JP6588354B2 - Photosensitive resin composition, cured film, liquid crystal display device, organic electroluminescence display device, and method for producing cured film - Google Patents

Description

The present invention relates to a photosensitive resin composition, a cured film, a liquid crystal display device, an organic EL display device, and a method for producing a cured film. Specifically, a photosensitive resin composition capable of forming a cured film having excellent flatness when applied on a base having a step and having a large pattern taper angle obtained by pattern exposure and development, and The present invention relates to a used cured film, a liquid crystal display device, an organic EL display device, and a method for producing a cured film.
More specifically, it is suitable for the formation of flattening films, protective films and interlayer insulating films for electronic components such as liquid crystal display devices, organic EL (organic electroluminescence) display devices, touch panels, integrated circuit elements, and solid-state imaging devices. The present invention relates to a resin composition, a cured film using the same, a liquid crystal display device, an organic EL display device, and a method for producing the cured film.

  Electronic parts such as a liquid crystal display device, an organic EL display device, a touch panel, an integrated circuit element, and a solid-state imaging element are provided with a cured film such as a planarization film, a protective film, and an interlayer insulating film in a pattern shape. In forming these cured films, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern is small.

As a photosensitive resin composition, a cured film such as an interlayer insulating film is formed using a chemically amplified positive composition containing a polymer having a structural unit having an acid group protected with an acid-decomposable group. It has been tried.
For example, Patent Document 1 discloses [A] a polymer having a structural unit (I) containing an acid-dissociable group having a specific structure in the same or different polymer molecule and an epoxy group-containing structural unit, and [B] an oxime sulfonate compound. And at least one compound selected from the group consisting of onium salt compounds, and [C] an organic solvent, having a solid content concentration of 10% by mass to 30% by mass, and a viscosity at 25 ° C. of 2.0 mPa -Positive radiation sensitivity for a discharge nozzle type coating method containing s to 12 mPa · s, and [C] an organic solvent containing at least (C1) an organic solvent having a vapor pressure at 20 ° C of 0.1 mmHg to less than 1 mmHg. A composition is described.

Patent Document 2 discloses a polymer component containing a polymer satisfying at least one of the following components (1) and (2):
(1) a polymer having a structural unit having a group in which an a1 acid group is protected with an acid-decomposable group, and a structural unit having an a2 crosslinkable group;
(2) a polymer having a structural unit having a group in which an a1 acid group is protected by an acid-decomposable group, and a polymer having a structural unit having an a2 crosslinkable group,
(Component C) containing a photoacid generator and (Component D) a solvent, and (Component X) containing a silicon compound having two or more specific hydrolyzable silyl groups and / or silanol groups in one molecule A positive photosensitive resin composition is described.

JP 2011-248331 A JP 2013-218265 A

In recent years, in the design of a high-definition image display panel, the level difference of the base of a cured film such as a flattening film, a protective film, and an interlayer insulating film has increased more than before. The fact that three-dimensional wiring such as laminated wiring used in the semiconductor field has also been made in the design of the image display panel is also a cause of an increase in the level difference of the base of the cured film. Examples of the base step include a metal wiring pattern, an arbitrary resin layer having a step due to the step of the metal wiring pattern, an arbitrary resin layer having a step due to the step of the resin pattern, and the like. it can.
When the inventor applied the photosensitive resin composition on a base having a step, there is a problem that a step is also generated on the surface of the cured film formed from the photosensitive resin composition due to the influence of the base step. I understood it. When a substrate with a large step is used in recent years, when an electronic component is manufactured by laminating a plurality of films, the upper film of the cured film cannot be formed well due to the effect of the step generated on the surface of the cured film. As a result, the performance of the electronic component is reduced. Thus, the present inventor finds a novel problem that has not been known so far, which provides a photosensitive resin composition capable of forming a cured film having excellent flatness when coated on a base having a step. It came.

In order to solve this new problem, the present inventor has a photosensitive resin composition having a composition in which the photosensitive resin composition absorbs the base level difference when the base level difference is large and the level difference does not occur on the surface. ,Study was carried out.
A chemically amplified positive resist having a conventionally known composition does not sufficiently assume that the photosensitive resin composition absorbs the base step when the base step is large. However, there was room for further improvement. The chemical amplification type positive resist having a conventionally known composition has a design philosophy of modifying a polymer component containing an acid-decomposable group with a small amount of a photosensitizer (acid generator). There were many. Therefore, in the process of volatilizing the solvent in the photosensitive resin composition and the thermosetting process after pattern exposure and development of the photosensitive resin composition, there is little deformation of the shape of the coating film, and it is not possible to absorb the underlying step. It was thought that steps were likely to occur on the surface of the cured film.

  On the other hand, when the present inventor reduced the amount of the polymer component containing an acid-decomposable group and increased the deformation of the shape of the coating film, there was a problem that the shape of the cured film after pattern exposure and development was easily deformed. I found out that In particular, it has been found that there is a problem in that the side portion of the cured film pattern becomes gentle and the taper angle becomes small. When the taper angle of the cured film pattern is reduced, for example, when forming a contact hole for connecting the upper and lower wirings of the cured film such as an interlayer insulating film, the small contact hole required for designing a high-definition image display panel is reduced. This leads to the problem that it cannot be formed with high precision.

In this way, a new problem of forming a cured film having excellent flatness when applied on a base having a step and a cured film having a large taper angle of a pattern obtained by pattern exposure and development are formed. The solution to the problem was in a trade-off relationship.
The problem to be solved by the present invention is a photosensitive resin which can form a cured film having excellent flatness when coated on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. It is to provide a composition. Moreover, the subject which this invention tends to solve is providing the manufacturing method of a cured film, a liquid crystal display device, an organic electroluminescence display device, and a cured film which applied the photosensitive resin composition.

As a result of the study by the present inventors under the above circumstances, the content of the polymer component is reduced as compared with the conventional chemically amplified positive resist, and the content of the specific crosslinking agent having a small molecular weight is increased. Therefore, it is possible to provide a photosensitive resin composition that can form a cured film that has excellent flatness when applied on a base having a step and has a large taper angle of a pattern obtained by pattern exposure and development. The headline and the present invention were completed.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <12>.
<1> Component A Polymer component having a weight average molecular weight of 10,000 or more,
Component B photoacid generator,
A photosensitive resin composition containing a component C solvent and a component E crosslinking agent,
Component A contains a polymer that satisfies at least one of Polymer 1 and Polymer 2 below,
Polymer 1: a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, and a structural unit having an a1-2 crosslinkable group,
Polymer 2: a polymer having a structural unit having a group in which an a1 acid group is protected by an acid-decomposable group, and a polymer having a structural unit having an a1-2 crosslinkable group,
The content of component A is 75% by mass or less in the total solid content,
The molecular weight of component E is 3000 or less,
The content of component E is 15% by mass or more in the total solid content,
A photosensitive resin composition in which component E is at least one of a compound having two or more groups represented by the following formula X1 in the molecule and a compound having two or more unsaturated double bonds in the molecule;
In formula X1, at least one of R ^{X1 to} R ^X3 is a hydrolyzable selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group, and an isopropenoxy group. The remaining R ^{X1 to} R ^X3 each independently represents a hydrogen atom, a halogen atom, or a monovalent organic substituent.
<2> The photosensitive resin composition according to <1>, wherein the content of component E is 20% by mass or more based on the total solid content.
<3> The photosensitive resin composition according to <1>, wherein the content of component E is 25% by mass or more based on the total solid content.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the component E is a compound having two or more groups represented by the following formula X1 in the molecule;
In formula X1, at least one of R ^{X1 to} R ^X3 is a hydrolyzable selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group, and an isopropenoxy group. The remaining R ^{X1 to} R ^X3 each independently represents a hydrogen atom, a halogen atom, or a monovalent organic substituent.
<5> The photosensitive resin composition according to <4>, wherein Component E is a compound having an isocyanuric skeleton.
<6> The photosensitive resin composition according to any one of <1> to <3>, wherein Component E is a compound having two or more unsaturated double bonds in the molecule.
<7> The photosensitive resin composition according to <6>, wherein Component E is a compound having a urethane structure.
<8> A cured film of the photosensitive resin composition according to any one of <1> to <7>.
<9> The cured film according to <8>, which is an interlayer insulating film.
<10> An organic electroluminescence display device having the cured film according to <8> or <9>.
<11> A liquid crystal display device having the cured film according to <8> or <9>.
<12> A method for producing a cured film comprising at least the following steps 1 to 5 in this order;
Process 1: The process of apply | coating the photosensitive resin composition as described in any one of <1>-<7> on a base | substrate;
Process 2: The process of removing at least one part of a solvent from the apply | coated photosensitive resin composition;
Step 3: An exposure step of exposing the photosensitive resin composition from which at least a part of the solvent has been removed to a pattern with actinic rays;
Step 4: Development step of developing the exposed photosensitive resin composition with a developer;
Step 5: a step of thermosetting the developed photosensitive resin composition.
<13> The method for producing a cured film according to <12>, wherein the base is a base having a step.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form the cured film which is excellent in flatness when apply | coated on the base | substrate which has a level | step difference, and has a large taper angle of the pattern obtained by pattern exposure and development is provided. it can. Moreover, according to this invention, the manufacturing method of a cured film, a liquid crystal display device, an organic electroluminescent display device, and a cured film which applied this photosensitive resin composition can be provided.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. The conventional photosensitive resin composition is apply | coated on the base | substrate which has a level | step difference, it dries, prebakes, the cross-sectional schematic diagram of the shape of the cured film obtained by pattern exposure and image development is represented. The photosensitive resin composition of this invention is apply | coated on the base | substrate which has a level | step difference, it dries, prebakes, the cross-sectional schematic diagram of the shape of the cured film obtained by pattern exposure and image development is represented. The flatness evaluation of an Example WHEREIN: The photosensitive resin composition is apply | coated on the base | substrate which has a level | step difference, dried, prebaked, the cross-sectional schematic diagram of the shape of the cured film obtained by pattern exposure and image development is represented.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.

In the present specification, unless otherwise specified, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values determined by GPC (Gel Permeation Chromatography) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID (inner diameter) × 15.0 cm) can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
The solid content in the present invention refers to a solid content at 25 ° C.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is a polymer component having a component A weight average molecular weight of 10,000 or more,
Component B photoacid generator,
A photosensitive resin composition containing a component C solvent and a component E crosslinking agent,
Component A contains a polymer that satisfies at least one of Polymer 1 and Polymer 2 below,
Polymer 1: a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, and a structural unit having an a1-2 crosslinkable group,
Polymer 2: a polymer having a structural unit having a group in which an a1 acid group is protected by an acid-decomposable group, and a polymer having a structural unit having an a1-2 crosslinkable group,
The content of component A is 75% by mass or less in the total solid content,
The molecular weight of component E is 3000 or less,
The content of component E is 15% by mass or more in the total solid content,
A photosensitive resin composition in which component E is at least one of a compound having two or more groups represented by the following formula X1 in the molecule and a compound having two or more unsaturated double bonds in the molecule;
In formula X1, at least one of R ^{X1 to} R ^X3 is a hydrolyzable selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group, and an isopropenoxy group. The remaining R ^{X1 to} R ^X3 each independently represents a hydrogen atom, a halogen atom, or a monovalent organic substituent.
With such a configuration, the photosensitive resin composition of the present invention is a cured film having excellent flatness when applied on a base having a step and having a large pattern taper angle obtained by pattern exposure and development. Can be formed.
Here, in Example of JP2011-248331A, Example 13 had the least polymer component. In this example, the content of the polymer component was 78% by mass in the total solid content, and the content of the polyfunctional (meth) acrylate compound was 12% by mass in the total solid content. Moreover, it was Example 31 with the least polymer component in the Example of Unexamined-Japanese-Patent No. 2013-218265. In this example, the content of the polymer component was 81% by mass in the total solid content, and the content of the polyfunctional alkoxysilane was 12% by mass in the total solid content.
On the other hand, in the photosensitive resin composition of the present invention, the content of the polymer component is reduced as compared with the conventional chemically amplified positive resist, the molecular weight is small, and two groups represented by the following formula X1 are present in the molecule. The taper angle of the cured film is kept large when it is applied on a substrate with a step by increasing the content of the compound having the above or a compound having two or more unsaturated double bonds in the molecule compared to the conventional one. However, the flatness can be improved.

FIG. 3 is a schematic cross-sectional view of the shape of a cured film obtained by applying a conventional photosensitive resin composition on a base having a step, drying under reduced pressure, pre-baking, pattern exposure and development. As shown in FIG. 3 (a), when a conventional photosensitive resin composition is applied on a base 100 having a step and dried by reduced pressure, the surface of the film of the photosensitive resin composition 103 is slightly stepped. It becomes. This is considered that a level | step difference generate | occur | produces by contraction of the film | membrane by solvent drying. Base 100 having steps includes a step lower 101 of the base 100 having a step, is composed from the step 102., D ₁ represents the height of the step of the base. In FIG. 3B, the surface of the film of the photosensitive resin composition 103 is slightly stepped after heating at about 110 ° C. in the pre-baking step. This is presumably because the film during prebaking does not flow in the conventional photosensitive resin composition. In FIG. 3C, after pattern exposure and development, and further heating (thermal curing) at about 230 ° C., the surface of the obtained cured film 104 has a large step. This is presumably because the step is emphasized by the shrinkage of the film due to the crosslinking reaction or volatilization of the components in the photosensitive resin composition. Let D ₂ be the thickness of the cured film in the portion where there is no step 102 on the base, and Δd be the height of the step on the surface of the cured film. The cured film 104 has a pattern, and the pattern end portion has a taper angle θ.
On the other hand, FIG. 4 is a schematic cross-sectional view of the shape of a cured film obtained by applying the photosensitive resin composition of the present invention on a base having a step, drying under reduced pressure, pre-baking, pattern exposure and development. Represents. As shown in FIG. 4A, when the photosensitive resin composition of the present invention is applied on the base 100 having a step and dried by reduced pressure, the surface of the film of the photosensitive resin composition 103 is slightly stepped. It becomes a state. This is considered that a level | step difference generate | occur | produces by shrinkage | contraction of the film | membrane by solvent drying. In FIG. 4 (b), the surface of the film of the photosensitive resin composition 103 is in a flat state after next heating at about 110 ° C. by pre-baking. This is presumably because the film of the photosensitive resin composition of the present invention flowed and became flat by heating in the pre-baking step. In FIG. 4C, after pattern exposure and development, and further heating (thermal curing) at about 230 ° C., the surface of the cured film 104 obtained is the height of the step on the surface of the cured film. A pattern having a small Δd and a large taper angle θ is obtained. This is considered to be because the film flows and becomes flat by heating in the thermosetting process, and the rapid curing of the side of the cured film 104 (pattern) remaining after being developed by the specific cross-linking agent proceeds.
As shown in FIG. 3 and FIG. 4, when the photosensitive resin composition of the present invention is applied on a base having a step, the conventional photosensitive resin composition is applied on the base having a step. Thus, a cured film having a pattern which is superior in flatness and has a large taper angle can be obtained.
Details of the present invention will be described below.

In order for the formed cured film to have high flatness, it is desirable that the film of the photosensitive resin composition be softened and fluidized in the pre-baking step to become flat. Since the temperature in the pre-baking step is, for example, about 70 to 130 ° C., generally about 80 to 110 ° C., the softening temperature of the photosensitive resin composition is preferably in the same range. If the softening temperature of the photosensitive resin composition is 110 ° C. or less, the planarization in the pre-baking process proceeds sufficiently. If the softening temperature of the photosensitive resin composition is 80 ° C. or higher, the softening and flow in the subsequent post-baking process do not proceed too quickly, and the photosensitive resin composition is cured before the taper angle of the pattern such as the contact hole of the cured film is reduced. Cheap.
The softening temperature of the photosensitive resin composition refers to a temperature at which deformation of the resin composition starts when the photosensitive resin composition of the present invention is continuously heated. The softening temperature of the photosensitive resin composition is measured by the following method.
Using TMA / SS-6000 (manufactured by Seiko Instruments Inc.), heating is performed from room temperature at a load of 1 N and a heating rate of 10 ° C./min, and the temperature at which 5% or more deformation is observed is defined as the softening temperature.

<Component A polymer component>
The photosensitive resin composition of the present invention includes a polymer component having a component A weight average molecular weight of 10,000 or more, and the component A includes a polymer that satisfies at least one of the following polymer 1 and polymer 2.
Polymer 1: a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, and a structural unit having an a1-2 crosslinkable group,
Polymer 2: a polymer having a structural unit having a group in which an a1 acid group is protected by an acid-decomposable group, and a polymer having a structural unit having an a1-2 crosslinkable group,
The content of component A is 75% by mass or less based on the total solid content.
These polymer components can be used singly or in combination of two or more. Furthermore, polymers other than these may be included. The component A polymer component in the present invention means, in addition to the polymer 1 and the polymer 2, unless otherwise specified, including other polymers added as necessary.
The photosensitive resin composition of the present invention has a flatness when the content of component A is 75% by mass or less in the total solid content and 70% by mass or less is applied on a base having a step. It is preferable from a viewpoint of forming the cured film which is excellent, and it is more preferable that it is 65 mass% or less. From the viewpoint of forming a cured film having a taper angle of a pattern obtained by pattern exposure and development, the photosensitive resin composition preferably has a component A content of 50% by mass or more based on the total solid content, and is 55% by mass. % Or more is more preferable, and 60% by mass or more is particularly preferable.
In the photosensitive resin composition of the present invention, it is also preferable to control the softening temperature of the photosensitive resin composition within a preferable range by setting the content of Component A within a preferable range.
In the photosensitive resin composition of the present invention, the content of Component A is preferably 19% by mass or less in the total amount (including the solvent) of the photosensitive resin composition, and it is 18% by mass or less. It is more preferable from the viewpoint of forming a cured film having excellent flatness when applied on the underlying substrate, and particularly preferably 16% by mass or less. The photosensitive resin composition is a cured film having a taper angle of a pattern obtained by pattern exposure and development that the content of component A is 13% by mass or more in the total amount (including the solvent) of the photosensitive resin composition Is preferable from the viewpoint of forming, more preferably 14% by mass or more, and particularly preferably 15% by mass or more.
The photosensitive resin composition of the present invention includes a polymer 2: a polymer having a structural unit having a group in which an a1 acid group is protected by an acid-decomposable group and a polymer having a structural unit having an a2 crosslinkable group. In this case, the ratio (molar ratio) between the polymer having a structural unit having a group in which the a1 acid group is protected with an acid-decomposable group and the polymer having a structural unit having an a2 crosslinkable group is 95: 5. To 5:95 is preferable, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is more preferable.

  The component A polymer component is preferably an addition polymerization type resin, and more preferably a polymer containing at least one of structural units derived from (meth) acrylic acid and its ester. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. “At least one of the structural units derived from (meth) acrylic acid and its ester” is also referred to as “acrylic structural unit”.

<< Constitutional unit having a group in which the a1 acid group is protected with an acid-decomposable group >>
The component A polymer component has at least a structural unit a1 having a group in which an acid group is protected with an acid-decomposable group. When the component A polymer component has the structural unit a1, a highly sensitive photosensitive resin composition can be obtained. These structural units a1 can be used individually by 1 type or in combination of 2 or more types.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) or an acid. A group that is relatively difficult to decompose (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used.

The structural unit a1 is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
Hereinafter, the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group and the structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in this order.

<<< Structural Unit Having a Protected Carboxyl Group Protected with an a1-1 Acid-Decomposable Group >>>
The structural unit a1-1 is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group which can be used for the said structural unit a1-1, A well-known structural unit can be used. Examples thereof include the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid.
Hereinafter, the structural unit a1-1-1 used as the structural unit having a carboxyl group will be described.

<<<<< Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in a1-1-1 Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention include those listed below.
That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. Examples include leuoxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
Moreover, the acid anhydride may be sufficient as unsaturated polycarboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among these, from the viewpoint of developability, in order to form the structural unit a1-1-1, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxy It is preferable to use ethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of unsaturated polyvalent carboxylic acid, and acrylic acid, methacrylic acid, 2- (meth) acryloyloxy More preferably, ethyl hexahydrophthalic acid is used.
The structural unit a1-1-1 may be composed of one kind alone, or may be composed of two or more kinds.

<<<<< Acid-decomposable group that can be used for the structural unit a1-1 >>>>
As the acid-decomposable group that can be used for the structural unit a1-1, the acid-decomposable groups described above can be used.
Among these acid-decomposable groups, an acid-decomposable group is preferably a group having a structure protected in the form of an acetal. For example, the carboxyl group is a protected carboxyl group protected in the form of an acetal, the basic physical properties of the photosensitive resin composition, especially the sensitivity and pattern shape, the formation of contact holes, the storage stability of the photosensitive resin composition From the viewpoint of Furthermore, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula a1-10. In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula a1-10, the entire protected carboxyl group is-(C = O) -O-CR ¹⁰¹ R ^102. The structure is (OR ¹⁰³ ).

Formula a1-10
(In Formula a1-10, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

In the general formula a1-10, R ^{101 to} R ¹⁰³ each independently represents a hydrogen atom or an alkyl group. The alkyl group may be linear, branched or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, (alpha) -methylphenyl group, a naphthyl group etc. can be illustrated. Examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, and a methoxy group or an ethoxy group is especially preferable.
When the alkyl group is a cyclic alkyl group, the cyclic alkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is directly In the case of a chain or branched alkyl group, it may have a C3-C12 cyclic alkyl group as a substituent.
These substituents may be further substituted with the above substituents.

In General Formula a1-10, when R ¹⁰¹ , R ^102, and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, and more preferably has 6 to 10 carbon atoms. . The aryl group may have a substituent, and preferred examples of the substituent include 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, and a 1-naphthyl group.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the cyclic structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
In General Formula a1-10, any one of R ¹⁰¹ and R ¹⁰² is preferably a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group protected in the form of the acetal represented by the general formula a1-10, a commercially available one may be used, or a known one may be used. What was synthesize | combined by the method of can also be used. For example, it can synthesize | combine with the synthesis | combination method etc. of Paragraph Nos. 0037-0040 of Unexamined-Japanese-Patent No. 2011-221494, This content is integrated in this specification.

A first preferred embodiment of the structural unit a1-1 is a structural unit represented by the following general formula A2 ′.
In formula A2 ′, R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² represents an alkyl group or an aryl group, and R ³ represents an alkyl group Or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. .
When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, 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, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.

A second preferred embodiment of the structural unit a1-1 is a structural unit represented by the following general formula 1-12.
Formula 1-12
In 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 phenylene group, and R ^{122 to} R ¹²⁸ each independently represent a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜4.
R ¹²¹ is preferably a hydrogen atom or a methyl group.
L ¹ is preferably a carbonyl group.
R ^{122 to} R ¹²⁸ are preferably a hydrogen atom.

  As preferred specific examples of the structural unit a1-1, the following structural units can be exemplified. In the structural units below, R represents a hydrogen atom or a methyl group.

<<< Structural Unit Having Protected Phenolic Hydroxyl Group Protected with a1-2 Acid-Decomposable Group >>>
The structural unit a1-2 is preferably a structural unit a1-2-1 in which the structural unit having a phenolic hydroxyl group has a protected phenolic hydroxyl group protected by an acid-decomposable group described in detail below.

<<<<< Constitutional Unit Having a1-2-1 Phenolic Hydroxyl Group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a structural unit in a hydroxystyrene-based structural unit and a novolac-based resin, and among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene, It is preferable from the viewpoint of sensitivity. Moreover, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula a1-20 is also preferable from the viewpoint of sensitivity.

Formula a1-20
In General 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 chain having 1 to 5 carbon atoms. A represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less. In addition, when two or more ^R222 exists, these ^R222 may mutually differ or may be the same.

In General Formula a1-20, R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²²¹ represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R ²²¹ may be exemplified alkylene groups, specific examples R ²²¹ is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Among these, it is preferable that R ²²¹ is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Moreover, although a represents the integer of 1-5, from the viewpoint of the effect of this invention and the point that manufacture is easy, it is preferable that a is 1 or 2, and it is more preferable that a is 1. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²²¹ is defined as the reference (first position).
R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
Specific examples include fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;

<<<< acid-decomposable group that can be used for the structural unit a1-2 >>>>
As the acid-decomposable group that can be used for the structural unit a1-2, a known group can be used as in the case of the acid-decomposable group that can be used for the structural unit a1-1, and is not particularly limited. Among the acid-decomposable groups, the structural unit having a protected phenolic hydroxyl group protected in the form of an acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, and storage stability of the photosensitive resin composition. From the viewpoint of forming a contact hole, it is preferable. Furthermore, among acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula a1-10. In addition, when the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula a1-10, the entire protected phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ). Ar represents an arylene group.
Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.
Moreover, as a radically polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of acetal, for example, paragraph number 0042 of JP2011-215590A is disclosed. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

  Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned. These can be used alone or in combination of two or more.

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

  Preferable specific examples of the structural unit a1-2 include the following structural units, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit a1 >>>
When the polymer containing the structural unit a1 is substantially free of the structural unit a2, the content of the structural unit a1 is preferably 20 to 100 mol%, preferably 30 to 90 mol in the component A polymer component. % Is more preferable.
In the case where the polymer containing the structural unit a1 contains the structural unit a2, the content of the structural unit a1 is preferably 3 to 70 mol% from the viewpoint of sensitivity in the component A polymer component, and 10 to 60 mol. % Is more preferable. In particular, when the acid-decomposable group that can be used for the structural unit a1 is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, 20 to 50 mol% is preferable.

  The structural unit a1-1 is developed faster than the structural unit a1-2. Therefore, when it is desired to develop quickly, it is preferable to use the structural unit a1-1. Conversely, when it is desired to delay the development, it is preferable to use the structural unit a1-2.

<< Structural Unit Having a2 Crosslinkable Group >>
The component A polymer component has a structural unit a2 having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. As a preferred embodiment of the structural unit having a crosslinkable group, an epoxy group, an oxetanyl group, a group represented by —NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene And a structural unit containing at least one selected from the group consisting of an unsaturated group, an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is a hydrogen atom or a carbon number of 1 to 20). The alkyl group is preferably at least one selected from the group represented by Among these, it is preferable that the photosensitive resin composition of this invention contains the structural unit in which a component A polymer component contains at least 1 among an epoxy group and an oxetanyl group. By using a unit containing at least one of an epoxy group and an oxetanyl group, the effects of the present invention are more effectively exhibited. These structural units a2 can be used individually by 1 type or in combination of 2 or more types. In more detail, the following are mentioned.

<<< Structural unit having at least one of a2-1 epoxy group and oxetanyl group >>>
It is preferable that the said component A polymer component contains the structural unit (henceforth the structural unit a2-1) which has at least one among an epoxy group and oxetanyl group.
The structural unit a2-1 only needs to have at least one epoxy group or oxetanyl group in one structural unit, one or more epoxy groups and one or more oxetanyl groups, two or more epoxy groups, Alternatively, it may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups or oxetanyl groups, and has a total of 1 or 2 epoxy groups or oxetanyl groups. Is more preferable, and it is more preferable to have one epoxy group or oxetanyl group.
The structural unit having an a2 crosslinkable group is a structural unit having an epoxy group among structural units having at least one of a2-1 epoxy group and oxetanyl group. This is preferable from the viewpoint of forming a cured film having a large taper angle.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, ortho-vinylbenzyl glycidyl ether, meta-vinylbenzyl glycidyl ether, para-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 And compounds containing an alicyclic epoxy skeleton can be mentioned, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used to form the structural unit a2-1 having at least one of the epoxy group and the oxetanyl group include a monomer containing a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.

  Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, ortho-vinylbenzyl glycidyl ether, meta-vinylbenzyl glycidyl ether, para-vinylbenzyl glycidyl. Ether, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl are preferred from the viewpoints of copolymerization reactivity and improved properties of the cured film. These structural units can be used individually by 1 type or in combination of 2 or more types.

  As preferred specific examples of the structural unit a2-1, the following structural units can be exemplified. In the structural units below, R represents a hydrogen atom or a methyl group.

<<< constituent unit having a2-2 ethylenically unsaturated group >>>
As one of the structural unit a2 having a crosslinkable group, there may be mentioned a structural unit a2-2 having an ethylenically unsaturated group. As the structural unit a2-2, a structural unit having an ethylenically unsaturated group in the side chain is preferable, and a structural unit having an ethylenically unsaturated group at the terminal and having a side chain having 3 to 16 carbon atoms is more preferable. .
In addition, as for the structural unit a2-2, the compounds described in paragraph numbers 0072 to 0090 of JP2011-215580A and paragraph numbers 0013 to 0031 of JP2008-256974A are preferable examples. Is incorporated herein by reference.

<<< Structural Unit Having a Group Represented by a2-3-NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>
The component A polymer component used in the present invention is also preferably a structural unit a2-3 having a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having the structural unit a2-3, a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit a2-3 is more preferably a structural unit having a group represented by the following general formula a2-30.
Formula a2-30
In General 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, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

<<< Preferred Aspect of Structural Unit a2 Having a Crosslinkable Group >>>
When the polymer containing the structural unit a2 is substantially free of the structural unit a1, the content of the structural unit a2 is preferably 5 to 90 mol% in the component A polymer component, and 20 to 80 mol. % Is more preferable.
When the polymer containing the structural unit a2 contains the structural unit a1, the content of the structural unit a2 is preferably 3 to 70 mol% from the viewpoint of chemical resistance in the component A polymer component. 60 mol% is more preferable.
In the present invention, the content of the structural unit a2 is preferably 3 to 70 mol%, and preferably 10 to 60 mol%, in all the structural units of the component A polymer component, regardless of any embodiment. Is more preferable.
By setting it within the above numerical range, a cured film having excellent characteristics can be formed.

<< Structural Unit a3 Having Acid Group >>
In the present invention, the polymer component A may have a structural unit a3 having an acid group. The structural unit a3 may be included in a polymer having the structural unit a1, or may be included in a polymer that does not substantially include the structural unit a1. When the polymer component has the structural unit a3, the polymer component is easily dissolved in an alkaline developer, and developability is improved. Furthermore, it is excellent in sensitivity.

  Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and acid anhydride groups of these acid groups. At least one of the phenolic hydroxyl groups is preferred. That is, the structural unit a3 is preferably a structural unit having a carboxyl group and a structural unit having a phenolic hydroxyl group.

  As the structural unit a3, at least one of a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and an ester thereof is more preferable. For example, compounds described in JP2012-88459A, paragraphs 0021 to 0023 and paragraphs 0029 to 0044 can be used, the contents of which are incorporated herein. Among these, structural units derived from para-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferable.

  The polymer having the structural unit a3 is preferably a polymer having a carboxyl group in the side chain. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxy group, and polymers having a (meth) acryloyl group in the side chain are also preferred.

For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.

  These polymers are commercially available, SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON. UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncry 690, Joncryl 678, Joncry 67, Joncry 586 (above, made using BASF), etc. You can also.

<<< Preferred Aspect of Structural Unit a3 >>>
When the polymer having the structural unit a3 has the structural unit a1 and the structural unit a2, the content of the structural unit a3 is preferably 1 to 30 mol%, preferably 3 to 20 mol based on all the structural units of the polymer. % Is more preferable, and 5 to 15 mol% is still more preferable.
When the polymer having the structural unit a3 has only one of the structural unit a1 and the structural unit a2, the content of the structural unit a3 is preferably 1 to 50 mol% with respect to all the structural units of the polymer. 5-45 mol% is more preferable and 10-40 mol% is still more preferable.
When the polymer containing the structural unit a3 is substantially free of the structural unit a1 and the structural unit a2, the content of the structural unit a3 is preferably 1 to 50 mol% with respect to all the structural units of the polymer. 2-40 mol% is more preferable and 3-30 mol% is still more preferable.
In the present invention, the content of the structural unit a3 is preferably 1 to 80 mol%, more preferably 1 to 50 mol% in all the structural units of the polymer component A regardless of any embodiment. 40 mol% is more preferable, 5-30 mol% is especially preferable, and 5-25 mol% is especially preferable.

<< other structural unit a4 >>
In the present invention, the component A polymer component may have a constituent unit a4 other than the constituent units a1 to a3 described above in addition to the constituent unit a1 and the constituent unit a2. The structural unit a4 may be included in the polymer 1 or the polymer 2. In addition to the polymer 1 or the polymer 2, a polymer having other structural unit a4 substantially not including the structural unit a1 and the structural unit a2 may be included.

  There is no restriction | limiting in particular as a monomer used as the structural unit a4, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, and other unsaturated compounds can be exemplified.

  Specifically, styrene, methyl styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester , Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, and the like.In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  The structural unit a4 is preferably a structural unit having a styrene or an aliphatic cyclic skeleton from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and the like.

  The structural unit a4 is preferably a (meth) acrylic acid alkyl ester from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.

  In all the structural units constituting the polymer, the content of the structural unit a4 is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more. Within the above numerical range, the properties of the cured film are good.

Although preferable embodiment of a polymer component is given to the following, this invention is not limited to these.
(First embodiment)
The aspect in which the polymer 1 further has one or more other structural units a4.
(Second Embodiment)
The aspect in which the polymer having a structural unit in which the a1 acid group is protected with an acid-decomposable group in the polymer 2 further has one or more other structural units a4.
(Third embodiment)
The aspect in which the polymer which has the structural unit which has a2 crosslinkable group in the polymer 2 further has 1 type, or 2 or more types of other structural units a4.
(Fourth embodiment)
In any one of the first to third embodiments, the other structural unit a4 includes a structural unit containing at least an acid group.
(Fifth embodiment)
In addition to the polymer 1 or the polymer 2, the aspect further includes a polymer having another structural unit a4 substantially not including the structural unit a1 and the structural unit a2.
(Sixth embodiment)
The form which consists of 2 or more combinations of the said 1st-5th embodiment.

  In an embodiment having a polymer having other structural unit a4 substantially free of a1 and a2, the total amount of the polymer having a1 or a2 and other components substantially free of a1 and a2 The weight ratio with respect to the total amount of the polymer having the unit a4 is preferably 99: 1 to 5:95, more preferably 97: 3 to 30:70, and still more preferably 95: 5 to 50:50.

<< weight average molecular weight of component A polymer component >>
The weight average molecular weight of the component A polymer component is 10,000 or more. The weight average molecular weight is a polystyrene equivalent weight average molecular weight. The weight average molecular weight of the component A polymer component is preferably in the range of 10,000 to 200,000, more preferably 10,000 to 50,000. Various characteristics are favorable in the range of said numerical value. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
The weight average molecular weight and the degree of dispersion of the component A polymer component are defined as polystyrene conversion values determined by GPC measurement.

<< Component A Polymer Component Synthesis Method >>
Various methods for synthesizing the component A polymer component are also known. For example, a radical polymerization initiator containing a radical polymerizable monomer mixture containing at least the radical polymerizable monomer used to form the structural units represented by a1 and a2 in an organic solvent is used. Can be synthesized by polymerization. It can also be synthesized by a so-called polymer reaction.
Although there is no restriction | limiting in particular as a radical polymerization initiator, For example, it is preferable to use V-601: dimethyl 2,2'-azobis (2-methylpropionate) (made by Wako Pure Chemical Industries Ltd.).
(A) The polymer component preferably contains 50 mol% or more, and 80 mol% or more of a structural unit derived from at least one of (meth) acrylic acid and its ester with respect to all the structural units. More preferred.

<Component B photoacid generator>
The photosensitive resin composition of the present invention contains Component B photoacid generator. The photoacid generator used in the present invention is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. As a photoacid generator used in the present invention, a photoacid that generates an acid having a pKa (acid dissociation index; power of Ka; Ka represents an acid dissociation constant, and pKa = −logKa) is 4 or less. A generator is preferable, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid of 2 or less is most preferable.

Examples of photoacid generators include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. .
Among these, onium salt compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferable, and onium salt compounds and oxime sulfonate compounds are particularly preferable. A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane compounds include compounds described in paragraphs 0083 to 0088 of JP2011-221494A; The compounds described in JP-A-2011-105645, paragraphs 0013 to 0049, can be exemplified, and the contents thereof are incorporated in the present specification.
Specific examples of the imide sulfonate compound include compounds described in paragraphs 0065 to 0075 of WO2011 / 087011, and the contents thereof are incorporated herein.

Preferred examples of the onium salt include diaryliodonium salts and triarylsulfonium salts.
Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2′-hydroxy- 1'-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecoxy) phenyliodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetra Decaoxy) phenyliodonium-para-toluenesulfonate is preferred.
Examples of triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium. Preferred is trifluoromethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

  Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1-1).

General formula (B1-1)
In General Formula (B1-1), R ²¹ represents an alkyl group or an aryl group. Wavy lines represent bonds with other groups.

In general formula (B1-1), any group may be substituted, and the alkyl group in R ²¹ may be linear, branched, or cyclic. Acceptable substituents are described below.
As the alkyl group for R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (such as a 7,7-dimethyl-2-oxonorbornyl group). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

  It is also preferable that the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is an oxime sulfonate compound described in paragraphs 0108 to 0133 of JP 2014-238438 A.

  As an imide sulfonate type compound, a naphthalene imide type compound is preferable, the description of international publication WO11 / 087011 pamphlet can be referred and these content is integrated in this specification. In the present invention, in particular, trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethyl sulfonate, phthalimide trifluoromethyl sulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxy- 5-norbornene-2,3-dicarboximidopropanesulfonate is preferred.

  In the photosensitive resin composition of the present invention, the content of the photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid component of the photosensitive resin composition. For example, the lower limit is more preferably 0.2 parts by mass or more, and further preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

<Component C solvent>
The photosensitive resin composition of this invention contains the component C solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. As a solvent used for the preparation of the photosensitive resin composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. Moreover, as a specific example of the solvent used for the photosensitive resin composition of this invention, the solvent of paragraph number 0174-0178 of Unexamined-Japanese-Patent No. 2011-221494, Paragraph number 0167-0168 of Unexamined-Japanese-Patent No. 2012-194290. And the contents thereof are incorporated herein.

  In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol as necessary for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is preferably a single type or a combination of two types, more preferably a single type, and even more preferably diethylene glycol dialkyl ethers.

In addition, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. From the viewpoint of improving the flatness of the film.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include 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 An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol ethyl methyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Bp 213 ° C.), 3-methoxybutyl ether acetate (bp 171 ° C.), diethylene glycol diethyl ether (bp 189 ° C.), diethylene glycol dimethyl ether (bp 162 ° C.), propylene glycol diacetate (bp 190 ° C.), diethylene glycol monoethyl ether acetate ( Examples include boiling point 220 ° C., dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.). Kill.

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, and preferably 60 to 90 parts by mass, per 100 parts by mass of all components in the photosensitive resin composition. Further preferred. Only one type of solvent may be included, or two or more types of solvents may be included. When two or more types are included, the total amount is preferably within the above range.
The total solid content in the photosensitive resin composition of the present invention is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of all components in the photosensitive resin composition. .

<Component E>
The photosensitive resin composition of the present invention contains a component E crosslinking agent, the molecular weight of component E is 3000 or less, the content of component E is 15% by mass or more in the total solid content, and component E is a molecule. And at least one of a compound having two or more groups represented by the following formula X1 and a compound having two or more unsaturated double bonds in the molecule.
In formula X1, at least one of R ^{X1 to} R ^X3 is a hydrolyzable selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group, and an isopropenoxy group. The remaining R ^{X1 to} R ^X3 each independently represents a hydrogen atom, a halogen atom, or a monovalent organic substituent.

Component E has a molecular weight of 3000 or less, preferably 2000 or less, and more preferably 1000 or less. When the molecular weight is in the above range, it is preferable from the viewpoint of forming a cured film having excellent flatness when applied on a base having a step.
The molecular weight of component E is preferably 100 or more, more preferably 200 or more, and particularly preferably 300 or more. However, from the viewpoint of forming a cured film having a large taper angle of a pattern obtained by pattern exposure and development, the molecular weight of component E may be 2000 or more.
Component E may be any of chemical forms such as a monomer, a prepolymer, and an oligomer, and is preferably a monomer. In the present invention, when Component E is a prepolymer or oligomer, the molecular weight of Component E can be read as a weight average molecular weight.

The photosensitive resin composition of the present invention has a step that the content of component E is 15% by mass or more in the total solid content and the content of component E is 20% by mass or more in the total solid content. It is preferable from the viewpoint of forming a cured film having excellent flatness when applied on the base, more preferably the content of component E is 22% by mass or more in the total solid content, and the content of component E is all It is particularly preferably 25% by mass or more based on the solid content. In the photosensitive resin composition, the content of component E is preferably 40% by mass or less, and 35% by mass or less can form a cured film having a large taper angle of the pattern obtained by pattern exposure and development. More preferable from the viewpoint.
In the photosensitive resin composition of the present invention, the value of component E / component A, which is the ratio of the content of component E in the total solid content to the content of component A in the total solid content, is 0.20 or more. It is preferably 0.30 or more, more preferably 0.32 or more from the viewpoint of forming a cured film having excellent flatness when coated on a base having a step. The value of Component E / Component A is preferably 0.70 or less, and more preferably 0.52 or less from the viewpoint of forming a cured film having a large taper angle of the pattern obtained by pattern exposure and development. The preferred range of the ratio of the content of component E in the total solid content to the total of the polymer 1 or the polymer 2 in the total solid content of the photosensitive resin composition of the present invention is as follows: This is the same as the preferred range of values.
The photosensitive resin composition of the present invention has a step that the content of component E is 30% by mass or more in the total solid content, and the value of component E / component A is 0.52 or less. It is preferable from the viewpoint of forming a cured film that is excellent in flatness when applied on a base and has a large taper angle of a pattern obtained by pattern exposure and development. In the photosensitive resin composition of the present invention, the content of component E is 30% by mass or more based on the total solid content, the value of component E / component A is 0.52 or less, and component E is represented by the formula It is more preferable that the compound has three or more groups represented by X1.
In the photosensitive resin composition of the present invention, the solid content other than Component A and Component E in the total solid content is preferably 15% by mass or less, more preferably 10% by mass or less. It is particularly preferable from the viewpoint of being able to form a cured film having excellent flatness when applied on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. In the photosensitive resin composition of the present invention, the content of component E is 25 to 35% by mass in the total solid content, and the content of solid content other than component A and component E in the total solid content is 5 More preferably, it is at most mass%. In the photosensitive resin composition of the present invention, the content of component E is 25 to 35% by mass in the total solid content, and the content of solid content other than component A and component E in the total solid content is 5% by mass. More preferably, Component E is a compound having three or more groups represented by Formula X1 in the molecule.
The photosensitive resin composition of this invention can also be set as the aspect which does not contain other crosslinking agents other than (E) component substantially.

  The photosensitive resin composition of this invention may contain only 1 type of component E crosslinking agent, and may contain it in combination of 2 or more types. When two or more types are included, the total amount is preferably within the above range.

In order to increase the taper angle of the pattern such as the contact hole of the cured film, it is preferable that the crosslinking initiation temperature of the crosslinking agent (in the present invention, the curing initiation temperature of the resin composition) is low. Since the crosslinking start temperature of the crosslinking agent is low, the crosslinking reaction at the time of post-baking proceeds quickly, and the pattern such as the contact hole of the cured film can be cured before flowing, and a pattern having a large taper angle can be obtained. Further, by increasing the crosslinking start temperature to such an extent that the film is not cured in the pre-baking step, patterning is facilitated by exposure and development. Specifically, if the curing start temperature of the resin composition of the present invention is 10 ° C. or more higher than the softening temperature of the photosensitive resin composition and not more than the heating temperature of the post-baking step, preferably about 120 ° C. to 140 ° C. The film can be cured before flowing during post-baking, and a cured film having a large taper angle of the pattern can be obtained.
The curing start temperature of the resin composition is a temperature measured by the following method. When the resin composition from which the solvent has been dried is heated at various temperatures for 30 minutes, the temperature at which the Young's modulus of the resin composition after heating is 1 kPa or more is defined as the curing start temperature of the resin composition.

<< Compound having two or more groups represented by formula X1 in the molecule >>
The photosensitive resin composition of the present invention is a cured film having a large pattern taper angle obtained by pattern exposure and development that component E is a compound having two or more groups represented by the following formula X1 in the molecule From the viewpoint that can be formed.
In formula X1, at least one of R ^{X1 to} R ^X3 is a hydrolyzable selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group, and an isopropenoxy group. The remaining R ^{X1 to} R ^X3 each independently represents a hydrogen atom, a halogen atom, or a monovalent organic substituent.

In formula X1, the hydrolyzable group bonded to the silicon atom is particularly preferably an alkoxy group or a halogen atom, and more preferably an alkoxy group.
As the alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable, an alkoxy group having 1 to 15 carbon atoms is more preferable, and an alkoxy group having 1 to 5 carbon atoms is further preferable, from the viewpoint of easily obtaining the effects of the present invention. A C1-C3 alkoxy group is still more preferable, and a methoxy group or an ethoxy group is particularly preferable.
Further, examples of the halogen atom include an F atom, a Cl atom, a Br atom, and an I atom. From the viewpoint of ease of synthesis and stability, a Cl atom and a Br atom are preferable, and a Cl atom is more preferable. Can be mentioned.

A compound having two or more groups represented by the formula X1 in the molecule has two or more groups represented by the formula X1. That is, a compound having two or more silicon atoms having a hydrolyzable group bonded in the molecule is preferably used. The number of silicon atoms to which the hydrolyzable group contained in the compound having two or more groups represented by the formula X1 in the molecule is preferably 2-6, more preferably 2-4, and 2 or 3 Further preferred.
By having two or more component X1, it functions as a crosslinking agent inside the cured film, and can improve the resistance of the cured film to the stripping solution and solvent.
A compound having two or more groups represented by the formula X1 in the molecule is a compound having three or more groups represented by the formula X1 in the molecule. It is more preferable from the viewpoint of forming a cured film having excellent properties.
The hydrolyzable group can be bonded to one silicon atom in the range of 1 to 4, and the total number of hydrolyzable groups in the formula X1 is preferably in the range of 2 or 3. It is particularly preferable that one hydrolyzable group is bonded. When two or more hydrolyzable groups are bonded to a silicon atom, they may be the same as or different from each other.

Preferred examples of the alkoxy group as the hydrolyzable group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, phenoxy group, and benzyloxy group. A plurality of these alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.
Examples of the alkoxysilyl group to which the alkoxy group is bonded include, for example, a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group; a dimethoxymethylsilyl group, a diethoxymethylsilyl group And dialkoxymonoalkylsilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group.

  The compound having two or more groups represented by the formula X1 in the molecule may contain a sulfur atom, an ester bond, a urethane bond, an ether bond, a urea bond, or an imino group. Among them, compounds having two or more groups represented by the formula X1 in the molecule are ester bonds, urethane bonds or ether bonds (especially ethers contained in oxyalkylene groups) that are easily decomposed with alkaline water from the viewpoint of alkali developability. It is preferable to contain a bond). Moreover, it is preferable that the compound which has 2 or more groups represented by Formula X1 in the molecule | numerator in this invention is a compound which does not have an ethylenically unsaturated bond. The compound having two or more groups represented by the formula X1 in the molecule preferably has only a hydrolyzable silyl group and / or a silanol group as the polymerizable group.

Examples of the compound having two or more groups represented by the formula X1 in the molecule according to the present invention include compounds in which a plurality of groups represented by the formula X1 are bonded through a divalent linking group. Examples of such a divalent linking group include a sulfide group (—S—), an imino group (—N (R) —), or a urethane bond (—OCON (R) — or N (R) COO— from the viewpoint of effects. ) Is preferred. R represents a hydrogen atom or a substituent. Examples of the substituent in R include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group.
There is no restriction | limiting in particular as a synthesis method of the compound which has two or more groups represented by Formula X1 in a molecule | numerator, It can synthesize | combine by a well-known method. Representative methods for synthesizing compounds having two or more groups represented by the formula X1 in the molecule include the methods described in [0098] to [0100] of JP2013-218265A. The contents are incorporated herein by reference.

  Specific examples of the compound having two or more groups represented by the formula X1 in the molecule include 1,2-bis (triethoxysilyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxy Silyl-4-trimethoxysilylbutane, 1,4-bis (methyldimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl -5-trimethoxysilylpentane, 1,5-bis (methyldimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis ( Trimethoxysilyl) hexane, 2,5-bis (trimethoxysilyl) hexane, 1,6-bis (methyldimethoxysilyl) Sun, 1,7-bis (trimethoxysilyl) heptane, 2,5-bis (trimethoxysilyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 2,5-bis (trimethoxysilyl) octane, 2,7-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1, 10-bis (trimethoxysilyl) decane, 3,8-bis (trimethoxysilyl) decane, vinyltrichlorosilane, 1,3-bis (trichlorosilane) propane, 1,3-bis (tribromosilane) propane, vinyl Trimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, γ-methacryloxypropyl Trimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N -(Β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, -Phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 2- (2-aminoethylthio) Ethyl) diethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, dimethoxymethyl-3- (3-phenoxypropylthiopropyl) silane, Bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, 1,4-bis (triethoxysilyl) benzene, bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilane) Yl) hexane, 1,8-bis (triethoxysilyl) octane, 1,2-bis (trimethoxysilyl) decane, bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) urea, γ-chloropropyl Examples include trimethoxysilane, γ-triethoxysilylpropyl (meth) acrylate, γ-ureidopropyltriethoxysilane, trimethylsilanol, diphenylsilanediol, and triphenylsilanol.

  In addition, although the compound shown below is mentioned as a compound which has two or more groups represented by Formula X1 in a preferable molecule | numerator, this invention is not restrict | limited to these compounds.

In the above formulas, R and R ¹ each represent a partial structure selected from the following structures. When a plurality of R and R ¹ are present in the molecule, these may be the same or different from each other, and are preferably the same in terms of synthesis suitability.

  A compound having two or more groups represented by the formula X1 in the molecule can be appropriately synthesized, but a commercially available product is preferably used from the viewpoint of cost. Examples of the compound having two or more groups represented by the formula X1 in the molecule include Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd., Momentive Performance Materials Co., Ltd. and Chisso Co., Ltd. Since commercially available products such as silane products and silane coupling agents correspond to this, these commercially available products may be appropriately selected and used for the photosensitive resin composition of the present invention. .

As the compound having two or more groups represented by the formula X1 in the molecule of the present invention, a partially hydrolyzed condensate obtained by using one compound having a group represented by the formula X1 in the molecule, or The partial cohydrolysis condensate obtained by using 2 or more types can be used. Hereinafter, these compounds may be referred to as “partial (co) hydrolysis condensates”.
Among silane compounds as partial (co) hydrolysis condensate precursors, from the viewpoint of versatility, cost, and film compatibility, it has a substituent selected from a methyl group and a phenyl group as a substituent on silicon. It is preferably a silane compound. Specifically, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane Is exemplified as a preferred precursor.
In this case, as a partial (co) hydrolysis condensate, dimers of the silane compound as described above (1 mol of water was allowed to act on 2 mol of the silane compound to remove 2 mol of alcohol to form disiloxane units. To 100-mer, preferably 2 to 50-mer, more preferably 2 to 30-mer, and a partial cohydrolysis condensate using two or more silane compounds as raw materials. It is also possible to use it.

  In addition, as such a partial (co) hydrolysis condensate, you may use what is marketed as a silicone alkoxy oligomer (for example, it is marketed from Shin-Etsu Chemical Co., Ltd.), etc. You may use what was manufactured by removing by-products, such as alcohol and hydrochloric acid, after making the hydrolysis water of less than an equivalent react with a hydrolysable silane compound based on a conventional method. In production, for example, when using alkoxysilanes or acyloxysilanes as described above as the precursor hydrolyzable silane compound, acids such as hydrochloric acid and sulfuric acid, sodium hydroxide, hydroxide What is necessary is just to carry out partial hydrolysis condensation using alkali metal such as potassium or hydroxide of alkaline earth metal, alkaline organic substance such as triethylamine and the like as a reaction catalyst. In the case of producing directly from chlorosilanes, water and alcohol may be reacted using hydrochloric acid as a by-product as a catalyst.

  Bis (trialkoxysilyl) alkane is more preferred from the viewpoints of excellent curability, adhesiveness, heat-resistant coloring stability, and a balance between transparency and adhesive strength, and excellent heat-and-moisture resistance. Methoxysilylpropyl) amine, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxy) More preferred is at least one selected from the group consisting of (silyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane, and 1,6-bis (trimethoxysilyl) Hexane and bis- (3-trimethoxysilylpropyl) amine are more preferable.

The compound having two or more groups represented by the formula X1 in the molecule used in the present invention is particularly preferably a silicon compound represented by the formula X2.
(In the formula, X represents a group represented by the above formula X1, a represents an integer of 2 or more, and Ro represents an a-valent linking group.)
X in Formula X2 has the same meaning as the group represented by Formula X1, and the preferred range is also the same.
In formula X2, a is preferably 2 to 4, more preferably 2 or 3.
The compound represented by the formula X2 is more preferably a compound represented by the following formula X3.
(Wherein X represents the above formula X1, a represents an integer of 2 or more, n represents an integer of 1 to 5. Roo represents a single bond or an a-valent linking group.)
X in Formula X3 has the same meaning as the group represented by Formula X1, and the preferred range is also the same.
In the formula X3, a is preferably 2 to 4, more preferably 2 or 3, and particularly preferably 2.
In Formula X3, Roo is a single bond, and —CR ₂ — (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), —S—, —CO—, —O—, a phenylene group, an isocyanuric skeleton, and A group consisting of a combination of two or more of these is preferred.
In the photosensitive resin composition of the present invention, the component E is preferably a compound having an isocyanuric skeleton from the viewpoint of forming a cured film having a large taper angle of a pattern obtained by pattern exposure and development.

In Formula X3, Roo is more preferably a single bond, and —CR ₂ — (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), —S—, —CO—, —O—, and these A group consisting of a combination, more preferably a single bond, and a group consisting of —CH ₂ —, —S—, and a combination thereof.
In Formula X3, n is preferably an integer of 1 to 3, and more preferably 1 or 2.
The molecular weight of the component E used in the present invention is 3000 or less, and when the component E is a compound having two or more groups represented by the formula X1 in the molecule, two groups represented by the formula X1 are present in the molecule. The molecular weight of the compound having the above is preferably 100 to 1500, and more preferably 250 to 1100.

In the present invention, the following compounds (E-1), (E-2), (S-2) to (S-17) are particularly preferable as compounds having two or more groups represented by the formula X1 in the molecule. Preferably employed.
Compound (E-1) is commercially available as KBM-9659 (manufactured by Shin-Etsu Chemical), and compound (E-2) is commercially available as KBE-3026 (manufactured by Shin-Etsu Chemical).

<< Compound having two or more unsaturated double bonds in the molecule >>
The photosensitive resin composition of the present invention forms a cured film having excellent flatness when applied to a substrate having a step that component E is a compound having two or more unsaturated double bonds in the molecule. It is preferable from a viewpoint that can be made.

  The compound having two or more unsaturated double bonds in the molecule is more preferably a compound having three or more unsaturated double bonds in the molecule, and has four or more unsaturated double bonds in the molecule. More preferably, it is a compound. The upper limit of the number of unsaturated double bonds in the molecule is preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less.

  The unsaturated double bond of the compound having two or more unsaturated double bonds in the molecule is preferably an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

  The compound having two or more unsaturated double bonds in the molecule is preferably a (meth) acrylate compound. The (meth) acrylate compound is preferably a compound having two or more (meth) acryloyl groups in the molecule, more preferably a compound having three or more (meth) acryloyl groups in the molecule, It is more preferable that the compound has 4 or more (meth) acryloyl groups. The upper limit of the number of (meth) acryloyl groups is preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. Specific examples of these compounds include compounds described in paragraphs 0095 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-29760A, and paragraph numbers 0254 to 0257 of JP2008-292970A. Which is incorporated herein by reference.

  Compounds having two or more unsaturated double bonds in the molecule are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate ( As commercial products, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues Structure (eg, SR454, commercially available from Sartomer, Inc. R499) is preferable. These oligomer types can also be used. Moreover, KAYARAD RP-1040, DPCA-20 (Nippon Kayaku Co., Ltd. product), and M-321 (Toagosei Co., Ltd. product) can also be used.

  A compound having two or more unsaturated double bonds in the molecule may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. A preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developability is good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent. As a commercial item of the polymeric compound which has an acid group, M-305, M-510, M-520 etc. are mentioned as a polybasic acid modified acrylic oligomer by Toagosei Co., Ltd., for example.

  A compound having two or more unsaturated double bonds in the molecule is also a preferable embodiment having a caprolactone structure. Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

  As the compound having two or more unsaturated double bonds in the molecule, a polymerizable compound having an alkyleneoxy group can also be used. The compound having two or more unsaturated double bonds in the molecule having an alkyleneoxy group is preferably at least one of compounds having two or more unsaturated double bonds in the molecule having an ethyleneoxy group and a propyleneoxy group. A compound having two or more unsaturated double bonds in the molecule having an ethyleneoxy group is more preferable, and a (meth) acrylate compound having 4 to 20 ethyleneoxy groups is more preferable. Examples of commercially available compounds having two or more unsaturated double bonds in the molecule having an alkyleneoxy group include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, Nippon Kayaku ( DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy groups, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy groups, are available.

In the photosensitive resin composition of the present invention, it is preferable that the component E is a compound having a urethane structure from the viewpoint of forming a cured film having excellent flatness when applied on a base having a step.
Examples of compounds having two or more unsaturated double bonds in the molecule, which are compounds having a urethane structure, include Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-332293, Urethane acrylates as described in JP-B-2-16765, JP-B 58-49860, JP-B 56-17654, JP-B 62-39417, JP-B 62-39418 Urethane compounds having an ethylene oxide skeleton are also suitable. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK oligo U-15HA, U-6LPA, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

<Other ingredients>
In addition to the above components, the photosensitive resin composition of the present invention may contain a solvent, a sensitizer, other crosslinking agents other than the above component E, a basic compound, a surfactant, and an antioxidant as necessary. Preferably it can be added. Further, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. 1 type, or 2 or more types can be added independently, respectively. Moreover, as these compounds, for example, the compounds described in paragraph Nos. 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
The photosensitive resin composition of the present invention can also be in an embodiment that does not substantially contain a polymerizable monomer other than Component E crosslinking agent. The phrase “substantially free” means that the total solid content is 0.5 mass% or less, and further 0.1 mass% or less.

<< Sensitizer >>
The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with a photoacid generator in order to promote its decomposition. The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolidin-11-one).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

  When the photosensitive resin composition of this invention contains a sensitizer, the addition amount of a sensitizer is 0.001-100 mass parts with respect to 100 mass parts of total solids in the photosensitive resin composition. It is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 20 parts by mass. The sensitizer may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.

<< basic compound >>
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include the compounds described in JP-A No. 2011-221494, paragraph numbers 0204 to 0207, the contents of which are incorporated herein.

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 the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, Pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7-undecene, 1,8-diazabicyclo [5.4.0] -7-undecene and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
The basic compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types together.

  When the photosensitive resin composition of this invention contains a basic compound, content of a basic compound is 0.001-3 mass parts with respect to 100 mass parts of total solids in the photosensitive resin composition. It is preferably 0.005 to 1 part by mass. When two or more types are included, the total amount is preferably within the above range.

<< Surfactant >>
The photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. As the surfactant, a nonionic surfactant is preferable, and a fluorosurfactant is more preferable.
Surfactants that can be used in the present invention include, for example, commercially available products such as Megafac F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 70
00, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103 SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footage 250 ( Neos Co., Ltd.). In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), MegaFuck (manufactured by DIC Corporation) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

  Moreover, as surfactant, the compound of Unexamined-Japanese-Patent No. 2014-238438 Paragraph 0151-0155 can also be mentioned as a preferable example.

The content of the surfactant in the photosensitive resin composition of the present invention is preferably 0.001 to 5.0 parts by mass with respect to 100 parts by mass in the total solid content of the photosensitive resin composition, 0.01-2.0 mass parts is more preferable.
Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.

<< Antioxidant >>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and the heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, Examples thereof include zinc sulfate, saccharides, nitrite, sulfite, thiosulfate, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing film thickness, with phenol-based antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and compounds described in paragraph numbers 0106 to 0116 of JP-A-2011-227106. Incorporated herein.
As a preferable commercial item, ADK STAB AO-60, ADK STAB AO-80 (made by ADEKA), Irganox 1035, and Irganox 1098 (made by BASF) can be mentioned.

  When the photosensitive resin composition of this invention contains antioxidant, content of antioxidant is 0.1-10 mass parts with respect to 100 mass parts of total solids in the photosensitive resin composition. Is preferably 0.2 to 5 parts by mass, and particularly preferably 0.5 to 4 parts by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good. Only one type of antioxidant may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

<< Acid Proliferator >>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
Specific examples of such an acid proliferating agent include the acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
The acid proliferating agent may be used alone or in combination of two or more.

<< Development accelerator >>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraph numbers 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive resin composition of the present invention contains a development accelerator, the addition amount of the development accelerator is 0 with respect to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and remaining film ratio. -30 mass parts is preferable, 0.1-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts. When two or more types are included, the total amount is preferably within the above range.
In addition, as other additives, a thermal radical generator described in paragraph Nos. 0120 to 0121 of JP2012-8223A, a nitrogen-containing compound and a thermal acid generator described in WO2011 / 136604A1, can also be used. Is incorporated herein by reference.

<Alkoxysilane compound>
The photosensitive resin composition of the present invention may further contain an alkoxysilane compound. The alkoxysilane compound is preferably a compound having an alkoxysilane structure and at least one selected from the group consisting of an epoxy group, a group having an ethylenically unsaturated bond, an alkyl group substituted with a chloro group, and a mercapto group. By mix | blending such a compound, while being able to improve a sensitivity more, adhesiveness with the base substrate at the time of hardening of the photosensitive resin composition can further be improved.
The alkoxysilane compound may contain only 1 type and may contain 2 or more types.
The molecular weight of the alkoxysilane compound is not particularly defined, but is preferably less than 1000 and more preferably 500 or less. The lower limit of the molecular weight of the alkoxysilane compound is not particularly defined, but is preferably 100 or more, and more preferably 200 or more.

Specific examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxypropyl. Trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane It is done.
Examples of commercially available products include KBM-403, KBM-5103, KBM-303, and KBM-803 manufactured by Shin-Etsu Silicone Co., Ltd.

  When the photosensitive resin composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.05 to 10% by mass in the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. The upper limit is more preferably 8% by mass or less, and particularly preferably 6% by mass or less.

<< Other crosslinking agents other than component E >>
The photosensitive resin composition of this invention can contain other crosslinking agents other than the component E in the range which does not impair the effect of this invention. Other crosslinking agents other than Component E are not limited as long as a crosslinking reaction is caused by heat.
Examples thereof include compounds having two or more epoxy groups or oxetanyl groups in the molecule, blocked isocyanate compounds, alkoxymethyl group-containing compounds, compounds having only one ethylenically unsaturated group in the molecule, and the like. Compounds having two or more epoxy groups or oxetanyl groups in the molecule, blocked isocyanate compounds and alkoxymethyl group-containing compounds are preferred, and compounds having two or more epoxy groups or oxetanyl groups in the molecule and alkoxymethyl group-containing compounds are More preferably, at least one of the compounds having two or more epoxy groups and oxetanyl groups in the molecule is more preferable. When at least one of the compounds having two or more epoxy groups and oxetanyl groups in the molecule is blended, a cured film particularly excellent in heat resistance is easily obtained.

Examples of compounds having two or more epoxy groups or oxetanyl groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.
These are available as commercial products. For example, compounds having two or more epoxy groups in the molecule include JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Corporation), paragraph number 0189 of JP2011-221494A. In addition, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, and the like are listed. EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX- 841, EX-911, EX-941, EX-920, EX-931, EX-212L, X-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (Nagase ChemteX Corporation )), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.), Celoxide 2021P, 2081, 3000, EHPE3150, Epolide GT400, Examples include Cellbiners B0134, B0177 (manufactured by Daicel Corporation), Epicron HP-720 (manufactured by DIC Corporation), and the like.
As the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

Although there is no restriction | limiting in particular in a block isocyanate compound, It is preferable that it is a compound which has a 2 or more block isocyanate group in 1 molecule from a sclerosing | hardenable viewpoint.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said blocked isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.

  The skeleton of the blocked isocyanate compound is not particularly limited, and any skeleton may be used as long as it has two isocyanate groups in one molecule, and is an aliphatic, alicyclic or aromatic polyisocyanate. It may be. Regarding specific examples of the skeleton, the description in paragraph 0144 of JP2014-238438A can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable. As a specific example of the blocking agent, the description in paragraph 0146 of JP2014-238438A can be referred to, and the contents thereof are incorporated in the present specification.

  The block isocyanate compound is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Death Module BL1100, BL1265 MPA / X, L3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co.) can be preferably used, and the like.

As the alkoxymethyl group-containing compound, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of outgas generation amount, A methyl group is particularly preferred.
Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
The alkoxymethyl group-containing compound is available as a commercial product, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid), Nicarax MX-750, MX-032, MX-706, MX-708, MX-40, MX-31, MX-270, MX-280, MX- 290, Nicarak MS-11, Nicarak MW-30HM, MW-100LM, MW-390 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

  As the compound having only one ethylenically unsaturated group in the molecule, a compound containing only one (meth) acryloyl group in the molecule is preferable. Examples of the compound containing only one (meth) acryloyl group in the molecule include compounds selected from the group consisting of acrylic acid esters and methacrylic acid esters.

  In the present invention, the molecular weight of other crosslinking agents other than Component E is preferably 200 to 1,000.

<Method for preparing photosensitive resin composition>
Each component is mixed at a predetermined ratio and by any method, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is possible to prepare a photosensitive resin composition by preparing a solution in which the components are previously dissolved in a solvent and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 μm.

[Method for producing cured film]
The method for producing a cured film of the present invention includes at least the following steps 1 to 5 in this order;
Process 1: The process of apply | coating the photosensitive resin composition of this invention on a base | substrate;
Process 2: The process of removing at least one part of a solvent from the apply | coated photosensitive resin composition;
Step 3: An exposure step of exposing the photosensitive resin composition from which at least a part of the solvent has been removed to a pattern with actinic rays;
Step 4: Development step of developing the exposed photosensitive resin composition with a developer;
Step 5: a step of thermosetting the developed photosensitive resin composition.

(1) The process of apply | coating the photosensitive resin composition of this invention on a foundation | substrate is called an application | coating process.
In the coating step, it is preferable to apply the photosensitive resin composition of the present invention on a base to form a wet film containing a solvent. The base is preferably a substrate.
In the method for producing a cured film of the present invention, the base is preferably a base having a step, and more preferably a substrate having a step.
There is no particular limitation on the “step” of the base having a step. An example of a substrate having a step is a substrate having a step. Even when the photosensitive resin composition of the present invention is applied to a substrate having a step larger than the conventional one, it is excellent in flatness when applied on a base having a step and is subjected to pattern exposure and development. The pattern having a large taper angle can form a cured film. By applying the present invention, the “step” having a step that can improve flatness has a height of 0.1 to 2.0 μm. It is preferable that it is 0.1-1.5 micrometers, and it is especially preferable that it is 0.1-1.0 micrometer.
The “step” of the base having a step is preferably 10 to 50% of the thickness of the cured film, more preferably 10 to 40%, and more preferably 10 to 20%. It is particularly preferred that
In addition, the preferable aspect of the "step" which the foundation | substrate which has a step has is as follows.
The step pattern is preferably a continuous pattern rather than an isolated pattern. In the case of a continuous pattern, the flatness is improved by the flow of the photosensitive resin composition.

Before applying the photosensitive resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor.
Examples of the substrate include an inorganic substrate, a resin substrate, and a resin composite material substrate.
Examples of the inorganic substrate include a substrate made of glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Fluorine resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound Plate, and the like.
These substrates are rarely used in the above-described form, and usually, a multilayer laminated structure such as a TFT element is formed depending on the form of the final product. In particular, in the present invention, it is preferable to use a substrate having a step, which is a base having a step.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 μm.
Furthermore, before applying the photosensitive resin composition used in the present invention to the substrate, it is possible to apply a so-called pre-wet method as described in JP-A-2009-145395.

(2) A step of removing at least a part of the solvent from the applied photosensitive resin composition is referred to as a solvent removal step.
In the solvent removal step, it is preferable to remove the solvent from the applied film by at least one of reduced pressure (vacuum) and heating to form a dry coating film on the base. In this invention, it is preferable that a solvent removal process is a prebaking process which heats the apply | coated photosensitive resin composition. The heating conditions for the pre-baking step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are within the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced. In the present invention, the heating condition of the pre-baking process is 80 ° C. to 110 ° C., and the temperature of the pre-baking process and the softening temperature of the photosensitive resin composition are easily set to the same level. It is preferable from the viewpoint of easily making it lower than the starting temperature.
When the photosensitive resin composition of the present invention contains a solvent having a boiling point of 160 ° C. or higher as the component C solvent, not all of the solvent may be removed in this solvent removing step, and at least the solvent having a boiling point of about 70 to 130 ° C. is removed. It only has to be done.

(3) An exposure process in which the photosensitive resin composition from which at least a part of the solvent has been removed is exposed in a pattern with actinic rays is referred to as an exposure process.
In the exposure step, it is preferable to irradiate actinic rays through a mask having a predetermined pattern on a base provided with a coating film. In this step, an acid group such as a carboxyl group or a phenolic hydroxyl group is generated in the exposed area, and the solubility in the developer in the exposed area is improved. That is, upon irradiation with actinic rays, the photoacid generator is decomposed to generate an acid. Then, the acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid to generate an acid group such as a carboxyl group or a phenolic hydroxyl group.
As an exposure light source used for actinic light, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, an LED (Light Emitting Diode) light source, an excimer laser generator, and the like can be used. I-line (365 nm), h-line Actinic rays having a wavelength of 300 nm to 450 nm, such as (405 nm) and g-line (436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the generation of an acid group such as a carboxyl group or a phenolic hydroxyl group from an acid group protected with an acid-decomposable group. The temperature when performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, when an acetal group is used as an acid-decomposable group, the activation energy of acid decomposition is low, and it is easily decomposed by an acid derived from an acid generator resulting from exposure to an acid group such as a carboxyl group or a phenolic hydroxyl group. Therefore, a pattern can be formed by development without necessarily performing PEB.

A development process for developing the exposed photosensitive resin composition with a developer will be described.
The developer is preferably an alkaline developer.
In the development step, it is preferable to develop a copolymer having a liberated carboxyl group or phenolic hydroxyl group using an alkaline developer. It is preferable to form a positive image by removing an exposed area containing a photosensitive resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkali developer.
The developer used in the development step preferably contains an aqueous solution of a basic compound. As the basic compound, compounds described in paragraph 0200 of JP-A-2014-238438 can be used.
Among these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide (TMAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline (2-hydroxyethyltrimethylammonium hydroxide) preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
As a preferred developer, a 0.4 to 2.5% aqueous solution of tetramethylammonium hydroxide can be mentioned. In the developer containing TMAH, the effect of the present invention is particularly effectively exhibited.
The pH of the developer (power of hydrogen) is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dip method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

(5) The process of thermosetting the developed photosensitive resin composition is also referred to as a post-baking process.
In the post-baking step of (5), the developed photosensitive resin composition is heated to thermally decompose the acid-decomposable group to generate an acid group such as a carboxyl group or a phenolic hydroxyl group, thereby producing a crosslinkable group or a crosslinkable group. A cured film can be formed by crosslinking with an agent or the like. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C., preferably 220 to 240 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, Heat treatment is preferably performed for 30 to 120 minutes. By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness and the like can be formed. Moreover, when performing heat processing, it can also improve transparency by performing in nitrogen atmosphere.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). Prior to post-baking, the entire surface of the patterned substrate is re-exposed (post-exposure) with actinic rays and then post-baked to generate acid from the photo-acid generator present in the unexposed areas and promote crosslinking. It can function as a catalyst. As conditions for performing the middle baking step and the post-exposure step, the conditions described in paragraph 0201 of JP-A-2014-238438 can be used.

  Furthermore, 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 curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

[Curing film]
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention.
The cured film of the present invention is suitable for use as an interlayer insulating film because it has excellent flatness when applied on a base having a step and has a large taper angle of a pattern obtained by pattern exposure and development. it can. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention mentioned above.

  When the cured film of the present invention has a thickness of 0.1 to 2.0 μm and is disposed on a base having a step, it is easy to form a cured film having excellent flatness and a large taper angle of the pattern. From the viewpoint, it is preferably 0.1 to 1.5 μm, and more preferably 0.1 to 1.0 μm.

The cured film of the present invention has excellent flatness when placed on a base having a step. When arranged on a base having a step, the step formed on the surface of the cured film of the present invention (the step on the orthogonal projection of the “step” of the base having a step) is less than 0.4 μm. Is preferably less than 0.3 μm, particularly preferably less than 0.2 μm, and particularly preferably less than 0.1 μm.
In addition, when arranged on a base having a step, the height of the step formed on the surface of the cured film of the present invention (the step on the orthographic projection of the “step” of the base having the step) is It is preferably less than 40%, more preferably less than 30%, particularly preferably less than 20%, and particularly preferably less than 10% of the height of the “step” of the underlying substrate.

The cured film of the present invention has a large pattern taper angle. The cured film of the present invention is preferably a pattern constituting a hole (in other words, a pattern in which a plurality of hole-shaped spaces are hollowed out). The cured film of the present invention has a hole diameter of 3 to 50 μm, which is excellent in flatness when placed on a base having a step and can easily form a cured film having a large pattern taper angle. From the viewpoint, it is preferably 3 to 30 μm, more preferably 3 to 10 μm.
The taper angle of the pattern constituting the hole of the cured film of the present invention is preferably 30 degrees or more, more preferably 50 degrees or more, particularly preferably 60 degrees or more, and 70 degrees or more. Is more particularly preferred.

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent flatness when applied on a base having a step and having a large pattern taper angle obtained by pattern exposure and development can be obtained.
The interlayer insulating film using the photosensitive resin composition of the present invention has excellent flatness when applied on a base having a step, and has a large taper angle of a pattern obtained by pattern exposure and development. It is useful for liquid crystal display devices, organic EL display devices, and touch panel applications. For example, the liquid crystal display device described in JP-A-2014-238438, paragraphs 0207 to 0208, the organic EL display device described in JP-A-2014-238438, paragraph 0209, and paragraphs 0212-0223 of JP-A-2014-238438 Touch panel display device, and uses described in JP-A-2014-238438, paragraph 0210.

  The cured film of the present invention can also be used for forming a partition wall of a MEMS (Micro Electro Mechanical Systems) device. Examples of the MEMS device include parts such as a SAW (Surface Acoustic Wave) filter, a BAW (Bulk Acoustic Wave) filter, a gyro sensor, a micro shutter for display, an image sensor, an electronic paper, an inkjet head, a biochip, and a sealant. It is done. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  The cured film of the present invention includes, for example, the bank layer (16) and the flattening film (57) described in FIG. 2 of Japanese Patent Application Laid-Open No. 2011-107476, and the method described in FIG. 4A of Japanese Patent Application Laid-Open No. 2010-9793. Partition wall (12) and planarization film (102), bank layer (221) and third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591, FIG. 4 of Japanese Patent Application Laid-Open No. 2009-128577 The second interlayer insulating film (125) and the third interlayer insulating film (126) described in (a), the planarization film (12) and the pixel isolation insulating film (14 described in FIG. 3 of Japanese Patent Application Laid-Open No. 2010-182638) ), The pixel isolation film (19) and the planarization film (17) described in FIG. 1 of JP2012-203121A, the high resistance layer (18) and the pixel described in FIG. 1 of JP2013-196919A, and the pixel. Inter-insulating film (16), layer Insulating film (14) can also be used for the formation of an interlayer insulating film (12c). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.

A touch panel using the cured film of the present invention will be described.
The touch panel is preferably a touch panel having the cured film of the present invention.
An example of the touch panel is a touch panel in which all or part of the insulating layer is made of the cured film of the present invention. The touch panel preferably includes at least a transparent substrate, an ITO (Indium Tin Oxide) electrode, and an insulating layer.
Moreover, the manufacturing method of a touch panel is a manufacturing method of the touch panel which has a transparent substrate, an ITO electrode, and an insulating layer, Comprising: The process of apply | coating the photosensitive resin composition of this invention so that an ITO electrode may be contacted, The said photosensitive resin A step of placing a mask having an opening pattern of a predetermined shape on the composition, irradiating with active energy rays and exposing, a step of developing the photosensitive resin composition after exposure, and a photosensitive resin composition after development It is preferable to include a step of manufacturing the insulating layer by heating.

Preferred examples of the transparent substrate in the touch panel include a glass substrate, a quartz substrate, a transparent resin substrate, and the like.
The application in the step of applying the photosensitive resin composition of the present invention so as to be in contact with the ITO electrode can be performed in the same manner as the application step described above, and the preferred embodiment is also the same. Moreover, in the said process, it is preferable that at least one part of the apply | coated photosensitive resin composition of this invention is in contact with the ITO electrode.
The step of placing a mask having an opening pattern of a predetermined shape on the photosensitive resin composition, performing exposure by irradiating with active energy rays, and developing the photosensitive resin composition after exposure include the exposure step described above. It can carry out similarly and a preferable aspect is also the same.
The process of manufacturing the insulating layer by heating the photosensitive resin composition after the development can be performed in the same manner as the heat treatment process described above, and the preferred embodiment is also the same.

[Liquid Crystal Display]
The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention preferably has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention. The liquid crystal display device of the present invention is not particularly limited except that it has the cured film of the present invention, and examples thereof include known liquid crystal display devices having various structures.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. When the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be taken by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (OCB) (Optical Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) disclosed in Japanese Patent Laid-Open No. 2005-284291 or It can be used as an organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is disposed on all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. Corresponding TFT 16 elements are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, a color filter 22 of RGB (R means red, G means green, and B means blue) each having a liquid crystal 20 layer and a black matrix is provided. In the liquid crystal display device 10, the “step” of the base having a step corresponds to the TFT 16.
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, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP 2011-145686 A and the interlayer insulating film (520) described in JP 2009-258758 A. Can do. Further, the liquid crystal display device 100 shown in FIG. 9 described in the pamphlet of International Publication No. WO11 / 087011, the liquid crystal display device 200 shown in FIG. 18, the liquid crystal display device 300 shown in FIG. For example, in the liquid crystal display device 100, organic interlayer insulating films 51 and 51a are stacked and used. The photosensitive resin composition of the present invention can be used for both the organic insulating film 51 and the organic insulating film 51. In the liquid crystal display device 100, the “step” of the base having a step corresponds to the organic insulating film 51a.

[Organic EL display device]
The organic EL display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature 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. 1 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness resulting from the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state where the unevenness resulting from the wiring 2 is embedded. In FIG. 1, one of the underlying “steps” having a step corresponds to a step on the surface of the insulating film 3, and the step on the surface of the insulating film 3 is a step caused by the wiring 2. The cured film of the present invention is not directly provided on the wiring 2 that causes the step, but the cured film of the present invention is formed on the insulating film 3 having a step formed on the wiring 2 as shown in FIG. May be provided.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. In FIG. 1, one of the underlying “steps” having a step corresponds to the step formed by the wiring 2, the first electrode 5, and the contact hole 7. Thus, the cured film of this invention may be provided on the level | step difference which a some member comprises in this way.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.
Further, the organic EL display device of the present invention can be the organic EL display device shown in Embodiments 3 to 6 shown in paragraph 0250 of the pamphlet of International Publication No. WO11 / 087011. For example, in an embodiment in which the liquid crystal display device 100 is an organic EL display device, the organic interlayer insulating films 51 and 51a are stacked and used. The photosensitive resin composition of the present invention can be used for both the organic insulating film 51 and the organic insulating film 51. Note that the “step” of the base having a step in this embodiment corresponds to the organic insulating film 51a.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

[Synthesis example]
In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
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-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate AICA: Itaconic anhydride (manufactured by Tokyo Chemical Industry)
MAAN: Maleic anhydride (manufactured by Tokyo Chemical Industry)
γBLMA: γ-butyrolactone methacrylate (manufactured by Osaka Organic Chemical Industry)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring the reaction solution for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, and the organic phase was extracted with ethyl acetate (500 mL). The organic phase was dried over magnesium sulfate, the insoluble matter was filtered, concentrated under reduced pressure at 40 ° C. or lower, and removed. The residual yellow oil was distilled under reduced pressure, and 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) in the fraction of boiling point (bp.) 54-56 ° C./3.5 mmHg (1 mmHg = 133.322 Pa) was colorless. Obtained as an oil (yield 80%).

<Synthesis of Component A Polymer A-1>
PGMEA (propylene glycol monomethyl ether acetate) (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MAA (amount to be 9.5 mol% in all monomer components), MATH (amount to be 43 mol% in all monomer components), GMA (47.5 mol% in all monomer components) ), V-601 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) was dissolved dropwise in PGMEA (89 g) at room temperature over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, a polymer A-1 was obtained. In addition, it prepared so that the density | concentration of components (referred to as solid content) other than a solvent might be 40 mass%.
In the synthesis of polymer A-1 and other polymers of component A, the numerical values of the polymerization initiator and the additive are mol% when the monomer component is 100 mol%. The solid content concentration is shown as monomer mass / (monomer mass + solvent mass) × 100 (unit mass%). V-601 was used as a polymerization initiator, and the reaction temperature was 90 ° C.
The weight average molecular weight of the component A polymer component is defined as a polystyrene conversion value obtained by GPC (Gel Permeation Chromatography) measurement. The weight average molecular weight (Mw) of the component A polymer component is HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) is used as a column. This was determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

<Synthesis of other polymer of component A>
Other types of monomers were changed as shown in Table 1 below, and other polymers were synthesized following the synthesis of Polymer A-1.
In Table 1 below, the raw material a1 is a raw material capable of forming a structural unit having a group in which the a1 acid group is protected with an acid-decomposable group. The raw material of a2 is a raw material which can form the structural unit which has a2 crosslinkable group.

  In Table 1 below, the numerical values in Table 1 not having a unit are in mol%. The numerical value of the polymerization initiator is the amount (mol%) of the polymerization initiator when the total amount of the monomer components is 100 mol%.

[Examples 1-30, Comparative Examples 1-8]
<Preparation of photosensitive resin composition>
Each component is blended so as to have a solid content ratio (unit: mass%) described in Table 2 below, and dissolved and mixed in a solvent (MEDG) until the solid content concentration becomes 15 mass%. It filtered with the filter made from a tetrafluoroethylene, and obtained the photosensitive resin composition of each Example and a comparative example.
When the softening temperature of the photosensitive resin composition of each Example was measured by the method as described in this specification, all were the range of 80-110 degreeC.

  The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.

<< Component B Photoacid Generator >>
B-1: Structure shown below (synthesis examples will be described later)

<<< Synthesis of B-1 >>>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) are added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture is heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, a 4 mol / L aqueous HCl solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic phase and reacted at 40 ° C. for 1 hour. Then, 2 mol / L aqueous HCl (60 mL) was added and liquid-separated. After the organic phase was concentrated, the crystals were converted to diisopropyl ether. (10 mL) was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and para-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered and dried to obtain the compound of B-1 (the above structure) (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-1 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).

B-2: Structure shown below (PAG-103, manufactured by BASF, photoacid generator that generates an acid of pKa3 or less)
B-3: Structure shown below (PAI-101, manufactured by Midori Chemical Co., Ltd., a photoacid generator that generates an acid of pKa3 or less), Me represents a methyl group.
B-4: Structure shown below (GSID-26-1, triarylsulfonium salt (manufactured by BASF), photoacid generator that generates an acid of pKa3 or less)

<< basic compound >>
N-1: Compound having the following structure
N-2: DBU 1,8-diazabicyclo [5.4.0] undec-7-ene N-3: TPI triphenylimidazole

<< Component E cross-linking agent >>
The weight average molecular weight of the component E crosslinking agent is defined as a polystyrene equivalent value obtained by GPC (Gel Permeation Chromatography) measurement. The weight average molecular weight (Mw) of the component E cross-linking agent is HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) is used as a column. It was determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
<<< Compound having two or more groups represented by formula X1 in the molecule >>>
E-1: KBM-9659 (manufactured by Shin-Etsu Chemical), molecular weight 383, compound having isocyanuric skeleton E-2: KBE-3026 (manufactured by Shin-Etsu Chemical), molecular weight 616

<<< Compound having two or more unsaturated double bonds in the molecule >>>
E-3: KAYARAD DPHA (manufactured by Nippon Kayaku), a mixture of compounds having molecular weights of 578 and 524 E-4: NK oligo U-15HA (manufactured by Shin-Nakamura Chemical), weight average molecular weight 2,300, compound having urethane structure

  When the crosslinking initiation temperatures of E-1 to E-4 used as Component E crosslinking agents were determined by the method described in this specification, all were in the range of 120 to 140 ° C.

<<< Crosslinking agent used in comparative example >>>
e-1: Alfon US-6110 (manufactured by Toagosei), weight average molecular weight 3,200
e-2: UV-7620EA (manufactured by Nippon Synthetic Chemical), weight average molecular weight 4,100
e-3: UV-7610B (manufactured by Nippon Synthetic Chemical), weight average molecular weight 11,000
e-4: KBM-3103 (manufactured by Shin-Etsu Chemical), molecular weight 263, monoalkoxysilane e-5: JER-828 (manufactured by Mitsubishi Chemical), molecular weight 370, bifunctional epoxy e-6: JER-1007 (manufactured by Mitsubishi Chemical) , Weight average molecular weight 2,900, bifunctional epoxy

<< Surfactant >>
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)
W-2: The following structure (structural unit S′-1-1: structural unit S′-1-2 = 20: 80 (mass ratio), Mw = 2600)

<< Component C Solvent >>
C-1: MEDG (diethylene glycol ethyl methyl ether): Hisolv EDM (manufactured by Toho Chemical Industries)
C-2: PGMEA (propylene glycol monomethyl ether acetate): Showa Denko

<< Other additives >>
F-1: KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., component S-2, having only one group represented by the formula X1 in the molecule)
F-2: Takenate B-870N (manufactured by Mitsui Chemicals, Ltd., other crosslinking agent other than component E)
F-3: Irganox 1035 (made by BASF, antioxidant)

[Comparative Example 9]
The photosensitive resin composition prepared according to Example 13 of JP 2011-248331 A was used as the photosensitive resin composition of Comparative Example 9. In the photosensitive resin composition of Comparative Example 9, the content of the polymer component having a component A weight average molecular weight of 10,000 or more was 78% by mass in the total solid content. In the photosensitive resin composition of Comparative Example 10, the content of the polyfunctional (meth) acrylate compound corresponding to Component E crosslinking agent, which is a compound having two or more unsaturated double bonds in the molecule, is in the total solid content. It was 12% by mass.

[Comparative Example 10]
The photosensitive resin composition prepared according to Example 31 of JP2013-218265A was used as the photosensitive resin composition of Comparative Example 10. In the photosensitive resin composition of Comparative Example 10, the content of the polymer component having a component A weight average molecular weight of 10,000 or more was 81% by mass in the total solid content. In the photosensitive resin composition of Comparative Example 10, the content of the silicon compound corresponding to the component E crosslinking agent, which is a compound having two or more groups represented by the formula X1 in the molecule, is 12% by mass in the total solid content. Met.

[Evaluation]
<Flatness>
(1) Production of Substrate Having Line and Space Pattern Cured Film as a Substrate As a pretreatment for improving the wettability of a glass substrate (EAGLE XG, 0.7 mm thickness (Corning)) that has been washed with water, the substrate is treated with HMDS. (1,1,1,3,3,3-hexamethyldisilazane, hexanemethyldisilazane) Exposure to steam for 30 seconds, followed by slit coating of the photosensitive resin composition of Example 1, followed by hot at 110 ° C. for 2 minutes The solvent was volatilized by pre-baking on the plate.
Next, using the MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc., the obtained photosensitive resin composition layer was 100 mJ / cm ² (through a line-and-space pattern mask having a line width of 10 μm and a space of 100 μm. (Energy intensity: 20 mW / cm ² , i-line). The exposed photosensitive resin composition layer was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface is exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount is 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then the substrate is heated in an oven at 230 ° C. for 30 minutes. Thus, a substrate having a line and space pattern cured film having a thickness of 1 μm and a width of 10 μm was obtained. The substrate having the cured film of the line and space pattern was used as a sample of a substrate having a step difference in the base and having a step height D ₁ = 1 μm.

(2) Flatness evaluation of the photosensitive resin compositions of Examples and Comparative Examples applied on the substrate Each Example and Comparative Example on a substrate having a cured film of the line and space pattern obtained in (1) above The photosensitive resin composition was slit-coated and then pre-baked on a hot plate at 110 ° C. for 2 minutes to volatilize the solvent. Then, it exposed at 300 mJ / cm < ² > using the high pressure mercury lamp. Thereafter, this substrate was heated in an oven at 230 ° C./30 minutes to obtain a cured film 104 having a thickness D ₂ = 2 μm of the cured film at a location where the underlying step 102 was not present.
By these operations, a laminated film of the base 100 having a step and the cured film 104 having the configuration shown in FIG. 5 is formed. The height Δd of the level difference on the surface of the cured film of the photosensitive resin composition of each example and comparative example, which was generated at this time, was measured, and an average value at 10 locations was obtained.
The average value of the height Δd of the step on the surface of the obtained cured film was determined based on the following criteria.
5: Average value of Δd is less than 0.1 μm 4: Average value of Δd is 0.1 μm or more and less than 0.2 μm 3: Average value of Δd is 0.2 μm or more and less than 0.3 μm 2: Average value of Δd is 0.3 μm or more and less than 0.4 μm 1: The average value of Δd is 0.4 μm or more. The results obtained are shown in Table 2 below.

<Taper angle>
As a pretreatment for improving the wettability of a glass substrate (EAGLE XG, 0.7 mm thickness (manufactured by Corning)) that has been washed with water, the substrate is exposed to HMDS vapor for 30 seconds, and then each photosensitive resin composition is slit-coated. Then, the solvent was volatilized by pre-baking on a hot plate at 110 ° C. for 2 minutes.
Next, the obtained photosensitive resin composition layer was 100 mJ / cm ² (energy intensity: 20 mW / cm) through a hole pattern mask having a diameter of 10 μm, using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. ² and i line). The exposed photosensitive resin composition layer was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface is exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount is 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then the substrate is heated in an oven at 230 ° C. for 30 minutes. As a result, a hole pattern cured film having a thickness of 2 μm and a diameter of 10 μm was obtained.
The cross-sectional shape of the obtained hole pattern was observed, the taper angle was measured, and the average value of 10 locations was obtained.
The average value of the obtained taper angles was determined based on the following criteria.
5: The average value of the taper angle is 70 degrees or more 4: The average value of the taper angle is 60 degrees or more and less than 70 degrees 3: The average value of the taper angle is 50 degrees or more and less than 60 degrees 2: The average value of the taper angle is 30 More than 50 degrees and less than 50 degrees 1: The average taper angle is less than 30 degrees. The results obtained are shown in Table 2 below.

As is clear from Table 2 above, the photosensitive resin composition of each example has excellent flatness when applied on a base having a step, and the taper angle of the pattern obtained by pattern exposure and development is high. It has been found that a large cured film can be provided.
On the other hand, it turned out that the flatness is inferior in the photosensitive resin composition of the comparative example 1 which does not contain the component E crosslinking agent. It turned out that the photosensitive resin composition of the comparative example 2 with little content of component E crosslinking agent is inferior in flatness. It was found that the photosensitive resin compositions of Comparative Examples 3 to 5 using the crosslinking agents e-1, e-2, and e-3 having a large weight average molecular weight of Component E crosslinking agent were inferior in flatness. It was found that the photosensitive resin composition of Comparative Example 6 using a crosslinking agent having only one group represented by Formula X1 in the molecule had a small taper angle. It was found that the photosensitive resin compositions of Comparative Examples 7 and 8 using a crosslinking agent having an epoxy group as Component E crosslinking agent had a small taper angle. It was found that the photosensitive resin composition of Comparative Example 9 prepared in accordance with Example 13 of JP2011-248331A has a high content of component A and a low content of component E has poor flatness. . It was found that the photosensitive resin composition of Comparative Example 10 prepared according to Example 31 of JP2013-218265A has a high content of component A and a low content of component E has poor flatness. .

[First application example]
<Example 100>
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film is formed as the interlayer insulating film 17 of FIG. 1 of Japanese Patent No. 3321003 as follows, and the liquid crystal display of Example 100 Got the device. That is, using the photosensitive resin composition of Example 3, a cured film was formed as the interlayer insulating film 17 in FIG. 1 of Japanese Patent No. 3312003. The interlayer insulating film 17 in FIG. 1 of Japanese Patent No. 3321003 is formed on a base having a step, and a contact hole 17a is formed. The average step was 0.7 μm.
That is, the substrate was exposed to HMDS vapor for 30 seconds as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003. Then, after slit-coating the photosensitive resin composition of Example 3 prepared above, it prebaked on a hot plate at 110 ° C. for 2 minutes to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3 μm was formed. Formed. Next, the obtained photosensitive resin composition layer was 100 mJ / cm ² (energy intensity: 20 mW / cm) through a hole pattern mask having a diameter of 10 μm, using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. ² and i line). The exposed photosensitive resin composition layer was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
The photosensitive resin composition of Example 3 was able to provide a cured film having excellent flatness when applied on a base having a step and having a large pattern taper angle obtained by pattern exposure and development. Moreover, the applicability | paintability at the time of apply | coating the said photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle or a crack was not recognized in the cured film obtained after exposure, image development, and a heating.

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

<Example 101>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. In other words, even if the exposure apparatus is changed from MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation, performance as a cured film and a liquid crystal display device is also achieved. As good as 100.

<Example 102>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. That is, even if the exposure apparatus is changed from MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. to “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec), the cured film and the liquid crystal display The device performance was also good as in Example 100.

<Example 103>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. In other words, even if a vacuum drying step (VCD) is introduced after pre-baking, it is excellent in flatness when formed on a substrate having a step, and the pattern obtained by pattern exposure and development is cured with a large taper angle. It was a membrane. Further, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was as good as in Example 100. It is also preferable to introduce a reduced-pressure drying step from the viewpoint of suppressing coating unevenness according to the solid content concentration and the film thickness of the composition.

<Example 104>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. That is, even if a PEB process is introduced between the mask exposure and the development process, it is excellent in flatness when formed on a base having a step, and the pattern taper obtained by pattern exposure and development The cured film had a large angle. Further, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was as good as in Example 100. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.

<Example 105>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. That is, even when the alkaline developer is changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution, the flatness is improved when formed on a base having a step. The cured film was excellent and had a large taper angle of the pattern obtained by pattern exposure and development. Further, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was as good as in Example 100. This seems to be because the photosensitive resin composition of Example 3 is excellent in adhesion to the substrate.

<Example 106>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. In other words, even if the alkali development method is changed from paddle development to shower development, the flatness is excellent when formed on a base having a step, and the taper angle of the pattern obtained by pattern exposure and development is large. It was a cured film. Further, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was as good as in Example 100. This seems to be because the photosensitive resin composition of Example 3 is excellent in adhesion to the substrate.

<Example 107>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. That is, even when the alkali developer is changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution, the flatness is excellent when formed on a base having a step, and The cured film had a large taper angle of the pattern obtained by pattern exposure and development. Further, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was as good as in Example 100. This seems to be because the photosensitive resin composition of Example 3 is excellent in adhesion to the substrate.

<Example 108>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. That is, the entire surface exposure step after development and rinsing was omitted, and the cured film was obtained by heating in an oven at 230 ° C. for 30 minutes. The performance as the obtained cured film and the liquid crystal display device was as good as in Example 100. This seems to be because the photosensitive resin composition of Example 3 is excellent in chemical resistance. From the viewpoint of improving productivity, it is also preferable to omit the entire exposure process.

<Example 109>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. That is, a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. The performance as the obtained cured film and the liquid crystal display device was as good as in Example 100. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.

<Example 110>
A liquid crystal display device similar to that of Example 100 was changed to obtain a similar liquid crystal display device. That is, a process of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinse process and the entire surface exposure process. The performance as the obtained cured film and the liquid crystal display device was as good as in Example 100. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.

<Example 111>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness on the surface of the insulating film 3 due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 3 on a substrate, pre-baking (110 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating i-line (365 nm) with 100 mJ / cm ² (energy intensity 20 mW / cm ² ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern. Was used to expose the entire surface so that the integrated dose was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and a heat treatment was performed at 230 ° C./30 minutes.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and heating. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm. The photosensitive resin composition of Example 3 is a flattened film which is a cured film having excellent flatness when coated on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. 4 could be provided.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 3 was used, and the insulating film 8 was formed by the same method as described above. The photosensitive resin composition of Example 3 is an insulating film 8 that is a cured film having excellent flatness when applied on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. Was able to provide. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

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

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

[Second application example]
<Example 112>
Similarly to the first application example described above, a cured film was formed as an interlayer insulating film of a liquid crystal display device using the photosensitive resin composition of Example 6 to obtain a liquid crystal display device. The photosensitive resin composition of Example 6 is an interlayer insulating film which is a cured film having excellent flatness when applied on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. Was able to provide. Further, when a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

<Example 113>
Further, similarly to the first application example described above, a planarization film and an insulating film of an organic EL display device using a thin film transistor (TFT) are formed using the photosensitive resin composition of Example 6, and organic An EL display device was produced. The photosensitive resin composition of Example 6 is a flattened film that is a cured film having excellent flatness when applied on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. And could provide insulation film. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

[Third application example]
<Example 114>
Similarly to the first application example described above, a cured film was formed as an interlayer insulating film of a liquid crystal display device using the photosensitive resin composition of Example 25, and a liquid crystal display device was obtained. The photosensitive resin composition of Example 25 is an interlayer insulating film which is a cured film having excellent flatness when applied on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. Was able to provide. Further, when a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

<Example 115>
Further, similarly to the first application example described above, a planarization film and an insulating film of an organic EL display device using a thin film transistor (TFT) are formed using the photosensitive resin composition of Example 25, and organic An EL display device was produced. The photosensitive resin composition of Example 25 is a flattened film which is a cured film having excellent flatness when applied on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. And could provide insulation film. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

<Example 116>
Similarly to Example 14 described in JP 2012-242522 A, a cured film is formed as an interlayer insulating film of a liquid crystal display device having a color filter on array structure using the photosensitive resin composition of Example 1, A liquid crystal display device was obtained. The average step of the base of the interlayer insulating film of the color filter on array liquid crystal display device was 1.0 μm. The photosensitive resin composition of Example 14 is an interlayer insulating film which is a cured film having excellent flatness when applied on a base having a step and having a large taper angle of a pattern obtained by pattern exposure and development. Was able to provide. Further, when a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter 100: Base having a step 101: Lower step 102: Step 103: Photosensitive resin composition 104: Cured film D ₁ : Base Step height D ₂ : Thickness of cured film Δd: Height of step on cured film surface θ: Taper angle

Claims (13)

Component A Polymer component having a weight average molecular weight of 10,000 or more,
Component B photoacid generator,
A photosensitive resin composition containing a component C solvent and a component E crosslinking agent,
The component A includes a polymer satisfying at least one of the following polymer 1 and polymer 2,
Polymer 1: a polymer having a structural unit having a group in which an a1 acid group is protected with an acid-decomposable group, and a structural unit having an a2 crosslinkable group,
Polymer 2: a polymer having a structural unit in which the a1 acid group is protected by an acid-decomposable group, and a polymer having a structural unit having an a2 crosslinkable group (provided that the a1 acid group is acid-decomposable) A polymer having a structural unit having a group protected by a group and a polymer having a structural unit having the a2 crosslinkable group each have a weight average molecular weight of 10,000 or more) .
The content of component A is 75% by mass or less based on the total solid content,
The molecular weight of component E is 3000 or less,
The content of the component E is 15% by mass or more in the total solid content,
At least one of ethylenically unsaturated saturated Kazuyui if the compound having two or more compounds and the molecules having groups of the component E is represented by the following formula X1 in the molecule two or more, the photosensitive resin composition ;
In the formula X1, at least one of R ^{X1 to} R ^X3 is a hydrolysis selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group, and an isopropenoxy group. The remaining R ^{X1 to} R ^X3 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic substituent.   The photosensitive resin composition according to claim 1, wherein the content of the component E is 20% by mass or more based on the total solid content.   The photosensitive resin composition of Claim 1 whose content of the said component E is 25 mass% or more in the total solid. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component E is a compound having two or more groups represented by the following formula X1 in the molecule.
In the formula X1, at least one of R ^{X1 to} R ^X3 is a hydrolysis selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group, and an isopropenoxy group. The remaining R ^{X1 to} R ^X3 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic substituent.   The photosensitive resin composition according to claim 4, wherein the component E is a compound having an isocyanuric skeleton. The photosensitive resin composition according to claim 1 wherein component E is a compound having two or more ethylenically unsaturated saturated Kazuyui case in the molecule.   The photosensitive resin composition according to claim 6, wherein the component E is a compound having a urethane structure.   The cured film of the photosensitive resin composition as described in any one of Claims 1-7.   The cured film according to claim 8, which is an interlayer insulating film.   A liquid crystal display device having the cured film according to claim 8.   An organic electroluminescence display device having the cured film according to claim 8. A method for producing a cured film comprising at least the following steps 1 to 5 in this order;
Process 1: The process of apply | coating the photosensitive resin composition as described in any one of Claims 1-7 on a foundation | substrate;
Step 2: a step of removing at least a part of the solvent from the applied photosensitive resin composition;
Step 3: An exposure step of exposing the photosensitive resin composition from which at least a part of the solvent has been removed to a pattern with actinic rays;
Step 4: Development step of developing the exposed photosensitive resin composition with a developer;
Step 5: a step of thermosetting the developed photosensitive resin composition.   The manufacturing method of the cured film of Claim 12 whose said foundation | substrate is a foundation | substrate which has a level | step difference.