JP2014238438A - Photosensitive resin composition, production method of resin pattern, cured product, cured film, liquid crystal display device, organic electroluminescence (el) display device, and touch panel display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which excels in transparency of a cured product obtained therefrom and in adhesiveness after developed, and to provide a production method of a resin pattern using the photosensitive resin composition, a cured product and a cured film obtained by curing the photosensitive resin composition, and a liquid crystal display device, an organic EL display device and a touch panel device having the cured film.SOLUTION: The photosensitive resin composition comprises (component A) metal oxide particles, (component B) a solvent, (component C) a polymer containing a structural unit having a group in which an acid group is protected by an acid decomposable group, (component D) a photoacid generator, and (component S) a compound having a single sulfide bond and two or more moiety structures expressed by formula (1) in the molecule. In the formula, Rand Reach independently represent a hydrogen atom or an alkyl group; n represents an integer of 1 to 3; and a wavy line represents a bonding position with other structures.

Description

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the resin composition of the present invention” or “the composition of the present invention”). Moreover, the resin pattern manufacturing method using the said photosensitive resin composition, the hardened | cured material formed by hardening | curing the said photosensitive resin composition, the cured film formed by hardening | curing the said photosensitive resin composition, and the said cured film The present invention relates to various image display devices used.
More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film or an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit element, and a solid-state imaging element. And a method for producing a cured film using the same.

With the development of solid-state imaging devices and liquid crystal display devices, it has become widely practiced to produce optical members such as microlenses, optical waveguides, and antireflection films using organic materials (resins).
As a conventional photosensitive resin composition, a photosensitive resin composition containing particles is known (see Patent Document 1).
Moreover, the photosensitive resin composition of patent document 2 is known as a conventional photosensitive resin composition.

JP2013-80192A JP 2011-48064 A

  The problem to be solved by the present invention is a photosensitive resin composition excellent in transparency of the cured product obtained and adhesion after development, a resin pattern production method using the photosensitive resin composition, and the photosensitive resin It is to provide a cured product and a cured film obtained by curing the composition, and a liquid crystal display device, an organic EL display device, and a touch panel display device having the cured film.

The above-described problems of the present invention have been solved by means described in the following <1>, <9> to <11>, or <13> to <15>. It describes below with <2>-<8> and <12> which are preferable embodiments.
<1> (component A) metal oxide particles, (component B) solvent, (component C) a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, (component D) photoacid generation A photosensitive resin composition comprising: an agent; and (Component S) a compound having one or more sulfide bonds in the molecule and two or more partial structures represented by the following formula (1): object,

（式（１）中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子又はアルキル基を表し、ｎは１〜３の整数を表し、波線部分は他の構造との結合位置を表す。）

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group, n represents an integer of 1 to 3, and the wavy line represents the bonding position with another structure.)

  <2> The photosensitive resin composition according to <1>, wherein the component S is a compound represented by the following formula (2):

（式（２）中、Ｒ³〜Ｒ⁶はそれぞれ独立に、水素原子又はアルキル基を表し、Ｌ¹及びＬ²はそれぞれ独立に、単結合又は二価の連結基を表し、ｐは１〜４の整数を表し、ｑ及びｒはそれぞれ独立に、１〜３の整数を表す。）

(In Formula (2), R < ³ > -R < ⁶ > represents a hydrogen atom or an alkyl group each independently, L < ¹ > and L < ² > represent a single bond or a bivalent coupling group each independently, p is 1- 4 represents an integer of 4, and q and r each independently represent an integer of 1 to 3.)

<3> The photosensitive resin composition according to <2>, wherein L ¹ and L ² are each independently a single bond or an alkylene group,
<4> (Component E) The photosensitive resin composition according to any one of <1> to <3>, further containing a dispersant,
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the component C satisfies at least one of the polymer components represented by the following (1) and (2):
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group (2) (a1) an acid group having an acid-decomposable group And (a2) a polymer having a structural unit having a crosslinkable group. <6> The above R ¹ and R ² are each independently an alkyl group. <1>-<5> photosensitive resin composition as described in any one of these,
<7> The photosensitive material according to any one of <1> to <6>, wherein the content of component S is 0.05 to 20% by mass with respect to the total solid content of the photosensitive resin composition. Functional resin composition,
<8> The photosensitive resin according to any one of <1> to <7>, wherein the content of component A is 10 to 70% by mass with respect to the total solid content of the photosensitive resin composition. Composition,
<9> A resin pattern manufacturing method comprising at least steps (1) to (4) in this order,
(1) Application step of applying the photosensitive resin composition according to any one of the above <1> to <8> on a substrate (2) Solvent removal step of removing the solvent from the applied resin composition ( 3) Exposure step of exposing the resin composition from which the solvent has been removed to a pattern with actinic rays (4) Development step of developing the exposed resin composition or the unexposed resin composition with an aqueous developer <10> A cured product obtained by the resin pattern manufacturing method according to <9>,
<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <8> above,
<12> The cured film according to <11>, which is an interlayer insulating film,
<13> A liquid crystal display device having the cured film according to <11> or <12> above,
<14> An organic EL display device having the cured film according to <11> or <12> above,
<15> A touch panel display device having the cured film according to <11> or <12>.

  According to the present invention, a photosensitive resin composition excellent in transparency of the resulting cured product and adhesion after development, a method for producing a resin pattern using the photosensitive resin composition, and curing the photosensitive resin composition The hardened | cured material and cured film which are formed, and the liquid crystal display device which has the said cured film, an organic electroluminescent display device, and a touchscreen display device can be 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. 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. It is sectional drawing which shows the structure of an electrostatic capacitance type input device. It is explanatory drawing which shows an example of a front plate. It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.

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 specification of the present application, “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 present invention, “(component A) metal oxide particles” or the like is also simply referred to as “component A” or the like, “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group” or the like. Is also simply referred to as “structural unit (a1)”.
Furthermore, in the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present invention, “parts by mass” and “% by mass” are synonymous with “parts by weight” and “% by weight”, respectively.
In the present invention, a combination of preferred embodiments is more preferred.

  The photosensitive resin composition of the present invention (hereinafter also simply referred to as “resin composition”) has (Component A) metal oxide particles, (Component B) solvent, and (Component C) acid groups having acid-decomposable groups. A polymer containing a structural unit having a protected group, (Component D) a photoacid generator, and (Component S) a partial structure represented by the following formula (1) with at least one sulfide bond in the molecule And a compound having two or more.

（式（１）中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子又はアルキル基を表し、ｎは１〜３の整数を表し、波線部分は他の構造との結合位置を表す。）

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group, n represents an integer of 1 to 3, and the wavy line represents the bonding position with another structure.)

The photosensitive resin composition of the present invention can be suitably used as a positive resist composition.
The photosensitive resin composition of the present invention is preferably a resin composition having a property of being cured by heat.
The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition, and is a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). Is more preferable.
The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
On the other hand, (Component D) photoacid generator used in the present invention is such that an acid generated in response to actinic light acts as a catalyst for deprotection of protected acid groups in Component C. Therefore, the acid generated by the action of one photon contributes to a number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, which is a result of so-called chemical amplification. As a result, high sensitivity can be obtained.

  Furthermore, the photosensitive resin composition of the present invention is a resin composition for optical members such as microlenses, optical waveguides, antireflection films, LED sealing materials, and LED chip coating materials, or wiring used for touch panels. A resin composition for reducing the visibility of an electrode is preferable. In addition, the composition for reducing the visibility of the wiring electrode used for the touch panel is a composition for a member that reduces the visibility of the wiring electrode used for the touch panel, that is, makes the wiring electrode difficult to see. Examples thereof include an interlayer insulating film between ITO (indium tin oxide) electrodes, and the photosensitive resin composition of the present invention can be suitably used for the application.

In order to improve the refractive index, when metal oxide particles are used, it is preferable to contain many metal oxide particles as a solid content in the composition.
However, as a result of investigations by the present inventors, it has been found that when the photosensitive resin composition contains metal oxide particles, the cured product obtained is inferior in adhesion and transparency after development.
As a result of intensive studies in view of the above-mentioned viewpoints, the present inventors have made a photosensitive resin composition containing Component A to Component D and Component S, thereby providing adhesion and transparency after development of the resulting cured product. The present invention has been found to be excellent, and the present invention has been completed.
It is presumed that component A and component S have some interaction, possibly the interaction between the surface of component A and the sulfur atom of the sulfide bond of component S, and the cured product obtained has excellent adhesion and transparency after development. However, the detailed mechanism of the effect is unclear.
Further, the photosensitive resin composition of the present invention is a substrate having both a hydrophilic surface and a hydrophobic surface that are difficult to maintain adhesion after development, for example, a glass (hydrophilic) substrate having ITO (hydrophobic) wiring. Also, the adhesion after development is excellent.
Hereinafter, the composition of the present invention will be described in detail.

(Component S) Compound having one or more sulfide bonds in the molecule and two or more partial structures represented by the formula (1) The photosensitive resin composition of the present invention comprises (Component S) sulfide in the molecule. A compound having one or more bonds and two or more partial structures represented by the following formula (1) is contained. By containing the component S, the resulting cured product is excellent in transparency and adhesion after development.

（式（１）中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子又はアルキル基を表し、ｎは１〜３の整数を表し、波線部分は他の構造との結合位置を表す。）

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group, n represents an integer of 1 to 3, and the wavy line represents the bonding position with another structure.)

R ¹ and R ² are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. It is more preferable that it is a methyl group or an ethyl group. It is excellent in transparency of the obtained hardened | cured material and adhesiveness after image development as it is the said aspect.
From the viewpoint of storage stability, R ¹ and R ² are preferably each independently an alkyl group.
n is preferably 2 or 3, and particularly preferably 3.
When n is 2 or 3 in Formula (1), two or more R ^{1 s} may be the same group or different groups.
In the formula (1), when n is 1, two or more R ^{2 s} may be the same group or different groups.

Component S preferably has 1 to 10 sulfur atoms, more preferably 1 to 4 and even more preferably 2 to 4. It is excellent in transparency of the obtained hardened | cured material and adhesiveness after image development as it is the said aspect.
Further, the sulfide bond in component S may be a monosulfide bond or a polysulfide bond. Component S is preferably a compound having a monosulfide bond, a disulfide bond or a tetrasulfide bond, and more preferably a compound having a disulfide bond or a tetrasulfide bond. It is excellent in transparency of the obtained hardened | cured material and adhesiveness after image development as it is the said aspect.
Furthermore, the component S preferably has 2 to 10 partial structures represented by the above formula (1), more preferably 2 to 6, more preferably 2 to 4, and further preferably 2 or 3 It is particularly preferable to have two, and most preferably two. It is excellent in transparency of the obtained hardened | cured material and adhesiveness after image development as it is the said aspect.

  Component S is preferably a compound represented by the following formula (2) or formula (3), and more preferably a compound represented by the following formula (2).

（式（２）及び式（３）中、Ｒ³〜Ｒ⁸はそれぞれ独立に、水素原子又はアルキル基を表し、Ｌ¹〜Ｌ³はそれぞれ独立に、単結合又は二価の連結基を表し、Ｌ⁴はｙ価の連結基を表し、ｐは１〜４の整数を表し、ｑ、ｒ及びｘはそれぞれ独立に、１〜３の整数を表し、ｙは２〜６の整数を表す。）

(In Formula (2) and Formula (3), R ^{3 to} R ⁸ each independently represents a hydrogen atom or an alkyl group, and L ^{1 to} L ³ each independently represents a single bond or a divalent linking group. , L ⁴ represents a y-valent linking group, p represents an integer of 1 to 4, q, r and x each independently represent an integer of 1 to 3, and y represents an integer of 2 to 6. )

R ^{3 to} R ⁸ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. It is more preferable that it is a methyl group or an ethyl group. It is excellent in transparency of the obtained hardened | cured material and adhesiveness after image development as it is the said aspect.
L ^{1 to} L ³ are each independently preferably a single bond or an alkylene group, more preferably an alkylene group, still more preferably an alkylene group having 2 to 8 carbon atoms, and 1,3-propylene Particularly preferred is a group.
L ⁴ is preferably a group composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom, a y-valent hydrocarbon group, or 1 to y More preferably, it is a group in which two or more valent hydrocarbon groups, ester bonds, ether bonds and imino groups are combined. An alkylene group, an arylene group, or a group obtained by combining two or more of an alkylene group, an arylene group, an ester bond, an ether bond, and an imino group is more preferable.
The number of carbon atoms of L ⁴ are, preferably 2 to 60, more preferably 6 to 30.
p is preferably an integer of 2 to 4, and more preferably 2 or 4.
q, r, and x are each independently synonymous with n in Formula (1), and a preferable aspect is also the same.
y is preferably an integer of 2 to 4, and more preferably 2 or 3.

There is no restriction | limiting in particular as the synthesis method of component S, It can synthesize | combine by a well-known synthesis method, a substituent introduction method, and a substituent conversion method. Moreover, as a synthesis | combining method of component S, the synthesis | combining method as described in the paragraph 0019 of Unexamined-Japanese-Patent No. 2011-136429 can also be referred, for example. Moreover, as a component S, you may use a commercial item.
Specific examples of the component S include the following S-1 to S-6, but it is needless to say that the component S is not limited to these.

Moreover, the component S may be used individually by 1 type and can also use 2 or more types together.
The content of component S in the resin composition of the present invention is preferably 0.05 to 20% by mass, and preferably 0.1 to 10% by mass, based on the total solid content of the resin composition of the present invention. More preferably, it is more preferable to set it as 0.2-8 mass%, and it is especially preferable to set it as 0.5-5 mass%. It is excellent in transparency of the obtained hardened | cured material and adhesiveness after image development as it is the said aspect.

(Component A) Metal Oxide Particles The resin composition of the present invention contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a positive photosensitive resin composition having a high refractive index and excellent transparency can be obtained.
Component A preferably has a refractive index higher than the refractive index of the resin composition made of a material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is 1.50. The above particles are more preferable, particles having a refractive index of 1.70 or more are further preferable, and particles having a refractive index of 1.90 or more are particularly preferable.
Here, that the refractive index in light having a wavelength of 400 to 750 nm is 1.50 or more means that the average refractive index in light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more. The average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.

Note that the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te.
The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium oxide is most preferable. Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.

  From the viewpoint of the transparency of the resin composition, the average primary particle size of Component A is preferably 1 to 200 nm, more preferably 3 to 80 nm, and particularly preferably 5 to 50 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.

Moreover, the component A may be used individually by 1 type, and can also use 2 or more types together.
The content of the metal oxide particles in the resin composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, etc. It is preferable to set it as 5-80 mass% with respect to the total solid of the resin composition of this, It is more preferable to set it as 10-70 mass%, It is further more preferable to set it as 20-65 mass%, 25-60 It is especially preferable to set it as the mass%.

In the present invention, the metal oxide particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.
Examples of the solvent used for preparing the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, in addition to the (Component B) solvent described below. -Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. Can be mentioned.
These solvents can be used singly or in combination of two or more.

(Component B) Solvent The photosensitive resin composition of the present invention contains (Component B) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving or dispersing essential components and optional components described later in (Component B) solvent.
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. Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, and paragraphs 0167 to 0168 of JP2012-194290A. The solvents described are also included, the contents of which 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-nonal 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. It is preferable that the solvent which can be used for this invention is single 1 type, or uses 2 types together.

Component B 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.
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 methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
Among these, the solvent is preferably at least one solvent selected from the group consisting of propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers and esters, and includes propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether and / or Alternatively, ethyl 3-ethoxypropionate is more preferable, and propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, and ethyl 3-ethoxypropionate are particularly preferable.

  The content of the (component B) 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 component C in the photosensitive resin composition. More preferably.

(Component C) Polymer having a constitutional unit having a group in which an acid group is protected by an acid-decomposable group The photosensitive resin composition of the present invention is a group in which (Component C) an acid group is protected by an acid-decomposable group The polymer which has a structural unit which has is contained.
In the present invention, the “structural unit having a group in which an acid group is protected by an acid-decomposable group” is also referred to as “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group”.

The photosensitive resin composition of the present invention may further contain a polymer other than a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group.
The photosensitive resin composition of the present invention preferably contains a polymer component including a polymer that satisfies at least one of the following (1) and (2).
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group (2) (a1) an acid group having an acid-decomposable group And (a2) a polymer having a structural unit having a crosslinkable group The photosensitive resin composition of the present invention further contains a polymer other than these. May be. Unless otherwise stated, component C in the present invention means one including other polymers added as necessary in addition to the above (1) and / or (2).
It is preferable that the photosensitive resin composition of this invention contains the component which satisfy | fills said (1) as a component C from a viewpoint of the transparency (haze) after hardening, and the remaining film rate of an unexposed part.
On the other hand, from the viewpoint of the degree of freedom in molecular design, the photosensitive resin composition of the present invention preferably contains a component satisfying the above (2) as the component C.
In addition, even when it contains a component satisfying the above (1), (a1) an acrylic resin having a structural unit having a group in which an acid group is protected with an acid-decomposable group and / or (a2) cross-linking You may contain the acrylic resin which has a structural unit which has a sex group.
Moreover, even when it contains a component satisfying the above (2), it has (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group. When it contains at least what corresponds to a polymer, it corresponds when it contains the component which satisfy | fills said (1).

Component C is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. Further, “(meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.

<Structural unit (a1)>
Component C includes (a1) a polymer having at least a structural unit having a group in which an acid group is protected with an acid-decomposable group. When component C contains a polymer having the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
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. Examples of the acid-decomposable group include groups that are relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (a1-10) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). Acetal-based functional groups) and groups that are relatively difficult to decompose by acid (for example, tertiary alkyl groups such as tert-butyl ester groups and tertiary alkyl carbonate groups such as tert-butyl carbonate groups) can be used. .

(A1) A structural unit having a group in which an acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group in which a carboxyl group is protected with an acid-decomposable group (“protection protected with an acid-decomposable group” A structural unit having a protected phenolic hydroxyl group in which a phenolic hydroxyl group is protected with an acid-decomposable group (having a protected phenolic hydroxyl group protected with an acid-decomposable group). It is also preferably referred to as a “structural unit”.
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. To do.

<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a group.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group as a structural unit which can be used for the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, a 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, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, (a1-1-1) used as a structural unit having a carboxyl group, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) ethylene The structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.

<<< (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule 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, and 2- (meth) acryloyl. Examples include loxyethyl 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 polyhydric carboxylic 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. 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 them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, anhydride of unsaturated polyvalent carboxylic acid, etc. It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.

<<< (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride reacts a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

-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) having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable group can be used.
Among these acid-decomposable groups, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. Basic properties of the photosensitive resin composition, in particular, sensitivity and pattern shape, contact hole formation, photosensitive resin It is preferable from the viewpoint of the storage stability of the composition. Furthermore, among the acid-decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10) from the viewpoint of sensitivity. In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10), the entire protected carboxyl group is-(C = O) -O-CR ¹⁰¹ R. The structure is ¹⁰² (OR ¹⁰³ ).

（式（ａ１−１０）中、Ｒ¹⁰¹及びＲ¹⁰²はそれぞれ独立に、水素原子又はアルキル基を表す。ただし、Ｒ¹⁰¹とＲ¹⁰²とが共に水素原子の場合を除く。Ｒ¹⁰³は、アルキル基を表す。Ｒ¹⁰¹又はＲ¹⁰²と、Ｒ¹⁰³とが連結して環状エーテルを形成してもよい。）

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

In formula (a1-10), R ^{101 to} R ¹⁰³ each independently represents a hydrogen atom or an alkyl group, and 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.

In the above formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.
The linear or branched alkyl group 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.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, Among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable and a C6-C12 aryl group is more preferable. Specifically, a phenyl group, an α-methylphenyl group, a naphthyl group and the like can be exemplified, and as an entire alkyl group substituted with an aryl group, that is, as an aralkyl group, a benzyl group, an α-methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
As said alkoxy group, a C1-C6 alkoxy group is preferable, a C1-C4 alkoxy group is more preferable, and a methoxy group or an ethoxy group is still more preferable.
Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In the above formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 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 together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include, for example, 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 the above formula (a1-10), it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the above formula (a1-10), a commercially available one may be used, or one synthesized by a known method. Can also be used. For example, it can be synthesized by a synthesis method described in paragraphs 0037 to 0040 of JP2011-221494A.

  The 1st preferable aspect of the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group is a structural unit represented by a following formula.

（式中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲ¹及びＲ²のいずれか一方がアルキル基又はアリール基であり、Ｒ³は、アルキル基又はアリール基を表し、Ｒ¹又はＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子又はメチル基を表し、Ｘは単結合又はアリーレン基を表す。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group. Or 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 preferably each independently 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 preferable.

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

（式中、Ｒ¹²¹は水素原子又は炭素数１〜４のアルキル基を表し、Ｌ¹はカルボニル基又はフェニレン基を表し、Ｒ¹²²〜Ｒ¹²⁸はそれぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。）

(In the formula, 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 represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of

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.

  Preferable specific examples of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>
The structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic component in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a hydroxyl group.

<<< (a1-2-1) Structural unit having phenolic hydroxyl group >>>
Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is sensitive. From the viewpoint of Moreover, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following formula (a1-20) is also preferable from the viewpoint of sensitivity.

（式（ａ１−２０）中、Ｒ²²⁰は水素原子又はメチル基を表し、Ｒ²²¹は単結合又は２価の連結基を表し、Ｒ²²²はハロゲン原子又は炭素数１〜５の直鎖若しくは分岐鎖状のアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ²²²が２以上存在する場合、これらのＲ²²²は相互に異なっていてもよいし同じでもよい。）

(In the formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a linear or branched group having 1 to 5 carbon atoms. Represents a chain alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R ²²² is 2 or more, these R ²²² May be different from each other or the same.)

In the formula (A1-20), R ²²⁰ represents a hydrogen atom or a methyl group, and 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. As the divalent linking group for 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, R ²²¹ is preferably 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 each independently represents 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)-
The acid-decomposable group that can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group has a protected carboxyl group protected with the acid-decomposable group. Similarly to the acid-decomposable group that can be used for the unit (a1-1), a known one can be used and is not particularly limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among the 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 above 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 above formula (a1-10), the entire protected phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R ^102. The structure is (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 and a combination of R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph 0042 of JP2011-215590A 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 individually by 1 type or in combination of 2 or more types.

  As the radical polymerizable monomer used to form the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group, a commercially available one may be used, or a known method may be used. What was synthesize | combined by can also 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) having a protected phenolic hydroxyl group protected with the acid-decomposable group include the following structural units, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom or a methyl group.

-Preferred embodiment of the structural unit (a1)-
When the polymer having the structural unit (a1) does not substantially have the structural unit (a2), the structural unit (a1) is 20 to 100 mol% in the polymer having the structural unit (a1). Preferably, 30 to 90 mol% is more preferable.
When the polymer having the structural unit (a1) has the following structural unit (a2), the single structural unit (a1) has a sensitivity in the polymer having the structural unit (a1) and the structural unit (a2). From a viewpoint, 3-70 mol% is preferable and 10-60 mol% is more preferable. In particular, when 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.
In the present invention, when the content of the “structural unit” is defined in terms of molar ratio, the “structural unit” is synonymous with the “monomer unit”. In the present invention, the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

  The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred when developing quickly. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<(A2) Structural unit having a crosslinkable group>
Component C contains a polymer having 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 mode of the constituent unit having a preferred crosslinking group, represented by an epoxy group, oxetanyl _{group, -NH-CH 2 -O-R} (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) And a structural unit containing at least one selected from the group consisting of a group and an ethylenically unsaturated group, an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is a hydrogen atom or a carbon number) It is preferably at least one selected from the group consisting of groups represented by 1 to 20 alkyl groups. Among them, in the photosensitive resin composition of the present invention, it is more preferable that the component C includes a structural unit including at least one of an epoxy group and an oxetanyl group. In more detail, the following are mentioned.

<< (a2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>
Component C preferably contains a polymer having a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group. The 3-membered cyclic ether group is also called an epoxy group, and the 4-membered cyclic ether group is also called an oxetanyl group.
The structural unit (a2-1) having the epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one It may have an oxetanyl group, two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

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, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic epoch Such compounds may be mentioned containing shea skeleton, 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, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Acid esters and the like, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used to form the structural unit (a2-1) having the epoxy group and / or 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, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a2-1) having an epoxy group and / or oxetanyl group include the following structural units. R represents a hydrogen atom or a methyl group.

<< (a2-2) Structural unit having an ethylenically unsaturated group >>
One example of the structural unit (a2) having a crosslinkable group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a2-2)”). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms. A structural unit having a side chain is more preferred.

  In addition, regarding the structural unit having (a2-2) an ethylenically unsaturated group, refer to the description of paragraphs 0072 to 0090 of JP2011-215580A and the description of paragraphs 0013 to 0031 of JP2008-256974A. The contents of which are incorporated herein by reference.

_{<< (a2-3) -NH-CH 2} -O-R (R represents. A hydrogen atom or an alkyl group having 1 to 20 carbon atoms) The structural unit having a group represented by >>
The copolymer used in the present invention is a structural unit (a2-3) having a group represented by —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferable. 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 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still 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) is more preferably a structural unit having a group represented by the following formula (a2-30).

（式（ａ２−３０）中、Ｒ³¹は水素原子又はメチル基を表し、Ｒ³²は炭素数１〜２０のアルキル基を表す。）

(In formula (a2-30), R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents an alkyl group having 1 to 20 carbon atoms.)

R ³² 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 ³² 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, an i-butyl group, an n-butyl group, and a methyl group are preferable.

-Preferred embodiment of the structural unit (a2)-
When the polymer having the structural unit (a2) does not substantially have the structural unit (a1), the structural unit (a2) is 5 to 90 mol% in the polymer having the structural unit (a2). Preferably, 20 to 80 mol% is more preferable.
When the polymer having the structural unit (a2) has the structural unit (a1), the single structural unit (a2) has chemical resistance in the polymer having the structural unit (a1) and the structural unit (a2). From a viewpoint, 3-70 mol% is preferable and 10-60 mol% is more preferable.
In this invention, it is preferable to contain 3-70 mol% of structural units (a2) in all the structural units of (A) component irrespective of any aspect, and it is more preferable to contain 10-60 mol%. preferable.
Within the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.

<(A3) Other structural units>
In the present invention, component C may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2). In addition to the polymer component (1) or (2), the polymer component has another structural unit (a3) substantially free from the structural unit (a1) and the structural unit (a2). It may be. Apart from the polymer component (1) or (2), in the case of containing a polymer component having other structural unit (a3) substantially without the structural unit (a1) and the structural unit (a2), The blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.

  There is no restriction | limiting in particular as a monomer used as another structural unit (a3), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a3) can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the other structural unit (a3) include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, and vinyl. Ethyl benzoate, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) Isopropyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) a Mention may be made of a structural unit due to Relate. In addition, compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  Further, as the other structural unit (a3), a structural unit derived from a monomer having a styrene or an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

  Furthermore, as the other structural unit (a3), a structural unit derived from a (meth) acrylic acid alkyl ester is preferable 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 the structural unit constituting the polymer, the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and 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. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

The polymer contained in Component C preferably has a structural unit having an acid group as the other structural unit (a3). When the polymer has an acid group, the polymer easily dissolves in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 10.5. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Examples of the acid group used in the present invention include a carboxylic acid 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, And the group etc. which neutralized these acid groups and made it into salt structure are illustrated, and a carboxylic acid group and / or a phenolic hydroxyl group are preferable. Although there is no restriction | limiting in particular as said salt, An alkali metal salt, alkaline-earth metal salt, and organic ammonium salt can illustrate preferably.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . For example, the 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 p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferable.

In the present invention, apart from the polymer component (1) or (2), a polymer having another structural unit (a3) substantially not including the structural unit (a1) and the structural unit (a2) is included. You may go out.
As such a polymer, a resin having a carboxyl group in the side chain is preferable. 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 hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

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 in the present specification.
These polymers may contain only 1 type and may contain 2 or more types.

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

  In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group. For example, the compounds described in JP2012-88459A, paragraphs 0021 to 0023 and paragraphs 0029 to 0044 can be used, the contents of which are incorporated herein.

  The structural unit containing an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 40 mol%, and particularly preferably 5 to 30 mol% of the structural units of all polymer components. 5 to 20 mol% is most preferable.

Hereinafter, preferred embodiments of the polymer component in the present invention will be described, but the present invention is not limited thereto.
-First embodiment-
The aspect in which the polymer component (1) further has one or more other structural units (a3).
-Second Embodiment-
The polymer having a structural unit in which the (a1) acid group of the polymer component (2) has a group protected with an acid-decomposable group further has one or more other structural units (a3). Aspect.
-Third embodiment-
The aspect which the polymer which has a structural unit which has a (a2) crosslinkable group of a polymer component (2) further has 1 type, or 2 or more types of other structural units (a3).
-Fourth Embodiment-
In any one of the first to third embodiments, any polymer includes a structural unit containing at least an acid group as the other structural unit (a3).
-Fifth embodiment-
In addition to the polymer component (1) or (2), an embodiment having a polymer having another structural unit (a3) substantially not having the structural unit (a1) and the structural unit (a2). .
-Sixth Embodiment-
The aspect which consists of two or more combinations of the said 1st-5th embodiment.

-Molecular weight of polymer in component C-
The molecular weight of the polymer in Component C is a polystyrene-equivalent weight average molecular weight, and is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value. The ratio of the number average molecular weight Mn to the weight average molecular weight Mw (dispersity, Mw / Mn) is preferably 1.0 to 5.0, and more preferably 1.5 to 3.5.

-Method for producing polymer in component C-
Various methods for synthesizing the polymer in Component C are also known. For example, radicals used to form at least the structural unit (a1) and the structural unit (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

  The content of Component C in the photosensitive resin composition of the present invention is preferably 10 to 95% by mass and preferably 15 to 85% by mass with respect to the total solid content of the photosensitive resin composition. More preferably, the content is 20 to 75% by mass. When the content is within this range, the pattern formability during development is good, and a cured product having a higher refractive index can be obtained. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.

(Component D) Photoacid Generator The photosensitive resin composition of the present invention contains (Component D) a photoacid generator. The photoacid generator (also referred to as “component D”) 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. The structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if 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. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. Most preferred is a photoacid generator that generates an acid.

  Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation and sensitivity. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP2011-221494A. It can be illustrated.

  As an oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following formula (D1) can be preferably exemplified, and the contents thereof are incorporated herein.

（式（Ｄ１）中、Ｒ²¹は、アルキル基又はアリール基を表し、波線部分は他の基との結合箇所を表す。）

(In the formula (D1), R ²¹ represents an alkyl group or an aryl group, and a wavy line represents a bonding site with another group.)

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 an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged type fat It may be substituted with a cyclic 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 an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

  The compound containing an oxime sulfonate structure represented by the above formula (D1) is also preferably an oxime sulfonate compound represented by the following formula (D2).

（式（Ｄ２）中、Ｒ⁴²は、アルキル基又はアリール基を表し、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｍ４は、０〜３の整数を表し、ｍ４が２又は３であるとき、複数のＸは同一でも異なっていてもよい。）

(In the formula (D2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 is 2 or 3. In some cases, multiple Xs may be the same or different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above formula (D2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl. A compound which is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  The compound containing an oxime sulfonate structure represented by the above formula (D1) is also preferably an oxime sulfonate compound represented by the following formula (D3).

（式（Ｄ３）中、Ｒ⁴³は、アルキル基又はアリール基を表し、Ｘ¹は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基又はニトロ基を表し、ｎ４は０〜５の整数を表す。）

(In the formula (D3), R ⁴³ represents an alkyl group or an aryl group, and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. Represents a group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the above formula (D3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, the integer of 0-2 is preferable and 0 or 1 is especially preferable.

  As specific examples of the compound represented by the formula (D3) and preferable examples of the oxime sulfonate compound, the description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification. It is.

  The compound containing an oxime sulfonate structure represented by the above formula (D1) is also preferably a compound represented by the following formula (OS-1).

In the above formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or hetero Represents an aryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or Represents an aryl group. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
R ^{121 to} R ¹²⁴ are each independently preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Can be mentioned. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The compound represented by the formula (OS-1) is preferably, for example, a compound represented by the formula (OS-2) described in paragraphs 0087 to 0089 of JP2012-163937A, This content is incorporated herein.

  Specific examples of the compound represented by the formula (OS-1) that can be suitably used in the present invention include compounds described in paragraphs 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b- 34), but the present invention is not limited to this.

  In the present invention, the compound containing the oxime sulfonate structure represented by the formula (D1) is represented by the following formula (OS-3), the following formula (OS-4), or the following formula (OS-5). It is preferably an oxime sulfonate compound.

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ²²、Ｒ²⁵及びＲ²⁸はそれぞれ独立に、アルキル基、アリール基又はヘテロアリール基を表し、Ｒ²³、Ｒ²⁶及びＲ²⁹はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、Ｒ²⁴、Ｒ²⁷及びＲ³⁰はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、Ｘ¹〜Ｘ³はそれぞれ独立に、酸素原子又は硫黄原子を表し、ｎ¹〜ｎ³はそれぞれ独立に、１又は２を表し、ｍ¹〜ｍ³はそれぞれ独立に、０〜６の整数を表す。）

(In Formula (OS-3) to Formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxy group. Represents a sulfonyl group, X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents 0 Represents an integer of ~ 6)

  Moreover, the compound containing the oxime sulfonate structure represented by the said formula (D1) is described in the paragraph 0117 of Unexamined-Japanese-Patent No. 2012-163937, for example, General formula (OS-6)-(OS-11) It is particularly preferred that the compound is represented by any of the above), the contents of which are incorporated herein.

  The preferable range in the general formulas (OS-6) to (OS-11) is preferably the general formulas (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of JP2011-221494A. Similar to range.

  Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP2011-221494A. The invention is not limited to these.

  The compound containing an oxime sulfonate structure represented by the above formula (D1) is also preferably an oxime sulfonate compound represented by the following formula (D1-4).

（式（Ｄ１−４）中、Ｒ^d1は、アルキル基又はアリール基を表し、Ｒ^d2は、アルキル基、アリール基、又はヘテロアリール基を表す。Ｒ^d3〜Ｒ^d6は、それぞれ、水素原子、アルキル基、アリール基、ハロゲン原子を表す。ただし、Ｒ^d3とＲ^d4、Ｒ^d4とＲ^d5、又はＲ^d5とＲ^d6が結合して脂環又は芳香環を形成してもよい。Ｘ^dは、−Ｏ−又は−Ｓ−を表す。）

(In Formula (D1-4), R ^d1 represents an alkyl group or an aryl group, R ^d2 represents an alkyl group, an aryl group, or a heteroaryl group. R ^{d3 to} R ^d6 each represent a hydrogen atom, alkyl group, an aryl group, a halogen atom. However, R ^d3 and R ^d4, R ^d4 and R ^d5, or may be formed an alicyclic or aromatic ring R ^d5 and R ^d6 are bonded to .X ^d is , -O- or -S-).

R ^d1 represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable. Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. , 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
Carbon number of an aryl group becomes like this. Preferably it is 6-12, More preferably, it is 6-8, More preferably, it is 6-7. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ^d1 may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (eg, a methyl group, an ethyl group, a propyl group), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

In the photosensitive resin composition of the present invention, R ^d1 is preferably an alkyl group from the viewpoint of transparency, and R ^d1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. . By adopting such a bulky group (particularly a bulky alkyl group) as R ^e1 , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ^d2 represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ^d2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, and a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ^d2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which ^Rd1 represents may have.
R ^d2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ^{d3 to} R ^d6 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). The alkyl group represented by R ^{d3 to} R ^d6 has the same meaning as the alkyl group represented by R ^d2 , and the preferred range is also the same. The aryl group represented by R ^{d3 to} R ^d6 has the same meaning as the aryl group represented by R ^d1 , and the preferred range is also the same.
Among R ^{d3 to} R ^d6 , R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6 may combine to form a ring, and the ring forms an alicyclic ring or aromatic ring And a benzene ring is more preferable.
R ^{d3 to} R ^d6 are a hydrogen atom, an alkyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom), or R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6. Benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, or R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6 are bonded It is more preferable that a benzene ring is formed.
Preferred embodiments of R ^{d3 to} R ^d6 are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6 are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the above aspects 1 and 2 and / or an aspect satisfying the above aspects 1 and 3.

X ^d represents —O— or —S—.

  Specific examples of the formula (D1-4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

  In the photosensitive resin composition of the present invention, (Component D) the photoacid generator is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of Component C in the photosensitive resin composition. It is more preferable to use 5 to 10 parts by mass. Moreover, the component E may be used individually by 1 type, and can also use 2 or more types together.

(Component E) Dispersant The photosensitive resin composition of the present invention preferably contains (Component E) a dispersant. By containing the dispersant, the dispersibility of the component A in the resin composition can be further improved.
As the dispersant, a known dispersant can be used. For example, a known pigment dispersant can be appropriately selected and used.
As the dispersant, a polymer dispersant can be preferably used. The polymer dispersant is a dispersant having a molecular weight (weight average molecular weight) of 1,000 or more.

  As the dispersant, many types of compounds can be used. Specifically, for example, (meth) acrylic acid-based (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), DE Polymer dispersing agents such as Sparse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000 , 26000, 28000, and the like (manufactured by AstraZeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103 , F108, L121, P-123 (manufactured by ADEKA Corporation) and Isonet S-20 (manufactured by Sanyo Chemical Industries), DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140 142 , 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

A dispersing agent may be used individually by 1 type, or may be used together 2 or more types.
The content of the dispersant in the photosensitive resin composition of the present invention is preferably in the range of 5 to 70% by mass and more preferably in the range of 10 to 50% by mass with respect to the total solid content of the photosensitive resin composition.

(Component F) Crosslinking agent The photosensitive resin composition of the present invention preferably contains (Component F) a crosslinking agent, if necessary. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (except for component C). That is, a thermal crosslinking agent is preferably used as the crosslinking agent. For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, or a blocked isocyanate compound, etc. Can be added. Especially, the compound which has 2 or more epoxy groups or oxetanyl groups in a molecule | numerator is preferable, and the compound which has 2 or more epoxy groups in a molecule | numerator is more preferable.
It is preferable that the addition amount of the crosslinking agent in the photosensitive resin composition of this invention is 0.01-50 mass parts with respect to 100 mass parts of total solids of the photosensitive resin composition, 0.1-30 It is more preferable that it is a mass part, and it is still more preferable that it is 0.5-20 mass parts. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.

<Compound having two or more epoxy groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more epoxy 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, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like are listed in JP01-221494A, paragraph 0189, etc. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN- 502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX- 313, EX-314, EX- 21, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC- 301, DLC-402 (above, manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, Nippon Steel Chemical Co., Ltd.) Manufactured).
These can be used alone or in combination of two or more.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

As specific examples of 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.

  As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A, compounds having at least one ethylenically unsaturated double bond, and the like are also preferably used. be able to. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

<Block isocyanate compound>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
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.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic. Polyisocyanate may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate And prepolymer-type skeleton compounds derived from these compounds can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention 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.

Examples of the oxime compound include aldoxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
As said amine compound, a primary amine and a secondary amine are mentioned, Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may be sufficient, An aniline, diphenylamine, ethyleneimine, polyethyleneimine etc. can be illustrated.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

  The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, 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 (and above) , Manufactured by Asahi Kasei Chemicals Corporation, Death Module BL 100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.), etc. are preferably used can do.

(Component G) Basic Compound The photosensitive resin composition of the present invention may contain (Component G) a basic compound.
(Component G) 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 compounds described in paragraphs 0204 to 0207 of JP2011-221494A.

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, 2,4,5-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-di And azabicyclo [5.3.0] -7-undecene.
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.
Among these, heterocyclic amines are preferable, and 2,4,5-triphenylimidazole and / or N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea is particularly preferable.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is -3 mass parts.

(Component H) Surfactant The photosensitive resin composition of the present invention may contain (Component H) a surfactant.
As (Component H) surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include those described in paragraphs 0201 to 0205 of JP2012-88459A and those described in paragraphs 0185 to 0188 of JP2011-215580A. And these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), Mega Fuck (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Surflon Each series of S-242 (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.), and footgent FTX-218G (manufactured by Neos) Can be mentioned.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (H-1), and is a polystyrene equivalent weight measured by gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent. Preferred examples include copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

（式（Ｈ−１）中、Ｒ⁴⁰¹及びＲ⁴⁰³はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ⁴⁰²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴⁰⁴は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。）

(In Formula (H-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. A numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 to 18 and s represents an integer of 1 to 10)

L is preferably a branched alkylene group represented by the following formula (H-2). R ⁴⁰⁵ in formula (H-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

  The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. Part is more preferable, and 0.01 to 3 parts by mass is still more preferable.

(Component I) Antioxidant The photosensitive resin composition of the present invention preferably contains 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 heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, 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 the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, the contents of which are incorporated herein.

  Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 , ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS 90, ADK STAB ZS 90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Company, Ltd.), Tinuvin 405 (manufactured by BASF), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, Irganox 1098, and Tinuvin 405 can be preferably used.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% 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 can be improved.
Further, as additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives” (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators, and the like are used in the present invention. You may add to a resin composition.

(Component J) Alkoxysilane Compound In addition to Component S, the photosensitive resin composition of the present invention may contain (Component J) an alkoxysilane compound (also simply referred to as “silane compound”). When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. The (component J) alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, gold, copper, molybdenum, titanium, A compound that improves the adhesion between a metal such as aluminum and the insulating film is preferable. Specifically, a known silane coupling agent or the like is also effective.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacrylic acid. Roxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxy A silane is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.

Moreover, the compound represented by the following formula can also be preferably employed.
_{^{(R 1) 4-n -Si-}} (OR 2) n
In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group, R ² is an alkyl group or a phenyl group having 1 to 3 carbon atoms, n represents an integer from 1 to 3 is there.
Specific examples include the following compounds. Ph represents a phenyl group.

The (Component J) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and known compounds can be used.
As for content of the alkoxysilane compound in the photosensitive resin composition of this invention, 0.1-30 mass parts is preferable with respect to 100 mass parts of total solids in the photosensitive resin composition, 0.5-20 masses Part is more preferred.

(Component K) Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (Component D) a photoacid generator. The sensitizer absorbs actinic rays or radiation 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 (Eg, merocyanine, carbomerocyanine), rhodocyanins, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridineo , Chloroflavin, acriflavine), acridones (for example, acridone, 10-butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), styryls, base styryls ( For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (eg, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2, 3, 6 , 7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolidine-11-non).
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.

The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition, and 10 to 500 parts. It is more preferable that it is a mass part, and it is still more preferable that it is 50-200 mass parts.
Moreover, a sensitizer may be used individually by 1 type and can also use 2 or more types together.

(Component L) Heterocyclic compound having two or more nitrogen atoms The photosensitive resin composition of the present invention preferably contains (Component L) a heterocyclic compound having two or more nitrogen atoms. When the component L is adsorbed on the surface of the inorganic particles, electrostatic repulsion and steric repulsion between the inorganic particles are caused, and in particular, the haze is reduced in order to prevent aggregation of the inorganic particles when the composition is applied and dried. Presumed. A part of the compound corresponding to component L also corresponds to component G.
Component L is not particularly limited except that it has two or more nitrogen atoms, but is preferably a heterocyclic compound having two or more nitrogen atoms as a ring member of the heterocyclic ring, and nitrogen at the 1,3-position. A compound having a heterocyclic structure having at least an atom is more preferable, and a compound having a 5-membered or 6-membered heterocyclic structure having at least a nitrogen atom at the 1,3-positions is more preferable. If it is the said aspect, the hardened | cured material which is excellent by the dispersibility of an inorganic particle and has a smaller haze will be obtained.
The “heterocyclic structure having at least a nitrogen atom at positions 1 and 3” may be a structure in which nitrogen atoms are bonded to both sides of a carbon atom in the heterocyclic ring. It does not have to be in the third or third place.

The ring member of the heterocyclic ring in component L is preferably composed of at least a carbon atom and a nitrogen atom, and may further contain an oxygen atom or a sulfur atom as a ring member, but consists of a carbon atom and a nitrogen atom. Is particularly preferred.
The number of nitrogen atoms contained in the component L is 2 or more, preferably 2 to 6, and more preferably 2 to 4. Component L preferably has 2 to 4 nitrogen atoms as ring members of the heterocyclic ring, more preferably 2 or 3, and preferably 2 Further preferred.
The heterocyclic ring in component L may be a saturated heterocyclic ring, an unsaturated heterocyclic ring, or an aromatic heterocyclic ring.
In addition, the heterocyclic ring in component L may be further condensed with another ring. Moreover, as said other ring, not only a heterocyclic ring but an aliphatic ring or an aromatic ring may be sufficient.

  Specific examples of the heterocyclic structure of component L include imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline. Preferred examples thereof include a ring structure selected from the group consisting of a structure, 4-imidazoline structure (2,3-dihydroimidazole structure), imidazolidine structure, pyrimidine structure, quinoxaline structure, purine structure, pteridine structure, and peridimine structure, Imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline structure, 4-imidazoline structure, imidazolidine structure, and More ring structures selected from the group consisting of pyrimidine structures Mentioned preferred, benzimidazole structure or imidazolidine structure are exemplified particularly preferred. If it is the said aspect, the hardened | cured material which is excellent by the dispersibility of a metal oxide particle, and has a smaller haze is obtained.

Component L preferably has a mercapto group (—SH) or a thioxo group (═S). If it is the said aspect, the hardened | cured material which is excellent by the dispersibility of a metal oxide particle, and has a smaller haze is obtained.
Component L is preferably a compound represented by the following formula (La).

（式（Ｌ−ａ）中、Ｒ^a1及びＲ^a2はそれぞれ独立に、水素原子、ハロゲン原子又は一価の有機基を表し、Ｒ^a1とＲ^a2とが結合して二価の有機基であってもよく、Ｒ^a3及びＲ^a4はそれぞれ独立に、水素原子又は一価の有機基を表し、Ｌ^a1は５員環又は６員環を形成する二価の連結基を表し、Ｒ^a3又はＲ^a4とＬ^a1とが結合して環を形成していてもよく、また、点線の結合は、点線で記載した含窒素二重結合が存在する場合は、Ｒ^a2及びＲ^a4が存在しないことを表し、点線で記載した含窒素二重結合が存在しない場合は、Ｒ^a2及びＲ^a4が存在することを表す。）

(In Formula ( ^La ), R ^a1 and R ^a2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and R ^a1 and R ^a2 are bonded to form a divalent organic group. R ^a3 and R ^a4 each independently represents a hydrogen atom or a monovalent organic group, L ^a1 represents a divalent linking group forming a 5-membered or 6-membered ring, and R ^a3 or R a ^a4 and L ^a1 may be bonded to form a ring, and the dotted bond indicates that when the nitrogen-containing double bond described by the dotted line is present, R ^a2 and R ^a4 are not present. When the nitrogen-containing double bond represented by the dotted line is not present, it represents that R ^a2 and R ^a4 are present.)

^Examples of the monovalent organic group in R ^{a1 to} R ^a4 include an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), and alkynyl. Group, aryl group, heterocyclic group (also referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group , Aryloxycarbonylamino group , Sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, alkyldithio group, aryldithio group, heterocyclic dithio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, a thioureido group, a boronic acid group (-B (OH) _2), phosphato group (-OPO (OH) _2), a sulfato group (-OSO ₃ H), and other Examples of known substituents of That. Moreover, the said group may be further substituted by the substituent.

Of these, a mercapto group is particularly preferable as the monovalent organic group for R ^a1 and R ^a2 .
In addition, the carbon number of the monovalent organic group in R ^a1 and R ^a2 is preferably 0 to 20, more preferably 0 to 8, and particularly preferably 0.
Examples of the divalent organic group formed by combining R ^a1 and R ^a2 include an oxo group, a thioxo group, and an alkylidene group. Of these, a thioxo group is particularly preferable.
R ^a1 and R ^a2 are each independently preferably a hydrogen atom or a mercapto group, and when R ^a1 and R ^a2 are combined to form a divalent organic group, they are thioxo groups. Is particularly preferred.

The monovalent organic group for R ^a3 and R ^a4 is preferably an alkyl group or an aryl group, more preferably a morpholinomethyl group or a phenyl group. The alkyl group or aryl group may be substituted with a substituent.
The carbon number of the monovalent organic group in R ^a3 and R ^a4 is preferably 0-20, more preferably 1-10, and even more preferably 4-8.
R ^a3 and R ^a4 are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a morpholinomethyl group or a phenyl group, and a hydrogen atom or a phenyl group. Further preferred.

L ^a1 represents a divalent linking group that forms a 5-membered ring or a 6-membered ring, and forms a heterocyclic ring together with the carbon atom and the two nitrogen atoms in the formula (La).
The divalent linking group is not particularly limited as long as it is a group that forms a 5-membered heterocyclic ring or a 6-membered heterocyclic ring with the carbon atom and the two nitrogen atoms in the formula (La), but the ring member Is preferably a group formed from a carbon atom and / or a nitrogen atom, and more preferably a group forming a specific example of the heterocyclic structure described above. Among them, a group that forms a benzimidazole structure, that is, a 1,2-phenylene group, a group that forms an imidazolidine structure, or a 1,2-ethylene group is particularly preferable.

  Furthermore, the component L is more preferably a compound represented by the following formula (La-1) or formula (La-2).

（式（Ｌ−ａ−１）及び式（Ｌ−ａ−２）中、Ｒ^a6〜Ｒ^a8はそれぞれ独立に、水素原子又は一価の有機基を表し、Ｌ^a2及びＬ^a3はそれぞれ独立に、５員環又は６員環を形成する二価の連結基を表し、Ｒ^a6とＬ^a2とが結合して環を形成していてもよく、Ｒ^a7又はＲ^a8とＬ^a3とが結合して環を形成していてもよい。）

(In formula (La-1) and formula ( ^La -2), R ^{a6 to} R ^a8 each independently represents a hydrogen atom or a monovalent organic group, and L ^a2 and L ^a3 each independently Represents a divalent linking group that forms a 5-membered or 6-membered ring, R ^a6 and L ^a2 may be bonded to form a ring, and R ^a7 or R ^a8 and L ^a3 are bonded And may form a ring.)

R ^{a6 to} R ^a8 in the formula ( ^La -1) or the formula ( ^La -2) have the same ^{meanings as} R ^a3 and R ^a4 in the above formula ( ^La ), and preferred embodiments are also the same.
Further, L ^a2 and L ^a3 in Formula (L-a1) or formula (L-a2) has the same meaning as L ^a1 in formula (L-a), preferable embodiments thereof are also the same.
Preferred specific examples (L-1 to L-11) of component L are shown below. However, the present invention is not limited to these.

Among these, L-3 to L-11 are preferable, L-3, L-5, L-6, or L-9 is more preferable, and L-5 or L-9 is particularly preferable.
The synthesis method of component L is not particularly limited, and can be synthesized by a known synthesis method, substituent introduction method, or substituent conversion method.

Moreover, the component L may be used individually by 1 type, and can also use 2 or more types together.
It is preferable that content of the component L in the photosensitive resin composition of this invention is 0.1-20 mass% with respect to the total solid of the photosensitive resin composition of this invention, 0.5-15 It is more preferable that it is mass%, and it is still more preferable that it is 0.5-10 mass%. When it is in the above range, a cured product having excellent dispersibility of the inorganic particles and smaller haze can be obtained.

<Other ingredients>
In addition to the above components, the photosensitive resin composition of the present invention includes an ultraviolet absorber, a metal deactivator, an acid proliferator, a development accelerator, a plasticizer, a thermal radical generator, a heat as necessary. Known additives such as acid generators, thickeners, and organic or inorganic suspending agents can be added. Moreover, as these compounds, the description of paragraph 0201-0224 of Unexamined-Japanese-Patent No. 2012-88459 can also be considered, for example, The content of these is integrated in this-application specification.

[Acid multiplication agent]
The photosensitive resin composition of the present invention may use an acid proliferating agent 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 paragraphs 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.

  The content of the acid multiplier in the photosensitive resin composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, in view of the dissolution contrast between the exposed part and the unexposed part. To 20 to 500 parts by mass.

[Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, and the development accelerator may be a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group. Preferably, a compound having a carboxyl group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is most preferable.
As the development accelerator, the description in paragraphs 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.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition, from the viewpoints of sensitivity and residual film ratio. 0.1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
The molecular weight of the development accelerator is preferably from 100 to 2,000, more preferably from 150 to 1,500, still more preferably from 150 to 1,000.

[Plasticizer]
The resin composition of the present invention may contain a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The plasticizer content in the resin composition of the present invention is preferably 0.1 to 30 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of component A. .

  Further, as other additives, a thermal radical generator described in paragraphs 0120 to 0121 of JP2012-8223A, and a nitrogen-containing compound and a thermal acid generator described in International Publication No. 2011-136704 are also used. The contents of which are incorporated herein by reference.

<Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance 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.
In the present invention, a metal oxide particle dispersion containing (component A) metal oxide particles, (component B) solvent, and (component E) dispersant is prepared in advance. It is particularly preferable to prepare a photosensitive resin composition by adding Component S, Component C and Component D, and optional components.

(Resin pattern manufacturing method)
Next, the resin pattern manufacturing method of the present invention will be described.
The resin pattern manufacturing method of the present invention preferably includes the following steps (1) to (4), and more preferably includes the following steps (1) to (5).
(1) A coating process for coating the photosensitive resin composition of the present invention on a substrate;
(2) a solvent removal step of removing the solvent from the applied resin composition;
(3) An exposure step of exposing the resin composition from which the solvent has been removed to a pattern with actinic rays;
(4) Development step of developing the exposed resin composition with an aqueous developer;
(5) A heat treatment step of heat-treating the developed resin composition.
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. It is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate is improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and plastic substrates such as cellulose triacetate (TAC).
Examples of the inorganic substrate include 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.
Resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, Is it a synthetic resin such as aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin, etc. Substrate made of, and the like.
These substrates are rarely used in the above-described form, and usually have a multilayer laminated structure such as a TFT element formed depending on the form of the final product.

Among these, in the present invention, it is preferable that all or part of the surface of the substrate is at least one selected from the group consisting of glass, SiO, ITO, IZO, a metal film, and a metal oxide film. It is particularly preferable that all or part of the surface of the substrate is ITO.
As a result of intensive studies by the present inventors, it has been found that when all or a part of the surface of the substrate is ITO (Indium Tin Oxide), the occurrence of development residue on the ITO is particularly remarkable. . The photosensitive resin composition of the present invention has a very remarkable effect that generation of development residues can be suppressed even when all or part of the surface of the substrate is ITO.

The coating method on the substrate is not particularly limited, and for example, a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
The coating film thickness is not particularly limited and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 μm.

Ink jet method application, compared with conventional application methods such as spin coating method and slit coating method, the amount of coating liquid used is greatly reduced, and the influence of mist adhering to the spin coating method is reduced. This is preferable from a comprehensive point of view, for example, generation of foreign matter is suppressed.
For example, the application conditions by the ink jet method may be appropriately selected depending on the composition of the photosensitive resin composition, the type of coating film to be manufactured, and the like. In order to adjust the thickness of the coating film, the discharge amount of the liquid photosensitive resin composition and the number of discharges to the same portion may be adjusted. Moreover, what is necessary is just to select suitably the shape and position which apply | coat the photosensitive resin composition as desired. There is no restriction | limiting in particular as an apparatus used for the application | coating of an inkjet system, What is necessary is just to apply a well-known inkjet coating apparatus.
Specific examples include on-demand ink jet coating apparatuses IJ-DESK-S, IJ-DESK-H (manufactured by PMT Co., Ltd.), Dimadix Material Printer DMP2831, DMP-3000 (manufactured by FUJIFILM Dimatix), and the like. It is done.

  There is no restriction | limiting in particular as an inkjet recording device which can be used for the said inkjet coating system, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. That is, if it is a well-known inkjet recording apparatus containing a commercial item, the application | coating by the inkjet application system of the photosensitive resin composition of this invention on the board | substrate in the said application | coating process can be implemented.

Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including a composition supply system and a temperature sensor.
The ink supply system includes, for example, an original tank containing the photosensitive resin composition of the present invention, a supply pipe, a composition supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo-type inkjet head preferably has a multi-size dot of 1 to 100 pl, more preferably 8 to 30 pl, preferably 320 × 320 to 4,000 × 4,000 dpi (dot per inch), more preferably 400 × 400. ˜1,600 × 1,600 dpi, more preferably 720 × 720 dpi. In the present invention, dpi represents the number of dots per 2.54 cm.
The coating film thickness is not particularly limited and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 μm.

In the solvent removal step (2), it is preferable to remove the solvent from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal 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 adhesion is good and the residue can be reduced.
The coating step (1) and the solvent removal step (2) may be performed in this order, simultaneously, or alternately. For example, after all of the inkjet application in the application step (1) is completed, the solvent removal step (2) may be performed, or the substrate is heated, and the photosensitive by the inkjet application method in the application step (1). The solvent may be removed while discharging the conductive resin composition.
In particular, it is preferable to perform the solvent removal step (2) after all the inkjet coating in the coating step (1) is completed.

In the exposure step (3), it is preferable to irradiate the substrate provided with the coating film with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 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.
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, 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 formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for 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, the acid-decomposable group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group. A positive image can be formed by development without performing PEB.

In the developing step (4), it is preferable to develop a copolymer having a liberated acid group, for example, a carboxyl group or a phenolic hydroxyl group, using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having an acid group that easily dissolves in an alkaline developer, such as a carboxyl group or a phenolic hydroxyl group.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. 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.
Preferred examples of the developer include a 0.4% by mass aqueous solution, a 0.5% by mass aqueous solution, a 0.7% by mass aqueous solution, or a 2.38% by mass aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After the development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
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, a shower rinse, a dip rinse, etc. can be mentioned.

In the heat treatment step (post-bake) of (5), the obtained positive image is heated to thermally decompose the acid-decomposable group to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group, and a crosslinkable group, A cured film can be formed by crosslinking with a crosslinking 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 ° C. to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. By proceeding with a crosslinking reaction that is preferably treated, a protective film and an interlayer insulating film having excellent heat resistance, hardness, and the like can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere. When using a plastic substrate, it is preferable to heat-process at 80 to 140 degreeC for 5 to 120 minutes.
Prior to the heat treatment step (post-bake), the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  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 heat treatment step is used as a dry etching resist, dry etching processing such as ashing, plasma etching, ozone etching, or the like can be performed as the etching processing.

(Cured film)
The cured film of the present invention is a film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. The cured film of the present invention is preferably a film obtained by the method for producing a cured product of the present invention or the resin pattern production method of the present invention, and is a film obtained by the resin pattern production method of the present invention. It is more preferable.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for applications of organic EL display devices, liquid crystal display devices, and touch panel display devices.

(Hardened product and manufacturing method thereof)
The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. As described above, the shape does not have to be a film, and may be any shape.
In addition, the cured product of the present invention may be a cured product in which the hardness is increased by removing at least a part of the solvent from the photosensitive resin composition of the present invention, but from the photosensitive resin composition of the present invention. A cured product obtained by removing the solvent and thermosetting is preferable.
Although the manufacturing method of the hardened | cured material of this invention does not have a restriction | limiting in particular, It is preferable that the following process (a)-(c) is included at least in this order.
(A) A coating process for coating the photosensitive resin composition of the present invention on a substrate;
(B) a solvent removal step of removing the solvent from the applied resin composition;
(C) A heat treatment step of heat treating the resin composition from which the solvent has been removed.

Process (a) and process (b) are synonymous with the said application | coating process and the said solvent removal process, respectively, A preferable aspect is also the same.
Step (c) is the same step as the heat treatment step except that the heat treatment target is a resin composition from which the solvent obtained in step (b) has been removed. Preferred embodiments such as time and heating means are also preferred.
Moreover, it is preferable that the hardened | cured material of this invention is the hardened | cured material obtained by the resin pattern manufacturing method of this invention.

The cured product of the present invention is an optical member such as a microlens, an optical waveguide, an antireflection film, an LED sealing material and an LED chip coating material, or a cured product for reducing the visibility of wiring electrodes used in touch panels. It can be used suitably.
In addition, the cured product of the present invention has a constant thickness of a planarizing film, an interlayer insulating film, a color filter protective film, and a liquid crystal layer in a liquid crystal display device as described later, for example, in a liquid crystal display device or an organic EL device. It can be suitably used for spacers for holding, structural members of MEMS (Micro Electro Mechanical Systems) devices, and the like.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises the cured product of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
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, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, liquid crystal driving methods that the liquid crystal display device of the present invention can take are TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, 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 Allay) type liquid crystal display device. For example, the organic insulating film (115) described in JP-A-2005-284291, It can be used as the organic insulating film (212) described in Japanese Unexamined Patent Application Publication No. 2005-346054.
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer alignment may be supported by the PSA (Polymer Sustained Alignment) technique described in JP2003-149647A or JP2011-257734A.
Moreover, the photosensitive resin composition of this invention and the hardened | cured material 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. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to 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, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interphase insulating film (48) described in JP2011-145686A or the interphase insulating film (520) described in JP2009-258758A. Can do.

(Organic EL display device)
The organic EL display device of the present invention comprises the cured product 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 organic materials having various structures. An EL display device and a liquid crystal display device can be given.
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, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram 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 used to connect 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 due to the formation of the wiring 2, a planarizing layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
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.
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.

  Since the photosensitive resin composition of the present invention is excellent in photosensitivity and film characteristics, a resist pattern formed by using the photosensitive resin composition of the present invention as a partition as a structural member of a MEMS device, or a machine-driven component Used as a part of. Examples of such MEMS devices include SAW (surface acoustic wave) filters, BAW (bulk acoustic wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. And the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP2011-107476A, JP2010-2010A. Partition wall (12) and planarization film (102) described in FIG. 4A of JP-A-9793, and bank layer (221) and third interlayer insulating film (FIG. 10 of JP 2010-27591A). 216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4 (a) of Japanese Patent Laid-Open No. 2009-128577, and FIG. 3 of Japanese Patent Laid-Open No. 2010-182638. It can also be used to form a planarization film (12), a pixel isolation insulating film (14), and the like.

(Touch panel display)
The touch panel display device of the present invention includes a capacitive input device having the cured product of the present invention. Moreover, the capacitance-type input device of the present invention is characterized by having the film of the present invention.
The capacitance-type input device of the present invention has at least the following elements (1) to (5) on the front plate and the non-contact side of the front plate, and the above (4) is the heat-treated product of the present invention. Preferably there is.
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric A plurality of second transparent electrode patterns comprising a plurality of pad portions which are insulated and extend in a direction intersecting the first direction. (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern of (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the above Conductive element different from the second transparent electrode pattern In the capacitive input device of the present invention, a transparent protective layer is further provided so as to cover all or part of the elements (1) to (5). The transparent protective layer is preferably And more preferably the cured film.

  First, the configuration of the capacitive input device will be described. FIG. 3 is a cross-sectional view showing the configuration of the capacitive input device. In FIG. 3, the capacitive input device 30 includes a front plate 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.

  The front plate 31 is made of a light-transmitting substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, in FIG. 3, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive input device 30 of the present invention, input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the front plate 31. Hereinafter, the front plate may be referred to as a “base material”.

A mask layer 32 is provided on the non-contact surface of the front plate 31. The mask layer 32 is a frame-like pattern around the display area formed on the non-contact side of the touch panel front plate, and is formed so as not to show the lead wiring and the like.
In the capacitive input device of the present invention, as shown in FIG. 4, a mask layer 32 is provided so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 4). . Further, the front plate 31 can be provided with an opening 38 in a part thereof as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.

As shown in FIG. 5, on the contact surface of the front plate 31, a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns 34 each including a plurality of pad portions that are electrically insulated from one transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the electrode pattern 33 and the second transparent electrode pattern 34 is formed. The first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later are translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a conductive metal oxide film. Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the film thickness of each element can be 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. In addition, the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 described later use a photosensitive transfer material having a photosensitive resin composition using the conductive fibers. Can also be manufactured. In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to.

  In addition, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region opposite to the front plate 31 of the mask layer 32. Can be installed. In FIG. 3, a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface opposite to the front plate 31 of the mask layer 32. Yes.

  The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. FIG. 5 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention. As shown in FIG. 5, the first transparent electrode pattern 33 is formed such that a pad portion 33a extends in a first direction via a connection portion 33b. The second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35 and extends in a direction intersecting the first direction (second direction in FIG. 5). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be manufactured as one body, or only the connection portion 33b is manufactured, and the pad portion 33a and the second portion 33b are formed. The transparent electrode pattern 34 may be integrally formed (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 5, a part of the connection part 33b and a part of the pad part 33a are connected, and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.

  In FIG. 3, a conductive element 36 is provided on the side of the mask layer 32 opposite to the front plate 31. The conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element. In FIG. 3, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.

  Moreover, in FIG. 3, the transparent protective layer 37 is installed so that all of each component may be covered. The transparent protective layer 37 may be configured to cover only a part of each component. The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.

<Capacitance type input device and touch panel display device provided with capacitance type input device>
The capacitance-type input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitance-type input device as a constituent element are “latest touch panel technology” (issued July 6, 2009 (stock) ) Techno Times), supervised by Yuji Mitani, “Technology and Development of Touch Panel”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. Can be applied.

<Touch panel and manufacturing method thereof>
The touch panel of the present invention is a touch panel in which all or a part of the insulating layer is made of a heat-treated product of the resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an ITO electrode, and an insulating layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention.
Moreover, the manufacturing method of the touchscreen of this invention is a manufacturing method of the touchscreen which has a transparent substrate, an ITO electrode, and an insulating layer, Comprising: Inkjet application | coating the photosensitive resin composition for inkjet application | coating of this invention so that an ITO electrode may be touched A step of applying by a method, a step of placing a mask having an opening pattern of a predetermined shape on the resin composition, an exposure step by irradiating with active energy rays, a step of developing the resin composition after exposure, and a post-development It is preferable to include a step of heating the resin composition to produce an insulating layer.

As a transparent substrate in the touch panel of this invention, a glass substrate, a quartz substrate, a transparent resin substrate, etc. are mentioned preferably.
Ink-jet application in the step of applying the photosensitive resin composition for ink-jet application of the present invention by the ink-jet application method so as to be in contact with the ITO electrode can be performed in the same manner as the above-described application step, and the preferred embodiment is also the same. . Moreover, in the said process, at least one part of the apply | coated photosensitive resin composition of this invention should just be in contact with the ITO electrode.
The step of placing a mask having an opening pattern of a predetermined shape on the resin composition, irradiating with exposure to active energy rays, and the step of developing the resin composition after exposure are performed in the same manner as the exposure step described above. The preferred embodiment is also the same.
The step of heating the resin composition after development to produce an insulating layer can be performed in the same manner as the heat treatment step described above, and the preferred embodiment is also the same.
Moreover, as an example of the ITO electrode pattern in the touch panel of this invention, the pattern shown in FIG. 5 mentioned above is mentioned preferably.

  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.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: tetrahydrofuran-2-yl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MACHOE: 1- (cyclohexyloxy) ethyl methacrylate (synthetic product)
MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPMA: Dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
MEDG: Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industry Co., Ltd., High Solve EDM)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko KK)
EEP: Ethyl 3-ethoxypropionate (manufactured by Sankyo Chemical Co., Ltd.)

MATHF was synthesized according to the synthesis example described in paragraph 0187 of JP2013-80203A.
MACHOE was synthesized in the same manner as MATH, except that 2-dihydrofuran was changed to the corresponding compound.

<Synthesis of Polymer C-1>
MEDG (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. Dissolve MAEVE 0.4 molar equivalent, GMA 0.3 molar equivalent, MAA 0.1 molar equivalent, HEMA 0.2 molar equivalent, V-65 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) in the solution. And added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby, a polymer C-1 was obtained. The ratio of MEDG to the total amount of other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared.

<Synthesis of Polymers C-2 to C-10>
Other polymers were synthesized in the same manner as the synthesis of polymer C-1, except that the type of monomer used, the polymerization initiator, and the like were changed as shown in Table 1 below.

<Preparation of dispersion E1>
A dispersion having the following composition was prepared, mixed with 17,000 parts of zirconia beads (0.3 mmφ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mmφ) were filtered off to obtain dispersion D1.
Titanium dioxide (Ishihara Sangyo Co., Ltd., trade name: TTO-51 (A), average primary particle size: 10-30 nm): 1,875 parts DISPERBYK-111 (Bic Chemie Japan Co., Ltd.) 30% PGMEA solution: 2,200 parts ・ Solvent PGMEA: 3,425 parts

Example 1
<Preparation of photosensitive resin composition>
After mixing and mixing with the following composition to make a uniform solution, the mixture was filtered using a polyethylene filter having a pore size of 0.2 μm to prepare a photosensitive resin composition of Example 1. Various evaluations described later were performed using the obtained photosensitive resin composition. The evaluation results are shown in Table 2 described later.
-PGMEA: 100.0 parts-EEP: 150.0 parts-0.2% PGMEA solution of the following compound (Toyo Kasei Kogyo Co., Ltd., CMTU): 25.7 parts-30% MEDG of polymer C-1 Solution: 263.3 parts · Photoacid generator D-1 (the following compound): 5.1 parts · JER157S65 (epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq): 7.9 parts Irganox 1726 (antioxidant, manufactured by BASF): 3.0 parts. 2.0% PGMEA solution of perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation): 11.0 Parts / dispersion E1: 478.4 parts / additive S-1 (Z-6920 manufactured by Toray Dow Corning Co., Ltd.): 7.9 parts / compound L-1 (following compound, Wako Pure Chemical Industries, Ltd.) Manufactured): 2.8 parts

<Synthesis of D-1>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry 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 p-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 D-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).

<Various evaluations>
The following evaluation was performed using the obtained photosensitive resin composition of Example 1. The evaluation results are shown in Table 2.

<Evaluation of haze (transparency)>
On a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning), the obtained photosensitive resin composition was applied with a spin coater so that the dry film thickness was 2.0 μm, and hot at 80 ° C. The plate was dried (pre-baked) for 120 seconds. Furthermore, the coating film was subjected to a heat treatment (post-bake) for 15 minutes in an oven at 120 ° C., and the haze after the post-bake was subjected to a plastic product test with NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. The haze (haze value) was measured according to the method (JIS K7136, JIS K7361, ASTM D1003).
In addition, a haze value refers to the value represented by the ratio (%) of the diffuse transmitted light with respect to all the light transmitted light. The smaller the haze value, the higher the transparency. The evaluation criteria are shown below. The practical range is 3 or less.
1: The haze value was less than 0.5%.
2: The haze value was 0.5% or more and less than 0.7%.
3: The haze value was 0.7% or more and less than 1.0%.
4: The haze value was 1.0% or more and less than 2.0%.
5: Haze value was 2.0% or more.

<Evaluation of development adhesion>
The obtained photosensitive resin composition was applied with a spin coater to a film thickness of 2.0 μm on a glass substrate on which a ITO film was partially formed by etching on a glass surface of 100 mm × 100 mm. It was dried (prebaked) for 120 seconds on a hot plate.
Next, using a ghi-line high-pressure mercury lamp exposure machine, the film was exposed through a 1% to 60% gradation mask with a line and space of 1: 1 at an illuminance of 20 mW / cm ² and 200 mJ / cm ² .
Next, the film was developed with a 0.5 mass% aqueous tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 15 seconds by immersing, and further rinsed with ultrapure water for 10 seconds. Subsequently, an evaluation substrate was obtained by heating at 220 ° C. for 45 minutes. The obtained substrate was observed with an optical microscope and evaluated according to the following criteria.
1: No peeling is observed at all.
2: Peeling is observed with a line and space pattern of less than 10 μm, but no more is observed.
3: Peeling is observed with a line and space pattern of less than 20 μm, but no more is observed.
4: Peeling is observed with a line-and-space pattern of less than 40 μm, but no more is observed.
5: Peeling is observed in a line and space pattern of 40 μm or more.

(Examples 2 to 25 and Comparative Examples 1 to 7)
A photosensitive resin composition was prepared in the same manner as in Example 1, except that the polymer, photoacid generator, compound L-1 and / or additive were changed as shown in Table 2. Evaluation was performed in the same manner as in Example 1 using each of the obtained photosensitive resin compositions. The evaluation results are shown in Table 2.
In addition, the ratio of Table 2 in the case of using 2 types of polymers represents a mass ratio.

  As is clear from the results shown in Table 2 above, the photosensitive resin composition of the present invention also had good development adhesion and haze (transparency). In contrast, the photosensitive resin composition of the comparative example was inferior in development adhesion and transparency.

  The details of the abbreviations indicating the compounds shown in Table 2 other than those described above are as follows.

<Photo acid generator>
D-2: Structure shown below (synthesis examples will be described later)

<Synthesis of D-2>
4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) is suspended in 16 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) and sodium hydrogen carbonate (Wako Pure Chemical Industries, Ltd.). After addition of 3.4 g (manufactured by Co., Ltd.), 4.9 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and heated at 120 ° C. for 2 hours in a nitrogen atmosphere. . After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude D-2A. Crude D-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate D-2A.
D-2A (1.7 g) and p-xylene (6 mL) are mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) is added, and 140 ° C. for 2 hours. Heated. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude D-2B.
THF (2 mL) and the whole amount of crude D-2B were mixed, and 2 mL of 2M hydrochloric acid / THF solution under ice cooling was added dropwise, and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) was added dropwise. The mixture was heated to (25 ° C.) and stirred for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain Intermediate Intermediate D-2C.
The total amount of intermediate crude D-2C was mixed with acetone (10 mL), and triethylamine (Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonyl chloride (Tokyo Chemical Industry Co., Ltd.) were cooled with ice. ) (1.4 g) was added, and the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture to separate the solution, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude D-2. Crude D-2 was reslurried with cold methanol, filtered and dried to obtain D-2 (1.2 g).

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of D-2 is δ = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7. -7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H) there were.

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

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

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

  S-2 to S-4 and S-C1 to S-C5: the following compounds (S-2: KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd., S-C1: KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd., S -C4: Shin-Etsu Chemical Co., Ltd. KBM-803, S-C5: Shin-Etsu Chemical Co., Ltd. KBM-3103)

(Example 26)
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device of Example 26. That is, the photosensitive resin composition of Example 1 was spin-coated on a substrate, pre-baked (90 ° C./120 seconds) on a hot plate, and then i-line (365 nm) was 45 mJ / mm from the mask using a high-pressure mercury lamp. After irradiation with cm ² (illuminance 20 mW / cm ² ), development was performed with an alkaline aqueous solution to form a pattern, and heat treatment was performed at 230 ° C./30 minutes to form a cured film 17 as an interlayer insulating film.

  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 27)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 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 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 due to the formation of the wiring 2, the flattening film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by applying the photosensitive resin composition of Example 1 on the substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then starting from the mask with a high-pressure mercury lamp. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm), a pattern was formed by developing with an alkaline aqueous solution, followed by heat treatment 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 baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  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 1 was used, and the insulating film 8 was formed by the same method as described above. 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.

(Example 28)
A touch panel display device was produced using the photosensitive resin composition having a high refractive index of the present invention by the method described below.

<Formation of first transparent electrode pattern>
(Formation of transparent electrode layer)
A front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a mask layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO ₂ content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.

Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 μm, pattern exposure is performed at an exposure amount of 50 mJ / cm ² (i-line), and then a dedicated developer And a post-baking treatment at 130 ° C. for 30 minutes to obtain a front plate on which a transparent electrode layer and an etching photosensitive resin layer pattern were formed.

The front plate on which the transparent electrode layer and the photo-sensitive resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist. The exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
Next, the front plate with the transparent electrode layer pattern with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the photosensitive resin layer for etching is removed, and the mask layer and the first transparent electrode pattern A front plate formed was obtained.

(Formation of insulating layer)
On the front plate on which the mask layer and the first transparent electrode pattern were formed, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds) to form a photosensitive resin composition layer. Got. The distance between the exposure mask (quartz exposure mask having an insulating layer pattern) surface and the photosensitive resin composition layer was set to 30 μm, and pattern exposure was performed at an exposure amount of 50 mJ / cm ² (i-line).
Next, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds by immersion and further rinsed with ultrapure water for 10 seconds. Subsequently, a post-bake treatment at 220 ° C. for 45 minutes was performed to obtain a front plate on which a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.

<Formation of second transparent electrode pattern>
(Formation of transparent electrode layer)
In the same manner as the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
Similarly to the formation of the first transparent electrode pattern, using a commercially available etching resist, the first transparent electrode pattern, an insulating layer pattern formed using the photosensitive resin composition of Example 1, a transparent electrode layer, A front plate on which an etching resist pattern was formed was obtained (post-baking treatment; 130 ° C. for 30 minutes).
Further, etching was performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer was removed to form the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.

<Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Insulating layer formed using the first transparent electrode pattern, the photosensitive resin composition of Example 1, using a commercially available etching resist in the same manner as the formation of the first and second transparent electrode patterns. A front plate on which a pattern, a second transparent electrode pattern, and an etching resist pattern were formed was obtained (post-bake treatment; 130 ° C. for 30 minutes).
Further, in the same manner as the formation of the first transparent electrode pattern, etching (30 ° C. for 50 seconds) is performed, and the etching resist layer is removed (45 ° C. for 200 seconds). A front plate on which a conductive element different from the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns formed using the photosensitive resin composition of Example 1 was obtained was obtained.

<Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film. Furthermore, the front exposure is performed with an exposure amount of 50 mJ / cm ² (i-line) without using an exposure mask, development, post-exposure (1,000 mJ / cm ² ), and post-bake treatment are performed to obtain a mask layer and a first transparent The electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, the second transparent electrode pattern, and all the conductive elements different from the first and second transparent electrode patterns are covered. The front board which laminated | stacked the insulating layer (transparent protective layer) formed using the photosensitive resin composition of Example 1 was obtained.

<Production of image display device (touch panel)>
A liquid crystal display device manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 is bonded to the previously manufactured front plate, and an image display device including a capacitive input device as a constituent element is manufactured by a known method. did.

<Evaluation of front plate and image display device>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained. Furthermore, the first and second transparent electrode patterns were hardly visible and an image display device having excellent display characteristics was obtained.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: planarization film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12: Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 30: Capacitive input device 31: front plate, 32: mask layer, 33: first transparent electrode pattern, 33a: pad portion, 33b: connection portion, 34: second transparent electrode pattern, 35: insulating layer, 36: conductive element, 37: Transparent protective layer, 38: Opening

Claims (15)

(Component A) metal oxide particles,
(Component B) solvent,
(Component C) a polymer containing a structural unit having an acid group protected by an acid-decomposable group,
(Component D) a photoacid generator, and
(Component S) A photosensitive resin composition comprising a compound having one or more sulfide bonds and two or more partial structures represented by the following formula (1) in the molecule.

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group, n represents an integer of 1 to 3, and the wavy line represents the bonding position with another structure.) The photosensitive resin composition of Claim 1 whose component S is a compound represented by following formula (2).

(In Formula (2), R < ³ > -R < ⁶ > represents a hydrogen atom or an alkyl group each independently, L < ¹ > and L < ² > represent a single bond or a bivalent coupling group each independently, p is 1- 4 represents an integer of 4, and q and r each independently represent an integer of 1 to 3.) The photosensitive resin composition according to claim 2, wherein L ¹ and L ² are each independently a single bond or an alkylene group.   The photosensitive resin composition according to claim 1, further comprising (Component E) a dispersant. The photosensitive resin composition of any one of Claims 1-4 with which the component C satisfy | fills at least one of the polymer component represented by following (1) and (2).
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group (2) (a1) an acid group having an acid-decomposable group And a polymer having a structural unit having a group protected by (a2) and a structural unit having a crosslinkable group The photosensitive resin composition according to claim 1, wherein R ¹ and R ² are each independently an alkyl group.   The photosensitive resin composition of any one of Claims 1-6 whose content of the component S is 0.05-20 mass% with respect to the total solid of the photosensitive resin composition.   The photosensitive resin composition of any one of Claims 1-7 whose content of the component A is 10-70 mass% with respect to the total solid of the photosensitive resin composition. A resin pattern manufacturing method comprising at least steps (1) to (4) in this order.
(1) Application step of applying the photosensitive resin composition according to any one of claims 1 to 8 on a substrate (2) Solvent removal step of removing a solvent from the applied resin composition (3) Solvent Step of exposing the resin composition from which the resin has been removed in a pattern with actinic rays (4) Development step of developing the exposed resin composition or the unexposed resin composition with an aqueous developer   Hardened | cured material obtained by the resin pattern manufacturing method of Claim 9.   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-8.   The cured film according to claim 11, which is an interlayer insulating film.   A liquid crystal display device having the cured film according to claim 11.   An organic EL display device having the cured film according to claim 11.   A touch panel display device comprising the cured film according to claim 11.

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