) Other structural units>>

Further, in the polymer component (A-2), the structural unit (a2-1) and the structure may be contained together with the structural unit (a2-1) and the structural unit (a2-2). Structural unit (a2-3) other than unit (a2-2).

The monomer forming the structural unit (a2-3) is not particularly limited as long as it is an unsaturated compound other than the structural unit (a2-1) and the structural unit (a2-2).

For example, styrene, alkyl (meth)acrylate, (meth)acrylic acid a cyclic alkyl ester, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, a bicyclic unsaturated compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene compound, Other unsaturated compounds. The monomers forming the structural unit (a2-3) may be used alone or in combination of two or more.

(A-2) All structural units of the polymer component preferably contain 3 mol% to 70 mol% of the structural unit (a2-1), more preferably 10 mol% to 60 mol%, and even more preferably 15 mol% to 50 mol. %.

(A-2) All structural units of the polymer component preferably contain 3 mol% to 70 mol% of the structural unit (a2-2), more preferably 10 mol% to 60 mol%, and even more preferably 15 mol% to 40 mol. %.

(A-2) All structural units of the polymer component preferably contain 1 mol% to 80 mol% of the structural unit (a2-3), more preferably 5 mol% to 50 mol%, and even more preferably 8 mol% to 30 mol. %.

The composition of the second aspect of the present invention preferably contains the polymer component (A-2) in a proportion of 70% by mass or more of the solid content of the composition.

<(B-2) 醌diazide compound>

As the quinonediazide compound used in the composition of the present invention, a 1,2-quinonediazide compound which generates a carboxylic acid by irradiation with actinic rays can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and 1,2-naphthoquinonediazidesulfonium halide can be used. Specific examples of such a compound can be referred to, for example, the description of Paragraph No. 0075 to Paragraph No. 0078 of JP-A-2012-088459, the contents of which are incorporated herein by reference.

In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) with a 1,2-naphthoquinonediazidesulfonium halide, the number of OH groups in the phenolic compound or the alcoholic compound can be used to be preferably equivalent. It is 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol% of 1,2-naphthoquinonediazidesulfonium halide. The condensation reaction can be carried out by a known method.

Further, as the 1,2-quinonediazide compound, a 1,2-naphthoquinonediazidesulfonamide which changes the ester bond of the exemplified parent core to a guanamine bond, for example, 2 can also be preferably used. 3,4-Triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide and the like. Alternatively, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1 may also be used. a condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (3.0 mol), 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone a condensate of diazide-5-sulfonyl chloride (2.0 mol), 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5 a condensate of a sulfonate (2.44 mole) or the like.

These quinonediazide compounds may be used alone or in combination of two or more. The amount of the quinonediazide compound in the photosensitive resin composition of the present invention is preferably from 1 part by mass to 50 parts by mass, more preferably from 100 parts by mass of the total solid content in the photosensitive resin composition. 2 parts by mass to 40 parts by mass, and more preferably 10 parts by mass to 25 parts by mass.

By setting the blending amount of the (B-2) quinonediazide compound to the above range, the difference in solubility between the irradiated portion of the actinic ray and the unirradiated portion in the alkaline aqueous solution to be the developing solution is large, and the patterning property is obtained. It became good, and the solvent resistance of the obtained cured film became favorable.

<(S) component>

The composition of the second aspect of the present invention contains the same component (S) as the component (S) in the composition of the first embodiment described above, and the preferred range is also the same.

The (S) component is preferably contained in a ratio of 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, based on the total mass of the photosensitive resin composition of the second embodiment. Further, it is preferably contained in a proportion of from 1% by mass to 10% by mass, and more preferably from 2% by mass to 5% by mass. The (S) component may be one type or two or more types. When the (S) component is two or more, it is preferred that the total amount thereof is in the above range.

<(C-2) Solvent>

The photosensitive resin composition of the present invention contains a solvent. The solvent used in the photosensitive resin composition of the present invention can be the (C-1) solvent of the first aspect described above, and the preferred range is also the same.

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, more preferably 60 parts by mass to 90 parts by mass, per 100 parts by mass of all the components in the photosensitive resin composition. The solvent may be used singly or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof becomes the above range.

<Other ingredients>

In addition to the above components, the composition of the present invention may preferably contain a crosslinking agent, a basic compound, a surfactant, and an antioxidant as needed within the range not impairing the effects of the present invention. Further, in the photosensitive resin composition of the present invention, it is possible to add A known additive such as a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, a UV absorber, a thickener, and an organic or inorganic anti-precipitation agent. These components are the same as the first aspect described above, and the preferred ranges are also the same. In addition, a decane coupling agent other than the component (S) may be contained, and the amount of the decane coupling agent other than the component (S) may be set to be less than 0.1% by mass of the solid content of the composition of the present invention. These components may be used alone or in combination of two or more.

[The third aspect of the composition of the present invention]

The composition of the third aspect of the present invention is characterized by comprising: (A-3) a polymerizable monomer; (B-3) a photopolymerization initiator; (A-4) comprising the following (1) and ( 2) a polymer component of at least one polymer, (1) a polymer comprising (a4-1) a structural unit having an acid group, and (a4-2) a structural unit having a crosslinkable group, (2) a polymer containing (a4-1) a structural unit having an acid group, and a polymer containing (a4-2) a structural unit having a crosslinkable group; (S) a general formula (1) and/or a general formula (2) ) a compound represented; and (C-3) a solvent.

(A-3) Polymerizable monomer

The polymerizable monomer used in the present invention can be appropriately selected and used as a monomer suitable for such a composition, and among them, an ethylenically unsaturated compound is preferably used.

An ethylenically unsaturated compound is a polymer having at least one ethylenically unsaturated double bond Synthetic compound. Examples of the ethylenically unsaturated compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof, guanamines, preferably. An ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound is used.

For example, the components described in paragraph 0011 of JP-A-2006-23696, or the components described in paragraphs 0031 to 0047 of JP-A-2006-64921, the contents of which are incorporated herein by reference. In the case description.

Further, a urethane addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also preferred. Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 2-32293, and Japanese Patent Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. Sho 56-196760, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39417 A urethane compound having an oxirane skeleton described in Japanese Patent Publication No. Sho 62-39418 is also preferred, and the description is incorporated into the specification of the present application.

Other examples include polyester acrylates as described in each of the publications of Japanese Laid-Open Patent Publication No. SHO-49-64183, Japanese Patent Publication No. SHO-49-43191, and Japanese Patent Publication No. Sho 52-30490. A polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by reacting an oxygen resin with (meth)acrylic acid is incorporated in the specification of the present application. Further, a compound which is described as a photocurable monomer and an oligomer in "Japanese Association of Associations" (vol. 20, No. 7, pp. 300-308 (1984)) can also be used.

Regarding the ethylenically unsaturated compound, the details of the structure, the use alone or in combination, the amount of addition, and the like can be arbitrarily set according to the performance design of the final sensitive material. For example, it can be selected according to the following points.

The polymerizable monomer is preferably polyfunctional, more preferably trifunctional or more, and still more preferably tetrafunctional or higher. The upper limit is not particularly present, and the 10-functional or less is more practical. Further, it is also effective to adjust the mechanical properties by using a compound having a different number of functional groups and/or a different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound).

Further, from the viewpoint of adjusting the developability, a carboxyl group-containing polymerizable compound is also preferable. In this case, it is preferred to improve the mechanical properties by crosslinking the resin with the component (C-3).

Further, from the viewpoints of adhesion to a substrate, compatibility with a radical polymerization initiator, and the like, it is also preferable to contain an ethylene oxide (EO (Ethylene Oxide) modified body, an amine group A). Acid ester bond.

From the above viewpoints, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris((A) are preferred. Alkenyloxyethyl)isophthalocyanate, pentaerythritol tetra(meth)acrylate EO modified body, dipentaerythritol hexa(meth)acrylate EO modified body, and the like, and commercially available products KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-TMMT, NK Ester A-TMPT, NK Ester A-TMM-3, NK Oligo UA-32P, NK Oligo UA-7200 (above new) Nakamura Chemical Industry Co., Ltd., Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Asia Aronix M-402, TO-1382 (above is manufactured by East Asia Synthetic Co., Ltd.), V#802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The polymerizable monomer to be used in the present invention is preferably a compound represented by the following formula (A-3-1).

Formula (A-3-1)

In the formula (A-3-1), L represents a divalent or higher linking group. The linking group is not particularly limited, and examples thereof include an alkyl group, a carbonyl group, an imido group, an ether group (-O-), a thioether group (-S-), or a combination thereof. The carbon number of the linking group is not particularly limited, but is preferably 2 to 24, more preferably 2 to 12. Among them, a branched alkyl group having a carbon number is preferred.

In the formula (A-3-1), A represents a polymerizable functional group. The polymerizable functional group is preferably a vinyl group or a vinyl group-containing group. Examples of the vinyl group-containing group include an acryloyl group, a methacryloyl group, an acryloxy group, a methacryloxy group, a vinyl phenyl group, and the like.

In the formula (A-3-1), Ra represents a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 21 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms), and an aryl group (preferably having 6 to 24 carbon atoms). These substituents may further have a substituent, and examples of the substituent which may be exemplified are a hydroxyl group, an alkoxy group (preferably having a carbon number of 1 to 6), a carboxyl group, and the like. Sulfhydryl (preferably carbon number 1 to 6) and the like.

In the formula (A-3-1), na represents an integer of 1 to 10, preferably 3 to 8. Nb represents an integer of 0 to 9, preferably 2 to 7. Na+nb is 10 or less, preferably 2 to 8. When na and nb are 2 or more, the plurality of structural portions defined by the plurality of structures may be different from each other.

The content of the polymerizable monomer is preferably from 5 parts by mass to 60 parts by mass, more preferably from 10 parts by mass to 50 parts by mass, even more preferably from 15 parts by mass to the total of the (A-3) polymer component. Parts by mass to 45 parts by mass.

The photosensitive resin composition of the present invention preferably contains a polymerizable monomer in a proportion of from 5% by mass to 60% by mass, more preferably from 10% by mass to 50% by mass, based on the total solid content. Jia is contained in a ratio of 15% by mass to 45% by mass. The polymerizable monomer may be used alone or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof becomes the above range.

(B-3) Photopolymerization initiator

The photopolymerization initiator which can be used in the present invention is a compound which is photosensitive by actinic rays, which initiates and promotes polymerization of the polymerizable monomer.

The photopolymerization initiator which can be used in the present invention is preferably a compound which is photosensitive by actinic rays, which initiates and promotes polymerization of the ethylenically unsaturated compound.

In the present invention, the "radiation" is not particularly limited as long as it is an energy source capable of imparting energy to the starting species by the component B-3 by irradiation, and broadly includes α rays, γ rays, and X rays. , ultraviolet (UV), visible light, electron beam, etc.

The photopolymerization initiator is a compound which induces and accelerates the polymerization of the (A-3) polymerizable monomer, preferably an actinic ray having a wavelength of 300 nm or more, more preferably 300 nm to 450 nm. In addition, the photopolymerization initiator which does not directly induce actinic rays having a wavelength of 300 nm or more can be combined with a sensitizer as long as it is a compound which induces actinic rays having a wavelength of 300 nm or more by using in combination with a sensitizer. It is preferably used.

The photopolymerization initiator may, for example, be an oxime ester compound or an organic halogenated compound. , oxydiazole compound, carbonyl compound, ketal compound, benzoin compound, acridine compound, organic peroxidation compound, azo compound, coumarin compound, azide compound, metallocene compound, hexaarylbiimidazole compound An organoboric acid compound, a disulfonic acid compound, an alpha aminoketone compound, a phosphonium salt compound, or a mercaptophosphine (oxide) compound. Among these, from the viewpoint of sensitivity, an oxime ester compound, an α-aminoketone compound, and a hexaarylbiimidazole compound are preferable, and an oxime ester compound or an α-aminoketone compound is more preferable.

Specific examples of such compounds can be found in the description of Paragraph No. 0061 to Paragraph No. 0073 of JP-A-2011-186398, the contents of which are incorporated herein by reference.

Commercially available products can also be used as the photopolymerization initiator. For example, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF), or the like can be used.

The photopolymerization initiator may be used alone or in combination of two or more. In addition, when using an initiator that does not absorb the exposure wavelength, sensitization must be used. Agent.

The content of the photopolymerization initiator in the photosensitive resin composition of the present invention is preferably from 0.5 part by weight to 30 parts by weight, more preferably 2, based on 100 parts by mass of the total of the (A-3) polymer component. Parts by weight to 20 parts by weight.

The photosensitive resin composition of the present invention preferably contains a photopolymerization initiator in a proportion of 0.5% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, based on the total solid content.

(A-4) Polymer composition

The (A-4) polymer component used in the present invention contains at least one of the following polymers: a polymer containing (a4-1) a structural unit having an acid group and (a4-2) a repeating unit having a crosslinkable group. And a polymer containing (a4-1) a structural unit having an acid group and a polymer containing (a4-2) a structural unit having a crosslinkable group. Further, in the polymer component (A-4), the structural unit (a4-1) and the structural unit (a4-1) and the structural unit (a4-2) may be contained together Structural unit (a4-3) other than the structural unit (a4-2).

(A-4) The structural unit having an acid group (a4-1) contained in the polymer may be as described in the (A-2) polymer component of the second aspect described above (a2-1) The structural units having an acid group are the same, and the preferred ranges are also the same.

(A-4) The structural unit having a crosslinkable group (a4-2) contained in the polymer may be as described in the (A-2) polymer component of the second aspect described above (a2) -2) The structural units having a crosslinkable group are the same, and the preferred ranges are also the same.

(A-4) The structural unit (a4-3) contained in the polymer can be, for example, the above The (a2-3) other structural unit described in the (A-2) polymer component of the second aspect described above is the same, and the preferred range is also the same.

The composition of the present invention preferably contains the polymer component (A-4) in a proportion of 30% by mass or more of the solid content of the composition.

<(C-3) Solvent>

The photosensitive resin composition of the present invention contains a solvent. The photosensitive resin composition of the present invention is preferably prepared in the form of a solution in which each component of the present invention is dissolved in a solvent.

The solvent used in the photosensitive resin composition of the present invention can be a known solvent, for example, the (C-1) solvent of the first aspect described above.

The content of the solvent in the photosensitive resin composition of the present invention is preferably from 50 parts by mass to 95 parts by mass, more preferably from 60 parts by mass to 90 parts by mass, per 100 parts by mass of the total component of the photosensitive resin composition. The solvent may be used singly or in combination of two or more. When two or more cases are used, it is preferable that the total amount thereof becomes the above range.

<(S) component>

The composition of the present invention contains the component (S) described above. The (S) component used in the second aspect can be used as the (S) component of the first aspect described above, and the preferred range is also the same.

The (S) component is preferably contained in a proportion of 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass based on the total mass of the photosensitive resin composition, and further preferably Contained in a ratio of 1% by mass to 10% by mass, especially It is contained in a ratio of 2% by mass to 5% by mass. The (S) component may be one type or two or more types. When the (S) component is two or more, it is preferred that the total amount thereof is in the above range.

<Other ingredients>

In addition to the above components, the photosensitive resin composition of the present invention may preferably be added with a surfactant, a polymerization inhibitor or the like as needed.

As the surfactant, the same compound as the surfactant of the first aspect described above can be used, and the preferred range is also the same.

The polymerization inhibitor can be, for example, a thermal polymerization inhibitor described in Paragraph No. 0101 to Paragraph No. 0102 of JP-A-2008-250074, which is incorporated herein by reference. In addition, a decane coupling agent other than the component (S) may be contained, and the amount of the decane coupling agent other than the component (S) may be set to be less than 0.1% by mass of the solid content of the composition of the present invention. These components may be used alone or in combination of two or more.

<Method for Preparing Photosensitive Resin Composition>

Each component was mixed at a predetermined ratio by an arbitrary method, and stirred and dissolved to prepare a photosensitive resin composition. For example, a solution in which components are previously dissolved in a solvent may be prepared, and these solutions may be mixed in a predetermined ratio to prepare a resin composition. The composition solution prepared as above can also be used after being filtered using, for example, a filter having a pore size of 0.2 μm.

<Method for Producing Cured Film According to First Aspect of the Present Invention>

The method for producing a cured film according to the first aspect of the present invention preferably includes the following Steps of (1-1)~(5-1).

(1-1) a step of applying the photosensitive resin composition of the first aspect of the present invention to a substrate; (2-1) a step of removing a solvent from the applied photosensitive resin composition; (3) -1) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4-1) a step of developing the exposed photosensitive resin composition by an aqueous developing solution; (5- 1) A post-baking step of thermally curing the developed photosensitive resin composition.

The steps are described in order below.

In the coating step of (1-1), it is preferred to apply the photosensitive resin composition of the present invention to a substrate to form a wet film containing a solvent. It is preferred to perform cleaning of the substrate such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition onto the substrate, and it is more preferable to further treat the surface of the substrate with hexamethyldioxane after the substrate cleaning. . 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.

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, and tantalum nitride, and composite substrates of molybdenum, titanium, aluminum, copper, and the like are deposited on the substrates of the materials.

The resin may, for example, be a substrate comprising the following resins: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, poly Carbonate, polyfluorene, polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimide, polyamidimide, polyether quinone, polybenzoxazole, Polyphenylene sulfide, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorene ketone resin, ionic polymer resin, cyanate resin, and A synthetic resin such as a bifuranic acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound.

These substrates are rarely used in the form described above, and a multilayer laminated structure such as a TFT element is usually formed depending on 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 can be used.

In the case of the slit coating method, the relative moving speed of the substrate and the slit die is preferably 50 mm/sec to 120 mm/sec.

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

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

In the solvent removal step of (2-1), the solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating condition in the solvent removal step is preferably from about 30 seconds to about 300 seconds at 70 ° C to 130 ° C. When the temperature and time are in the above range, the adhesion of the pattern is further improved, and the tendency of the residue can be further reduced.

In the exposure step of (3-1), the substrate provided with the coating film is irradiated with actinic rays of 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 light source for exposure using actinic rays can use 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., and can preferably use i. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as ray (365 nm), h-ray (405 nm), or g-ray (436 nm). Further, the illumination light may be adjusted by a long wavelength cut filter, a short wavelength cut filter, or a band pass filter like a spectral filter as needed. The exposure amount is preferably from 1 mJ/cm ² to 500 mJ/cm ² .

Exposure devices can be used: mirror projection aligner, stepper, scanner, proximity, contact, microlens array, lens Various types of exposure machines such as a lens scanner 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 the PEB, the formation of a carboxyl group or a phenolic hydroxyl group by an acid-decomposable group can be promoted. The temperature in the case of performing PEB is preferably 30 ° C or more and 130 ° C or less, more preferably 40 ° C. Above 110 ° C, more preferably 50 ° C or more, 100 ° C or less.

In particular, the acid decomposition of the acid-decomposable group of the present invention has a low activation energy, and is easily decomposed by an acid derived from an acid generator due to exposure to form a carboxyl group or a phenolic hydroxyl group. Therefore, PEB may not necessarily be carried out. A positive image is formed by development.

In the developing step of (4-1), a copolymer having a free carboxyl group or a phenolic hydroxyl group is developed using an alkaline developing solution. A positive image is formed by removing an exposed portion region containing a resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in an alkaline developing solution.

The developing solution used in the developing step is preferably an aqueous solution containing a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate, potassium carbonate or cesium carbonate; or a base such as sodium bicarbonate or potassium bicarbonate; Metal bicarbonate; tetramethylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or diethyldimethylammonium hydroxide a hydroxy acid (hydroxyalkyl) trialkylammonium such as choline; a citrate such as sodium citrate or sodium metasilicate; an alkylamine such as ethylamine, propylamine, diethylamine or triethylamine; Alcoholamines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5- An alicyclic amine such as a terpene.

Among these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (hydrogen hydroxide-2) are preferred. -hydroxyethyltrimethylammonium).

In addition, an appropriate amount of methanol or B may be added to the aqueous solution of the base. An aqueous solution obtained by using a water-soluble organic solvent such as an alcohol or a surfactant is used as a developing 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.

After the development, a rinsing step can also be performed. In the elution step, the developed developer is removed by washing the developed substrate with pure water or the like, and the developed 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 (5-1), the obtained positive image is heated to thermally decompose the acid-decomposable group to form a carboxyl group or a phenolic hydroxyl group, and to crosslink the crosslinking group or the crosslinking agent. 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, heat treatment is performed for 5 minutes to 90 minutes. If it is an oven, heat it for 30 minutes to 120 minutes. By performing the crosslinking reaction as described above, it is possible to form a protective film or an interlayer insulating film which is more excellent in heat resistance and hardness. Further, when the heat treatment is performed, the transparency can be further improved by performing in a nitrogen atmosphere.

Post-baking may also be performed after baking at a relatively low temperature before the post-baking (additional baking step). In the case of in-process baking, it is preferably heated at 90 ° C to 150 ° C for 1 minute to 60 minutes, and then post-baked at a high temperature of 200 ° C or higher. In addition, the middle baking and the post baking may be divided into three stages or more in multiple stages for heating. The pattern can be adjusted by setting such a baking and post baking angle. For the heating of these baking, a known heating method such as a hot plate, an oven, or an infrared heater can be used.

Furthermore, after the post-baking, the substrate on which the pattern is formed is subjected to full re-exposure (post-exposure) by actinic rays, and post-baking is performed, whereby the photoacid generator present in the unexposed portion is formed. The acid is generated and functions as a catalyst for promoting the crosslinking step, thereby promoting the hardening reaction of the film. The preferred exposure amount in the case of including the post-exposure step is preferably 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 may be used as a dry etching resist. In the case where a cured film obtained by thermal curing by a post-baking step is used as a dry etching resist, a dry etching treatment such as ashing, plasma etching, or ozone etching may be performed on the etching treatment.

<Method for Producing Cured Film According to Second Aspect of the Present Invention>

The method for producing a cured film according to the second aspect of the present invention preferably includes the following steps (1-2) to (5-2).

(1-2) a step of applying a photosensitive resin composition of a second aspect of the present invention to a substrate; (2-2) a step of removing a solvent from the applied photosensitive resin composition; (3) -2) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4-2) a step of developing the exposed photosensitive resin composition by an aqueous developing solution; (5-2) A post-baking step of thermally curing the developed photosensitive resin composition.

(1-1) to (5) of each of the steps (1-2) to (5-2) of the method for producing a cured film of the present invention, respectively, and the method for producing a cured film of the first aspect described above. The steps of -1) are carried out in the same manner, and the preferred conditions are also the same.

The cured film obtained from the composition of the present invention can also be used as an etching resist.

[Method for Producing Cured Film of Third Aspect of the Present Invention]

The method for producing a cured film according to the third aspect of the present invention preferably includes the following steps (1-3) to (5-3).

(1-3) a step of applying a photosensitive resin composition of a third aspect of the present invention to a substrate; (2-3) a step of removing a solvent from the applied photosensitive resin composition; (3) -3) a step of exposing the solvent-removed photosensitive resin composition by active radiation; (4-3) a step of developing the exposed photosensitive resin composition by an aqueous developing solution or the like; (5- 3) A post-baking step of thermally curing the developed photosensitive resin composition.

The steps are described in order below.

In the coating step of (1-3), the photosensitive resin composition is applied onto a substrate.

For the preparation of the photosensitive resin composition, for example, the inclusion may be made into After separately dissolving the solutions previously dissolved in the solvent, the solutions were mixed in a predetermined ratio to prepare a resin composition. The composition solution prepared as above can also be used after being filtered using, for example, a filter having a pore size of 0.2 μm.

In the coating step of (1-3), the substrate described in the above (1-1) step may be used, and the coating described in the above (1-1) step may be used. method.

In the solvent removal step of (2-3), it is preferred to remove the solvent from the applied photosensitive resin composition by pressure reduction and/or heating to form a dried coating film on the substrate. (2-3) The heating conditions in the solvent removal step differ depending on the type of each component or the mixing ratio, and it is preferably from about 30 to about 120 seconds at 80 to 130 °C.

In the exposure step of (3-3), it is preferred that the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less in a predetermined pattern. In this step, the polymerizable monomer (polymerizable compound) is polymerized and hardened by the action of a polymerization initiator.

Regarding the exposure by actinic rays, the actinic rays listed in the description of the exposure step in the method for producing a cured film according to the first aspect described above can be used. Further, the illumination light may be adjusted by a long wavelength cut filter, a short wavelength cut filter, or a band pass filter like a spectral filter as needed.

In the developing step of (4-3), it is preferred to carry out development using an alkaline developing solution. A negative image is formed by removing an unexposed portion region containing a resin composition having an acid group.

The developer used in the developing step preferably contains a basic compound. Alkaline As the compound, for example, the basic compound exemplified in the description of the development step in the method for producing a cured film of the first aspect described above can be used.

The pH of the developer is preferably from 10.0 to 14.0. The development time is preferably from 30 seconds to 180 seconds, and the development method may be any one of a liquid coating method and a dipping method. After development, it can be washed with running water for 30 seconds to 90 seconds to form a desired pattern. After the development, the rinsing step may be performed in the same manner as the method for producing the cured film of the first aspect described above.

In the post-baking step of (5-3), the obtained negative image is heated, thereby removing the remaining solvent component, and if necessary, promoting crosslinking of the resin, whereby a cured film can be formed. The heating is preferably carried out to a high temperature of 150 ° C or higher, more preferably to 180 ° C to 250 ° C, and particularly preferably to 200 ° C to 240 ° C. The heating time can be appropriately set depending on the heating temperature and the like, and is preferably set to be in the range of 10 minutes to 120 minutes, and may be baked in the same manner as in the method for producing a cured film according to the first aspect described above.

If the step of irradiating the entire surface of the developing pattern with actinic rays, preferably ultraviolet rays, is added before the post-baking step (post-exposure step), the crosslinking reaction can be promoted by irradiation with actinic rays. Further, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.

In the case where a cured film obtained by thermal hardening by the post-baking step of (5-3) is used as a dry etching resist, dry etching such as ashing, plasma etching, ozone etching, or the like may be performed on the etching treatment. deal with.

[hardened film]

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the first aspect to the third aspect of the present invention described above.

The cured film of the present invention can be preferably 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 according to the first aspect to the third aspect of the present invention described above.

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

[Liquid Crystal Display Device]

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

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

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 polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

Further, examples of the liquid crystal driving method that can be obtained by the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and an in-plane switching (IPS) method. Formula, Fringe Field Switching (FFS) method, Optical Compensated Bend (OCB) method, etc.

Regarding the panel structure, the cured film of the present invention can also be used in a color filter on Array (COA) type liquid crystal display device, for example, as an organic insulating film of Japanese Patent Laid-Open Publication No. 2005-284291 ( 115) or an organic insulating film (212) of JP-A-2005-346054. Further, a specific alignment method of the liquid crystal alignment film which can be obtained by the liquid crystal display device of the present invention includes a rubbing alignment method, a light alignment method, and the like. Further, 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 in various applications. For example, in addition to the planarization film or the interlayer insulating film, a protective film for a color filter or a spacer for holding a liquid crystal layer in a liquid crystal display device at a certain thickness or A microlens or the like provided on a color filter in a solid-state image sensor.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and all the pixel phases disposed between the two glass substrates 14 and the glass substrate 15 to which the polarizing film is attached are disposed in the liquid crystal panel. Corresponding components of the TFT 16. Each element formed on the glass substrate passes through the contact hole 18 formed in the cured film 17, and is wired to form indium tin oxide (ITO) of the pixel electrode. Transparent electrode 19. On the ITO transparent electrode 19, a layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are provided.

The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue/red/green, a fluorescent lamp (cold cathode tube), an organic EL, or the like can be given.

In addition, the liquid crystal display device can be set to a three-dimensional (3D) (stereoscopic) type, or can be set to a touch panel type. In addition, the second interlayer insulating film (48) described in Japanese Laid-Open Patent Publication No. 2011-145686, or the interlayer insulating film described in Japanese Laid-Open Patent Publication No. 2009-258758 ( 520).

Further, even in the static drive type liquid crystal display device, a design pattern can be displayed by applying the present invention. As an example, the present invention can be used as an insulating film of a polymer network type liquid crystal as described in Japanese Laid-Open Patent Publication No. 2001-125086.

[Organic EL display device]

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

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

For example, specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include amorphous germanium-TFT and low Warm polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

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

A bottom gate type TFT 1 is formed on 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 in 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 a wiring for connecting the TFTs 1 or connecting the organic EL elements formed in the subsequent steps to the TFT 1.

Further, in order to flatten 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 due to the wiring 2 is filled.

On the planarizing film 4, a bottom emission type organic EL element is formed. 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 edge of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, although not shown in FIG. 2, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by interposing a desired pattern, and then Al is formed on the entire upper surface of the substrate. The two electrodes are bonded together using a sealing glass plate and an ultraviolet curable epoxy resin, thereby sealing and obtaining connection to each organic EL element. An active matrix type organic EL display device for driving the TFT 1 of the organic EL element.

Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, a resist pattern formed using the photosensitive resin composition of the present invention is used as a structural member of a microelectromechanical systems (MEMS) device. Used as a partition or as part of a mechanically driven part. Examples of such MEMS devices include a surface acoustic wave (SAW) filter, a Bulk Acoustic Wave (BAW) filter, a gyro sensor, and a microshutter for a display. Image sensors, electronic paper, inkjet heads, biochips, sealants and more. More specific examples are exemplified in Japanese Patent Laid-Open No. 2007-522531, Japanese Patent Laid-Open No. 2008-250200, Japanese Patent Laid-Open No. 2009-263544, and the like.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, it can be used, for example, to form the bank layer (16) and the planarizing film (57) shown in Fig. 2 of JP-A-2011-107476. The partition wall (12) and the flattening film (102) described in Fig. 4 (a) of Japanese Patent Laid-Open Publication No. 2010-9793, and the bank layer described in Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 (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, Japan The planarizing film (12) and the pixel separating insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638. In addition, it can also be preferably used for a spacer for holding a liquid crystal layer in a liquid crystal display device at a certain thickness, or a facsimile machine. (facsimile), an imaging optical system of an on-chip color filter such as an electronic photocopier, a solid-state imaging device, or a microlens of an optical fiber connector.

[Examples]

The invention is more specifically illustrated by the following examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate 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, unless otherwise indicated, "part" and "%" are the quality standards.

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

MATHF: 2-tetrahydrofuran methacrylate (synthetic)

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

PHSEVE: 1-Ethyl Ethyl Ester Protector of p-Hydroxystyrene

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

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

NBMA: n-Butoxymethyl propylene decylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

HEMA: Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

MAA: Methacrylic Acid (manufactured 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

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

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

[First Embodiment]

<Synthesis of MATHF>

Methyl acrylate (86 g, 1 mol) was cooled to 15 ° C, and 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, a saturated sodium hydrogencarbonate (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL), and dried over magnesium sulfate, and the insolubles were filtered and concentrated under reduced pressure at 40 ° C or less to give a yellow oily residue. Distillation under reduced pressure to obtain tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) of 54 ° C / 3.5 mmHg - 56 ° C / 3.5 mmHg in the form of a colorless oil. (Yield 80%).

<Synthesis Example of Polymer P-1>

PGMEA (propylene glycol monomethyl ether acetate) (89 g) was added to a three-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. MAA (to be 9.5 mol% of all monomer components), MATHF (to be 43 mol% of all monomer components), and GMA (corresponding to all monomer components) were added dropwise to the solution over 2 hours. A solution of 47.5 mol%) and V-65 (corresponding to 100 mol% of all the monomer components and corresponding to 4 mol%) dissolved in PGMEA (89 g) at room temperature. 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. In addition, the concentration of the component other than the solvent (referred to as a solid component) was adjusted to 40% by mass.

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

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

<Preparation of photosensitive resin composition>

The components were prepared so as to have a solid content ratio as described in the following table, and dissolved and mixed in a solvent (PGMEA: MEDG = 1:1) until the solid content concentration became 15%, and made of polytetrafluoroethylene having a diameter of 0.2 μm. The filter was filtered to obtain photosensitive resin compositions of various examples and comparative examples.

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

(polymerizable monomer)

A-3-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(photoacid generator)

B-1-1: Structure shown below (synthesis example will be described later)

[化44]

B-1-2: Structure shown below (synthesis example will be described later)

B-1-3: Structure shown below (synthesized according to the method described in paragraph 0108 of JP-A-2002-528451)

B-1-4: PAG-103 (trade name, structure shown below, manufactured by BASF)

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

B-1-6: Adeka Optomer SPO-82 (made by ADEKA)

(醌 叠 azide compound)

B-2-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and Condensation of 1,2-naphthoquinonediazide-5-sulfonyl chloride (3.0 mol) Object

B-2-2: condensate of 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

B-2-3: condensate of 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonate (2.44 mol)

(photopolymerization initiator)

B-3-1: IRGACURE OXE 01 (Manufactured by BASF)

((S) component)

S-1: structure shown below, molecular weight 341.48

S-2: structure shown below, molecular weight 366.57

S-9: the structure shown below, molecular weight 269.46 (synthesis example will be described later)

S-14: structure shown below, molecular weight 252.41 (synthesis example will be described later)

S-15: Structure shown below, molecular weight 314.48

S-16: Structure shown below, molecular weight 264.49

[化55]

S'-11: 3-glycidoxypropylmethyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-402)

S'-12: 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)

(CH ₃ O) ₃ SiC ₃ H ₆ SH

S'-13: 3-methacryloxypropyltrimethoxydecane (Shin-Etsu Chemical KBM-503)

S'-14: 3-glycidoxypropyltrimethoxydecane (Shin-Etsu Chemical) KBM-403)

S'-15: a compound of the following structure

S'-16: a compound of the following structure

S'-17: a compound of the following structure

(sensitizer)

DBA: 9,10-dibutoxy oxime (manufactured by Kawasaki Chemical Co., Ltd.)

(alkaline compound)

H-1: a compound of the following structure

(surfactant)

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

(solvent)

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)

(other additives)

F-1: JER828 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)

F-2: JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)

F-3: JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)

J-1: Adekastab AO-60 (made by Eddy Co.)

J-2: Irganox 1035 (made by BASF)

J-3: Irganox 1098 (made by BASF)

<Synthesis of B-1-1>

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 and reacted for 2 hours. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction mixture under ice-cooling, and ethyl acetate (50 mL) was added. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour, and then a 2N aqueous HCl solution (60 mL) was added to the mixture, and the organic layer was concentrated, and then crystallised from diisopropyl ether (10 mL) Pulping, filtration, and drying gave 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-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was warmed to room temperature and reacted for 1 hour. Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, and then repulped with methanol (20 mL), filtered, and dried to obtain a compound (the structure) (2.3 g) of B-1-1.

Furthermore, the ¹ H-nuclear magnetic resonance (NMR) spectrum of B-1-1 (300 MHz, CDCl ₃ ) is 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-1-2>

4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 16 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.), and sodium hydrogencarbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Thereafter, 4.9 g of methyl 4,4'-dimethyl-3-oxopentanoate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and heated at 120 ° C for 2 hours under a nitrogen atmosphere. After standing to cool, water and ethyl acetate were added to the reaction mixture and liquid separation was carried out, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain crude B-1-2A. The crude B-1-2A was subjected to silica gel column chromatography purification to obtain 1.7 g of intermediate B-1-2A.

B-1-2A (1.7 g) was mixed with p-xylene (6 mL), and 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 ° C for 2 hours. After standing to cool, water and ethyl acetate were added to the reaction mixture, and liquid separation was carried out, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain crude B-1-2B.

Mix THF (2 mL) with the total amount of crude B-1-2B and drop in an ice bath 6.0 mL of a 2 M hydrochloric acid/THF solution was added, followed by dropwise addition of isoamyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g), and the mixture was stirred at room temperature for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture, and the organic layer was washed with water, dried with magnesium sulfate, filtered, and concentrated to obtain a crude B-1-2C intermediate.

The total amount of the crude intermediate B-1-2C was mixed with acetone (10 mL), and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added under ice cooling. After 1.4 g), the mixture was stirred at room temperature for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture, and liquid separation was carried out, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain crude B-1-2. The crude B-1-2 was repulped with cooling methanol, filtered, and dried to obtain B-1-2 (1.2 g).

Further, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-1-2 was δ=8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7.6 (m, 2H), 7.6-7.5 (m, 1H) 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H).

<Synthesis of S-9>

73.1 g (1.0 mol) of methyl isothiocyanate, 0.9 g (0.0023 mol) of tin (II) 2-ethylhexanoate, and 316.1 g of toluene were placed in a 1 L flask equipped with a reflux condenser, a dropping funnel and a thermometer. Heat to 70 ° C. 243.2 g (1.02 mol) of γ-mercaptopropyltrimethoxydecane was added dropwise thereto, followed by heating and stirring at 110 ° C for 3 hours. It was confirmed by infrared (IR) measurement that the absorption peak of the isothiocyanate group derived from the raw material disappeared, and the absorption peak derived from the dithiocarbamate bond was present to complete the reaction. Then, the reaction solution was distilled off under reduced pressure to remove toluene, whereby a pale yellow transparent liquid was obtained. Identification was carried out by using ¹ H-NMR spectrum.

<Synthesis of S-14>

73.1 g (1.0 mol) of methyl isothiocyanate and 316.1 g of toluene were placed in a 1 L flask equipped with a reflux condenser, a dropping funnel and a thermometer, and the mixture was heated to 70 °C. 225.4 g (1.02 mol) of γ-aminopropyltrimethoxydecane was added dropwise thereto, followed by heating and stirring at 110 ° C for 3 hours. It was confirmed by IR measurement that the absorption peak of the isothiocyanate group derived from the raw material disappeared, and the absorption peak derived from the thiourea bond was present to complete the reaction. Then, the reaction solution was distilled off under reduced pressure to remove toluene, whereby a pale yellow transparent liquid was obtained. Identification was carried out by using ¹ H-NMR spectrum.

<Adhesion evaluation>

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 for 120 seconds to volatilize the solvent to form a film thickness of 3.0 μm. A photosensitive resin composition layer. Then, the ultrahigh pressure mercury lamp was used for exposure so that the cumulative irradiation amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and thereafter, the substrate was heated in an oven at 230 ° C for 30 minutes to obtain Hardened film.

Then, a cutter was used for the cured film, and the slit was cut vertically and horizontally at intervals of 1 mm, and the tape peeling test was performed using a scotch tape (100-frame cross-cut method: according to Japanese Industrial Standards (JIS) 5600 ). The adhesion between the cured film and the substrate was evaluated based on the area of the cured film transferred onto the back surface of the tape. The results are shown in the following table. The larger the value, the higher the adhesion to the base substrate, and the 6 points, 5 minutes, or 4 are classified into practical levels.

6: The transfer area is less than 1%

5: The transfer area is 1% or more and less than 5%.

4: The transfer area is 5% or more and less than 10%.

3: The transfer area is 10% or more and less than 30%.

2: The transfer area is 30% or more, less than 50% and 50% or more.

1: The transfer area is 50% or more

<Evaluation of cone angle after baking>

The photosensitive resin composition was applied onto a substrate (10 cm × 10 cm) obtained by forming a glass substrate on which a Mo (molybdenum) film was formed by using a slit coater so that the dried film thickness was 3 μm. The solvent was volatilized by prebaking on a hot plate at 90 ° C for 2 minutes. Then, through a mask capable of reproducing a hole of 10 μm (1:3), exposure was performed using an ultrahigh pressure mercury lamp at a cumulative irradiation amount of 40 mJ/cm ² (illuminance: 20 mW/cm ² , i-ray), and thereafter, by alkali development. The solution (2.38 mass% of TMAH aqueous solution) was developed at 23 ° C for 60 seconds, and then rinsed with ultrapure water for 1 minute. Then, using a hot plate, baking was performed at 230 ° C for 30 minutes.

The obtained substrate was cut, and the hole shape was observed by a scanning electron microscope (SEM) from the lateral direction, and the angle formed by the substrate interface portion and the hole wall surface was measured as a taper angle. The results are shown in the following table. From the viewpoint of high resolution, it is preferably 3 or more.

5: cone angle exceeds 80 degrees

4: The cone angle exceeds 60 degrees and is less than 80 degrees

3: the cone angle exceeds 40 degrees and is less than 60 degrees

2: the taper angle exceeds 20 degrees and is less than 40 degrees

1: cone angle is less than 20 degrees

<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 was spin-coated. After the composition, the mixture was prebaked on a hot plate at 90 ° C for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3.0 μm.

Then, using the obtained photosensitive resin composition layer, Canon (share) The manufactured MPA 5500CF (high pressure mercury lamp) is exposed to a predetermined mask. Then, the exposed photosensitive resin composition layer was developed by an alkali developer (0.4% aqueous tetramethylammonium hydroxide 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.

5: less than 20mJ/cm ²

4:20 mJ/cm ² or more and less than 40 mJ/cm ²

3: 40 mJ/cm ² or more and less than 80 mJ/cm ²

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

1:160mJ/cm ² or more

As shown by the results, it was found that in Examples 1 to 69 containing the (S) component, the adhesion was excellent and the taper angle was also high. And I know that the sensitivity is also good. On the other hand, it was found that the adhesion and the taper angle of Comparative Example 1 to Comparative Example 11 which did not contain the (S) component were inferior to those of the Examples.

[First Embodiment]

<Example 101>

In the active matrix liquid crystal display device of FIG. 1 of the Japanese Patent No. 3321003, the cured film 17 is formed as an interlayer insulating film as follows, whereby the liquid crystal display device of the example 101 is obtained. That is, the cured film 17 was formed using the photosensitive resin composition of Example 1 as an interlayer insulating film.

That is, as a pretreatment for improving the wettability of the substrate and the interlayer insulating 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and then spin-coated. After the photosensitive resin composition of Example 1 was applied, 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, the obtained photosensitive resin composition layer was made of MPA 5500CF (high-pressure mercury lamp) manufactured by Canon Co., Ltd., and a mask of a hole pattern of 10 μm Φ was interposed so as to be 40 mJ/cm ² (energy intensity: Exposure was carried out in a manner of ²⁰ mW/cm ² , i-ray). Further, the exposed photosensitive resin composition layer was subjected to a liquid-repellent development at 23 ° C for 60 seconds using an alkali developing solution (0.4% aqueous tetramethylammonium hydroxide solution), and then rinsed with ultrapure water for 20 seconds. bell. Then, the entire surface exposure was performed using an ultrahigh pressure mercury lamp so that the cumulative irradiation amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and thereafter, the substrate was heated in an oven at 230 ° C for 30 minutes. A cured film is obtained.

The coating property at the time of applying the photosensitive resin composition was good, and no occurrence of wrinkles or cracks was observed in 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 to have good display characteristics, and it was found to be a highly reliable liquid crystal display device.

<Example 102>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the exposure apparatus is changed from MPA 5500CF (high-pressure mercury lamp) manufactured by Canon (Canon) to FX-803M (gh-Line stepper) manufactured by Nikon, the performance of the liquid crystal display device It was also as good as Example 101.

<Example 103>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the exposure apparatus is changed from MPA 5500CF (high-pressure mercury lamp) manufactured by Canon (share) to "AEGIS" (wavelength 355 nm pulse width 6nsec) manufactured by V-Technology, liquid crystal display The performance of the device was also as good as in Example 101.

<Example 104>

The same liquid crystal display device was obtained only by changing the following process from Example 101. In other words, even 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 excellent in pattern-free defects or peeling. status. Further, the performance of the liquid crystal display device was also as good as that of the example 101. 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 substrate.

<Example 105>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even after the pre-baking, a vacuum drying step (Vapor Compression Distillation (VCD)) is introduced, the obtained cured film is in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. From the viewpoint of suppressing coating unevenness in accordance with the solid content concentration or film thickness of the composition, it is also preferred to introduce a vacuum drying step.

<Example 106>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the PEB step is introduced between the exposure of the mask and the development step, the obtained cured film is in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. From the standpoint of improving dimensional stability, it is also preferred to introduce the PEB step.

<Example 107>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the alkali developing solution was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a 2.38% aqueous solution of tetramethylammonium hydroxide, the obtained cured film was in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 108>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the alkali development method is changed from the overcoat development to the shower development, the obtained cured film is in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 109>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, even if the alkali developing solution was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a 0.04% aqueous KOH solution, the obtained cured film was in a good state of no pattern defect or peeling. Further, the performance of the liquid crystal display device was also as good as that of the example 101. The reason for this is considered to be that the composition of the present invention is excellent in adhesion to a substrate.

<Example 110>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, the step of the entire surface exposure after development and rinsing was omitted, and the film was heated at 230 ° C for 30 minutes in an oven to obtain a cured film. The performance of the obtained liquid crystal display device was as good as that of Example 101. The reason is considered to be the chemical resistance of the composition of the present invention. Excellent. From the viewpoint of improving productivity, it is also preferred to omit the step of the entire surface exposure.

<Example 111>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, a step of heating on a hot plate at 100 ° C for 3 minutes was added between the step of exposing the entire surface 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 101. It is also preferable to add the above steps from the viewpoint of aligning the shape of the hole pattern.

<Example 112>

The same liquid crystal display device was obtained only by changing the following process from Example 101. That is, a step of heating on a hot plate at 100 ° C for 3 minutes was added between the steps of development, rinsing, and the entire surface exposure. The performance of the obtained liquid crystal display device was as good as that of Example 101. It is also preferable to add the above steps from the viewpoint of aligning the shape of the hole pattern.

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).

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 in 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 a wiring for connecting the TFTs 1 or connecting the organic EL elements formed in the subsequent steps to the TFT 1.

Further, in order to flatten 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 due to the wiring 2 is filled. The planarization film 4 on the insulating film 3 is formed by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking on a hot plate (90 ° C / 120 seconds), and self-masking. The i-ray (365 nm) of 45 mJ/cm ² (energy intensity: 20 mW/cm ² ) was irradiated with a high-pressure mercury lamp above the cover, and then developed by an aqueous alkali solution (0.4% aqueous TMAH solution) to form a pattern, and the ultrahigh pressure mercury lamp was used for total irradiation. The amount was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and the entire surface was exposed, 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 in the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the thickness of the produced planarizing film 4 was 2,000 nm.

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

Then, an insulating film 8 covering the shape of the edge of the first electrode 5 is formed. With regard to the insulating film 8, the insulating film 8 was formed by the same method as described above using the photosensitive resin composition of Example 1. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

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

An active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to the respective organic EL elements is obtained as described above. When a voltage was applied via the drive circuit, it was found to have good display characteristics, and it was found to be a highly reliable organic EL display device.

[Second Embodiment]

<Example 113>

A liquid crystal display device was obtained using the photosensitive resin composition of Example 40 in the same manner as in the first embodiment. When a driving voltage was applied to the obtained liquid crystal display device, it was found to have good display characteristics, and it was found to be a highly reliable liquid crystal display device.

Further, in the same manner as in the first embodiment, an organic EL display device using a thin film transistor (TFT) was produced using the photosensitive resin composition of Example 40. When a voltage was applied via the drive circuit, it was found to have good display characteristics, and it was found to be a highly reliable organic EL display device.

[Third embodiment]

<Example 114>

In the same manner as in the first embodiment, a liquid crystal display device was obtained using the photosensitive resin composition of Example 51. Applying a driving voltage to the obtained liquid crystal display device, As a result, good display characteristics were exhibited, and it was found to be a highly reliable liquid crystal display device.

Further, in the same manner as in the first embodiment, an organic EL display device using a thin film transistor (TFT) was produced using the photosensitive resin composition of Example 51. When a voltage was applied via the drive circuit, it was found to have good display characteristics, and it was found to be a highly reliable organic EL display device.

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 (18)

A photosensitive resin composition comprising: (A-1) a polymer component containing a polymer satisfying at least one of the following (1) and (2), and (1) containing (a1-1) having an acid group via an acid a structural unit of a group decomposable with a decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group, and (2) a group having (a1-1) an acid group-protected group a polymer of a structural unit, and a polymer containing (a1-2) a structural unit having a crosslinkable group; (S) a compound represented by the formula (1) and/or a compound represented by the formula (2) (B-1) photoacid generator; and (C-1) solvent; In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ¹ represents a single bond or a divalent linking group; and X ¹ represents -S. - or -NH-, R ³ represents a monovalent organic group; In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ² represents a single bond or a divalent linking group; and X ² represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom. A photosensitive resin composition comprising: (A-2) a polymer component containing a polymer satisfying at least one of the following (1) and (2), and (1) comprising (a2-1) a structure having an acid group a unit, and (a2-2) a polymer having a structural unit having a crosslinkable group, (2) a polymer containing (a2-1) a structural unit having an acid group, and containing (a2-2) having crosslinkability a polymer of a structural unit of the group; (B-2) a quinonediazide compound; and (S) a compound represented by the formula (1) and/or a compound represented by the formula (2); (C-2) Solvent In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ¹ represents a single bond or a divalent linking group; and X ¹ represents -S. - or -NH-, R ³ represents a monovalent organic group; In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ² represents a single bond or a divalent linking group; and X ² represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom. A photosensitive resin composition comprising: (A-3) a polymerizable monomer; (B-3) a photopolymerization initiator; (A-4) comprising at least one of the following (1) and (2) The polymer component of the polymer, (1) a polymer comprising (a4-1) a structural unit having an acid group, and (a4-2) a structural unit having a crosslinkable group, and (2) containing (a4-1) a polymer having a structural unit having an acid group, and a polymer containing (a4-2) a structural unit having a crosslinkable group; (S) a compound represented by the formula (1) and/or a formula (2) a compound represented; and (C-3) a solvent; In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ¹ represents a single bond or a divalent linking group; and X ¹ represents -S. - or -NH-, R ³ represents a monovalent organic group; In the formula (2), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2; L ² represents a single bond or a divalent linking group; and X ² represents -S. - or -NH-, A represents a heterocyclic ring containing a carbon atom and a nitrogen atom. The photosensitive resin composition according to any one of the first to third aspects of the invention, wherein (S) the compound represented by the formula (1) and/or the solid component of the photosensitive resin composition The compounding amount of the compound represented by the formula (2) is from 0.1% by mass to 20% by mass. The photosensitive resin composition according to any one of the items 1 to 3, wherein R ³ in the formula (1) represents an alkyl group having 1 to 10 carbon atoms or a carbon number of 6 to 20 Aryl. The photosensitive resin composition according to any one of the items 1 to 3, wherein R ⁴ in the formula (2) represents a pyridyl group or a thiazolyl group. The photosensitive resin composition according to any one of the items 1 to 3, wherein L ¹ in the general formula (1) or L ² in the general formula (2) is a carbon number 2 to ² , respectively. 8 alkylene. The photosensitive resin composition according to any one of the items 1 to 3, wherein (S) a compound represented by the formula (1) and/or a compound represented by the formula (2) The molecular weights are each 1000 or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the crosslinkable group is selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR ( R is at least one of a group represented by a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The photosensitive resin composition as described in claim 1, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal. The photosensitive resin composition according to any one of the items 1 to 3, wherein (S) the compound represented by the formula (1) and/or the compound represented by the formula (2) is Any of the compounds represented by the following (S-1) to (S-2), (S-9), and (S-14) to (S-16); wherein, Me represents a methyl group, Et Indicates an ethyl group; 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 11 to a substrate; a step of removing a solvent from the photosensitive resin composition of the cloth; (3) exposing the photosensitive resin composition from which the solvent has been removed by using actinic rays a step of light; (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. The method for producing a cured film according to claim 12, wherein after the developing step and before the post-baking step, (6) performing full-surface exposure on the developed photosensitive resin composition step. The method for producing a cured film according to claim 12, further comprising the step of dry etching a substrate having a cured film obtained by thermally curing the post-baking step. A cured film obtained by hardening a photosensitive resin composition according to any one of claims 1 to 11, or by any of items 12 to 14 of the patent application scope. A method of producing a cured film as described above. The cured film according to claim 15, which is an interlayer insulating film. An organic electroluminescence display device comprising the cured film according to claim 15 or claim 16. A liquid crystal display device having a cured film as described in claim 15 or claim 16.