JPWO2014126033A1 - Manufacturing method of cured film, cured film, liquid crystal display device, organic EL display device, and touch panel display device - Google Patents

Abstract

A method for producing a cured film having a high refractive index and excellent resolution and taper shape, a cured film obtained by the production method, a liquid crystal display device using the cured film, an organic EL display device, and a touch panel display An object is to provide an apparatus. The manufacturing method of the cured film of this invention is characterized by including process (a) and (b) in this order. (A) (Component A) inorganic particles, (Component B) a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (Component C) a photosensitizer containing a photoacid generator A layer forming step (b) of satisfying the formula (2) and forming a layer made of the solid content of the photosensitive resin composition on the substrate using the resin composition; and (b) forming a layer made of the solid content of the photosensitive resin composition Heat treatment step shrinkage ratio r2 = (t20−t21) /t20≧0.15 (2) t20 represents the thickness of the layer composed of the solid content of the photosensitive resin composition, and t21 heats the layer at 200 ° C. for 20 minutes. It represents the thickness after the process.

Description

The present invention relates to a method for producing a cured film, a cured film obtained by the production method, a liquid crystal display device using the cured film, an organic EL display device, and a touch panel display device.
More specifically, the present invention relates to a method for producing a cured film suitable for forming a planarizing film, a protective film, and an interlayer insulating film of electronic components 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 device. .

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).
In order to make these optical members have a high refractive index, it has been studied to add particles such as titanium oxide (see Patent Document 1 below).
Moreover, the photosensitive resin composition described in patent document 2 is known as a conventional photosensitive resin composition.

JP 2006-98985 A Korean Published Patent No. 10-2012-0121850

Conventionally, high refractive index materials have obtained the required refractive index by increasing the filling rate of inorganic particles such as TiO ₂ and ZrO ₂ . However, when the filling rate is increased, the resolution is lowered and the taper shape is deteriorated.
As a result of detailed studies, the inventors of the present invention use a positive photosensitive resin composition and increase the shrinkage rate (shrink rate) of the film. It was found that by leaving the particles, the content of inorganic particles apparently increased, the refractive index could be increased by a considerable amount, and the resolution and taper shape were also excellent.

  The present invention is a method for producing a cured film having a high refractive index and excellent resolution and taper shape, a cured film obtained by the above production method, a liquid crystal display device using the cured film, an organic EL display device, An object of the present invention is to provide a touch panel display device.

The above-described problems of the present invention have been solved by means described in the following <1>, <12>, and <14> to <16>. It describes below with <2>-<11> and <13> which are preferable embodiments.
<1> A method for producing a cured film comprising steps (a) and (b) in this order,
(A) (Component A) inorganic particles, (Component B) a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (Component C) a photosensitizer containing a photoacid generator A layer forming step of forming a layer composed of the solid content of the photosensitive resin composition on the substrate by using the resin composition and satisfying the following formula (2); and (b) a layer composed of the solid content of the photosensitive resin composition. Heat treatment step of heat treating the material shrinkage ratio r ₂ = (t ₂₀ −t ₂₁ ) / t ₂₀ ≧ 0.15 (2)
(In the formula, t ₂₀ represents the thickness of the layer composed of the solid content of the photosensitive resin composition, and t ₂₁ represents the thickness after heating the above layer at 200 ° C. for 20 minutes.)
<2> The method for producing a cured film according to <1>, wherein the temperature of the heat treatment is 120 ° C. or higher and 200 ° C. or lower,
<3> The method for producing a cured film according to <1> or <2>, wherein the temperature of the heat treatment is 120 ° C. or higher and 175 ° C. or lower,
<4> The method for producing a cured film according to any one of <1> to <3>, wherein the heat treatment is performed at a temperature of 120 ° C. or higher and 175 ° C. or lower for 30 to 180 minutes.
<5> The ratio of the structural unit in which the acid group has a group protected by an acid-decomposable group with respect to all the structural units of the polymer including the structural unit in which the acid group has a group protected by an acid-decomposable group Is a method for producing a cured film according to any one of the above <1> to <4>, wherein
<6> The ratio of the structural unit in which the acid group has a group protected by an acid-decomposable group with respect to all the structural units of the polymer including the structural unit in which the acid group has a group protected by an acid-decomposable group Is a method for producing a cured film according to any one of the above <1> to <5>, which is 65 to 85 mol%,
<7> Any of the above <1> to <6>, wherein the structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit represented by the following formula (a1-1-1) Or a method for producing the cured film according to claim 1,

（式中、Ｒは水素原子又はメチル基を表す。）

(In the formula, R represents a hydrogen atom or a methyl group.)

<8> The method for producing a cured film according to any one of <1> to <7>, wherein the component A is metal oxide particles,
<9> The method for producing a cured film according to any one of <1> to <8>, wherein the component A is titanium oxide particles or zirconium oxide particles,
<10> (Component D) The method for producing a cured film according to any one of <1> to <9>, further including a thermal crosslinking agent,
<11> (Component E) The method for producing a cured film according to any one of the above <1> to <10>, further comprising an antioxidant,
<12> A cured film obtained by the method for producing a cured film according to any one of <1> to <11> above,
<13> The cured film according to <12>, which is an interlayer insulating film,
<14> A liquid crystal display device having the cured film according to <12> or <13> above,
<15> An organic EL display device having the cured film according to <12> or <13> above,
<16> A touch panel display device having the cured film according to <12> or <13>.

  ADVANTAGE OF THE INVENTION According to this invention, it is a high refractive index, the manufacturing method of the cured film excellent in resolving power and a taper shape, the cured film obtained by the said manufacturing method, the liquid crystal display device using the said cured film, and organic electroluminescent display An apparatus and a touch panel 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. It is a partial schematic diagram which shows an example in case the taper angle in pattern cross-sectional shape is 20 degrees or more and 30 degrees or less. It is a partial schematic diagram which shows an example in case the taper angle in pattern cross-sectional shape is less than 20 degrees. It is a partial schematic diagram which shows an example in case the taper angle in pattern cross-sectional shape exceeds 75 degrees and is 90 degrees or less. It is a partial schematic diagram which shows an example in case the taper angle in pattern cross-sectional shape exceeds 90 degrees.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit. Further, “parts by mass” and “% by mass” are synonymous with “parts by weight” and “% by weight”, respectively.
Furthermore, in the present invention, “(component A) inorganic particles” or the like is also simply referred to as “component A” or the like, and “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group” and the like described later. Is also simply referred to as “structural unit (a1)”.
In addition, in the description of groups (atomic groups) in the present specification, the description that does not indicate substitution and non-substitution includes those having no substituent and those having 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 following description, a combination of a preferred embodiment and another preferred embodiment is a more preferred embodiment.

(Method for producing cured film)
The manufacturing method of the cured film of this invention is characterized by including process (a) and (b) in this order.
(A) (Component A) inorganic particles, (Component B) a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (Component C) a photosensitizer containing a photoacid generator A layer forming step of forming a layer composed of the solid content of the photosensitive resin composition on the substrate by using the resin composition and satisfying the following formula (2); and (b) a layer composed of the solid content of the photosensitive resin composition. Heat treatment step of heat treating the material shrinkage ratio r ₂ = (t ₂₀ −t ₂₁ ) / t ₂₀ ≧ 0.15 (2)
(In the formula, t ₂₀ represents the thickness of the layer composed of the solid content of the photosensitive resin composition, and t ₂₁ represents the thickness after heating the above layer at 200 ° C. for 20 minutes.)

Conventionally, a resist layer formed from a negative photosensitive resin composition has a large shrinkage ratio due to volume shrinkage at the time of polymerization, but a resist layer formed from a positive photosensitive resin composition is smaller than a negative type. The shrinkage rate is small.
In the method for producing a cured film of the present invention, by using a positive photosensitive resin composition containing inorganic particles and having a large shrinkage rate, the content of the inorganic particles is apparently increased, and the refractive index is increased. In addition, the resolution and taper shape are excellent.

The cured film obtained by the method for producing a cured film of the present invention is a wiring used for 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 touch panel. It can be suitably used as a cured product for reducing the visibility of electrodes.
The cured film obtained by the method for producing a cured film of the present invention includes, for example, a flattening film, an interlayer insulating film, a color filter protective film, and a liquid crystal display in a liquid crystal display device or an organic EL device as described later. It can be suitably used as a spacer for keeping the thickness of the liquid crystal layer in the apparatus constant, a structural member of a MEMS (Micro Electro Mechanical Systems) device, or the like.

<Layer formation process>
The method for producing a cured film of the present invention comprises (a) (component A) inorganic particles, (component B) a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (component C). ) A layer forming step (step (a) in which a photosensitive resin composition containing a photoacid generator is used, a layer satisfying the above formula (2) and formed of a solid content of the photosensitive resin composition is formed on a substrate. ))including.
The photosensitive resin composition used in the present invention will be described in detail later.
In the layer forming step, a layer made of the solid content of the photosensitive resin composition is formed on the substrate.
When the said photosensitive resin composition contains a solvent, it is preferable that the layer which consists of solid content of the said photosensitive resin composition is a layer which removed the solvent.
That is, it is preferable that the said layer formation process includes the solvent removal process of removing a solvent from the apply | coated photosensitive resin composition layer.
In addition, the layer which consists of solid content of the said photosensitive resin composition should just be a layer which does not contain a solvent substantially, It is preferable that content of a solvent is 1 mass% or less, and is 0.5 mass% or less. More preferably, it is more preferably 0.1% by mass or less.
There is no restriction | limiting in particular in the formation method of the layer which consists of solid content of the photosensitive resin composition, What is necessary is just to perform by a well-known method. In addition, solid content of the photosensitive resin composition represents the composition except volatile components, such as a solvent, in the photosensitive resin composition.

In the layer forming step, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition to the substrate, and further, the substrate surface may be treated with hexamethyldisilazane after the substrate cleaning. More preferred. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate is improved. The method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, resin composite materials, indium tin oxide (ITO), indium zinc oxide (IZO), Cu substrates, polyethylene terephthalate, cellulose triacetate (TAC), and other plastic substrates.
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, Synthetic resins such as aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin It is below.
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.
The coating method on the substrate is not particularly limited, and for example, methods such as a slit coating method, a spray coating method, a roll coating method, a spin coating method, a casting coating method, and 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.

Liquid-saving coaters such as slit coat and spray coat greatly reduce the amount of coating solution used, reduce the influence of mist that adheres when using the spin coat method, and suppress foreign matter generation. This is also preferable from a comprehensive viewpoint.
For example, the coating conditions by the slit coating 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. For example, the lip width at the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm. In order to adjust the thickness of the coating film, the running speed of the lip and the discharge amount of the liquid curable resin composition from the lip may be adjusted.
There is no restriction | limiting in particular as a spray coater used for the spray coat method, What is necessary is just to apply a well-known spray coating method and injection apparatus. Specific examples include an ultrasonic spray coating apparatus, a two-fluid spray coating apparatus, and a one-fluid spray coating apparatus.

Moreover, in the said solvent removal process, it is preferable to remove a solvent from a photosensitive resin composition layer by pressure reduction (vacuum) and / or heating, and to form a dry coating film on a board | 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 thickness of the layer composed of the solid content of the photosensitive resin composition is not particularly limited and can be formed with a thickness according to the use, but is preferably in the range of 0.5 to 10 μm. The range of 0.8 to 5.0 μm is more preferable, and the range of 1.0 to 4.0 μm is more preferable.

Moreover, the layer which consists of solid content of the said photosensitive resin composition is a layer which satisfy | fills Formula (2).
Shrinkage rate r ₂ = (t ₂₀ −t ₂₁ ) / t ₂₀ ≧ 0.15 (2)
(In the formula, t ₂₀ represents the thickness of the layer composed of the solid content of the photosensitive resin composition, and t ₂₁ represents the thickness after heating the above layer at 200 ° C. for 20 minutes.)
In the measurement of the shrinkage ratio r ₂ , the photosensitive resin composition was dried and the solvent was removed to prepare a layer composed of the solid content of the photosensitive resin composition, and the thickness was measured. It is preferable to measure the thickness of the layer after heating at 20 ° C. for 20 minutes to measure t ₂₀ and t ₂₁ . Moreover, it is preferable to provide the layer which consists of solid content of the said photosensitive resin composition on the glass substrate of 100 mm x 100 mm processed for 3 minutes using hexamethyldisilazane (HMDS).
The film thickness is preferably calculated by measuring the central part of the film at several points and taking an average value. Specifically, it is preferable to use a stylus type surface shape measuring device Dektak (manufactured by ULVAC, Inc.), measure the three locations (N = 3) in the central portion of the film, take an average value, and calculate. Can be mentioned.
The shrinkage rate (also referred to as “shrink rate”) r ₂ in Formula (2) is 0.15 or more, preferably 0.18 or more, more preferably 0.20 or more, and More preferably, it is 25 or more. It is excellent in the refractive index and taper shape of the cured film obtained as it is the said aspect.
Further, r ₂ is preferably 0.50 or less, more preferably 0.45 or less, further preferably 0.40 or less, and most preferably 0.35 or less. It is excellent in the taper shape of the cured film obtained as it is the said aspect.

<Heat treatment process>
The manufacturing method of the cured film of this invention includes the heat processing process (process (b)) which heat-processes the layer which consists of (b) solid content of the said photosensitive resin composition.
In the heat treatment step (post-bake), the obtained positive image is heated to cause thermal shrinkage, and a cured film having excellent refractive index and taper shape is obtained.
In the heat treatment step, the acid-decomposable group of component B is thermally decomposed to form an acid group, for example, a carboxyl group or a phenolic hydroxyl group, and a cured film is formed by crosslinking with a crosslinkable group, a crosslinking agent, or the like. It is preferable to do.
The heat treatment in the heat treatment step is preferably performed using a heating device such as a hot plate, an oven, or an infrared heater.
Further, the heat treatment in the heat treatment step is preferably performed at a lower temperature and for a longer time than conventional post-baking. When it is in the above range, a cured film that is more excellent in a tapered shape can be obtained.
The heat treatment temperature in the heat treatment step is preferably 120 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and lower than 180 ° C., further preferably 120 ° C. or higher and 175 ° C. or lower, and 140 ° C. or higher and 175 ° C. or lower. It is particularly preferable that the temperature is not higher than ° C. When it is in the above range, a cured film that is more excellent in refractive index and tapered shape can be obtained.
The heat treatment time in the heat treatment step is preferably 10 to 240 minutes, more preferably 30 to 180 minutes, further preferably 45 to 120 minutes, and more preferably 45 to 90 minutes. Particularly preferred. When it is in the above range, a cured film that is more excellent in refractive index and tapered shape can be obtained.
Further, when the heat treatment is performed, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

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 middle baking is performed, it is preferable to perform post baking 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 (post-exposure) with actinic rays and post-baked to generate acid from the photoacid generator present in the unexposed areas, thereby promoting crosslinking. It can function as a catalyst that promotes the film curing reaction. As an exposure amount when performing a post-exposure process, 100-3,000 mJ / cm < ² > is preferable and 100-500 mJ / cm < ² > is especially preferable.

In the method for producing a cured film of the present invention, an exposure step of exposing a layer comprising the solid content of the photosensitive resin composition in a pattern with active light between the step (a) and the step (b), and It is preferable to include a developing step of developing the exposed layer with an aqueous developer.
That is, the method for producing a cured film of the present invention comprises (Component A) inorganic particles, (Component B) a polymer containing a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (Component C). A layer forming step in which a photosensitive resin composition containing a photoacid generator is used and a layer made of the solid content of the photosensitive resin composition and satisfying the formula (2) is formed on a substrate; and the photosensitive resin An exposure step of exposing the solid layer of the composition in a pattern with actinic rays, a development step of developing the exposed layer with an aqueous developer, and a heat treatment step of heat-treating the developed layer. preferable.

<Exposure process>
The manufacturing method of the cured film of this invention includes the exposure process which exposes the layer which consists of solid content of the said photosensitive resin composition to a pattern shape with actinic light between the said process (a) and a process (b). Is preferred.
In the exposure step, the substrate provided with the coating film is irradiated 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, etc. can be used, and g-line (436 nm), i-line (365 nm), h-line ( 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 addition, 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.

<Development process>
It is preferable that the manufacturing method of the cured film of this invention includes the image development process which develops the said exposed layer with an aqueous developing solution between the said exposure process and the said process (b).
In the development step, a copolymer having a liberated acid group such as a carboxyl group or a phenolic hydroxyl group is developed using an aqueous developer, preferably an alkaline aqueous 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 aqueous 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; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide: (hydroxyalkyl) trines such as choline Alkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; alkyls such as ethylamine, propylamine, diethylamine and triethylamine Amines; Alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene The alicyclic amines can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above basic compound can also be used as a developer.
Preferable developers 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 9.0 to 14, and more preferably 10.0 to 14.0. The concentration of the developer is preferably from 0.1 to 20% by mass, and more preferably from 0.1 to 5.0% by mass.
The development time is preferably 1 to 500 seconds, more preferably 10 to 180 seconds. Further, the developing method may be any of a liquid filling method, a dip method, a shower method, and the like. After development, washing with running water can be performed to form a desired pattern. The running water washing time is preferably 30 to 300 seconds, more preferably 30 to 90 seconds.

Moreover, the manufacturing method of the cured film of this invention may include well-known processes other than the process mentioned above.
For example, a rinsing step of rinsing the developed layer with a rinsing liquid can be performed after the developing step. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with a rinse solution such as pure water. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.

  Furthermore, the cured film obtained by the method for producing a cured film of the present invention can be used as a dry etching resist. When the cured film is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

<Photosensitive resin composition>
The photosensitive resin composition that can be used in the present invention includes at least (Component A) inorganic particles, (Component B) a polymer containing a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (Component C) contains a photoacid generator.
The photosensitive resin composition can be suitably used as a positive resist composition.
The photosensitive resin composition is preferably a resin composition having a property of being cured by heat.
The photosensitive resin composition is preferably a positive photosensitive resin composition, and more preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). preferable.
The photosensitive resin composition preferably does not contain a 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. The 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
On the other hand, (Component C) photoacid generator used in the present invention is such that an acid generated in response to actinic rays acts as a catalyst for deprotection of the protected acid group in Component B. 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.
Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

(Component A) Inorganic Particle The photosensitive resin composition that can be used in the present invention contains (Component A) inorganic particles. The photosensitive resin composition contains inorganic particles for the purpose of adjusting the refractive index and light transmittance.
Component A preferably has a refractive index higher than the refractive index of the photosensitive resin composition made of the material excluding the particles, and specifically has a refractive index of 1 in light having a wavelength of 400 to 750 nm. More preferably, particles having a refractive index of 1.70 or more are more preferable, and particles having a refractive index of 1.90 or more are particularly preferable. The upper limit of the refractive index is not particularly limited, but particles of 5.00 or less are preferable from the viewpoint of availability.
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.

As such inorganic particles having a high refractive index, inorganic oxide particles are preferable and metal oxide particles are more preferable because of high transparency and light transmittance.
The light-transmitting and high refractive index inorganic 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, Bi, Te, etc. are preferred, titanium oxide, zinc oxide, zirconium oxide, indium / tin oxide, or Antimony / tin oxide is more preferable, titanium oxide particles or zirconium oxide is further preferable, titanium oxide is particularly preferable, and titanium dioxide is most preferable. Titanium dioxide is particularly preferably a rutile type having a high refractive index. The surface of these inorganic particles can also be treated with an organic material to impart dispersion stability.

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 dioxide is most preferable. Titanium dioxide 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.

The average primary particle diameter of the inorganic particles is preferably 1 to 200 nm, more preferably 2 to 100 nm, still more preferably 1 to 60 nm, and particularly preferably 5 to 50 nm. Within the above range, a cured product having excellent particle dispersibility, a high refractive index, and excellent transparency can be obtained.
The average primary particle diameter of the inorganic particles can be obtained from a photograph obtained by observing the dispersed inorganic particles with a transmission electron microscope. Specifically, the projected area of the inorganic particles is obtained, and the corresponding equivalent circle diameter is defined as the average primary particle diameter of the inorganic particles. In addition, let the average primary particle diameter in this invention be the arithmetic mean value of the equivalent circle diameter calculated | required about 300 inorganic particles.
In the present invention, the number average particle diameter can also be used as an index of the average primary particle diameter. The number average particle size of the inorganic particles in the present invention is measured by using a dynamic light scattering method for a diluted solution obtained by diluting a mixture or dispersion containing inorganic particles 80 times with propylene glycol monomethyl ether acetate. The value obtained by doing. This measurement is preferably the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

There is no restriction | limiting in particular in the shape of an inorganic particle. For example, it can be a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.
The average aspect ratio (long side / short side) of the inorganic particles is preferably 1 to 5, more preferably 1 to 4.5, still more preferably 1 to 4, and 1 to 3 It is particularly preferred.
The average aspect ratio is measured by the following method. That is, an average value obtained by measuring 300 aspect ratios (long side / short side) of a particle image captured with a transmission electron microscope (TEM) was defined as an average aspect ratio.

The refractive index of the metal oxide particles is not particularly limited, but is preferably 1.70 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index. .
The specific surface area of the metal oxide particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The metal oxide particles may have been surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, stearic acid is preferred.
The surface treatment may be carried out by using a single surface treatment agent or a combination of two or more surface treatment agents.
Moreover, it is also preferable that the surface of the metal oxide particles is covered with an oxide such as aluminum, silicon, or zirconia. Thereby, a weather resistance improves more.

  As a metal oxide particle in this invention, what is marketed can be used preferably. Specifically, for example, as titanium oxide particles, TTO series (TTO-51 (A), TTO-51 (C), etc.) manufactured by Ishihara Sangyo Co., Ltd., TTO-S, V series (TTO-S-1, TTO) -S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by Teika Co., Ltd., Optolake TR-502, Optolake TR-504 as tin oxide-titanium oxide composite particles. Optolake TR-503, Optlake TR-513, Optlake TR-520, Optlake TR-521, Optlake TR-527, Zirconium oxide particles (Co) ), Tin oxide-zirconium oxide composite particles (manufactured by JGC Catalysts & Chemicals Co., Ltd.), and niobium oxide particles such as viral Nb-X10 (many Chemical Co., Ltd.), and the like.

Moreover, the component A may be used individually by 1 type, and can also use 2 or more types together.
The content of the inorganic particles in the photosensitive resin composition may be appropriately determined in consideration of the refractive index required for the optical member obtained from the photosensitive resin composition, light transmittance, and the like. The total solid content of the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. Moreover, it is preferable that it is 80 mass% or less, and it is more preferable that it is 70 mass% or less. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.

(Component B) A polymer containing a structural unit having a group in which an acid group is protected with an acid-decomposable group The photosensitive resin composition that can be used in the present invention has (Component B) an acid group having an acid-decomposable group A polymer containing a structural unit having a protected group 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 may further contain a polymer other than a polymer containing a structural unit having a group in which an acid group is protected with an acid-decomposable group.
The photosensitive resin composition preferably contains a polymer component including a polymer that satisfies at least one of the following (1) and (2).
(1) (a1) a polymer comprising a structural unit having an acid group protected by 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 with (a2) a polymer having a structural unit having a crosslinkable group. The photosensitive resin composition may further contain a polymer other than these. Good. Unless otherwise stated, component B 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 said photosensitive resin composition contains the component which satisfy | fills said (1) as a component B 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 preferably contains a component satisfying the above (2) as the component B.
In addition, even when it contains a component satisfying the above (1), (a1) an acrylic resin and / or (a2) a crosslink containing a structural unit having a group in which an acid group is protected by an acid-decomposable group 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).
In addition, when Component B is a component satisfying the above (2), (a1) a polymer containing 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 The content ratio with respect to the polymer having a weight ratio is preferably 95: 5 to 60:40, more preferably 95: 5 to 70:30, and 95: 5 to 75:25. Is more preferable, and 90:10 to 80:20 is particularly preferable. It is excellent in the refractive index and taper shape of the cured film obtained as it is the said range.

Component B 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 B 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 B 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. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). A functional group) or a group that is relatively difficult to decompose by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).

(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, the carboxyl group is a protected carboxyl group protected in the form of an acetal. 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し、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 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.

  A second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the 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は単結合又は二価の連結基を表し、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. The divalent linking group of R ²²¹ may be exemplified alkylene groups, specific examples R ²²¹ is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Among these, 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. Specifically, 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 can be mentioned. 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)-
In the polymer having the structural unit (a1), it is preferable that the content of the structural unit (a1) is large because the shrinkage rate can be further increased and the taper shape is excellent.
When the polymer having the structural unit (a1) does not substantially have the structural unit (a2), the content of the structural unit (a1) is 50 to 100 in the polymer having the structural unit (a1). Mol% is preferable, 55-90 mol% is more preferable, 60-85 mol% is still more preferable, 65-85 mol% is especially preferable, and 70-80 mol% is the most preferable. It is excellent in the refractive index and taper shape of the cured film obtained as it is the said range.
When the polymer having the structural unit (a1) has the following structural unit (a2), the content of the structural unit (a1) is in the polymer having the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, it is preferably 50 to 95 mol%, more preferably 55 to 90 mol%, still more preferably 60 to 85 mol%, particularly preferably 65 to 85 mol%, and most preferably 70 to 80 mol%. It is excellent in the refractive index and taper shape of the cured film obtained as it is the said range.
In the present invention, the structural unit (a1) is preferably contained in an amount of 50 to 95 mol%, more preferably 55 to 90 mol%, regardless of any embodiment. It is more preferable to include 60 to 85 mol%, particularly preferable to include 65 to 85 mol%, and most preferable to include 70 to 80 mol%.
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.
Moreover, the structural unit which has a group in which an acid group is protected by an acid-decomposable group is represented by the following formulas (a1-1-1) to (a1-1-3) from the viewpoints of resolving power and refractive index. A structural unit is particularly preferable, and a structural unit represented by the following formula (a1-1-1) is most preferable.

（式中、Ｒは水素原子又はメチル基を表す。）

(In the formula, R represents a hydrogen atom or a methyl group.)

<(A2) Structural unit having a crosslinkable group>
Component B 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 these, it is more preferable that the photosensitive resin composition includes a structural unit in which Component B includes 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 B 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 Compounds containing shea skeleton, and the like.
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. Examples include acid esters.
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.

_{<< (a2-3) -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). It is also preferable to have 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 content of the structural unit (a2) is 5 to 90 in the polymer having the structural unit (a2). Mol% is preferable and 20-80 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 the present invention, the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol%, in all the structural units of Component B, regardless of any embodiment.
Within the above numerical range, the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition will be good.

<(A3) Other structural units>
In the present invention, component B may have other structural units (a3) in addition to the structural units (a1) and / or (a2). These structural units may contain a polymer component that satisfies the above (1) and / or (2). In addition to the polymer component satisfying the above (1) or (2), a polymer component having another structural unit (a3) substantially not including the structural unit (a1) and the structural unit (a2). You may have. In addition to the polymer component satisfying the above (1) or (2), a polymer component having substantially no structural unit (a1) and other structural unit (a3) without the structural unit (a2) is included. In this case, 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.
Such a polymer component does not include compounds corresponding to Component D, Component F, and Component I described later.

  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.

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 satisfying (1) further has one or more other structural units (a3).
-Second Embodiment-
(A1) The polymer component satisfying (2) is a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and one or more other structural units (a3) The aspect which has.
-Third embodiment-
The aspect which the polymer which has the structural unit which has (a2) crosslinkable group of the polymer component which satisfy | fills (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 satisfying (1) or (2), the polymer further has a polymer having another structural unit (a3) without substantially including the structural unit (a1) and the structural unit (a2). Aspect.
-Sixth Embodiment-
The aspect which consists of two or more combinations of the said 1st-5th embodiment.

  The structural unit (a3) is specifically styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a structural unit due. 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 B 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 having an acid group using a monomer capable of forming an acid group. By including such a structural unit having 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 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 these Examples include a group obtained by neutralizing an acid group to form a salt structure, and a carboxylic acid group and / or a phenolic hydroxyl group is 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 having an acid group used in the present invention is more preferably a structural unit derived from a styrene compound, a structural unit derived from a vinyl compound, (meth) acrylic acid and / or an ester thereof. preferable.
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.

  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.

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.
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.

-Molecular weight of polymer in component B-
The molecular weight of the polymer in component B is preferably from 1,000 to 200,000, and more preferably from 2,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight. 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.
In addition, the measurement of the weight average molecular weight in this invention and a number average molecular weight was measured by the gel permeation chromatography method (GPC). In the measurement by gel permeation chromatography in the present invention, HLC-8020GPC (manufactured by Tosoh Corporation) is used, and TSKgel Super HZ MH, TSK gel Super HZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns. ) Was used as the eluent in THF (tetrahydrofuran).

-Method for producing polymer in component B-
Various methods for synthesizing the polymer in Component B are also known. To give an 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 B in the photosensitive resin composition is preferably 20 to 99.9% by mass and more preferably 50 to 98% by mass with respect to the total solid content of the photosensitive resin composition. Preferably, it is 70-95 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.

(Component C) Photoacid Generator The photosensitive resin composition that can be used in the present invention contains (Component C) a photoacid generator.
The photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can 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. The lower limit of pKa is not particularly limited, but is preferably −15 or more from the viewpoint of availability.

  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.

  Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following formula (C1).

（式（Ｃ１）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 (C1), 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.
Preferred examples of the compound having an oxime sulfonate structure include the compounds described in paragraphs 0092 to 0171 of JP2011-221494A, but the present invention is not limited thereto.

The content of (Component C) photoacid generator in the photosensitive resin composition is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of Component B in the photosensitive resin composition. It is more preferable that it is 5-10 mass parts.
In addition, Component C may be used alone or in combination of two or more.

(Component D) Thermal crosslinking agent It is preferable that the photosensitive resin composition which can be used for this invention contains a thermal crosslinking agent as needed. By adding a thermal crosslinking agent, the cured film obtained by the method for producing a cured film of the present invention can be made stronger.
The thermal crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (excluding component B). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described in paragraphs 0188 to 0191 of JP2011-221494A, an alkoxymethyl described in paragraphs 0192 to 0194 of JP2011-221494A A group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond described in paragraphs 0195 to 0199 of JP2011-221494A, or paragraphs 0147 to 0149 of JP2012-208200A Although the described blocked isocyanate compounds and the like can be added, the present invention is not limited to these.

The photosensitive resin composition preferably contains, as component D, a compound having two or more epoxy groups or oxetanyl groups in the molecule, and contains a compound having two or more epoxy groups in the molecule. Is more preferable, and an epoxy resin is still more preferable.
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 compounds, and the like. Can do. The aliphatic epoxy compound is a resin having a linear and / or branched carbon chain and an epoxy group, and an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, and the like are bonded to the carbon chain in addition to a hydrogen atom. You may do it. The aliphatic epoxy compound is particularly preferably a resin composed of a linear and / or branched carbon chain, a hydrogen atom, and an epoxy group, or a resin in which a hydroxyl group is substituted on the resin.

  These are available as commercial products. For example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051 And bisphenol F-type epoxy resins such as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Co., Ltd.), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.) As the phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (or higher) The cresol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), etc., and as an aliphatic epoxy resin, ADEKA RESIN EP -4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), aliphatic epoxy compounds include Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, and PB 4700 (The above is made by Daicel Chemical Industries, Ltd.). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation) and the like can be mentioned.

  The addition amount of the thermal crosslinking agent in the photosensitive resin composition is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. It is 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 thermal crosslinking agents can be used in combination, and in that case, the content is calculated by adding all the thermal crosslinking agents.

(Component E) Antioxidant The photosensitive resin composition that can be used in the present invention preferably contains (Component E) 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, phenolic antioxidants, amide antioxidants, hydrazide antioxidants and sulfur antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness, and phenolic antioxidants are more preferred. preferable. These may be used alone or in combination of two or more.
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 MD1024, Irganox 1035FF, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafoss 168 Irgamod 295 (manufactured by BASF Corporation). Among them, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035FF, and Irganox 1098 can be preferably used.

  The content of the antioxidant is preferably 0.1 to 6% 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 becomes good.

(Component F) Dispersant The dispersion composition of the present invention preferably contains (Component F) a dispersant. By containing the dispersant, the dispersibility of the component A in the composition can be further improved.
As the dispersant, 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, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (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, etc. (AstraZeneca Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103 , F108, L121, P-123 (manufactured by ADEKA) and Ionette 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.

In the present invention, the dispersant is preferably a dispersant having an acid group. Having an acid group is preferable because the dispersibility of Component A is excellent.
Examples of the dispersant having an acid group include “DISPERBYK101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110, 111, 180 (copolymer containing an acid group), 130 (polyamide), manufactured by BYK Chemie. , 162, 163, 164, 165, 166, 168, 170 (polymer copolymer) ”,“ BYK-2001 (acrylic block copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) Acid), "EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid) manufactured by EFKA Acid salt), 6220 (fatty acid polyester) Teru), “Ajisper PB821, PB822” manufactured by Ajinomoto Fintechno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow No. 50E, No. 300 (acrylic copolymer)” “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd. "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)", "Homogenol L-18 (polymer polycarboxylic acid)" Acid) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ", Burizoru Co. 24000,28000,32000,32500,35200,38500 (graft polymer) ", and the like.

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 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 G) Solvent The photosensitive resin composition that can be used in the present invention preferably contains (Component G) a solvent. In the layer forming step, the solvent is removed from the photosensitive resin composition layer. A layer composed of the solid content of the photosensitive resin composition is formed. The photosensitive resin composition that can be used in the present invention is preferably prepared as a solution in which the essential components of components A to C and further optional components described below are dissolved and / or dispersed in a solvent. .
As the solvent used in the photosensitive resin composition, 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 acetates, Examples thereof include esters, ketones, amides, and lactones. Moreover, the solvent of Paragraph 0174-0178 of Unexamined-Japanese-Patent No. 2011-221494 is also mentioned.

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.

Moreover, you may prepare the dispersion liquid which mixed the inorganic particle, the dispersing agent, the solvent, etc. before preparing the photosensitive resin composition. For example, it is prepared by mixing and dispersing the above components using a mixing apparatus such as a bead mill, 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, and 1-pentanol in addition to the solvents described above. , 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol and the like. it can.
These solvents can be used singly or in combination of two or more.

Component G 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. (Bp 213 ° C.), 3-methoxybutyl ether acetate (bp 171 ° C.), diethylene glycol diethyl ether (bp 189 ° C.), diethylene glycol dimethyl ether (bp 162 ° C.), propylene glycol diacetate (bp 190 ° C.), diethylene glycol monoethyl ether acetate ( Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) Kill.
Among these, as the solvent, propylene glycol monoalkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

  The content of the solvent in the photosensitive resin composition is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and more preferably 150 to 1,500 parts per 100 parts by weight of Component B. More preferably, it is part by mass.

(Component H) Basic Compound The photosensitive resin composition that can be used in the present invention preferably contains (Component H) a basic compound from the viewpoint of liquid storage stability.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, 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, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea is 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 is preferably 0.001 to 1 part by mass and more preferably 0.002 to 0.2 part by mass with respect to 100 parts by mass of Component B. .

(Component I) Surfactant The photosensitive resin composition that can be used in the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
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. . Specific examples of fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950. , JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2001-330953, etc. An activator can be mentioned and a commercially available surfactant can also be used. In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), and Megafuck (manufactured by DIC Corporation). Fluorard (manufactured by Sumitomo 3M), Asahi Guard (manufactured by Asahi Glass Co., Ltd.), Surflon (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Co., Ltd.) And other series).
Among these, a fluorine-based surfactant or a silicone-based surfactant is preferable, a fluorine-based surfactant is more preferable, a fluorine-based nonionic surfactant is further preferable, and a perfluoro group-containing nonionic surfactant is particularly preferable.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (I-1), and is a polystyrene equivalent weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. Preferred examples include copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

（式（Ｉ−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 (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 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)

The L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in formula (I-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 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. It is more preferable, and it is still more preferable that it is 0.01-3 mass parts.

(Component J) Adhesion Improving Agent The photosensitive resin composition that can be used in the present invention may contain an adhesion improving agent.
The adhesion improver that can be used for the photosensitive resin composition is an inorganic substance as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, adhesion between a metal such as gold, copper, or aluminum and an insulating film. It is a compound that improves Specific examples include silane coupling agents and thiol compounds. Among these, a silane coupling agent is preferable.
The silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.

Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacrylate. Roxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxy Examples include silane.
Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

These can be used alone or in combination of two or more. These are effective for improving the adhesion to the substrate and also for adjusting the taper angle with the substrate.
0.1-20 mass parts is preferable with respect to 100 mass parts of components B, and, as for content of the adhesion improving agent in the photosensitive resin composition, 0.5-10 mass parts is more preferable.

-Other ingredients-
In addition to the above-described components, the photosensitive resin composition that can be used in the present invention includes a sensitizer, an ultraviolet absorber, a metal deactivator, an acid proliferator, a development accelerator, a plasticizer, as necessary. Known additives such as an agent, a thermal radical generator, a thermal acid generator, a thickener, and an organic or inorganic suspending agent can be added.
In addition, as other additives, the thermal radical generator described in paragraphs 0120 to 0121 of JP2012-8223A, the nitrogen-containing compound and the thermal acid generator described in International Publication No. 2011/136004 are also used. Can do.

(Cured film)
The cured film of the present invention is a cured film obtained by the method for producing a cured film of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
By the method for producing a cured film of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at a high temperature can be obtained. Since the interlayer insulating film obtained by the method for producing a cured film of the present invention has high transparency and excellent cured film properties, it is useful for applications of organic EL display devices and liquid crystal display devices.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a cured film such as a flattened film or an interlayer insulating film obtained by the method for producing a cured film of the present invention, and known liquid crystals having various structures. A display device 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, the liquid crystal driving methods that the liquid crystal display device of the present invention can take are TN (Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane-Switching) method, FFS (Fringe 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 Array) 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 can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer 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 cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 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, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP2011-145686A or the interlayer 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 film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a cured film such as a flattened film or an interlayer insulating film obtained by the method for producing a cured film of the present invention, and is known in various structures. Examples include various organic EL display devices and liquid crystal display devices.
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 film 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 cured film obtained by the method for producing a cured film of the present invention has excellent cured film characteristics, a resist pattern formed using the cured film as a structural member of a MEMS device can be used as a partition wall or a mechanical drive component. Used as part of it. 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 cured film obtained by the method for producing a cured film of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarizing film (see FIG. 2 of JP2011-107476A) 57), the partition wall (12) and the planarization film (102) described in FIG. 4A of JP 2010-9793 A, the bank layer (221) described in FIG. 10 of JP 2010-27591 A, and Third interlayer insulating film (216b), second interlayer insulating film (125) and third interlayer insulating film (126) described in FIG. 4A of Japanese Unexamined Patent Application Publication No. 2009-128577, Japanese Unexamined Patent Application Publication No. 2010-182638 3 can be used to form the planarization film (12) and the pixel isolation insulating film (14) shown in FIG.

(Touch panel display)
The touch panel display device of the present invention includes a capacitive input device having the cured film of the present invention. Moreover, the capacitance-type input device of the present invention has the cured 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 non-contact side of the front plate and the front plate, and the above (4) is the cured 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 the first direction (X) via connecting portions (3) The first transparent electrode A plurality of second transparent electrode patterns comprising a plurality of pad portions that are electrically insulated from the pattern and extend in a direction intersecting the first direction (X). (4) The first transparent Insulating layer for electrically insulating the electrode pattern and the second transparent electrode pattern (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, Conductive element different from the transparent electrode pattern and the second transparent electrode pattern of the present invention The capacitance type input device of the present invention further covers all or part of the elements (1) to (5). It is preferable to install a transparent protective layer, the above transparent More preferably Mamoruso is cured film of the present invention.

  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 part as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.

As shown in FIG. 5, a plurality of first transparent electrode patterns 33 are formed on the contact surface of the front plate 31 by a plurality of pad portions extending in the first direction (X) via the connection portions. And a plurality of second transparent electrode patterns 34 each including a plurality of pad portions that are electrically insulated from the first transparent electrode pattern 33 and extend in a direction intersecting the first direction (X). And the insulating layer 35 which electrically insulates the 1st transparent electrode pattern 33 and the 2nd 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, for example, 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 are a photocurable transfer material having a photosensitive resin composition using the conductive fibers. It 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 the pad portion 33a extends in the first direction (X) via the 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 intersects the first direction (X) (second direction in FIG. 5). (Y)) is constituted by a plurality of pad portions formed to extend. 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 capacitive input device of the present invention and the touch panel display device including the capacitive input device as a constituent element are “latest touch panel technology” (issued July 6, 2009, Techno Times), Supervised by Yuji Mitani, “Touch Panel Technology and Development,” CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. it can.

  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 examples, the following symbols represent the following compounds, respectively.
MATHF: tetrahydrofuran-2-yl methacrylate (synthetic product)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate

MAEVE: 1-ethoxyethyl methacrylate (synthetic product)
MACHOE: 1- (cyclohexyloxy) ethyl methacrylate (synthetic product)
MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, filtered to insoluble matter and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Distillation under reduced pressure gave 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

<Method for measuring acid value>
The acid value of the polymer was measured by titration using potassium hydroxide.

<Measurement of volume average particle diameter>
Measurement was performed with a laser diffraction / scattering particle size distribution analyzer MT3000II manufactured by Nikkiso Co., Ltd. The dispersion was measured by diluting 100 times with PGMEA.

<Preparation of dispersion D1>
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 (C), average primary particle size: 10 to 30 nm): 1,875 parts Dispersant (DISPERBYK-111, 30% by mass PGMEA solution): 2,200 parts, solvent PGMEA (propylene glycol monomethyl ether acetate): 3,425 parts

<Preparation of dispersions D2 and D3>
Dispersions D2 and D3 were obtained in the same manner as in the preparation of Dispersion D1, except that TTO-51 (C) and the dispersant were changed to those shown in Table 1, respectively.

In addition, abbreviations other than those described above used for the dispersions described in Table 1 are as shown below.
-Inorganic particles-
TTO-51 (C): Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size 10-30 nm, surface treatment species: Al (OH) ₃ / stearic acid TTO-51 (A): Titanium dioxide, Ishihara Sangyo ( Co., Ltd., average primary particle size 10-30 nm, surface treatment species: Al (OH) ₃
UEP-100: Zirconium dioxide, manufactured by Daiichi Elemental Chemical Co., Ltd., average primary particle size of 10 to 15 nm

-Dispersant-
DISPERBYK-111: a polymeric dispersant having one or more phosphate ester structures, manufactured by Big Chemie

-Polymer-
<Synthesis of Polymer P1-1>
Tetrahydrofuran-2-yl methacrylate (0.40 molar equivalent),
Methacrylic acid (0.10 molar equivalent),
100 parts total of (3-ethyloxetane-3-yl) methyl methacrylate (0.50 molar equivalent), and
A mixed solution of propylene glycol monomethyl ether acetate (PGMEA) (120 parts) was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, radical polymerization initiator V-601 (dimethyl-2,2′-azobis (2-methylpropionate), manufactured by Wako Pure Chemical Industries, Ltd., 12.0 parts) and PGMEA (80 parts) of the mixed solution was added dropwise over 3.5 hours. After the completion of the dropping, a PGMEA solution of polymer P1-1 was obtained by reacting at 70 ° C. for 2 hours. Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of the obtained polymer P1-1 was 15,000. The acid value was 45 mg KOH / g. In addition, in the obtained polymer P1-1, the molar ratio of each used monomer and the molar ratio with each corresponding monomer unit were the same. The same was true for the polymer described later.

<Synthesis of P1-2>
Tetrahydrofuran-2-yl methacrylate (0.40 molar equivalent) and methyl methacrylate (3-ethyloxetane-3-yl) methyl (0.50 molar equivalent) were added to tetrahydrofuran-2-yl methacrylate (0.50 molar equivalent). And PGMEA solution of polymer P1-2 was obtained in the same manner as the synthesis of polymer P1-1, except that it was changed to (3-ethyloxetane-3-yl) methyl methacrylate (0.40 molar equivalent). . Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer P1-2 was 15,000. The acid value was 45 mg KOH / g.

<Synthesis of P1-3>
Tetrahydrofuran-2-yl methacrylate (0.40 molar equivalent) and methacrylic acid (3-ethyloxetane-3-yl) methyl (0.50 molar equivalent) were added to tetrahydrofuran-2-yl methacrylate (0.55 molar equivalent). And PGMEA solution of polymer P1-3 was obtained in the same manner as the synthesis of polymer P1-1, except that it was changed to (3-ethyloxetane-3-yl) methyl methacrylate (0.35 molar equivalent). . Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer P1-3 was 15,000. The acid value was 45 mg KOH / g.

<Synthesis of P1-4>
Tetrahydrofuran-2-yl methacrylate (0.40 mole equivalent) and methyl methacrylate (3-ethyloxetane-3-yl) methyl (0.50 mole equivalent) were added to tetrahydrofuran-2-yl methacrylate (0.65 mole equivalent). And a PGMEA solution of the polymer P1-4 was obtained in the same manner as the synthesis of the polymer P1-1 except that it was changed to (3-ethyloxetane-3-yl) methyl methacrylate (0.25 molar equivalent). . Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The obtained polymer P1-4 had a weight average molecular weight (Mw) of 15,000 measured by gel permeation chromatography (GPC). The acid value was 45 mg KOH / g.

<Synthesis of P1-5>
Tetrahydrofuran-2-yl methacrylate (0.40 molar equivalent) and tetrahydrofuran (3-ethyloxetane-3-yl) methyl methacrylate (0.50 molar equivalent) were added to tetrahydrofuran-2-yl methacrylate (0.75 molar equivalent). And PGMEA solution of polymer P1-5 was obtained in the same manner as the synthesis of polymer P1-1, except that it was changed to (3-ethyloxetane-3-yl) methyl methacrylate (0.15 molar equivalent). . Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of the obtained polymer P1-5 was 15,000. The acid value was 45 mg KOH / g.

<Synthesis of P1-6>
Tetrahydrofuran-2-yl methacrylate (0.40 molar equivalent) and tetrahydrofuran (3-ethyloxetane-3-yl) methyl methacrylate (0.50 molar equivalent) were added to tetrahydrofuran-2-yl methacrylate (0.20 molar equivalent). And PGMEA solution of polymer P1-6 was obtained in the same manner as the synthesis of polymer P1-1, except that it was changed to (3-ethyloxetane-3-yl) methyl methacrylate (0.70 molar equivalent). . Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The obtained polymer P1-6 had a weight average molecular weight (Mw) of 15,000 as measured by gel permeation chromatography (GPC). The acid value was 45 mg KOH / g.

<Synthesis of Polymer P2-1>
A PGMEA solution of polymer P2-1 was obtained in the same manner as for polymer P1, except that the monomer composition was changed to the following. Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
Tetrahydrofuran-2-yl methacrylate (0.65 molar equivalent),
Methacrylic acid (0.15 molar equivalent),
Methyl methacrylate (0.20 molar equivalent)
The obtained polymer P2-1 had a weight average molecular weight (Mw) of 15,000 as measured by gel permeation chromatography (GPC). The acid value was 60 mgKOH / g.

<Synthesis of Polymer P2-2>
Tetrahydrofuran-2-yl methacrylate (0.65 molar equivalent), methacrylic acid (0.15 molar equivalent) and methyl methacrylate (0.20 molar equivalent) were added to tetrahydrofuran-2-yl methacrylate (0.80 molar equivalent), A PGMEA solution of a polymer P2-2 was obtained in the same manner as the synthesis of the polymer P2-1 except that methacrylic acid (0.10 molar equivalent) and methyl methacrylate (0.10 molar equivalent) were changed. Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The obtained polymer P2-2 had a weight average molecular weight (Mw) of 15,000 measured by gel permeation chromatography (GPC). The acid value was 60 mgKOH / g.

<Synthesis of Polymer P2-3>
Tetrahydrofuran-2-yl methacrylate (0.65 molar equivalent), methacrylic acid (0.15 molar equivalent) and methyl methacrylate (0.20 molar equivalent) were added to tetrahydrofuran-2-yl methacrylate (0.55 molar equivalent), Except having changed to methacrylic acid (0.20 molar equivalent) and methyl methacrylate (0.25 molar equivalent), it carried out similarly to the synthesis | combination of polymer P2-1, and obtained the PGMEA solution of polymer P2-3. Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The obtained polymer P2-3 had a weight average molecular weight (Mw) of 15,000 measured by gel permeation chromatography (GPC). The acid value was 60 mgKOH / g.

<Synthesis of Polymer P3>
A PGMEA solution of polymer P3 was obtained by the same method as polymer P1-1 except that the monomer composition was changed to the following. Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
Glycidyl methacrylate (0.70 molar equivalent),
Methacrylic acid (0.10 molar equivalent),
Styrene (0.15 molar equivalent),
Dicyclopentanyl methacrylate (0.05 molar equivalent)
The obtained polymer P3 had a weight average molecular weight (Mw) of 12,000 as measured by gel permeation chromatography (GPC). The acid value was 45 mg KOH / g.

<Synthesis of Polymer P4>
A PGMEA solution of polymer P4 was obtained in the same manner as the synthesis of polymer P1-1 except that tetrahydrofuran-2-yl methacrylate was changed to 1-ethoxyethyl methacrylate (MAEVE). Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of the obtained polymer P4 was 15,000. The acid value was 45 mg KOH / g.

<Synthesis of Polymer P5>
A PGMEA solution of polymer P5 was obtained in the same manner as the synthesis of polymer P1-1 except that tetrahydrofuran-2-yl methacrylate was changed to 1- (cyclohexyloxy) ethyl methacrylate (MACHOE). Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of the obtained polymer P5 was 15,000. The acid value was 45 mg KOH / g.

<Synthesis of Polymer P6>
A PGMEA solution of polymer P6 was obtained in the same manner as the synthesis of polymer P1-1 except that tetrahydrofuran-2-yl methacrylate was changed to tetrahydro-2H-pyran-2-yl methacrylate (MATHP). Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer P6 was 15,000. The acid value was 45 mg KOH / g.

MAEVE was synthesized in the same manner as MATH, except that 2-dihydrofuran was changed to the corresponding compound.
MACHOE was synthesized in the same manner as MATH, except that 2-dihydrofuran was changed to the corresponding compound.

<Synthesis of Polymer P7>
A PGMEA solution of polymer P7 was obtained in the same manner as the synthesis of polymer P3 except that glycidyl methacrylate was changed to (3-ethyloxetane-3-yl) methyl methacrylate (OXE-30). Further, PGMEA was added to adjust the solid content concentration to 30% by mass.
The obtained polymer P7 had a weight average molecular weight (Mw) of 12,000 as measured by gel permeation chromatography (GPC). The acid value was 45 mg KOH / g.

<Photo acid generator>
B1: Compound having the following structure (synthetic product)
B2: Compound having the following structure (synthetic product)
B3: Compound having the following structure (synthetic product)
B4: CGI-1397 (compound with the following structure, manufactured by BASF)
B5: Compound having the following structure (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)

<Synthesis of B1>
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. The slurry was then reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated to reflux for 10 hours. 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, reslurried with methanol (20 mL), filtered and dried to obtain B1 (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 ( d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2 .4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B2>
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 adding 3.4 g, 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. did. 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 B2A. Crude B2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B2A.
B2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated at 140 ° C. for 2 hours. . 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 B2B.
THF (2 mL) and the whole amount of crude B2B were mixed, and 6.0 mL of 2M hydrochloric acid / THF solution was added under ice cooling, followed by isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g), and the mixture was allowed to rise to room temperature The mixture was stirred for 2 hours after warming. 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 crude B2C.
The total amount of intermediate crude B2C 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.) (under ice cooling) ( After adding 1.4 g), the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the resulting reaction mixture to separate it, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B2. Crude B2 was reslurried with cold methanol, filtered and dried to obtain B2 (1.2 g).

The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B2 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) .

<Synthesis of B3>
B3 was synthesized in the same manner as B1, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B1.
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B3 is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 ( d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q, 1H), 1.7 (d , 3H).

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 Tables 3 and 4 below.
-Propylene glycol monomethyl ether acetate: 191.1 parts-0.2% PGMEA solution of the following compound (Toyo Kasei Kogyo Co., Ltd., CMTU): 25.7 parts-30% PGMEA solution of polymer P1: 263.3 Parts / photo acid generator B1: 5.1 parts / JER157S65 (epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq): 17.9 parts / 3-glycidoxypropyltrimethoxysilane ( KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 4.5 parts Irganox 1726 (antioxidant, 2,4-bis (dodecylthiomethyl) -6-methylphenol, manufactured by BASF): 3.0 Part 2.0% PGMEA solution of perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation): 11.0 parts Dispersion D1: 4 8.4 parts

<Measurement of shrink rate>
The resulting photosensitive resin composition has a thickness of 2.0 μm on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) treated with hexamethyldisilazane (HMDS) for 3 minutes. As described above, the solution was applied with a spin coater and dried (prebaked) for 120 seconds on a hot plate at 80 ° C. to remove the solvent. Subsequently, heating at 200 ° C. for 20 minutes was performed using a clean oven PVC-211 (manufactured by HORIBA, Ltd., which reached a film surface temperature of 195 ° C. or higher using a thermocouple at a preset temperature of 200 ° C. for 5 minutes) The subsequent film thickness was measured. In addition, the measurement of the film thickness was calculated by measuring three locations (N = 3) in the central portion of the film with a stylus type surface shape measuring device Dektak (manufactured by ULVAC, Inc.) and taking an average value. In Example 1, the shrink rate (= r ₂ × 100 (%)) was 28.9%.
The photosensitive resin composition layer from which the solvent was removed, developed with a 0.5% aqueous potassium hydroxide (KOH) solution at 23 ° C. for 30 seconds, and rinsed with ultrapure water for 10 seconds, The film thickness was measured. The layer after rinsing was heated at 200 ° C. for 20 minutes in the same manner as described above, and then the film thickness was measured. The film thickness after development and rinsing and the film thickness after development, rinsing and heating were measured. In Example 1, the shrink rate was the same as above.

<Measurement of refractive index>
The obtained photosensitive resin composition was applied on a silicon wafer substrate and dried at 80 ° C. for 120 seconds to form a film having a thickness of 0.5 μm. This substrate was exposed at 200 mJ / cm ² (measured with i-line) using an ultrahigh pressure mercury lamp, and then heated in an oven at 150 ° C. for 60 minutes.
The refractive index of the cured film at 589 nm was measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.). A higher refractive index is preferable, and 1.70 or more is more preferable.

<Resolution evaluation>
The resulting photosensitive resin composition has a thickness of 2.0 μm on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) treated with hexamethyldisilazane (HMDS) for 3 minutes. Thus, it was applied with a spin coater and dried (prebaked) for 120 seconds on an 80 ° C. 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% KOH aqueous solution at 23 ° C. for 30 seconds and rinsed with ultrapure water for 10 seconds. Subsequently, a pattern was obtained by heating at 150 ° C. for 60 minutes. This pattern was observed with an optical microscope.
This operation is started from the width of the mask line and space of 50 μm, and until 10 μm, the width is reduced by 5 μm by 10 μm, and the width is reduced by 1 μm. . 4 or 3 is a practical range.
4: The resolution was 5 μm or less.
3: The resolution was more than 5 μm and 10 μm or less.
2: The resolution was more than 10 μm and 50 μm or less.
1: A pattern could not be formed with a line and space width of 50 μm of the mask.

<Taper shape evaluation>
The taper shape of the section of the line-and-space width 50 μm formed above was observed with a scanning electron microscope (SEM). Using a ghi-line high-pressure mercury lamp exposure machine, the gap between the mask and the substrate was exposed to 100 μm at an illuminance of 20 mW / cm ² and 200 mJ / cm ² . The collimation angle was 2 degrees. Note that a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp was used as the exposure machine.
Evaluation criteria based on the taper angle of the tapered shape are shown below.
5: 20 ° or more and 30 ° or less 4: 30 ° or more and 40 ° or less 3: 40 ° or more and 50 ° or less 2: 50 ° or more and 75 ° or less, or 15 ° or more and less than 20 ° 1: Over 75 ° or below 15 °

The “taper angle” is an angle formed by the side surface of the pattern and the substrate plane on which the pattern is formed in the cross-sectional shape of the pattern in the line width direction. In addition, even when the cross-sectional shape of the pattern is a semicircle or an arcuate shape and the cross-section of the side surface is a curve, the tangent line at the midpoint between the uppermost part of the pattern and the substrate, that is, the point of the film thickness 1/2 and the plate substrate plane The angle formed by
As a specific example of the taper angle, θ in each pattern cross-sectional shape shown in FIGS. 6 to 9 is the taper angle.
The taper shape shown in FIG. 6 is an example when the taper angle is 20 ° or more and 30 ° or less. When the taper angle is 20 ° or more and 30 ° or less, the height of the cured film can be sufficiently obtained, and the occurrence of disconnection can be suppressed when a wiring such as ITO is deposited.
The taper shape shown in FIG. 7 is an example when the taper angle is less than 20 °. If the taper angle is less than 20 °, the height of the cured film cannot be obtained sufficiently, and the reproducibility of the exposure pattern is poor.
The taper shape shown in FIG. 8 is an example when the taper angle is more than 75 ° and not more than 90 °. When the taper angle exceeds 75 °, disconnection is likely to occur when wiring such as ITO is deposited.
The taper shape shown in FIG. 9 is an example when the taper angle exceeds 90 °. When the taper angle exceeds 90 °, the shape is similar to that of side etching in etching, and disconnection is very likely to occur when a wiring such as ITO is deposited.

(Examples 2 to 22 and Comparative Example 5)
Except having changed each component into the thing of Table 2, it prepared the photosensitive resin composition of Examples 2-22 and the comparative example 5 similarly to Example 1, and also obtained the photosensitive resin composition Various evaluations were performed using The evaluation results are shown in Tables 3 and 4 below.

(Comparative Examples 1-4)
Using the above dispersion D1, the mass ratio of the binder to the monomer is 1.0 so that the titanium oxide concentration is 50% by mass, the initiator shown in Table 2 is 3% by mass, and the surfactant Megafac F is used. -554 was 0.1% by mass, and each PGMEA solution having a total solid content of 14% by mass was prepared. Furthermore, various evaluation was performed using the obtained photosensitive resin composition. The evaluation results are shown in Tables 3 and 4 below.
-Binder: The following resin was synthesized according to a known method (Mw = 30,000).

-Monomer: DPHA (mixture of 70% by mass of dipentaerythritol hexaacrylate and 30% by mass of dipentaerythritol pentaacrylate)
OXE-02: initiator, the following compound, manufactured by BASF, IRGACURE OXE 02
OXE-01: initiator, the following compound, manufactured by BASF, IRGACURE OXE 01

In Comparative Example 4, film slippage due to development was observed.
Moreover, in the resolving power evaluation of Comparative Examples 1-3, the resolving power was a rank of 2, and the location where the line and space pattern was crushed in part was seen.

(Example 23)
In the active matrix 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, and a liquid crystal display device of an example was obtained. That is, the photosensitive resin composition of Example 1 was spin-coated on a substrate, pre-baked (80 ° C./120 seconds) on a hot plate, and then i-line (365 nm) was 200 mJ / mm from the mask using a high-pressure mercury lamp. After irradiation with cm ² (energy intensity 20 mW / cm ² ), development was performed with an alkaline aqueous solution to form a pattern, and heat treatment was performed at 150 ° C./60 minutes to form a cured film 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 24)
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. . This wiring 2 is a Cu wiring for connecting the TFT 1 to an organic EL element formed between 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 planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (80 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating i-line (365 nm) with 200 mJ / cm ² (energy intensity 20 mW / cm ² ) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 150 ° C./60 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 25)
A touch panel display device was produced using the high refractive index curable resin material 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 surface of the exposure mask (quartz exposure mask having a transparent electrode pattern) 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 resist layer pattern were formed.

The front plate on which the transparent electrode layer and the etching resist layer pattern are formed is immersed in an etching bath containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and covered with the etching resist layer. The exposed transparent electrode layer was removed by dissolution 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 etching resist layer is removed, and the mask layer and the first transparent electrode pattern are formed. A face plate 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, 80 ° 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 200 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 and 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, 100: substrate, 102: substrate surface, 104: cured film, X: first direction, Y: second direction, θ: taper angle

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 Tables 3 and 4 below.
Propylene glycol monomethyl ether acetate: 191.1 parts following compound (Toyo Kasei Kogyo Co., Ltd., CMTU) 0.2% PGMEA solution of: 25.7 parts Polymer P1 -5 of 30% PGMEA solution: 263 .3 parts Photo acid generator B1: 5.1 parts JER157S65 (epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq): 17.9 parts 3-glycidoxypropyltrimethoxy Silane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 4.5 parts Irganox 1726 (Antioxidant, 2,4-bis (dodecylthiomethyl) -6-methylphenol, manufactured by BASF): 3 1.0 part of a 2.0% PGMEA solution of a perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation): 11.0 part of a dispersion D1 : 478.4 parts

Claims (16)

The manufacturing method of the cured film characterized by including process (a) and (b) in this order.
(A) (Component A) inorganic particles, (Component B) a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (Component C) a photosensitizer containing a photoacid generator A layer forming step of forming a layer composed of the solid content of the photosensitive resin composition on the substrate using the resin composition and satisfying the following formula (2): (b) a layer composed of the solid content of the photosensitive resin composition Heat treatment step of heat treating the material shrinkage ratio r ₂ = (t ₂₀ −t ₂₁ ) / t ₂₀ ≧ 0.15 (2)
In the formula, t ₂₀ represents the thickness of the layer made of the solid content of the photosensitive resin composition, and t ₂₁ represents the thickness after heating the layer at 200 ° C. for 20 minutes.   The manufacturing method of the cured film of Claim 1 whose temperature of the said heat processing is 120 to 200 degreeC.   The manufacturing method of the cured film of Claim 1 or 2 whose temperature of the said heat processing is 120 to 175 degreeC.   The manufacturing method of the cured film of any one of Claims 1-3 with which the said heat processing is performed for 30 to 180 minutes at the temperature of 120 to 175 degreeC.   The ratio of the structural unit having a group in which the acid group is protected with an acid-decomposable group to the total structural unit of the polymer including the structural unit having a group in which the acid group is protected with an acid-decomposable group is 50 The manufacturing method of the cured film of any one of Claims 1-4 which is -95 mol%.   The ratio of the structural unit having a group in which the acid group is protected by an acid-decomposable group to the total structural unit of the polymer including the structural unit having a group in which the acid group is protected by an acid-decomposable group is 65 The manufacturing method of the cured film of any one of Claims 1-5 which is -85 mol%. The structural unit which has a group in which the acid group is protected with an acid-decomposable group is a structural unit represented by the following formula (a1-1-1). A method for producing a cured film.

In the formula, R represents a hydrogen atom or a methyl group.   The manufacturing method of the cured film of any one of Claims 1-7 whose component A is a metal oxide particle.   The manufacturing method of the cured film of any one of Claims 1-8 whose component A is a titanium oxide particle or a zirconium oxide particle.   (Component D) The manufacturing method of the cured film of any one of Claims 1-9 which further contains a thermal crosslinking agent.   (Component E) The manufacturing method of the cured film of any one of Claims 1-10 which further contains antioxidant.   The cured film obtained by the manufacturing method of the cured film of any one of Claims 1-11.   The cured film according to claim 12, which is an interlayer insulating film.   A liquid crystal display device having the cured film according to claim 12.   An organic EL display device having the cured film according to claim 12.   A touch panel display device having the cured film according to claim 12.

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