KR20150091380A - Photosensitive resin composition for inkjet application, heat-treated substance, manufacturing method therefor, resin-pattern manufacturing method, liquid-crystal display, organic electroluminescent display, touch panel, manufacturing method therefor, and touch-panel display - Google Patents

Abstract

And to provide a photosensitive resin composition excellent in inkjet dischargeability, dryness, storage stability, and transparency after heat treatment. The photosensitive resin composition for ink jet application of the present invention comprises (A) an inorganic particle, (Component B) a solvent, (Component C) a polymer containing a structural unit having an acid group-protected group with an acid-decomposable group, and (Component D) Wherein the component B has a boiling point of 177 캜 or higher and 227 캜 or lower and an I / O value of 0.50 or higher and 1.00 or lower.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for inkjet application, a heat treatment product, a method of manufacturing the same, a method of manufacturing a resin pattern, a liquid crystal display, an organic EL display, -TREATED SUBSTANCE, MANUFACTURING METHOD THEREFOR, RESIN-PATTERN MANUFACTURING METHOD, LIQUID-CRYSTAL DISPLAY, ORGANIC ELECTROLUMINESCENT DISPLAY, TOUCH PANEL, MANUFACTURING METHOD THEREFOR, AND TOUCH-PANEL DISPLAY}

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as " composition of the present invention "). The heat-treated product obtained by heat-treating the photosensitive resin composition and the production method thereof, the resin pattern production method using the photosensitive resin composition, the heat-treated product obtained by heat-treating the photosensitive resin composition, and the heat- And various image display devices.

More particularly, the present invention relates to a photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display, an organic EL display, a touch panel, a touch panel display, an integrated circuit element, And a method for producing a cured film.

BACKGROUND ART It has been widely practiced to manufacture optical members such as a microlens, an optical waveguide, and an antireflection film by an organic material (resin) in accordance with the development of solid-state image pickup devices and liquid crystal display devices.

It has been studied to add particles of titanium oxide or the like to these optical members in order to obtain a high refractive index (see Patent Document 1 below).

As the conventional photosensitive resin composition, the photosensitive resin compositions described in Patent Documents 2 to 4 are known.

Japanese Patent Application Laid-Open No. 2006-98985 Japanese Patent Application Laid-Open No. 2008-158281 Japanese Patent Application Laid-Open No. 2011-248331 Korean Patent Laid-Open No. 10-2012-0121850

An object of the present invention is to provide a photosensitive resin composition excellent in inkjet dischargeability, dryness, storage stability, and transparency after heat treatment.

The above object of the present invention is solved by the means described in the following <1>, <7> - <10> or <12> - <16>. Are described below together with <2> to <6> and <11> which are the preferred embodiments.

(Component C) a polymer comprising a constituent unit having an acid group protected by an acid-decomposable group, and (D) a photoacid generator, wherein the component B Wherein the non-alcohol solvent has a boiling point of 177 DEG C or higher and 227 DEG C or lower and an I / O value of 0.50 or more and 1.00 or less.

&Lt; 2 &gt; The method according to &lt; 1 &

Wherein the non-alcoholic solvent is at least one selected from the group consisting of an alkylene glycol monoalkyl ether acylate, a dialkylene glycol monoalkyl ether acylate, a dialkylene glycol dialkyl ether, and a trialkylene glycol dialkyl ether By weight based on the total weight of the photosensitive resin composition.

&Lt; 3 &gt; The method according to &lt; 1 &gt; or &lt; 2 &

Wherein the component A is a metal oxide particle.

&Lt; 4 &gt; A method according to any one of &lt; 1 &gt; to &lt; 3 &

Wherein the component A is titanium oxide particles or zirconium oxide particles.

&Lt; 5 &gt; A method according to any one of &lt; 1 &gt; to &lt; 4 &

(Component E) a dispersing agent.

&Lt; 6 &gt; A method according to any one of &lt; 1 &gt; to &lt; 5 &

(Component F) a thermal cross-linking agent.

&Lt; 7 &gt; A method for producing a heat-treated product, comprising at least the steps (a) to (c).

(a) a coating process for coating the photosensitive resin composition for inkjet application described in any one of &lt; 1 &gt; to &lt; 6 &gt;

(b) a solvent removing step of removing the solvent from the applied resin composition

(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed

&Lt; 8 &gt; A method for producing a resin pattern, comprising at least steps (1) to (5).

(1) A coating process for coating the photosensitive resin composition for inkjet application described in any one of &lt; 1 &gt; to &lt; 6 &gt;

(2) a solvent removing step of removing the solvent from the applied resin composition

(3) an exposure step of exposing the resin composition from which the solvent has been removed to a pattern shape by an actinic ray

(4) a developing step of developing the exposed resin composition with an aqueous developing solution

(5) Heat treatment process for heat-treating the developed resin composition

<9> A heat-treated product obtained by the method for producing a heat-treated product according to <7> or the method for producing a resin pattern according to <8>.

<10> A heat-treated product obtained by heat-treating the photosensitive resin composition for ink-jet application according to any one of <1> to <6>.

<11> In the above-mentioned <10>

Wherein the insulating film is an interlayer insulating film.

<12> A liquid crystal display device having the heat treatment described in <10> or <11>.

<13> An organic EL display device having the heat treatment described in <10> or <11>.

<14> A method of manufacturing a touch panel having a transparent substrate, an ITO electrode, and an insulating layer, wherein the photosensitive resin composition for inkjet coating according to any one of <1> to <6> A step of applying a mask having an opening pattern of a predetermined shape on the resin composition, a step of exposing the resin composition by exposure to active energy rays, a step of developing the resin composition after exposure, and a step of heating the resin composition after development, Wherein the method comprises the steps of:

<15> The touch panel according to any one of <1> to <6>, wherein all or a part of the insulating layer is formed by heat treatment of the photosensitive resin composition for inkjet application.

<16> A touch panel display device having the heat treatment product according to <10> or <11>, or the touch panel according to <15>.

(Effects of the Invention)

According to the present invention, it is possible to provide a photosensitive resin composition excellent in inkjet dischargeability, dryness, storage stability, and transparency after heat treatment.

Fig. 1 shows a configuration diagram of an example of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.
2 shows a configuration diagram of an example of the organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device and has a planarization film 4.
3 is a cross-sectional view showing the configuration of the capacitance type input device.
4 is an explanatory view showing an example of a front plate.
5 is an explanatory view showing an example of the first transparent electrode pattern and the second transparent electrode pattern.

Hereinafter, the contents of the present invention will be described in detail. The description of constituent elements described below may be made based on the exemplary embodiment of the present invention, but the present invention is not limited to such embodiment.

In the present specification, &quot; &quot; representing the numerical range is used to mean that numerical values written before and after the numerical value are included as a lower limit value and an upper limit value.

In the present invention, the term "(component A) inorganic particle" is also referred to simply as "component A" or the like, and the term "(a1) a structural unit having a group protected with an acid- a1) &quot;

The notation in which the substituent and the non-substituent are not described in the notation of the group (atomic group) in the present specification includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(Photosensitive resin composition for inkjet application)

The photosensitive resin composition for ink jet application (hereinafter, simply referred to as &quot; photosensitive resin composition &quot;) of the present invention is composed of (Component A) inorganic particles, (Component B) a solvent, (Component C) (B) a non-alcoholic solvent having a boiling point of 177 DEG C or higher and 227 DEG C or lower and an I / O value of 0.50 or higher and 1.00 or lower, wherein the component (B) do.

The photosensitive resin composition of the present invention can be preferably used as a positive resist composition.

The photosensitive resin composition of the present invention is preferably a curable resin composition having heat curing properties.

Further, the photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition, more preferably a positive-working photosensitive resin composition (chemically amplified positive photosensitive resin composition).

It is preferable that the photosensitive resin composition of the present invention does not contain a 1,2-quinonediazide compound as a photoacid generator sensitive to an actinic ray. The 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is necessarily 1 or less.

On the other hand, the photoacid generator (component D) used in the present invention is a compound in which the acid generated by the action of the actinic ray acts as a catalyst against the deprotection of the protected acid group in the component C, Contributes to the deprotection reaction, and the quantum yield exceeds 1 and becomes, for example, a large value such as a power of 10, resulting in a high sensitivity as a result of so-called chemical amplification.

Further, the photosensitive resin composition of the present invention is a resin composition for an optical member such as a microlens, an optical waveguide, an antireflection film, a sealing material for an LED and a chip coating material for an LED, or a resin composition for reducing visibility of a wiring electrode used in a touch panel . The composition for reducing the visibility of the wiring electrode used in the touch panel is a composition for a member which reduces the visibility of the wiring electrode used in the touch panel, that is, makes the wiring electrode difficult to see. For example, ITO (indium tin oxide) An interlayer insulating film between electrodes, and the like. The photosensitive resin composition of the present invention can be preferably used for the above applications.

Generally, in the positive photosensitive resin composition, when exposed to light, the acid-decomposable group contained in the polymer contained in the polymer is dissolved by the action of the photoacid generator to dissolve in the developer, and the unexposed portion is formed as a pattern.

To increase the refractive index of the resulting cured film, it is necessary to increase the content of inorganic particles in the photosensitive resin composition. When the content of the inorganic particles in the photosensitive resin composition is increased, the inorganic particles sometimes aggregate in the photosensitive resin composition, and the photosensitive resin composition is thickened, and as a result, there is a case where coating failure is caused by poor discharge from the inkjet nozzle. Further, it becomes difficult to control the drying property.

Even in the case of a spin coat method, even a resist which can be uniformly applied without spreading unevenness may be defective in ejection or can not be ejected if it is used for inkjet application. In addition, there is a problem in that unevenness of the coating film due to unevenness of discharge flow rate causes unevenness of the film shape of the stripe shape.

Further, by repeating the number of coating (the number of application), the tip of the discharge nozzle repeats wetting and drying. When the ink in which the inorganic particles are dispersed is dried at the tip of the nozzle, the concentration of the solid content increases sharply, resulting in agglomerates. The coagulation agglomerations of these particles cause irregularities in the discharge flow rate, resulting in nonuniform application due to discharge failure. Further, when the coagulated mass adheres to the tip of the nozzle and the ink is ejected again, it is peeled from the tip of the nozzle and moved onto the substrate. These agglomerated agglomerates are not easily removed in the subsequent steps but remain on the substrate until the last. Such agglomerates become defective and cause quality defects. If this bad phenomenon occurs frequently, it is considered to be one of the phenomena that must be avoided because the product yield is lowered.

In Patent Document 3, there is a substrate in the spin coat application and the slit die coat application, but the application to the ink jet application is not specifically disclosed, and the application by the ink jet application is not carried out in the Examples.

As a result of a detailed examination, the inventors of the present invention have found that a photosensitive resin composition containing the components A to D can be obtained which has excellent inkjet dischargeability, dryness, storage stability, and transparency after heat treatment.

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

(Component A)

The photosensitive resin composition of the present invention contains inorganic particles (component A) for the purpose of controlling the refractive index and light transmittance.

The component A preferably has a refractive index higher than the refractive index of the resin composition made of the material excluding the above-mentioned particles. Specifically, particles having a refractive index of 1.50 or higher in light having a wavelength of 400 to 750 nm are more preferable, and a refractive index is 1.70 Or more, more preferably 1.90 or more. Further, particles having a refractive index of 5.00 or less are preferable.

Here, when the refractive index in the light having the wavelength of 400 to 750 nm is 1.50 or more, it means that the average refractive index in the light having the wavelength in the above range is 1.50 or more, and the refractive index Does not need to be more than 1.50. The average refractive index is a value obtained by dividing the sum of measured values of refractive index for each light having a wavelength in the above range by the number of measurement points.

As the inorganic particles having such a high refractive index, metal oxide particles are preferable. Since metal oxide particles have high transparency and light transmittance, a photosensitive resin composition having high refractive index and excellent transparency can be easily obtained.

In addition, the metal of the metal oxide particle in the present invention includes a semi-metal such as B, Si, Ge, As, Sb and Te.

Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, and Ba are used as the metal oxide particles having high light transmittance and high refractive index. Oxide particles containing atoms such as Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi and Te are preferable, and titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / / Tin oxide is more preferable, and titanium oxide, titanium composite oxide and zirconium oxide are more preferable, and titanium oxide and zirconium oxide are particularly preferable, and titanium oxide is most preferable. As the titanium oxide, a rutile type having a particularly high refractive index is preferable. These metal oxide particles may be treated with an organic material to impart dispersion stability.

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

Component A may be used alone, or two or more kinds may be used in combination.

The content of the component A in the photosensitive resin composition of the present invention may be appropriately determined in consideration of the refractive index, light transmittance and the like required for the optical member obtained by the photosensitive resin composition, but it is preferably 5 to 80 mass parts relative to the total solid content of the photosensitive resin composition %, More preferably from 10 to 70% by mass. The solid content of the photosensitive resin composition refers to an amount excluding volatile components such as a solvent.

In the present invention, the inorganic particles may be provided for use as a dispersion prepared by mixing and dispersing in a dispersing agent and a solvent described later (component E) using a mixing device such as a ball mill or a rod mill.

Examples of the solvent used for preparing the dispersion include solvents such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2- Alcohols such as 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol and cyclohexanol have.

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

(Component B) Solvent

The photosensitive resin composition of the present invention contains (Component B) a solvent.

The component B includes a non-alcohol solvent (hereinafter, also referred to as a "specific solvent") having a boiling point of 177 ° C. or more and 227 ° C. or less and an I / O value of 0.50 or more and 1.00 or less. The photosensitive resin composition of the present invention is particularly excellent in dryability and inkjet discharge property by containing the above specific solvent.

The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential component of the present invention and any of the components described below are dissolved or dispersed in the (Component B) solvent.

The boiling point in the present invention is a boiling point at a standard boiling point, that is, at one atmosphere pressure (101, 325 Pa).

The specific solvent has a boiling point of 177 DEG C or higher and 227 DEG C or lower, preferably 178 DEG C or higher and 225 DEG C or lower, and more preferably 178 DEG C or higher and 220 DEG C or lower. Within this range, inkjet dischargeability, dryness, developability, and transparency after heat treatment are excellent.

If the boiling point of the specific solvent is less than 177 캜, the ink-jet dischargeability deteriorates. On the other hand, when the boiling point exceeds 227 ° C, dryness and developability are deteriorated.

The I / O value is a value that treats the polarity of various organic compounds, also referred to as an inorganic value / organic value, as an organic concept, and is one of the functional group contributing methods for setting parameters in each functional group.

The I / O value in the present invention is a value calculated based on the description of "New Edition Organic Conceptual Basics and Application" (Koda Yoshio, Satoshiro, Honma Yoshio, SANKYO PUBLISHING Co., Ltd. (2008)).

For example, the organic concept diagram can be preferably obtained by a calculation sheet (http://www.ecosci.jp/chem9/interaction.html).

For the I / O value, an organic concept diagram (SANKYO PUBLISHING Co., Ltd. (1984)), Yoshio Koda; KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, pp. 1-16 (1954); Area of Chemistry, Vol. 11, No. 10, pp. 719-725 (1957); FRAGRANCE JOURNAL LTD., No. 34, pp. 97-111 (1979); FRAGRANCE JOURNAL LTD., No. 50, pp. 79-82 (1981); And the like are also described in detail.

The concept of the I / O value is made by dividing the properties of the compound into an organic group that exhibits covalent bonding and an inorganic group that represents ionic bonding, and positions each organic compound on the direct axis coordinate axis .

The inorganic value is the numerical value of the influence of the various substituents or bonds of the organic compound on the boiling point based on the hydroxyl group. Specifically, when the distance between the boiling point curve of the straight chain alcohol and the boiling point curve of the straight chain paraffin is taken to be about 100 ° C., the influence of one hydroxyl group is defined as 100, and various substituents or various combinations The value obtained by quantifying the influence on the boiling point of the organic compound becomes the inorganic value of the substituent of the organic compound. For example, the inorganic value of the -COOH group is 150, and the inorganic value of the carbon-carbon double bond is 2. Therefore, the inorganic value of any kind of organic compound means the total sum of inorganic values such as various substituents and bonds possessed by the compound.

The organic value is determined based on the influence of the carbon atom representing the methylene group on the boiling point, with the methylene group in the molecule as a unit. That is, since the average value of the boiling point increase due to addition of one carbon in the vicinity of 5 to 10 carbon atoms of the straight chain saturated hydrocarbon compound is 20 ° C, the organic value of one carbon atom is set to 20 based on this, The value obtained by quantifying the influence on the boiling point of the compound or the bond is an organic value. For example, the organic value of the nitro group (-NO ₂ ) is 70.

As the I / O value becomes closer to 0, it indicates that the organic compound is nonpolar (hydrophobic and organic). The larger the value, the more the organic compound is of polarity (hydrophilic and inorganic).

The I / O value of the specific solvent is preferably 0.50 or more and 1.00 or less, more preferably 0.53 or more and 0.90 or less, still more preferably 0.53 or more and 0.85 or less, still more preferably 0.55 or more and 0.82 or less. Within the above range, developability, storage stability, and transparency after heat treatment are excellent.

If the I / O value of the specific solvent is less than 0.50, developability and storage stability deteriorate. On the other hand, if the I / O value exceeds 1.00, transparency after heat treatment deteriorates.

The specific solvent preferably has a surface tension (also referred to simply as &quot; surface tension &quot;) of 25 to 25 dyn / More preferably 23 to 31 dyn / cm &lt; 2 &gt;. Within the above range, the inkjet dischargeability and transparency after heat treatment are superior in the above range.

As a method of measuring the surface tension of the specific solvent at 25 캜, a known method can be used, but it is preferably measured by a wheel suspension method or a Wilhelmy method. For example, Kyowa Interface Science Co., LTD. A method of measuring using a manufactured automatic surface tension meter CBVP-Z, or a method of measuring using a SIGMA 702 manufactured by KSV Instruments Inc. can be preferably used.

The specific solvent is a non-alcohol solvent, that is, a solvent having no hydroxy group. If the specific solvent is an alcohol-based solvent, dryness, developability and storage stability are deteriorated.

As the specific solvent, at least one solvent selected from the group consisting of alkylene glycol monoalkyl ether acylate, dialkylene glycol monoalkyl ether acylate, dialkylene glycol dialkyl ether, and trialkylene glycol dialkyl ether More preferably at least one solvent selected from the group consisting of a dialkylene glycol dialkyl ether and a trialkylene glycol dialkyl ether, and more preferably a dialkylene glycol dialkyl ether . The above embodiment is superior in inkjet dischargeability, dryness, and transparency after heat treatment.

The above-mentioned specific solvents may be used alone or in combination of two or more.

Specific examples of the specific solvent include the following.

Ethylene glycol monobutyl ether acetate (BMGAC, boiling point 188 캜, surface tension 27.4 dyn / cm 2, I / O value 0.632)

Diethylene glycol monoethyl ether acetate (EDGAC, boiling point 217 캜, surface tension 30.9 dyn / cm 2, I / O value 0.818)

Dipropylene glycol monomethyl ether acetate (DPMA, boiling point 213 占 폚, surface tension 27.3 dyn / cm2, I / O value 0.556)

Propylene glycol monomethyl ether propionate (PGMEP, boiling point 178 캜, surface tension 27.2 dyn / cm 2, I / O value 0.571)

Diethylene glycol diethyl ether (EDE (DEDG), boiling point 189 캜, surface tension 25.1 dyn / cm 2, I / O value 0.636)

Triethyleneglycol dimethyl ether (MTM, boiling point 216 캜, surface tension 30.0 dyn / cm 2, I / O value 0.800)

Diethyleneglycol ethyl methyl ether (MEDG (EDM), boiling point 176 캜, surface tension 26.8 dyn / cm 2, I / O value 0.700)

Diethylene glycol isopropyl methyl ether (IPDM, boiling point 179 캜, surface tension 23.9 dyn / cm 2, I / O value 0.636)

(BDM, boiling point: 212 占 폚, surface tension: 24.1 dyn / cm2, I / O value: 0.583)

Among them, the specific solvent is preferably at least one selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, and triethylene glycol dimethyl ether It is preferable to include a solvent and at least one solvent selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol isopropyl methyl ether More preferably, diethylene glycol diethyl ether is particularly preferable. The above form is superior in inkjet dischargeability, dryness, and transparency after heat treatment.

The specific solvent is particularly preferably propylene glycol monomethyl ether propionate, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether.

As the solvent other than the above-mentioned specific solvent used in the photosensitive resin composition of the present invention, known solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl There may be mentioned 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, esters, ketones, amides, lactones, and the like. Specific examples of the solvent to be used in the photosensitive resin composition of the present invention include the solvent described in paragraphs 0174 to 0178 of Japanese Patent Application Laid-Open No. 2011-221494 and the solvent described in paragraphs 0167 to 0168 of Japanese Patent Application Laid- , The contents of which are incorporated herein by reference.

These solvents may optionally contain one or more solvents selected from the group consisting of benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, It is also possible to add a solvent such as octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate.

These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably a single solvent or a combination of two solvents.

Of these solvents, non-alcohol solvents are preferable as solvents other than the above-mentioned specific solvents, propylene glycol monoalkyl ether acetates are more preferable, and propylene glycol monomethyl ether acetate is particularly preferable. In the above-described embodiment, the ink jet discharging property is superior.

Also, it shows a boiling point, a surface tension, and / or an I / O value with respect to specific examples of the solvent other than the above-mentioned specific solvent which may be used as another solvent.

Propylene glycol diacetate (PGDA, boiling point 190 占 폚, surface tension 31.2 dyn / cm2, I / O value 1.200)

1,3-butylene glycol diacetate (1,3-BGDA, boiling point 232 ° C, surface tension 31.4 dyn / cm 2, I / O value 0.750)

1,4-butanediol diacetate (1,4-BDDA, boiling point 232 占 폚, surface tension 34.2 dyn / cm2, I / O value 0.750)

1,6-hexanediol diacetate (1,6-HDDA, boiling point 260 占 폚, surface tension 34.1 dyn / cm2, I / O value 0.600)

Cyclohexanol acetate (CHXA, boiling point 173 DEG C, surface tension 30.5 dyn / cm &lt; 2 &gt;, I / O value 0.438)

Propylene glycol monomethyl ether acetate (PGMEA, boiling point 146 캜, surface tension 26.7 dyn / cm 2, I / O value 0.667)

Ethoxy-2-propyl acetate (boiling point 160 캜, I / O value 0.571)

Diethylene glycol monobutyl ether acetate (BDGAC, boiling point 247 캜, surface tension 29.7 dyn / cm 2, I / O value 0.692)

Dipropylene glycol mono n-propyl ether acetate (DPNPA, boiling point 232 ° C, I / O value 0.455)

Dipropylene glycol mono n-butyl ether acetate (DPNBA, boiling point 251 캜, I / O value 0.417)

Butylene glycol methyl monomethyl ether acetate (MBA, boiling point 171 캜, surface tension 27.9 dyn / cm 2, I / O value 0.571)

Ethyl 3-ethoxypropionate (EEP, boiling point 170 캜, I / O value 0.571)

Diethylene glycol dimethyl ether (MDM, boiling point: 162 占 폚, surface tension: 28.1 dyn / cm2, I / O value: 0.778)

Diethylene glycol dibutyl ether (BDB, boiling point: 256 占 폚, surface tension: 24.9 dyn / cm2, I / O value: 0.467)

Tetraethyleneglycol dimethyl ether (MTEM, boiling point: 275 占 폚, surface tension: 31.8 dyn / cm2, I / O value: 0.813)

Tripropylene glycol dimethyl ether (MDPOM, boiling point 171 캜, surface tension 24.7 dyn / cm 2, I / O value 0.375)

Dipropylene glycol methyl-n-propyl ether (DPMNP, boiling point 203 캜, surface tension 25.2 dyn / cm 2, I / O value 0.300)

Propane (MTPOM, boiling point 215 占 폚, surface tension 26.4 dyn / cm2, I / O value 0.364) and 1,2-bis (2-methoxymethylethoxy)

Triethyleneglycol butyl methyl ether (BTM, boiling point 261 캜, surface tension 27.5 dyn / cm 2, I / O value 0.645)

Polyethylene glycol dimethyl ether (MPM, boiling point: 264 ° C to 294 ° C, surface tension: 33.4 dyn / cm 2)

Ethylene glycol dimethyl ether (MMM, boiling point 85 캜, surface tension 22.6 dyn / cm 2)

Triacetin (DRA-150, boiling point 260 占 폚, surface tension 35.2 dyn / cm2, I / O value 1.000)

Cyclohexanone (boiling point 156 캜, I / O value 0.625)

Methyl amyl ketone (2-heptanone, MAK, boiling point 151 ° C, I / O value 0.464)

Tetrahydrofurfuryl alcohol (THFA, boiling point 176 ° C, I / O value 1.300)

Dipropylene glycol monomethyl ether (DPM, boiling point 188 캜, surface tension 27.9 dyn / cm 2, I / O value 1.000)

Diethylene glycol monomethyl ether (DM, boiling point 194 占 폚, surface tension 34.3 dyn / cm2, I / O value 1.375)

Diethylene glycol monobutyl ether (DB, boiling point 230 캜, surface tension 29.1 dyn / cm 2, I / O value 1.000)

Ethylene glycol monophenyl ether (2-phenoxyethanol, EPH, boiling point of 245 캜, surface tension of 41.9 dyn / cm 2, I / O value of 0.844)

Triethyleneglycol monomethyl ether (TM, boiling point 249 캜, surface tension 36.4 dyn / cm 2, I / O value 1.217)

Polyethylene glycol monomethyl ether (PM, boiling point 290 캜 to 310 캜, surface tension 37.3 dyn / cm 2)

3-methoxybutanol (MB, boiling point 161 캜, surface tension 28.9 dyn / cm 2, I / O value 1.200)

1,3-butylene glycol (1,3-BG, boiling point 208 占 폚, surface tension 36.1 dyn / cm2, I / O value 2.500)

Propylene glycol mono n-propyl ether (PNP, boiling point: 150 캜, surface tension: 25.9 dyn / cm 2, I / O value: 1.000)

Propylene glycol mono n-butyl ether (PNB, boiling point: 170 캜, surface tension: 26.3 dyn / cm 2, I / O value: 0.875)

Diethylene glycol monoethyl ether (EDG, boiling point 202 占 폚, surface tension 31.3 dyn / cm2, I / O value 1.200)

Dipropylene glycol mono n-propyl ether (DPNP, boiling point 212 占 폚, surface tension 27.6 dyn / cm2, I / O value 0.778)

Dipropylene glycol mono n-butyl ether (DPNB, boiling point 229 캜, surface tension 28.8 dyn / cm 2, I / O value 0.700)

Tripropylene glycol monomethyl ether (TPM, boiling point: 242 캜, surface tension: 30.0 dyn / cm 2, I / O value: 0.800)

Tripropylene glycol mono n-butyl ether (TPNB, boiling point: 274 캜, surface tension: 29.7 dyn / cm 2, I / O value: 0.615)

Propylene glycol monomethyl ether (MMPG (PGME), boiling point 121 캜, surface tension 27.7 dyn / cm 2)

The content of the specific solvent is not particularly limited, but is preferably 1 to 100% by mass, more preferably 5 to 95% by mass, further preferably 5 to 90% by mass, based on the total mass of the solvent in the photosensitive resin composition Do. Within this range, the inkjet discharge property and drying property are better.

The content of the (component B) solvent in the photosensitive resin composition of the present invention is preferably 10 to 95% by mass, more preferably 50 to 95% by mass, more preferably 60 to 90% by mass with respect to the total mass of the photosensitive resin composition It is more desirable to be negative.

(Component C) A polymer comprising a constituent unit having an acid group protected with an acid-decomposable group

The photosensitive resin composition of the present invention (component C) contains a polymer containing a constituent unit having a group whose acid group is protected with an acid-decomposable group.

In the present invention, the term "(a1) a structural unit having a group protected with an acid-decomposable group" is also referred to as "(a1) a structural unit having a group protected with an acid-decomposable group"

The photosensitive resin composition of the present invention may further comprise a polymer other than the polymer containing a constituent unit having an acid group-protected group by an acid-decomposable group.

The photosensitive resin composition of the present invention preferably contains a polymer component comprising a polymer satisfying at least one of the following (1) and (2).

(1) a polymer having (a1) a structural unit having a group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group

(2) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group

The photosensitive resin composition of the present invention may further contain other polymers. Component C in the present invention is meant to include other polymers added as necessary in addition to the above-mentioned (1) and / or (2), unless otherwise specified. Further, component E and component F to be described later are excluded.

From the viewpoints of transparency (haze) after curing and a residual film ratio of unexposed portions, the photosensitive resin composition of the present invention preferably contains a component satisfying the above-mentioned (1) as Component C.

On the other hand, from the viewpoint of freedom of molecular design, the photosensitive resin composition of the present invention preferably contains a component satisfying the above-mentioned (2) as Component C.

(A1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and / or (a2) a polymer having a structural unit having a crosslinkable group, .

In addition, even in the case of containing a component satisfying the above-mentioned (2) (a1) the case where the acid group contains at least a constituent unit having a group protected with an acid-decomposable group and (a2) a polymer having a constituent unit having a crosslinkable group (1) in the present invention.

Component C is preferably an addition polymerizable resin, more preferably a polymer comprising a constituent unit derived from (meth) acrylic acid and / or an ester thereof. Further, it may contain a structural unit other than the structural unit derived from (meth) acrylic acid and / or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound.

Further, 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".

&Lt; Structural unit (a1) &gt;

Component C comprises (a1) a polymer having at least a constituent unit having an acid group protected by an acid-decomposable group. The component C contains a polymer having the constituent unit (a1), whereby a highly sensitive photosensitive resin composition can be obtained.

In the present invention, the "group protected with an acid-decomposable group" can be any group known as an acid group and an acid decomposable group, and is not particularly limited. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. The acid decomposable group is preferably a group which is relatively decomposable by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) (For example, a tertiary alkyl ester group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used.

(a1) The constituent unit in which the acid group has a group protected by an acid-decomposable group is a constituent unit in which the carboxyl group is protected by an acid-decomposable group (also referred to as a &quot; constituent unit having a protected carboxyl group protected with an acid-decomposable group &quot;) or a phenolic hydroxyl group Is preferably a structural unit having a protective phenolic hydroxyl group protected by an acid-decomposable group (also referred to as a &quot; structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group &quot;).

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 order.

<< (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 structural unit having a carboxyl group of a structural unit having a carboxyl group and having a protected carboxyl group protected by an acid-decomposable group described in detail below.

The structural unit having a carboxyl group which can be used for the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is not particularly limited and a known structural unit can be used. (A1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid, (A1-1-2) having both an ethylenic unsaturated group and a structure derived from an acid anhydride.

(A1-1-1) a constituent unit derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule and (a1-1-2) a constituent unit derived from an ethylenic unsaturated group and an acid And structural units having a structure derived from an anhydride will be described in order.

<<< (a1-1-1) Constituent derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule >>>

As the constituent unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule, the same as exemplified below is used as the unsaturated carboxylic acid used in the present invention. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethyl Hexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid used for obtaining the structural unit having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester of a polycarboxylic acid, for example, mono (2-acryloyloxyethyl) succinate, mono Acryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have. Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule from the viewpoint of developability, acrylic acid, methacrylic acid, 2- (meth) acryloyl (Meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, or an anhydride of an unsaturated polycarboxylic acid, and the like, and acrylic acid, methacrylic acid It is more preferable to use an acid such as 2- (meth) acryloyloxyethylhexahydrophthalic acid.

The structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone, or two or more kinds.

<<< (a1-1-2) Constituent units having a structure derived from an ethylenic unsaturated group and an acid anhydride together >>>

The structural unit (a1-1-2) having both the ethylenic unsaturated group and the structure derived from the acid anhydride is preferably a unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride in the structural unit having an ethylenic unsaturated group .

As the acid anhydrides, known ones can be used, and specific examples include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and anhydrous chlorendic acid; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride are 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 which can be used for the structural unit (a1-1)

As the acid decomposable group that can be used in the structural unit (a1-1) having a protected carboxyl group protected with the acid decomposable group, the acid decomposable group may be used.

Among these acid decomposable groups, the carboxyl group is preferably a protected carboxyl group protected with an acetal type from the viewpoints of the basic physical properties of the photosensitive resin composition, particularly from the viewpoints of sensitivity and pattern shape, contact hole formation, and storage stability of the photosensitive resin composition. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the carboxyl group is a protected carboxyl group protected by an acetal form represented by the following general formula (a1-10). When the carboxyl group is an acetal-protected protected carboxyl group represented by the following formula (a1-10), the protected carboxyl group as a whole has a structure of - (C═O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) have.

(In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom, an alkyl group or an aryl group, provided that R ¹⁰¹ and R ¹⁰² together form a hydrogen atom, R ¹⁰³ represents an alkyl group or an aryl group R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether)

In the formula (a1-10), the alkyl group in R ¹⁰¹ ~ R ¹⁰³ may be any one of straight chain, branched chain, cyclic it. Here, R ¹⁰¹ and R ¹⁰² both are not what indicates a hydrogen atom, at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

When R ¹⁰¹ , R ¹⁰² and R ^{103 in} the formula (a1-10) represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

The straight-chain or branched-chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec- (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 even 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 R ¹⁰¹ , R ¹⁰² and R ¹⁰³ have a halogen atom as a substituent, they are a haloalkyl group, and when they have an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are aralkyl groups.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Specific examples thereof include a phenyl group, an? -Methylphenyl group, and a naphthyl group. Examples of the alkyl group substituted as an aryl group, that is, an aralkyl group include benzyl group,? -Methylbenzyl group, phenethyl group and naphthylmethyl group .

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.

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. When the alkyl group is a straight chain or branched chain alkyl group, the cycloalkyl group may have 3 to 12 Or may have two or three cycloalkyl groups.

These substituents may be further substituted by the above substituents.

When R ¹⁰¹ , R ¹⁰² and R ¹⁰³ in the formula (a1-10) 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 as the substituent, an alkyl group having 1 to 6 carbon atoms may be preferably exemplified. Examples of the aryl group include phenyl, tolyl, xylyl, cumenyl, 1-naphthyl and the like.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other and taken together with the carbon atom to which they are bonded to form a ring. Examples of the ring structure in the case where 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, A t-butyl group, and a tetrahydropyranyl group.

In the formula (a1-10), it is preferable that either R ¹⁰¹ or R ¹⁰² is a hydrogen atom or a methyl group.

As the radical polymerizable monomer used for forming the constituent unit having a protective carboxyl group represented by the above formula (a1-10), a commercially available one may be used, or a compound synthesized by a known method may be used. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of JP-A-2011-221494.

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

(Wherein 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, R ³ is an alkyl group or an aryl group, and R ¹ Or R ² and R ³ may be connected 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 an alkyl group, the alkyl group preferably has 1 to 10 carbon atoms. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 alkyl groups.

X represents a single bond or an arylene group, with a single bond being preferred.

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

(Wherein 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 carbonyl group, and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms )

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 hydrogen atoms.

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

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

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

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

Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolak-based resin. Of these structural units, hydroxystyrene or? -Methylhydroxystyrene has a structural unit derived from hydroxystyrene or? . The structural unit represented by the following formula (a1-20) as a structural unit having a phenolic hydroxyl group is also preferable from the viewpoint of sensitivity.

(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, R ²²² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms , a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is not more than 5. When two or more R ²²² are present, these R ²²² may be the same or different )

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

R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R ²²¹ is exemplified by an alkylene group, preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of the case where R ²²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, a pentylene group, an isopentylene group, And the like. Among them, it is preferable that R ²²¹ is a single bond, a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, or a 2-hydroxy-1,3-propylene 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. Although a represents an integer of 1 to 5, a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of the effects of the present invention and ease of production.

The bonding position of the hydroxyl group in the benzene ring is preferably bonded at the 4-position when the carbon atom bonded to R ²²¹ is the reference (1-position).

R ²²² each independently represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, chlorine atom, bromine atom, methyl group or ethyl group is preferable from the viewpoint of easy production.

And b represents 0 or an integer of 1 to 4.

- acid decomposable group which can be used for the structural unit (a1-2)

The acid decomposable group which can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group is preferably an acid decomposable group which can be used for the structural unit (a1-1) having a protected carboxyl group protected with the acid- As with the acid-decomposable group, known ones can be used, and they are not particularly limited. Among the acid decomposable groups, structural units having a protective phenolic hydroxyl group protected by an acetal are preferred from the viewpoints of basic physical properties of the photosensitive resin composition, particularly from the viewpoints of sensitivity and pattern shape, storage stability of the photosensitive resin composition, and formability of contact holes. Among the acid decomposable groups, from the viewpoint of sensitivity, the phenolic hydroxyl group is more preferably a protective phenolic hydroxyl group protected by an acetal type represented by the above formula (a1-10). When the phenolic hydroxyl group is an acetal-protected protected phenolic hydroxyl group represented by the formula (a1-10), the structure of -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) as a whole of the protected phenolic hydroxyl group . Ar represents an arylene group.

Preferred examples of acetal ester structure of the phenolic hydroxyl group is R ¹⁰¹ = a hydrogen atom, R ¹⁰² = R ¹⁰³ = a methyl group or a combination of R ¹⁰¹ = a hydrogen atom, R ¹⁰² = a methyl group, and R ¹⁰³ = a combination of a benzyl group, R ¹⁰¹ = hydrogen Atom, R ¹⁰² = methyl group, and R ¹⁰³ = a combination of ethyl groups.

Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected with an acetal type include those described in paragraph 0042 of JP-A No. 2011-215590 .

Of these, a 1-alkoxyalkyl protected derivative of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protected derivative of 4-hydroxyphenyl methacrylate are preferred from the viewpoint of transparency.

Specific examples of the acetal protecting group of the phenolic hydroxyl group include 1-alkoxyalkyl groups, and examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, 1-cyclohexyloxy) ethyl group, 1- (2-cyclohexyloxy) ethyl group, 1-naphthyloxy group, Oxyethyl group, etc. These may be used singly or in combination of two or more.

The radical polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group may be commercially available or synthesized by a known method. For example, a compound having a phenolic hydroxyl group can be synthesized by reacting with a vinyl ether in the presence of an acid catalyst. The above-mentioned synthesis may be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with other monomers and then reacting with a 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 by 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 form of the structural unit (a1)

When the polymer having the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is preferably 20 to 100 mol%, more preferably 30 to 90 mol% Mol% is more preferable.

When the polymer having the structural unit (a1) has the following structural unit (a2), the structural unit (a1) has a structural unit (a1) and a structural unit (a2) Mol%, and more preferably 10 to 60 mol%. In particular, when the structural unit (a1) is a structural unit having a carboxyl group protected with an acetal form, the structural unit is preferably 20 to 50 mol%.

In the present invention, when the content of the &quot; constituent unit &quot; is defined as a molar ratio, the above-mentioned &quot; constituent unit &quot; In the present invention, the &quot; monomer unit &quot; 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 the acid-decomposable group is characterized in that the phenomenon is faster than that of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid decomposable group. Therefore, when a rapid development is desired, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

&Lt; (a2) Structural unit having a crosslinkable group &gt;

Component C contains a polymer having a structural unit (a2) having a crosslinkable group. The crosslinking group is not particularly limited as long as it is a group causing a curing reaction in the heat treatment. Examples of the preferred constituent unit having a crosslinkable group include a group consisting of an epoxy group, an oxetanyl group, a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and an ethylenic unsaturated group , And a group consisting of an epoxy group, an oxetanyl group, and a group represented by -NH-CH ₂ -OR (wherein R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) At least one kind selected from the group consisting of Among them, the photosensitive resin composition of the present invention preferably contains a constituent unit in which the component C contains at least one of an epoxy group and an oxetanyl group. More specifically, the following can be mentioned.

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

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

The structural unit (a2-1) having an epoxy group and / or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may contain at least one epoxy group and at least one oxetanyl group, Or more oxetanyl group, and it is not particularly limited, but it is preferable to have 1 to 3 epoxy groups and / or oxetanyl groups in total, and one or two epoxy groups and / or oxetanyl groups in total , More preferably one having an epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicyclohexylmethyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, -Epoxy cyclohexylmethyl,? -Ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Compounds containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of the publication No. 4168443, and the like, and the contents thereof are included in the specification of the present invention.

Specific examples of the radical polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylate esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953 , The contents of which are incorporated herein by reference.

Specific examples of the radically polymerizable monomer used to form the structural unit (a2-1) having an epoxy group and / or an oxetanyl group include monomers containing a methacrylic acid ester structure and monomers containing an acrylic ester structure desirable.

Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl. These constituent units may be used singly or in combination of two or more.

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

<< (a2-2) Structural unit having an ethylenic unsaturated group >>

(A2-2) having an ethylenic unsaturated group as one of the structural unit (a2) having a crosslinkable group (hereinafter also referred to as &quot; structural unit (a2-2) &quot;). As the structural unit (a2-2) having an ethylenically unsaturated group, a structural unit having an ethylenic unsaturated group in its side chain is preferable, and a structural unit having an ethylenic unsaturated group at its terminal and a side chain of 3 to 16 carbon atoms is more preferable.

Others (a2-2) With respect to the constituent unit having an ethylenic unsaturated group, reference is made to paragraphs 0072 to 0090 of Japanese Patent Laid-Open Publication No. 2011-215580 and paragraphs 0013 to 0031 of Japanese Patent Application Publication No. 2008-256974 , The contents of which are incorporated herein by reference.

<< Constituent unit having a group represented by the formula (a2-3) -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>

The copolymer used in the present invention is also preferably a structural unit (a2-3) having a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-3), the curing reaction can be caused by a gentle heat treatment, and a cured film excellent in all properties 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 any of linear, branched or cyclic alkyl groups, 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).

(In the 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, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, 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. Among them, an i-butyl group, an n-butyl group and a methyl group are preferable.

- Preferred embodiments of the constituent unit (a2)

When the polymer having the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is preferably from 5 to 90 mol%, more preferably from 20 to 80 mol% Mol% is more preferable.

When the polymer having the constituent unit (a2) has the above-mentioned constituent unit (a1), the content of the constituent unit (a2) in the polymer having the constituent unit (a1) and the constituent unit (a2) To 70 mol%, and more preferably 10 to 60 mol%.

In the present invention, regardless of the embodiment, the content of the structural unit (a2) in the total structural units of the component C is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.

Within this numerical range, the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition are improved.

<(A3) Other constituent units>

In the present invention, the component C may have other structural units (a3) in addition to the structural units (a1) and / or (a2). These constituent units may contain the polymer components (1) and / or (2). In addition, apart from the polymer component (1) or (2), a polymer component having substantially no structural unit (a1) and / or structural unit (a2) and having another structural unit (a3) may be contained. (A1) and the constituent unit (a2) other than the polymer component (1) or (2), the amount of the polymer component contained in the polymer component It is preferably 60 mass% or less, more preferably 40 mass% or less, and even more preferably 20 mass% or less in the polymer component. The lower limit value of the blending amount is 0 mass%.

The monomer constituting the other structural unit (a3) is not particularly limited and includes, for example, styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid di An unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, and other unsaturated compounds. It may have a structural unit having an acid group as described later. Monomers to be the other constituent unit (a3) may be used alone or in combination of two or more.

Specific examples of the other structural unit (a3) include styrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4- (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile and ethylene glycol monoacetoacetate mono . In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Application Laid-Open No. 2004-264623 can be mentioned.

As the other structural unit (a3), a structural unit derived from a styrene or a monomer having an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, hydroxystyrene,? -Methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl .

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 thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and n-butyl (meth) acrylate. More preferred is methyl (meth) acrylate. The content of the structural unit (a3) among the constituent units constituting the polymer is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less. The lower limit value may be 0 mol%, but is preferably 1 mol% or more, for example, and is more preferably 5 mol% or more. Within this numerical range, all the characteristics of the cured film obtained from the photosensitive resin composition are improved.

The polymer contained in the component C preferably has a structural unit having an acid group as the other structural unit (a3). When the polymer has an acid group, the polymer easily dissolves in an alkaline developer, and the effect of the present invention is 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 contained in the polymer as a constituent unit containing an acid group, using a monomer capable of forming an acid group. By incorporating such a structural unit containing an acid group in the polymer, it tends to be easily soluble in an alkaline developer.

Examples of the acid group include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and an acid anhydride group of these acid groups, And the like, and a carboxylic acid group and / or a phenolic hydroxyl group are preferable. The salt is not particularly limited, but an alkali metal salt, an alkaline earth metal salt, and an organic ammonium salt can be preferably exemplified.

The structural unit having an acid group used in the present invention is a structural unit derived from a styrene compound having an acid group, a structural unit derived from a vinyl compound having an acid group, a structural unit derived from a (meth) acrylic acid and / More preferably a structural unit derived from a (meth) acrylic acid ester. For example, compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP-A-2012-88459 can be used, the contents of which are incorporated herein by reference. Among them, a constituent unit derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid and maleic anhydride is preferable.

In the present invention, in addition to the polymer component (1) or (2), a polymer having substantially no other constituent unit (a1) and / or another constituent unit (a2) and having another constituent unit (a3) may be contained.

As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Laid-open No. 59-53836, Japanese Patent Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as described in each publication of JP-A-59-71048, , Acidic cellulose derivatives having a carboxyl group, acid anhydrides added to a polymer having a hydroxyl group, and the like, and polymer polymers having a (meth) acryloyl group in the side chain are also preferable.

(Meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, and JP-A No. 7-140654 (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, Japanese Patent Application Laid-Open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224 Publicly known polymer compounds described in JP-A-2000-56118, JP-A-2003-233179, and JP-A-2009-52020 can be used, and the contents thereof are included in the specification of the present invention.

These polymers may be contained in one kind alone or in two or more kinds.

SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, (Manufactured by TOAGOSEI CO., LTD.), JONCRYL 690, JONCRYL 678, JONCRYL 67 and JONCRYL 586 (manufactured by BASF Co., Ltd.) or the like may be used.

In the present invention, it is particularly preferable to contain a constituent unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group from the viewpoint of sensitivity. For example, compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP-A-2012-88459 can be used, and the contents thereof are included in the specification.

The constituent unit having an acid group is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 40 mol%, and particularly preferably from 5 to 30 mol%, of the constituent units of the whole polymer component , And most preferably 5 to 20 mol%.

Hereinafter, preferred embodiments of the polymer component in the present invention are described, but the present invention is not limited thereto.

- First Embodiment -

An embodiment wherein the polymer component (1) further comprises one or more other structural units (a3).

- Second Embodiment -

An embodiment wherein (a1) the polymer having a structural unit having a group protected with an acid-decomposable group further comprises one or more other structural units (a3) of the polymer component (2).

- Third Embodiment -

An embodiment wherein the polymer (a2) having a structural unit having a crosslinkable group in the polymer component (2) further comprises one or more other structural units (a3).

- Fourth Embodiment -

An embodiment wherein any one of the structural units (a3) in any one of the first to third embodiments has at least an acid group-containing structural unit in any one of the polymers.

- Fifth Embodiment -

An embodiment having a polymer having substantially no structural unit (a1) and structural unit (a2) and having another structural unit (a3) apart from the polymer component (1) or (2).

- Sixth Embodiment -

And a combination of two or more of the first to fifth embodiments.

The molecular weight of the polymer in component C -

The molecular weight of the polymer in Component C is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene reduced weight average molecular weight. All the properties are satisfactory in the above-mentioned numerical range. The ratio (dispersion degree, Mw / Mn) of the number average molecular weight Mn to the weight average molecular weight Mw is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

The measurement of the weight-average molecular weight and the number-average molecular weight in the present invention is preferably carried out by gel filtration chromatography. In the present invention, HLC-8020 GPC (manufactured by TOSOH CORPORATION) was used for the measurement by gel filtration chromatography, and TSKgel Super HZ MH, TSK gel Super HZ4000, TSKgel Super HZ200 (produced by TOSOH CORPORATION, 4.6 mm ID × 15 cm), and THF (tetrahydrofuran) is preferably used as an eluent.

- Method for preparing polymer in component C -

Various methods are also known for the synthesis of the polymer in Component C, but for example, at least a radical polymerizable monomer mixture containing a radical polymerizable monomer used for forming the structural unit (a1) is dissolved in an organic solvent Can be synthesized by polymerization using a curl polymerization initiator. It may also be synthesized by a so-called polymer reaction.

The content of the component C in the photosensitive resin composition of the present invention is preferably 20 to 99.9% by mass, more preferably 50 to 98% by mass, and more preferably 70 to 95% by mass based on the total solid content of the photosensitive resin composition More preferable. When the content is within this range, the patterning property upon development is improved, and a cured product having a higher refractive index is obtained. The solid content of the photosensitive resin composition refers to an amount excluding volatile components such as a solvent.

(Component D) Photoacid generator

The photosensitive resin composition of the present invention (component D) contains a photoacid generator. The photoacid generator used in the present invention is preferably a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, more preferably a wavelength of 300 to 450 nm, but is not limited to the chemical structure thereof. Also, for a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid in response to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer can be preferably used in combination with a sensitizer. As the photoacid generator used in the present invention, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, a photoacid generator that generates an acid with a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid with a pKa of 2 or less desirable. Further, a photoacid generator that generates an acid having a pKa of -15 or more is preferable.

Examples of photoacid generators include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds. Among them, it is preferable to use an oxime sulfonate compound from the viewpoints of insulation and sensitivity. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazine, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts and diazomethane derivatives include those described in paragraphs 0083 to 0088 of JP-A-2011-221494 Compounds can be exemplified.

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

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

The alkyl group in R &lt; ²¹ &gt; may be linear, branched or cyclic. The permissible 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 &lt; ²¹ &gt; is preferably an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a bridged alicyclic group such as a 7,7- A cycloalkyl 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.

It is also preferable that the compound containing an oxime sulfonate structure represented by the formula (D1) is an oxime sulfonate compound represented by the following formula (D2).

(Formula (D2) of, R ⁴² represents an alkyl group or an aryl group, X is an alkyl group, an alkoxy group or a halogen atom, m4 is an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X is The same or different)

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

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

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

m4 is preferably 0 or 1. In the formula (D2), and m4 are 1, and X is a methyl group, the substitution position of X is the ortho-position, R ⁴² is, C 1 -C 10 straight chain alkyl 7,7-dimethyl-2-oxo-norbornyl Methyl group, or p-toluyl group is particularly preferable.

It is also preferable that the compound containing an oxime sulfonate structure represented by the above formula (D1) is an oxime sulfonate compound represented by the following formula (D3).

(Formula (D3) of, R ⁴³ is the formula (and R ⁴² and consent of the D2), X ¹ is a halogen atom, a hydroxyl group, a C 1 -C 4 alkyl group, a 1-4C alkoxy group, a cyano group or a nitro group Group, and n4 represents an integer of 0 to 5)

As R ⁴³ in the formula (D3), a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- N-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.

X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

As n4, an integer of 0 to 2 is preferable, and 0 or 1 is particularly preferable.

As specific examples of the compound represented by the formula (D3) and specific examples of the preferable oxime sulfonate compound, reference may be made to paragraphs 0080 to 0082 of Japanese Patent Application Laid-Open No. 163937/1987, the contents of which are incorporated herein by reference do.

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

In the formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group . R ¹⁰² represents an alkyl group or an aryl group.

¹⁰¹ X is ^{-O-, -S-, -NH-, -NR 105} -, -CH 2 -, -CR 106 H-, or -CR ¹⁰⁵ R ¹⁰⁷ - represents a, R ¹⁰⁵ ~ R ¹⁰⁷ is an alkyl group, or Lt; / RTI &gt;

R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

As R ¹²¹ to R ^124, each independently preferably a hydrogen atom, a halogen atom, or an alkyl group, and an embodiment in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Among them, embodiments in which all of R ¹²¹ to R ¹²⁴ are hydrogen atoms are preferable from the viewpoint of sensitivity.

All of the functional groups described may have further substituents.

The compound represented by the above formula (OS-1) is preferably, for example, a compound represented by the general formula (OS-2) described in paragraphs 0087 to 0089 of Japanese Patent Application Laid- The contents of which are incorporated herein by reference.

Specific examples of the compound represented by the above formula (OS-1) that can be preferably used in the present invention include compounds (exemplified compounds b-1 to b-34) described in paragraphs 0128 to 0132 of JP-A No. 2011-221494 But the present invention is not limited to this.

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

(In the formulas (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ each independently R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and X ¹ to R ³⁰ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, X ³ each independently represents an oxygen atom or a sulfur atom, n ¹ to n ³ each independently represents 1 or 2, and m ¹ to m ³ each independently represent an integer of 0 to 6)

The compounds containing an oxime sulfonate structure represented by the above formula (D1) can be prepared, for example, by reacting a compound represented by the general formula (OS-6) to (OS-6) described in paragraph 0117 of Japanese Patent Application Laid- 11), and the contents thereof are included in the specification of the present invention.

A preferable range in the above general formulas (OS-6) to (OS-11) is as shown in general formulas (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of Japanese Patent Laid- Which is the same as the preferable range.

Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP-A No. 2011-221494, But are not limited thereto.

It is also preferable that the compound containing an oxime sulfonate structure represented by the formula (D1) is an oxime sulfonate compound represented by the following formula (D1-4).

Wherein R ^d1 represents an alkyl group or an aryl group, R ^d2 represents an alkyl group, an aryl group or a heteroaryl group, R ^d3 to R ^d6 each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom , R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6 may combine to form an alicyclic or aromatic ring, and X ^d represents -O- or -S-)

R ^d1 represents an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having a branched structure or an alkyl group having a cyclic structure.

The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, Hexyl group, 2-ethylhexyl group, cyclohexyl group, and octyl group, and is preferably isopropyl group, tert-butyl group, neopentyl group or cyclohexyl group.

The carbon number of the aryl group is preferably 6 to 12, more preferably 6 to 8, and still more preferably 6 or 7. Examples of the aryl group include a phenyl group and a naphthyl group, preferably a phenyl group.

The alkyl group and aryl group represented by R ^d1 may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a straight chain, branched or cyclic alkyl group (for example, a methyl group, an ethyl group or a propyl group), an alkenyl group, an alkynyl group, An alkyl group, an aryl group, an aryl group, a heterocyclic oxy group, an acyloxy group, an amino group, a nitro group, a hydrazino group, an acyl group, an acyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, a carboxyl group, Group, a heterocyclic group, and the like. Further, they may be further substituted by these groups. Preferably a halogen atom or a methyl group.

From the viewpoint of transparency, R ^d1 is preferably an alkyl group, and from the viewpoint of achieving both storage stability and sensitivity, R ^d1 is an alkyl group having a branched structure of 3 to 6 carbon atoms, a cyclic structure having 5 to 7 carbon atoms An alkyl group or a phenyl group is preferable and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. By employing such a bulky group (particularly, a bulky alkyl group) as R ^d1 , it becomes possible to further improve the transparency.

Of the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ^d2 represents an alkyl group, an aryl group or a heteroaryl group. The alkyl group represented by R ^d2 is preferably a straight chain, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, neopentyl, to be.

The aryl group is preferably an aryl group having 6 to 10 carbon atoms. As the aryl group, there can be mentioned a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group) and the like, preferably a phenyl group and a p-toluyl group.

Examples of the heteroaryl group include a pyrrolyl group, an indolyl group, a carbazolyl group, a furanyl group, and a thienyl group.

The alkyl group, aryl group and heteroaryl group represented by R ^d2 may have a substituent. As the substituent, the alkyl group represented by R ^d1 and the substituent which the aryl group may have are the same.

R ^d2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. The substituent of the phenyl group is preferably a methyl group.

R ^d3 to R ^d6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). The alkyl group represented by R ^d3 to R ^d6 is the same as the alkyl group represented by R ^d2 , and the preferable range is also the same. The aryl group represented by R ^d3 to R ^d6 is synonymous with the aryl group represented by R ^d1 , and the preferable range is also the same.

Among R ^d3 to R ^d6 , R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6 may be bonded to each other to form a ring. Preferably, the ring is an alicyclic or aromatic ring, desirable.

R ^d3 to R ^{d6 each independently} represent a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom), or R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6 , It is preferable that a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, or R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6 are combined to form a benzene ring desirable.

Preferred forms of R ^d3 to R ^d6 are as follows.

(Embodiment 1) At least two of them are hydrogen atoms.

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

(Embodiment 3) R ^d3 and R ^d4 , R ^d4 and R ^d5 , or R ^d5 and R ^d6 combine to form a benzene ring.

(Embodiment 4) An embodiment that satisfies Embodiments 1 and 2 and / or Embodiments 1 and 3 above.

X ^d represents -O- or -S-.

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

In the photosensitive resin composition of the present invention, the content of the photoacid generator (component D) is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 10 parts by mass, per 100 parts by mass of the component C in the photosensitive resin composition.

Component D may be used alone, or two or more kinds may be used in combination.

(Component E) Dispersant

The photosensitive resin composition of the present invention preferably contains (component E) a dispersing agent. The dispersibility of the component A in the resin composition can be further improved by containing a dispersant.

As the dispersing agent, a known dispersing agent can be used, and for example, a well-known pigment dispersing agent can be appropriately selected and used.

As the dispersing agent, a polymer dispersing agent 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 kinds of compounds can be used. Specific examples thereof include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid based (co) polymer POLYFLOW No. 75, .90, No. 95 (produced by KYOEISHA CHEMICAL Co., LTD.) And W001 (manufactured by Yusho Co Ltd); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol distearate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co Ltd); DISPERSE AID 6, DISPERSE AID 15, DISPERSE AID 15, DISPERSE AID 15, DISPERSE AID 15, EFKA Polymer 400, 9100 (all manufactured by SAN NOPCO LIMITED); Various SOLSPERSE dispersants (produced by AstraZeneca K.K.) such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by ADEKA CORPORATION) (Manufactured by Sanyo Chemical Industries, Ltd.), DISPER BYK 101,103,106,108,109,111,112,161,141,142,162,163,164,166,167,701,171,174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by BYK 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.

The dispersant may be used singly or in combination of two or more.

The content of the dispersant in the photosensitive resin composition of the present invention is preferably in the range of 5 to 70 mass%, more preferably in the range of 10 to 50 mass% with respect to the total solid content of the photosensitive resin composition.

(Component F) Heat crosslinking agent

The photosensitive resin composition of the present invention preferably contains a heat crosslinking agent if necessary. By adding a heat crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made into a stronger film.

The thermal crosslinking agent is not limited as long as it is crosslinked by heat (except for Component C). For example, a compound having two or more epoxy groups or oxetanyl groups in a molecule described below, a compound having an alkoxymethyl group, a compound having at least one ethylenically unsaturated double bond, or a block isocyanate compound may be added.

The addition amount of the heat crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition More preferable. When added in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of heat crosslinking agents may be used together. In that case, the total amount of the heat crosslinking agents is to be calculated.

&Lt; Compounds having two or more epoxy groups or oxetanyl groups in the molecule &

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

These are available as commercial products. For example, commercially available products such as JER152, JER157S70, JER157S65, JER806, JER828, and JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation), such as those disclosed in Japanese Patent Application Laid-Open Publication No. 2011-221494, paragraph 0189, and ADEKA RESIN EP- (Manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501 and EPPN- EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX- -321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-821, EX-821, DLC-204, DLC-205, DLC-206, DLC-201, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX- (Manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH- LTD.).

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

Among them, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin and an aliphatic epoxy resin are more preferable, and a bisphenol A type epoxy resin is particularly preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, ARON OXETANE OXT-121, OXT-221, OX-SQ and PNOX (manufactured by TOAGOSEI CO., LTD.) Can be used.

The oxetanyl group-containing compound is preferably used alone or in combination with a compound containing an epoxy group.

As other thermal crosslinking agents, the crosslinking agent containing an alkoxymethyl group and the compound having at least one ethylenically unsaturated double bond described in paragraphs 0107 to 0108 of JP-A-2012-8223 and the like can be preferably used. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

&Lt; Block isocyanate compound &gt;

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

In addition, the block isocyanate group in the present invention is a group capable of forming an isocyanate group by heat, and for example, a group in which an isocyanate group is protected by reacting a blocking agent with an isocyanate group can be preferably exemplified. The block isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C to 250 ° C.

The skeleton of the block isocyanate compound is not particularly limited and may be any of those having two isocyanate groups in one molecule. The skeleton may be an aliphatic, alicyclic or aromatic polyisocyanate, for example, 2,4-tolylene diisocyanate, 2 , 6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate , Diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p- Cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylenediisocyanate, 3-methylene diisocyanate, , 3'-methyleneditholylene-4,4'-diisocyanate, 4,4'-diphenylether diisocyanate, tetrachlorophenylenediisocyanate, norbornadiisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1 , And 4-xylylene diisocyanate, and compounds having a prepolymer type skeleton derived from these compounds can be preferably used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the parent structure of the block isocyanate compound in the photosensitive resin composition of the present invention include a burette type, an isocyanurate type, an adduct type, and a bifunctional prepolymer type.

As the block agent for forming the block structure of the block isocyanate compound, an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, . Of these, a block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable.

Examples of the oxime compounds include aldoxime and ketoxime. Specific examples of the oxime compounds include acetoxy, formaldehyde, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.

Examples of the lactam compound include ε-caprolactam, γ-butyrolactam, and the like.

Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.

Examples of the amine compound include primary amines and secondary amines, and examples thereof include aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine .

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole, and the like.

Examples of the mercaptan compound include alkyl mercaptans, aryl mercaptans, and the like.

Examples of the block isocyanate compound that can be used in the photosensitive resin composition of the present invention include commercially available products such as CORONATE AP Stable M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS- B-882N (manufactured by Mitsui Chemicals, Inc.), DURANATE (manufactured by Mitsui Chemicals, Inc.) MF-B60B, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (Above, Asahi Kasei (Manufactured by Sumika Bayer Urethane Co., Ltd.), Desmodur BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 May be preferably used.

<Other components>

The photosensitive resin composition of the present invention may contain, in addition to the above components, a sensitizer, (component H) alkoxysilane compound, (component I) basic compound, (component J) surfactant, (component K) antioxidant Can be preferably added. The photosensitive resin composition of the present invention may further contain known additives such as an ultraviolet absorber, a metal deactivator, an acid proliferator, a development promoter, a plasticizer, a heat radical generator, a thermal acid generator, a thickener and an organic or inorganic precipitation inhibitor Can be added. As the compound, for example, the description of paragraphs 0201 to 0224 of Japanese Patent Application Laid-Open No. 88459/1987 can be taken into consideration, and the contents of these compounds are included in the specification of the present invention.

(Component G) sensitizer

The photosensitive resin composition of the present invention preferably contains a sensitizer for accelerating the decomposition in combination with (Component D) a photoacid generator. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer brought into the electron-excited state comes into contact with the photoacid generator and generates an action such as electron movement, energy transfer, heat generation, and the like. As a result, the photoacid generator causes a chemical change to decompose to generate an acid. Examples of preferred sensitizers include compounds having an absorption wavelength in any one of the wavelength ranges from 350 nm to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- , Xanthones (e.g., xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), xanthone derivatives such as xanthan gum (e.g., fluorene, eosin, erythrosine, rhodamine B and rose bengal) (E.g., thiocarbocyanine, oxacarbocyanine), merocyanine (e.g., merocyanine, carbomerocyanine), rhodacyanines, oxonols, thiazines (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, 10-butyl-2-chloro-thiophene, (E.g., anthraquinone), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), styryls, (For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (for example, 7-diethylamino-4-methylcoumarin, Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-pne).

Of these sensitizers, polynuclear aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatic compounds are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The amount of the sensitizer added to the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass, more preferably 10 to 500 parts by mass, and still more preferably 50 to 200 parts by mass relative to 100 parts by mass of the photoacid generator of the photosensitive resin composition Is more preferable.

The sensitizers may be used singly or in combination of two or more.

(Component H) The alkoxysilane compound

The photosensitive resin composition of the present invention may contain (Component H) an alkoxysilane compound. When the alkoxysilane compound is used, the adhesion between the film formed by the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed by the photosensitive resin composition of the present invention can be adjusted. The alkoxysilane compound (Component H) that can be used in the photosensitive resin composition of the present invention is an alkoxysilane compound that can be used as an inorganic substance such as a silicon compound such as silicon, silicon oxide, or silicon nitride; a metal such as gold, copper, molybdenum, And a compound which improves the adhesion of the insulating film. Specifically, known silane coupling agents and the like are also effective.

Examples of the silane coupling agent include? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacrylate (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane, And vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is even more preferable, and 3-glycidoxypropyltrimethoxy Silane is particularly preferred. These may be used alone or in combination of two or more.

Further, a compound represented by the following formula can also be preferably employed.

(R ¹ ) _4-n- Si- (OR ² ) _n (H)

R ² represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; and n represents an integer of 1 to 3.) In the formula (H), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms and no reactive group;

Specific examples thereof include the following compounds. Ph represents a phenyl group.

The (ingredient H) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited to these and known ones can be used.

The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.

(Component I) The basic compound

The photosensitive resin composition of the present invention may contain (Component I) a basic compound.

(Component I) As the basic compound, any of those used as a chemically amplified resist may be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of Japanese Patent Laid-Open Publication No. 2011-221494.

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

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

Examples of the heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N- But are not limited to, dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, , 4-methylmorpholine, N-cyclohexyl-N '- [2- (4-morpholinyl) ethyl) piperidine, piperidine, piperidine, piperazine, morpholine, ] Thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-undecene.

Examples of quaternary ammonium hydroxides 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 them, heterocyclic amines are preferable, and N-cyclohexyl-N '- [2- (4-morpholinyl) ethyl] thiourea is particularly preferable.

The basic compounds usable in the present invention may be used singly or in combination of two or more kinds.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 1 part by mass based on 100 parts by mass of the total solid content in the photosensitive resin composition.

(Component J) Surfactant

The photosensitive resin composition of the present invention may contain (component J) a surfactant.

(Component J) As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants. As the surfactant used in the composition of the present invention, for example, those described in paragraphs 0201 to 0205 of Japanese Patent Application Laid-Open No. 88459/1986 and paragraphs 0185 to 0188 of Japanese Patent Application Laid-Open No. 2011-215580 can be used. Quot; is incorporated herein by reference.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 99C (manufactured by KYOEISHA CHEMICAL Co., LTD.), Eftop (manufactured by Mitsubishi Materials Electronic Chemicals Co., (Produced by DIC Corporation), FLUORAD Novec FC-4430 (manufactured by Sumitomo 3M Limited), SURFLONS-242 (manufactured by AGC SEIMI CHEMICAL CO., LTD.), PolyFox PF-6320 (manufactured by OMNOVA SOLUTIONS) -8400 (manufactured by Dow Corning Toray Silicone Co., Ltd.) and FTERGENT FTX-218G (manufactured by NEOS COMPANY LIMITED).

The weight ratio in terms of polystyrene measured by gel permeation chromatography when the surfactant contains the constituent unit A and the constituent unit B represented by the following formula (J-1) and tetrahydrofuran (THF) A preferred example is a copolymer having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

(In formula (J-1), R ⁴⁰¹ and R ⁴⁰³ each independently represents a hydrogen atom or a methyl group, R ⁴⁰² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴⁰⁴ represents a hydrogen atom or a And L represents a number of carbon atoms of not less than 3 but not more than 6 alkylene groups, p and q are mass percentages indicating polymerization ratios, and p is a value of not less than 10 mass% and not more than 80 mass% , Q represents a numerical value of 20 mass% or more and 90 mass% or less, R represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less)

It is preferable that L is a branched alkylene group represented by the following formula (J-2). R ⁴⁰⁵ in the formula (J-2) represents an alkyl group of 1 to 4 carbon atoms and is preferably an alkyl group of 1 to 3 carbon atoms from the viewpoint of compatibility and wettability to a surface to be coated, 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.

The photosensitive resin composition of the present invention preferably contains a phenyl ether surfactant as a surfactant, more preferably a polyoxyalkylene substituted phenyl ether surfactant. In the above embodiment, the occurrence of residue after development is suppressed. Particularly, the occurrence of a residue on the ITO substrate after remarkable development is suppressed.

The phenyl ether surfactant is preferably a compound represented by the following formula (J-3).

(Formula (J-3) of, R ^j is an alkylene group, nj is an integer of from 1 to 50, R ^{j 'denotes} a monovalent substituent, mj represents an integer of 1-5, the mj 2 , Plural R ^{j 's} may be the same or different, and when n j is 2 or more, plural R ^j present may be the same or different)

In the formula (J-3), R ^j represents an alkylene group. That is, (R ^j O) represents an alkyleneoxy group. R ^j is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, particularly preferably an ethylene group or a propylene group .

In the formula (J-3), R ^{j '} represents a monovalent substituent. As R ^{j '} , a halogen atom, an alkyl group, an aryl group, an alkenyl group, a hydroxy group, an alkoxy group and an aryloxy group are exemplified, and the substituent may be further substituted. The total carbon number of R ^{j '} is preferably 1 to 50, more preferably 1 to 20.

The compound represented by the formula (J-3) may be substituted with an aliphatic hydrocarbon group as R ^{j '} , such as polyoxyalkylene alkyl phenyl ether, but it is preferable that R ^{j '} is a monovalent group containing an aromatic hydrocarbon group.

The polyoxyalkylene substituted phenyl ether surfactant is preferably a compound represented by the following formula (J-4).

(Wherein ^(J-4), R ^j is an alkylene group, X ^j denotes a single bond, or a divalent connecting group, Q ^j denotes an alkyl group, xj denotes an integer of 0 ~ 5, mj is zero Nj represents an integer of 1 to 50, and when xj is 2 or more, plural Qs may be the same or different, and when mj is 2 or more, plural X ^j , benzene ring and Q ^The groups including ^j may be the same or different, and when nj is 2 or more, plural R ^j present may be the same or different)

In the formula (J-4), R ^j represents an alkylene group. That is, (R ^j O) represents an alkyleneoxy group. R ^j is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, particularly preferably an ethylene group or a propylene group . That is, it is particularly preferable to have a polyalkyleneoxy group having an ethyleneoxy group or a propyleneoxy group as a repeating unit. In the case of having two or more kinds of alkyleneoxy groups, for example, in the case of having a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups, the polyethyleneoxy group and the polypropyleneoxy group may be block copolymers, random copolymers, Further, both of the block copolymer portion and the random copolymer portion may be present, and there is no particular limitation.

In formula (J-4), X ^j is preferably a bivalent hydrocarbon group represented by a monovalent or divalent linking group, and is preferably an alkylene group having 1 to 8 carbon atoms (alkanediyl group), an alkenyl group having 2 to 8 carbon atoms A diazo group is preferable, and an alkylene group having 1 to 4 carbon atoms and an alkenediyl group having 2 to 4 carbon atoms are more preferable. X ^j is particularly preferably an alkylene group having 1 to 4 carbon atoms or an alkenediyl group having 2 to 4 carbon atoms. The alkylene group and alkenyldiyl group may be linear or branched.

In formula (J-4), Q ^j is a substituent for a benzene ring, preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group or a butyl group desirable.

Examples of the group (-X-Ph- (Q ^j ) _xj ) substituted in the benzene ring to which the alkyleneoxy group is bonded include a phenyl group (-Ph), a benzyl group (-CH ₂ -Ph), 2 - phenylpropan-2-yl group _{(-C (CH 3) 2 -Ph} ), it is exemplified a styryl group (-CH = CH-Ph), 1- phenylethyl _{(-CH (CH 3) -Ph)} . Ph represents a benzene ring, a monovalent phenyl group, and a divalent phenylene group.

In the formula (J-4), xj represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, more preferably 0 or 1, desirable.

In the formula (J-4), mj represents an integer of 0 to 5, preferably an integer of 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

In the formula (J-4), nj represents an integer of 1 to 50, more preferably an integer of 3 to 40, still more preferably an integer of 5 to 35, and an integer of 8 to 30.

The compound represented by the formula (J-4) is more preferably a compound represented by the following formula (J-5).

(In the formula (J-5), R ^j1 to R ^j4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n1 'and n2' each independently represent an integer of 0 to 50, and n1 '+ n2 'Represents an integer of 1 to 50, and mj' represents an integer of 1 to 5 except that R ^j1 and R ^j2 are the same)

In formula (J-5), R ^j1 and R ^j2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, except that R ^j1 and R ^j2 are the same. When R ^j1 and R ^j2 are the same, since a single alkyleneoxy group is repeated, n2 '= 0 and the total number of repeating units is represented by n1'. Each of R ^j1 and R ^j2 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group. That is, it is particularly preferable that the compound represented by the formula (J-5) has an ethyleneoxy group, a propyleneoxy group, or an ethyleneoxy group and a propyleneoxy group.

In the case of having a plurality of ethyleneoxy groups and propyleneoxy groups, the polyethyleneoxy group and the polypropyleneoxy group may be a block copolymer or a random copolymer, and both of a block copolymer portion and a random copolymer portion are present And is not particularly limited.

In formula (J-5), R ^j3 and R ^j4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group. R ^j3 and R ^j4 together are a methyl group, more preferably one hydrogen atom and the other is a methyl group, and it is particularly preferable that one is a hydrogen atom and the other is a methyl group.

In formula (J-5), n1 'and n2' each independently represents an integer of 0 to 50, and n1 '+ n2' represents an integer of 1 to 50. n1 '+ n2' is preferably an integer of 3 to 40, more preferably an integer of 5 to 35, and still more preferably an integer of 8 to 30.

In the formula (J-5), mj 'represents an integer of 1 to 5, more preferably an integer of 1 to 4, and still more preferably an integer of 1 to 3.

In the present invention, the total number of the benzene rings in one molecule of the polyoxyalkylene-substituted phenyl ether surfactant is preferably in the range of 1 to 4, more preferably 2 to 4. When the total number of benzene rings is within the above range, the occurrence of residue after development is suppressed.

In the present invention, the polyoxyalkylene-substituted phenyl ether surfactant preferably has an HLB value of 5 to 50, more preferably 8 to 30, further preferably 10 to 20, particularly preferably 12 to 16 Do. Within this range, the occurrence of residues is further suppressed.

Here, the HLB value is an abbreviation of hydrophile-lipophile balance, which is one of the indicators showing the effect of the surfactant, and the larger the HLB value, the higher the hydrophilicity. The molecular structure of the HLB value can be calculated from many experiments and is not particularly limited.

In the present invention, the HLB value is preferably measured by the Griffin method.

In the Griffin method, the HLB value is defined by the following equation.

HLB value = 20 × sum of food in hydrophilic part / molecular weight

Therefore, in the component F, the HLB value becomes as follows.

HLB value = 20 x (total amount of food of polyoxyalkylene moiety) / molecular weight

As the polyoxyalkylene-substituted phenyl ether surfactant, a synthetic product may be used, or a commercially available product may be used, and there is no particular limitation.

Products that have been marketed include Pioneer D-6112, Pionein D-6115, Pionein D-6112-W, Pionein D-6108-W, Pionein D- 6115X, Pionein D- Newcol CMP6, Newcol CMP-11, Newcol610, Newcol 710, and Phenonin D-6312 (manufactured by TAKEMOTO OIL & FAT Co., Ltd.) Newcol 710-F, Newcol 2609, Newcol 2600-FB (manufactured by Nippon Nyukazai Co., Ltd.). Of these, pionin D-6112-W and pionin D-6512 are preferred.

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

The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass to 10 parts by mass, and most preferably 0.01 parts by mass to 3 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition desirable.

(Component K) Antioxidant

The photosensitive resin composition of the present invention preferably contains an antioxidant. As the antioxidant, a known antioxidant may be contained. Addition of an antioxidant can prevent coloration of the cured film or reduce the film thickness reduction due to decomposition and has an advantage of excellent heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiosulfate, And hydroxylamine derivatives. Of these, a phenol-based antioxidant, an amide-based antioxidant, a hydrazide-based antioxidant, and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used singly or in combination of two or more kinds.

Specific examples include compounds described in paragraphs 0026 to 0031 of Japanese Patent Application Laid-Open No. 2005-29515, the contents of which are incorporated herein by reference.

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- 40, ADK STAB AO-50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO- ADK STAB PEP-24, ADK STAB PEP-36, ADK STABA-611, ADK STABA-612, ADK STABA-613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP- ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, 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-91 (manufactured by ADEKA CORPORATION), IRGANOX 245FF, IRGANOX 1010FF, IRGANOX 1010, IRGANOX MD1024, IRGANOX 1035FF, IRGANOX 1035 IRGANOX 1098, IRGANOX 1330, IRGANOX 1520L, IRGANOX 3114, IRGANOX 1726, IRGAFOS 168, IRGAMOD 295 (manufactured by BASF), and TINUVIN 405 (manufactured by BASF). Among them, ADK STAB AO-60, ADK STAB AO-80, IRGANOX 1726, IRGANOX 1035, IRGANOX 1098 and TINUVIN 405 can be preferably used.

The content of the antioxidant is preferably from 0.1 to 10% by mass, more preferably from 0.2 to 5% by mass, and particularly preferably from 0.5 to 4% by mass based on the total solid content of the photosensitive resin composition. With this range, sufficient transparency of the film formed can be obtained, and sensitivity at the time of pattern formation becomes good.

Various ultraviolet absorbers, metal deactivators, and the like described in " NIKKAN KOGYO SHIMBUN, LTD. &Quot;, as an additive other than the antioxidant may be added to the photosensitive resin composition of the present invention.

(Component L) A heterocyclic compound having two or more nitrogen atoms

The photosensitive composition of the present invention preferably contains (component L) a heterocyclic compound having two or more nitrogen atoms. The component L is adsorbed on the surface of the inorganic particles to cause electrostatic repulsion and three-dimensional repulsion between the inorganic particles, and it is presumed that the haze is reduced because the aggregation of the inorganic particles is prevented particularly when the composition is applied and dried.

The component L is preferably a heterocyclic compound having at least two nitrogen atoms as the reduction of the heterocyclic ring, and is preferably a heterocyclic compound having at least nitrogen atoms at the 1 and 3 positions, , More preferably a compound having a 5-membered or 6-membered heterocyclic structure having at least nitrogen atoms at 1 and 3 positions. In the above embodiment, a cured product having better dispersibility of inorganic particles and a smaller haze is obtained.

The "heterocyclic structure having at least nitrogen atom (s) at positions 1 and 3" is not particularly limited as long as it has a structure in which nitrogen atoms are bonded to both sides of a carbon atom in a heterocyclic ring, and may not be a 1-position or 3-position on a heterocyclic ring in a formal nomenclature .

The reduction of the heterocycle in the component L is preferably at least composed of a carbon atom and a nitrogen atom, and it may further contain an oxygen atom or a sulfur atom as a reduction atom, but it is particularly preferable that the atom is composed of a carbon atom and a nitrogen atom.

The number of nitrogen atoms of the component L is 2 or more, preferably 2 to 6, and more preferably 2 to 4. Further, as the reduction of the heterocycle, the component L preferably has 2 to 4 nitrogen atoms, more preferably 2 or 3, and further preferably 2.

The heterocyclic ring in the component L may be a saturated heterocyclic ring, an unsaturated heterocyclic ring, or an aromatic heterocyclic ring.

The heterocyclic ring in component L may be further condensed with another ring. The other ring may be an aliphatic ring or an aromatic ring as well as a heterocyclic ring.

Specific examples of the heterocyclic structure of the component L include an imidazole structure, a benzimidazole structure, a 1,2,4-triazole structure, a 4,5-dihydro-1,2,4-triazole structure, An imidazoline structure, a pyrimidine structure, a quinoxaline structure, a purine structure, a pteridine structure, and a pyrimidine structure, such as imidazoline structure, imidazoline structure, And a cyclic structure selected from the group consisting of an imidazole structure, a benzimidazole structure, a 1,2,4-triazole structure, a 4,5-dihydro-1,2,4-triazole structure , A tetrazole structure, a 2-imidazoline structure, a 4-imidazoline structure, an imidazolidine structure, and a pyrimidine structure, more preferably a benzimidazole structure or a Particularly preferred are the azolidine structures. In the above-described embodiment, a cured product having better dispersibility of metal oxide particles and a smaller haze is obtained.

The component L preferably has a mercapto group (-SH) or a thioxo group (= S). In the above-described embodiment, a cured product having better dispersibility of metal oxide particles and a smaller haze is obtained.

The component L is preferably a compound represented by the following formula (L-a).

(In the formula (La), R ^a1 and R ^a2 each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and R ^a1 and R ^a2 may be bonded to form a divalent organic group, and R ^a3 and R ^a4 may be Independently represent a hydrogen atom or a monovalent organic group, L ^a1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring, R ^a3 or R ^a4 and L ^a1 may combine to form a ring, is when the double bond-containing one nitrogen-based with a dotted line exists, indicates that there is no R ^a2 and R ^a4, when the double bond-containing nitrogen-based with a dotted line is not present indicates that the R ^a2 and R ^a4 presence )

^Examples of the monovalent organic group represented by R ^a1 to R ^a4 include an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, (Which may be a heterocyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, An alkoxycarbonylamino group, an aryloxycarbonylamino group, an aryloxycarbonylamino group, an aryloxycarbonylamino group, an aryloxycarbonylamino group, an aryloxycarbonylamino group, an aryloxycarbonylamino group, an aryloxycarbonylamino group, An arylthio group, an alkylthio group, an arylthio group, a heterocyclic dithio group, an alkylthio group, an arylthio group, an arylthio group, an arylthio group, an arylthio group, An alkyl group and an arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl and a heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group , Phosphinicosuccinic group, a phosphinylmethyl group, a phosphono group, a silyl group, a hydrazino group, a ureido group, thioureido ceramic, boron group (-B (OH) _2), phosphazene-earthenware (-OPO (OH) ₂ ), A sulfato group (-OSO ₃ H), and other known substituents. Further, the group may be further substituted by a substituent.

As the monovalent organic group in R ^a1 and R ^a2 , a mercapto group is particularly preferable.

The monovalent organic group in R ^a1 and R ^a2 preferably has 0 to 20 carbon atoms, more preferably 0 to 8 carbon atoms, and particularly preferably 0 carbon atoms.

Examples of the divalent organic group formed by combining R ^a1 and R ^a2 include an oxo group, a thioxo group, and an alkylidene group. Among them, a thioxo group is particularly preferable.

It is particularly preferable that R ^a1 and R ^a2 each independently represent a hydrogen atom or a mercapto group, and in the case where R ^a1 and R ^a2 are bonded to form a divalent organic group, it is particularly preferably a thioxo group.

As the monovalent organic group in R ^a3 and R ^a4 , an alkyl group or an aryl group is preferable, and a morpholinomethyl group or phenyl group is more preferable. The alkyl group or aryl group may be substituted by a substituent.

The monovalent organic group in R ^a3 and R ^a4 preferably has 0 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 4 to 8 carbon atoms.

R ^a3 and R ^a4 each independently represent a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a morpholinomethyl group or a phenyl group, more preferably a hydrogen atom or a phenyl group.

L ^a1 represents a divalent linking group which forms a 5-membered ring or a 6-membered ring and forms a heterocyclic ring together with a carbon atom and 2 nitrogen atoms in formula (La).

The divalent linking group is not particularly limited as far as it is a group forming a 5-membered heterocyclic ring or a 6-membered heterocyclic ring together with the carbon atom and two nitrogen atoms in formula (La), but the group in which the reduction is formed from a carbon atom and / More preferably a group forming a specific example of the above-described heterocyclic structure. Among them, a group forming a benzimidazole structure, that is, a group forming a 1,2-phenylene group or an imidazolidine structure, that is, a 1,2-ethylene group, a 1,1- Or an ethene-1,2-diyl group, and particularly preferably a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group or an ethene-1,2-diyl group.

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

(In the formulas (La-1) and (La-2), R ^a6 to R ^a8 each independently represent a hydrogen atom or a monovalent organic group, and L ^a2 and L ^a3 each independently form a 5-membered ring or a 6-membered ring R ^a6 and L ^a2 may be combined to form a ring, or R ^a7 or R ^a8 and L ^a3 may be combined to form a ring)

R ^a6 to R ^a8 in the formula (La-1) or the formula (La-2) are in agreement with R ^a3 and R ^a4 in the formula (La), and preferred embodiments are also the same.

In addition, L ^a2 and L ^a3 in the formula (La-1) or (La-2) are in agreement with the L ^a1 in the formula (La) and the preferred embodiments are also the same.

Preferred examples (AF-1 to AF-14) of component L are shown below. However, the present invention is not limited thereto.

Among them, AF-3 to AF-14 are preferable, and AF-3, AF-5, AF-6, AF-9, AF-12, AF- -9, AF-12, AF-13 or AF-14 are more preferable, and AF-9, AF-12, AF-13 or AF-14 are particularly preferable.

The component L may be used alone, or two or more kinds may be used in combination.

The content of the component L in the photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, more preferably 0.5 to 10% by mass based on the total solid content of the photosensitive resin composition of the present invention %. Within this range, a cured product having an excellent dispersibility of inorganic particles and a small haze can be obtained.

<Acid-proliferating agent>

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

The acid-proliferator which can be used in the present invention is a compound capable of increasing the acid concentration in the reaction system by further generating an acid by an acid catalytic reaction, and is a compound stably present in the absence of acid.

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

Such a compound accelerates the reaction in accordance with the progress of the reaction because at least one acid increases in a single reaction, but since the generated acid causes self-decomposition, the intensity of the acid generated here is the acid dissociation constant, pKa 3 or less, and particularly preferably 2 or less. The pKa is preferably -15 or more.

Specific examples of the acid proliferating agent include those described in paragraphs 0203 to 0223 of Japanese Patent Application Laid-Open No. 10-1508, paragraphs 0016 to 0055 of Japanese Patent Application Laid-Open No. 10-282642, and Japanese Patent Publication No. 9-512498, Line to page 47, the second line.

Examples of the acid growth agent usable in the present invention include acids having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and phenylphosphonic acid, which are decomposed by an acid generated from an acid generator . &Lt; / RTI &gt;

Specifically, the following compounds and the like can be mentioned.

The content of the acid repellent in the photosensitive resin composition is preferably from 10 to 1,000 parts by mass based on 100 parts by mass of the photo acid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion, more preferably from 20 to 500 parts by mass Do.

&Lt; Development accelerator &

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

As the development accelerator, any compound having a phenomenon of promoting development may be used, but it is preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group, and a compound having a carboxyl group or a phenolic hydroxyl group Compound is more preferable, and a compound having a phenolic hydroxyl group is most preferable.

As the phenomenon promoter, the description of paragraphs 0171 to 0172 of Japanese Patent Application Laid-Open Publication No. 2012-042837 may be taken into consideration, and the content of the present specification is included in the specification.

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

The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably from 0 to 30 parts by mass, more preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 0.5 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoints of sensitivity and residual film ratio. Most preferably 10 to 10 parts by mass.

The molecular weight of the development promoter is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 150 to 1,000.

<Plasticizer>

The resin composition of the present invention may contain a plasticizer.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartrate, dioctyl adipate, triacetyl glycerin and the like.

The content of the plasticizer in the resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the content of Component C. [

As the other additives, the heat radical generating agents described in paragraphs 0120 to 0121 of Japanese Patent Application Laid-Open Publication No. 2012-8223, the nitrogen containing compounds described in International Publication No. 2011/136074, and the thermal acid generation system can be used. Are incorporated herein by reference.

&Lt; Preferred physical properties of photosensitive resin composition &

The photosensitive resin composition of the present invention preferably has a solid content of 40% by mass or less, more preferably 35% by mass or less, from the viewpoint of improving the applicability of the inkjet. Further, from the viewpoint of inkjet ejection preferably, the solid content is more preferably 30 mass% or less. Within the above range, the discharge stability and handling property are excellent.

The solid content of the photosensitive resin composition of the present invention is preferably 10 to 30% by mass, more preferably 12 to 30% by mass. Within this range, higher discharge stability can be realized.

 From the viewpoint of improving the application property, the photosensitive resin composition of the present invention preferably has a viscosity at 25 ° C of 50 mPa · s or less, more preferably 30 mPa · s or less. Here, the viscosity measured at 25 占 폚 is measured using an E-type viscometer.

When the photosensitive resin composition of the present invention is used from the viewpoint of satisfactory ejection, the viscosity at the time of inkjet application is preferably 20 mPa 占 퐏 or less. Within the above range, the discharge stability and handling property are excellent.

When the photosensitive resin composition of the present invention is used, the viscosity range upon inkjet application is more preferably from 1 to 20 mPa · s, further preferably from 1 to 15 mPa · s. Within the above range, high discharge stability can be realized.

The surface tension of the photosensitive resin composition of the present invention at 25 캜 is preferably 18 mN / m or more and 35 mN / m or less, more preferably 22 mN / m or more and 35 mN / m or less, more preferably 26 mN / desirable. Within the above range, the discharge stability and handling property are excellent.

As the method of measuring the surface tension of the photosensitive resin composition at 25 캜, a known method can be used, but it is preferable to measure by the infrared method or the Wilhelmy method. For example, Kyowa Interface Science Co., LTD. A method of measuring using an automatic surface tension tester CBVP-Z or a method of measuring by using SIGMA702 manufactured by KSV Instruments Ltd. can be preferably used.

&Lt; Preparation method of photosensitive resin composition &gt;

The method for preparing the photosensitive resin composition of the present invention is not particularly limited and a known method can be used. For example, the photosensitive resin composition can be prepared by mixing and stirring the components in a predetermined ratio or by any method, and dissolving or dispersing them. Further, it is also possible to prepare a resin composition by, for example, preparing a solution in which each component is previously dissolved or dispersed in a solvent, and then mixing them at a predetermined ratio. The photosensitive resin composition prepared as described above may be used after being filtered using, for example, a filter having a pore size of 0.2 탆.

(Method for producing resin pattern)

Next, a method for producing the resin pattern of the present invention will be described.

The method for producing a resin pattern of the present invention preferably includes the following steps (1) to (5).

(1) a coating step of applying the photosensitive resin composition for inkjet coating of the present invention onto a substrate by an inkjet coating method;

(2) a solvent removing step of removing the solvent from the applied resin composition;

(3) an exposure step of exposing the resin composition from which the solvent has been removed to a pattern shape by an actinic ray;

(4) a developing step of developing the exposed resin composition by an aqueous developing solution;

(5) A heat treatment step for subjecting the developed resin composition to heat treatment.

Each step will be described below in order.

(1), it is preferable that the photosensitive resin composition of the present invention is applied to a substrate by an ink-jet coating method to form a wet film containing a solvent. It is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition to a substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after the substrate cleaning. By this treatment, the adhesion of the photosensitive resin composition to the substrate is improved. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and for example, a method of exposing the substrate to the hexamethyldisilazane vapor in the middle can be mentioned.

Examples of the substrate include plastic substrates such as inorganic substrates, resins, resin composite materials, ITO, IZO, Cu substrates, polyethylene terephthalate, and cellulose triacetate (TAC).

Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and composite substrates obtained by depositing molybdenum, titanium, aluminum, copper, or the like on a substrate such as glass, quartz, silicon or silicon nitride.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyallylate, allyldiglycol carbonate, polyamide, polyimide, polyamide A fluororesin such as polyetherimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin and polychlorotrifluoroethylene, a liquid crystal polymer, an acrylic resin, an epoxy resin, a silicone resin, an ionomer resin , A substrate made of a synthetic resin such as a cyanate resin, a crosslinked fumaric acid diester resin, a cyclic polyolefin, an aromatic ether resin, a maleimide-olefin resin, a cellulose or an episulfide resin.

These substrates are rarely used as they are in the above-mentioned form, and a multilayer laminate structure such as a TFT device is usually formed depending on the shape of the final product.

The application of the inkjet method significantly reduces the application amount of the coating liquid as compared with the conventional coating methods such as the spin coating method and the slit coat method and also reduces the influence of mist or the like adhering to the spin coating method, It is preferable from a comprehensive viewpoint.

For example, the coating conditions by the inkjet method may be appropriately selected depending on the composition of the photosensitive resin composition, the kind of coating film to be produced, and the like. In order to adjust the thickness of the coating film, the discharge amount of the liquid photosensitive resin composition or the number of times of discharge to the same part may be adjusted. The shape and position of the application of the photosensitive resin composition may be suitably selected in accordance with the requirements. A device used for applying the inkjet method is not particularly limited and a known inkjet application device may be used.

Specifically, on-demand ink jet application devices IJ-DESK-S, IJ-DESK-H (manufactured by PMT Corporation), Dimatix Material Printer DMP2831 and DMP-3000 (manufactured by FUJIFILM Dimatix, Inc.) are listed.

The inkjet recording apparatus that can be used in the inkjet coating method is not particularly limited, and a known inkjet recording apparatus capable of achieving a desired resolution can be arbitrarily selected and used. That is, in the case of a known inkjet recording apparatus containing a commercially available product, the application of the photosensitive resin composition of the present invention onto the substrate in the above-described coating step can be carried out by the inkjet coating method.

Examples of the inkjet recording apparatus that can be used in the present invention include an apparatus including a composition supply system and a temperature sensor.

The ink supply system includes, for example, a raw tank including the photosensitive resin composition of the present invention, a supply pipe, a composition supply tank just before the inkjet head, a filter, and a piezo-type inkjet head. The piezo type inkjet head preferably has a size of 1 to 100 pl, more preferably 8 to 30 pl, of a multi-size dot, preferably 320 × 320 to 4,000 × 4,000 dpi (dot per inch), more preferably 400 × 400 to 1,600 X 1,600 dpi, and more preferably, 720 x 720 dpi. The term &quot; dpi &quot; in the present invention indicates the number of dots per 2.54 cm.

The thickness of the coating film is not particularly limited, and it can be applied in a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 탆.

In the solvent removal step of (2), it is preferable to remove the solvent from the coated film by vacuum (vacuum pressure) and / or heating to form a dried coating film on the substrate. For example, heating and drying with a hot plate are preferable. The heating condition of the solvent removing step is preferably about 70 to 130 DEG C for about 30 to 300 seconds. When the temperature and the time are within the above range, the pattern adhesion is good and the residue can be also reduced.

The coating step (1) and the solvent removing step (2) may be performed in this order, simultaneously or alternately. For example, the solvent removal step (2) may be performed after the completion of the ink jet application in the application step (1), or the substrate may be heated and the ink jet application method (1) The solvent may be removed while discharging the photosensitive resin composition.

Among them, it is preferable to perform the solvent removal step (2) after all the inkjet application in the coating step of (1) is completed.

It is preferable that the substrate on which the coating film is formed is irradiated with an actinic ray through a mask having a predetermined pattern. In this process, the photoacid generator is decomposed to generate acid. The acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group.

(436 nm), i-line (365 nm), h-line (405 nm), and the like can be used as the exposure light source by the actinic light ray. Examples of the exposure light source include a low pressure mercury lamp, a high pressure mercury lamp, Nm) or the like having a wavelength of 300 nm or more and 450 nm or less can be preferably used. If necessary, irradiation light can be adjusted through a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a band-pass filter.

As the exposure apparatus, various types of exposure apparatus such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.

Post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as &quot; PEB &quot;) may be performed to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote the generation of a carboxyl group or a phenolic hydroxyl group from the acid decomposable group. The temperature for PEB is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 100 占 폚.

However, the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to form an acid group, for example, a carboxyl group or a phenolic hydroxyl group, A positive image may be formed by development without being performed.

It is preferable that the copolymer having an acid group liberated in the developing step of (4) is developed using an alkaline developer. A positive image is formed by removing the exposed region including a resin composition having an acid group easily soluble in an alkaline developer, for example, a carboxyl group or a phenolic hydroxyl group.

The developing solution used in the developing step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

As a preferable developing solution, a 0.4 mass% aqueous solution, 0.5 mass% aqueous solution, 0.7 mass% aqueous solution, or 2.38 mass% aqueous solution of tetraethylammonium hydroxide can be mentioned.

The pH of the developing solution is preferably 10.0 to 14.0.

The development time is preferably 30 to 500 seconds, and the developing method may be any of a puddle method and a dipping method. After the development, water washing can be performed for 30 to 300 seconds to form a desired solution.

After the development, a rinsing process may be performed. In the rinsing step, the developed substrate is cleaned with pure water or the like to remove the attached developing solution and remove the developing residue. As the rinsing method, known methods can be used. Examples thereof include shower rinses and deep rinses.

A cured film can be formed by thermally decomposing an acid-decomposable group by heating the obtained positive image to form an acid group, for example, a carboxyl group or a phenolic hydroxyl group, and crosslinking with a crosslinkable group, a crosslinking agent or the like in the heat treatment step (post-baking) have. The heating is carried out at a predetermined temperature, for example, 180 to 250 DEG C for a predetermined time, for example, 5 to 90 minutes in the case of a hot plate or 30 to 120 minutes in the case of an oven, using a heating apparatus such as a hot plate or an oven It is possible to form a protective film or an interlayer insulating film excellent in heat resistance, hardness and the like by proceeding a crosslinking reaction which is preferable to be treated. In addition, transparency can be improved by performing the heat treatment in a nitrogen atmosphere. When a plastic substrate is used, the heat treatment is preferably performed at 80 to 140 ° C for 5 to 120 minutes.

The heat treatment process may be performed after baking at a relatively low temperature before the heat treatment process (post-baking) (addition of the middle baking process). In the case of conducting the middle baking, post-baking is preferably performed at a high temperature of 200 DEG C or more after heating at 90 to 150 DEG C for 1 to 60 minutes. In addition, middle baking and post baking may be divided into three or more stages and heated. The taper angle of the pattern can be adjusted by the study of the middle bake and the post bake. These can be heated by a known heating method such as a hot plate, an oven, or an infrared heater.

In addition, a post-baking method in which a substrate on which a pattern is formed before post-baking is subjected to an entire surface re-exposure (post exposure) by an actinic ray, and then post-baked to generate an acid from a photoacid generator present in the unexposed portion to accelerate the cross- And the curing reaction of the film can be promoted. In the case of including the post exposure step, the preferable exposure amount is preferably 100 to 3,000 mJ / cm2, and particularly preferably 100 to 500 mJ / cm2.

The cured film obtained from the photosensitive resin composition of the present invention may also be used as a dry etching resist. When a cured film obtained by heat curing by a heat treatment process is used as a dry etching resist, dry etching treatment such as ashing, plasma etching, and ozone etching can be performed as the etching treatment.

(membrane)

The film of the present invention is a film obtained by heat-treating the photosensitive resin composition of the present invention.

The film of the present invention can be preferably used as an interlayer insulating film. The film of the present invention is preferably a film obtained by the method for producing a heat-treated product of the present invention or the method for producing a resin pattern of the present invention.

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent transparency can be obtained even when the insulating resin is excellent in bake at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention is useful for an organic EL display device, a liquid crystal display device, and a touch panel display device because it has high transparency and excellent physical properties of a cured film.

(Heat Treated Water and Manufacturing Method Thereof)

The heat-treated product (cured product) of the present invention is a heat-treated product obtained by heat-treating the photosensitive resin composition of the present invention, and the shape thereof may be any shape as long as it is not a film as described above.

The heat-treated product of the present invention may be at least a cured product obtained by removing at least a part of the solvent from the photosensitive resin composition of the present invention to increase the hardness. However, the cured product obtained by removing the solvent from the photosensitive resin composition of the present invention, .

The method for producing the heat-treated product of the present invention is not particularly limited, but preferably includes at least the following steps (a) to (c) in this order.

(a) a coating step of applying the photosensitive resin composition for inkjet coating of the present invention onto a substrate by an ink-jet coating method;

(b) a solvent removing step of removing the solvent from the applied resin composition;

(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed.

The steps (a) and (b) are in agreement with the coating step and the solvent removing step, respectively, and preferred embodiments are also the same.

The step (c) is a step similar to the heat treatment step except that the object to be heat treated is the resin composition from which the solvent obtained in the step (b) is removed. The heating temperature, the heating time, And the like are also preferable.

The heat-treated product (cured product) or film of the present invention is an optical member such as a microlens, an optical waveguide, an antireflection film, a sealant for LED, a chip coat material for LED, or a cured product for reducing visibility of a wiring electrode used in a touch panel Can be preferably used.

In addition, the heat-treated product (cured product) or film of the present invention can be used as a flattening film or an interlayer insulating film in a liquid crystal display device or an organic EL device, a protective film of a color filter, a liquid crystal layer A spacer for maintaining a constant thickness of the substrate, and a structural member of a MEMS (Micro Electro Mechanical Systems) device.

(Liquid crystal display device)

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

As the liquid crystal display device of the present invention, there is no particular limitation but a known liquid crystal display device having various structures other than those having a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention.

For example, specific examples of a TFT (Thin-Film Transistor) included in the liquid crystal display of the present invention include an amorphous silicon TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be preferably used in combination with these TFTs.

As a liquid crystal driving method that can be adopted by the liquid crystal display of the present invention, a TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Fringe Field Switching) An OCB (Optically Compensated Bend) method, and the like.

In the panel construction, the cured film of the present invention can also be used in a liquid crystal display device of a color filter on array (COA) type. For example, the organic insulating film 115 described in JP 2005-284291 A, And can be used as the organic insulating film 212 described in JP-A-346054.

Specific examples of the alignment method of the liquid crystal alignment film which the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. It may also be polymer-oriented supported by PSA (Polymer Sustained Aligment) technology described in Japanese Patent Laid-Open Nos. 2003-149647 and 2011-257734.

In addition, the photosensitive resin composition of the present invention and the film of the present invention are not limited to the above-mentioned uses and can be used for various purposes. For example, in addition to a planarizing film or an interlayer insulating film, a protective film for a color filter or a spacer for keeping the thickness of the liquid crystal layer in a liquid crystal display device constant, a microlens formed on a color filter in a solid- .

Fig. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. Fig. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel is a liquid crystal display panel that corresponds to all the pixels disposed between two glass substrates 14, And elements of the TFT 16 are arranged. An ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17 in each element formed on the glass substrate. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of a liquid crystal 20 and a black matrix are arranged is formed.

The light source of the backlight is not particularly limited and a known light source can be used. For example, white LEDs, multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), organic ELs, and the like.

The liquid crystal display device may be of a 3D (stereoscopic) type or a touch panel type. The second inter-phase insulating film 48 described in JP-A-2011-145686 or the inter-phase insulating film 520 described in JP-A-2009-258758 can be used.

(Organic EL display device)

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

As the organic EL display device of the present invention, there are no particular limitations other than those having a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices and liquid crystal display devices having various structures .

For example, specific examples of a TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include an amorphous silicon TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be preferably used in combination with these TFTs.

2 is a conceptual diagram showing an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

A bottom gate type TFT 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed in a state in which the TFT 1 is covered. A wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3 here. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

The planarization layer 4 is formed on the insulating film 3 in a state in which the irregularities due to the wiring 2 are buried in order to planarize the irregularities due to the formation of the wiring 2. [

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the planarization film 4 by being 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 is formed so as to cover the periphery of the first electrode 5. By forming the insulating film 8, a short circuit is formed between the first electrode 5 and the second electrode formed in the subsequent step .

Although not shown in FIG. 2, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited and formed through a desired pattern mask. Then, a second electrode made of Al is formed on the entire upper surface of the substrate, An organic EL display device of an active matrix type in which a glass plate for use and an ultraviolet curable epoxy resin are used to seal each other and to which a TFT 1 for driving each organic EL element is connected is obtained.

Since the photosensitive resin composition of the present invention is excellent in photosensitivity and film properties, the resist pattern formed by using the photosensitive resin composition of the present invention as a structural member of the MEMS device is used as a partition wall or as a part of a mechanical driving part. Examples of such MEMS devices include a surface acoustic wave (SAW) filter, a BAW (bulk acoustic wave) filter, a gyro sensor, a display micro shutter, an image sensor, an electronic paper, an ink jet head, . More specific examples are exemplified in Japanese Patent Publication Nos. 2007-522531, 2008-250200, and 2009-263544.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer 16 and the planarization film 57 shown in Fig. 2 of Japanese Patent Laid-Open Publication No. 2011-107476, Japanese Patent Application Laid- The bank layer 221 and the third interlayer insulating film 216b shown in Fig. 10 of Japanese Patent Application Laid-Open No. 2010-27591, the barrier layer 12 and the planarization film 102 described in Fig. 4 (a) The second interlayer insulating film 125 and the third interlayer insulating film 126 described in FIG. 4A of JP 2009-128577 A, the planarization film 12 described in FIG. 3 of JP 2010-182638 A, The insulating film 14 and the like.

(Touch panel display device)

A touch panel display device of the present invention comprises a capacitive input device having a film of the present invention. Further, the capacitance type input device of the present invention is characterized by having the film of the present invention.

It is preferable that the capacitive input device of the present invention has at least the following elements (1) to (5) on the face plate and a noncontact side of the face plate, and the following (4) is the heat treatment of the present invention.

(1) Mask layer

(2) a plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through connection portions

(3) a plurality of second transparent electrode patterns, which are electrically insulated from the first transparent electrode pattern and are formed of a plurality of pad portions extending in a direction crossing the first direction,

(4) An insulating layer for electrically insulating the first transparent electrode pattern and the second transparent electrode pattern

(5) A method of manufacturing a semiconductor device, which is electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and which is different from the first transparent electrode pattern and the second transparent electrode pattern

The capacitive input device of the present invention preferably further includes a transparent protective layer so as to cover all or a part of the elements (1) to (5), more preferably the transparent protective layer is the cured film of the present invention Do.

First, the configuration of the capacitive input device will be described. 3 is a cross-sectional view showing the configuration of the capacitance type input device. 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, a conductive element 36, and a transparent protective layer 37.

The front plate 31 is made of a light-transmissive substrate such as a glass substrate, and tempered glass represented by Gorilla glass of Corning Inc. can be used. In Fig. 3, the side where each element of the front plate 31 is formed is called a non-contact surface. In the capacitive input device 30 of the present invention, a finger or the like is brought into contact with the contact surface (the surface opposite to the non-contact surface) of the front plate 31 to make an input. Hereinafter, the front plate may be referred to as a &quot; substrate &quot;.

A mask layer 32 is formed 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 noncontact side of the front panel of the touch panel, and is formed so as not to see a watermark wiring or the like.

In the capacitive input device of the present invention, as shown in Fig. 4, a mask layer 32 is formed so as to cover a part of the area of the front plate 31 (an area other than the input surface in Fig. 4). As shown in Fig. 4, the front plate 31 may have an opening 38 formed in a part thereof. The opening portion 38 can be provided with a mechanical switch by pressing.

5, a plurality of first transparent electrode patterns 33 formed by extending a plurality of pad portions in a first direction through connection portions, a plurality of first transparent electrode patterns 33 formed on the contact surface of the front plate 31, A plurality of second transparent electrode patterns 34 formed of a plurality of pad portions electrically insulated from the first transparent electrode patterns 33 and extending in a direction crossing the first direction, 34 are formed on the insulating layer 35 to electrically isolate the insulating layer 35. [ The first transparent electrode pattern 33, the second transparent electrode pattern 34 and the conductive element 36 to be described later are formed of a transparent conductive material such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) A conductive metal oxide film can be formed. As such a metal film, an ITO film; Metal films of Al, Zn, Cu, Fe, Ni, Cr, and Mo; SiO ₂ And the like. At this time, the film thickness of each element can be set to 10 to 200 nm. In addition, since the ITO film of amorphous is formed into a polycrystalline ITO film by firing, the electrical resistance can be reduced. The first transparent electrode pattern 33, the second transparent electrode pattern 34 and the conductive element 36 to be described later may be manufactured using a photosensitive transfer material having a photosensitive resin composition using the conductive fibers have. In addition, when the first conductive pattern or the like is formed by ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to.

At least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 is formed on both of the noncontact surface of the front plate 31 and the surface opposite to the front plate 31 of the mask layer 32 Area. 3, the second transparent electrode pattern is provided over both the noncontact surface of the front plate 31 and the surface opposite to the front plate 31 of the mask layer 32. As shown in Fig.

The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. 5 is an explanatory view showing an example of a first transparent electrode pattern and a second transparent electrode pattern according to the present invention. As shown in Fig. 5, the first transparent electrode pattern 33 is formed by extending the pad portion 33a in the first direction through 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 is arranged in a direction crossing the first direction As shown in FIG. In this case, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be integrally formed. Alternatively, only the connection portion 33b may be formed, And the second transparent electrode patterns 34 may be integrally formed (patterned). A part of the connection portion 33b and a part of the pad portion 33a are connected as shown in Fig. 5 when the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned) Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by the insulating layer 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 the first transparent electrode pattern 33 and the second transparent electrode pattern 34 ). In Fig. 3, a diagram is shown in which the conductive element 36 is connected to the second transparent electrode pattern 34. Fig.

In Fig. 3, a transparent protective layer 37 is provided so as to cover all the constituent elements. The transparent protective layer 37 may be configured to cover only a part of each constituent element. The insulating layer 35 and the transparent protective layer 37 may be the same material or different materials.

&Lt; Capacitive input device, and touch panel display device provided with capacitive input device &gt;

The capacitive input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitive input device as a component are described in " Latest Touch Panel Technology " (issued on July 6, 2009, (2004, 12), FPD International 2009 Forum T-11 Lecture Text Book, Cypress Semiconductor Corporation Application Note AN2292 can be applied. have.

&Lt; Touch panel and manufacturing method thereof &

The touch panel of the present invention is a touch panel in which all or a part of the insulating layer is formed of the heat treatment of the resin composition of the present invention. The touch panel of the present invention preferably has at least a transparent substrate, an ITO electrode, and an insulating layer.

The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention.

The method of manufacturing a touch panel of the present invention is a method of manufacturing a touch panel having a transparent substrate, an ITO electrode, and an insulating layer, wherein the photosensitive resin composition for inkjet application of the present invention is applied by an inkjet coating method A step of exposing the resin composition to a mask having an opening pattern of a predetermined shape and irradiating it with active energy ray irradiation, a step of developing the resin composition after exposure, and a step of heating the resin composition after development to produce an insulating layer And a step of

As the transparent substrate in the touch panel of the present invention, a glass substrate, a quartz substrate, a transparent resin substrate and the like are preferably used.

The inkjet coating in the step of applying the photosensitive resin composition for inkjet coating of the present invention to the ITO electrodes by the inkjet coating method can be carried out in the same manner as in the above-described coating step, and the preferred embodiments are also the same. In the above step, at least a part of the applied photosensitive resin composition of the present invention may be in contact with the ITO electrode.

The step of exposing the resin composition with a mask having an opening pattern of a predetermined shape and performing the activation energy ray irradiation and the step of developing the resin composition after exposure can be performed in the same manner as in the above exposure step, same.

The step of heating the resin composition after the development to produce the insulating layer can be carried out in the same manner as the above-mentioned heat treatment step, and the preferred embodiments are also the same.

As an example of the ITO electrode pattern in the touch panel of the present invention, the above-described pattern shown in Fig. 5 is preferably used.

(Example)

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed unless they depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise stated, &quot; part &quot; and &quot;% &quot; are based on mass.

In the following Synthesis Examples, Examples and Comparative Examples, the following symbols respectively represent the following compounds.

MATHF: tetrahydrofuran-2-yl methacrylate (synthetic)

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

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

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

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

OXE-30: Methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)

NBMA: n-butoxymethylacrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)

MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

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

St: styrene (manufactured by 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.)

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

MEDG: Diethylene glycol ethyl methyl ether (Hyosolve EDM, manufactured by TOHO Chemical Industry Co., Ltd.)

PGMEA: Propylene glycol monomethyl ether acetate (produced by SHOWA DENKO K.K.)

MDM: Diethylene glycol dimethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

MDPOM: dipropylene glycol dimethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

EDM (MEDG): diethylene glycol ethyl methyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

DPM: dipropylene glycol monomethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

EDE: diethylene glycol diethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

DM: diethylene glycol monomethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

BDM: Diethylene glycol butyl methyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

MTPOM: Tripropylene glycol dimethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

MTM: triethylene glycol dimethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

DB: Diethylene glycol monobutyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

EPH: Ethylene glycol monophenyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

TM: triethylene glycol monomethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

BDB: Diethylene glycol dibutyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

BTM: triethylene glycol butyl methyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

MPM: polyethylene glycol dimethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

MTEM: tetraethylene glycol dimethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

PM: polyethylene glycol monomethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

MMM: ethylene glycol dimethyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

IPDM: diethylene glycol isopropyl methyl ether (manufactured by TOHO Chemical Industry Co., Ltd.)

THFA: tetrahydrofurfuryl alcohol (produced by Zhi Hiroshi Hanoka Kuyu Genkou Co., Ltd.)

PGDA: Propylene glycol diacetate (manufactured by Daicel Corporation)

1,3-BGDA: 1,3-butylene glycol diacetate (manufactured by Daicel Corporation)

1,4-BDDA: 1,4-butanediol diacetate (manufactured by Daicel Corporation)

1,6-HDDA: 1,6-hexanediol diacetate (manufactured by Daicel Corporation)

CHXA: cyclohexanol acetate (manufactured by Daicel Corporation)

PGMEP: Propylene glycol monomethyl ether propionate (manufactured by Daishin-Chemical Co., Ltd.)

BMGAC: ethylene glycol monobutyl ether acetate (manufactured by Daicel Corporation)

EDGAC: diethylene glycol monoethyl ether acetate (manufactured by Daicel Corporation)

BDGAC: Diethylene glycol monobutyl ether acetate (manufactured by Daicel Corporation)

DPMA: dipropylene glycol methyl ether acetate (Daicel Corporation)

DPMNP: dipropylene glycol methyl-n-propyl ether (manufactured by Daicel Corporation)

DRA-150: triacetin (manufactured by Daicel Corporation)

MB: 3-methoxybutanol (manufactured by Daicel Corporation)

1,3-BG: 1,3-butylene glycol (manufactured by Daicel Corporation)

PNP: Propylene glycol n-propyl ether (manufactured by Daicel Corporation)

PNB: Propylene glycol n-butyl ether (manufactured by Daicel Corporation)

EDG: Diethylene glycol monoethyl ether (manufactured by Daicel Corporation)

DPNP: dipropylene glycol n-propyl ether (Daicel Corporation)

DPNB: dipropylene glycol n-butyl ether (manufactured by Daicel Corporation)

TPM: tripropylene glycol methyl ether (manufactured by Daicel Corporation)

TPNB: tripropylene glycol n-butyl ether (manufactured by Daicel Corporation)

MAK: Methyl amyl ketone (manufactured by NAGASE & CO., LTD.)

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was cooled to 15 DEG C and camphorsulfonic acid (4.6 g, 0.02 mol) was added. 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise to the solution. After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added. The mixture was extracted with ethyl acetate (500 mL) and dried over magnesium sulfate. The insoluble material was filtered off and concentrated under reduced pressure at 40 ° C or lower. 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg as a distillate was obtained as a colorless oil (yield: 80%).

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

[Synthesis of polymer C1]

MEDG (89 g) was put in a three-necked flask, and the temperature was raised to 90 캜 under a nitrogen atmosphere. The amount of MAA (amount to be 9.5 mol% of total monomer components), MATHF (amount to become 43 mol% of total monomer components), GMA (corresponding to 47.5 mol% of total monomer components), V-65 (Corresponding to 4 mol% based on 100 mol% of the total) was dissolved and dissolved dropwise over 2 hours. After completion of dropwise addition, stirring was continued for 2 hours to terminate the reaction. Thereby, a polymer C1 was obtained. In addition, the ratio of the total amount of MEDG to the other components was 70:30. That is, a polymer solution having a solid content concentration of 30% was prepared.

The kind of the monomer to be used, the polymerization initiator and the like were changed as shown in the following table to synthesize another polymer.

In Table 1, numerical values in which units are not particularly specified are in mol%. The numerical value of the polymerization initiator is mol% based on 100 mol% of the monomer component.

The solid content concentration can be calculated by the following equation.

Solid content concentration: monomer mass / (monomer mass + solvent mass) 占 100 (unit: mass%)

When V-601 was used as an initiator, the reaction temperature was set to 90 ° C. When V-65 was used, the reaction temperature was set to 70 ° C.

The physical properties of the respective solvents used in Examples and Comparative Examples are shown in Table 2.

The boiling point of the solvent is described with reference to known literatures. The I / O value is calculated on the basis of the description of "New Edition Organic Conceptual Basics and Application" (Yoshio Koda, Satoshiro Sato, Yoshio Honma, SANKYO PUBLISHING Co., Ltd. (2008) //www.ecosci.jp/chem9/interaction.html). The surface tension was measured by Kyowa Interface Science Co., LTD. Manufactured by Automatic Surface Tensiometer CBVP-Z.

&Lt; Preparation of Dispersion P &

Dispersions having the following composition were combined, mixed with 17,000 parts of zirconia beads (0.3 mmφ), and dispersed for 12 hours using a paint shaker. The zirconia beads (0.3 mm?) Were filtered to obtain dispersion P.

· Titanium dioxide (manufactured by ISHIHARA SANGYO KAISHA, LTD., Trade name: TTO-51 (A), average primary particle diameter: 10 to 30 nm): 1,875 parts

DISPERBYK-111 (manufactured by BYK Chemie Japan) 30% PGMEA solution: 2,200 parts

Solvent PGMEA: 3,425 parts

&Lt; Preparation of Photosensitive Resin Composition &gt;

The solution was mixed with the following composition and mixed to obtain a homogeneous solution. The solution was filtered using a polyethylene filter having a pore size of 0.2 mu m to prepare a photosensitive resin composition of Example 1. The solid content of the obtained photosensitive resin composition was 17.0%, and various evaluations described later were performed using this photosensitive composition. The evaluation results are shown in Table 3 below.

Solvent EDE (B1): 307.5 parts

Basic compound I1 (the compound shown below, produced by TOYO KASEI CO., LTD., CMTU): 0.02 part

Polymer C1: 100.0 parts

Photoacid generator D1 (compound shown below): 1.9 parts

Thermal crosslinking agent F1 (the following compound): 6.9 parts

Alkoxysilane compound H1 (3-glycidoxypropyltrimethoxysilane, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1.7 parts

Surfactant W1 (nonionic surfactant containing perfluoroalkyl group, F-554, manufactured by DIC Corporation): 0.08 part

Dispersion P: 181.7 parts

The following compound L1: 0.2 part

&Lt; Examples 2 to 27 and Comparative Examples 1 to 16 &gt;

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the solvent and the solid content shown in Table 3 were changed. The evaluation results are shown in Table 3 below.

&Lt; Example 28 &gt;

The solution was mixed with the following composition and mixed to obtain a homogeneous solution. The solution was filtered using a polyethylene filter having a pore size of 0.2 μm to prepare a photosensitive resin composition of Example 28. The solid content of the obtained photosensitive resin composition was 17.0%, and various evaluations described later were performed using this photosensitive composition. The evaluation results are shown in Table 7 below.

Solvent EDE (B1): 307.5 parts

Basic compound I1 (the compound shown below, produced by TOYO KASEI CO., LTD., CMTU): 0.02 part

Polymer C2: 100.0 parts

Photoacid generator D1 (compound shown below): 1.9 parts

Thermal crosslinking agent F2 (the compound shown below): 6.9 parts

Alkoxysilane compound H1 (3-glycidoxypropyltrimethoxysilane, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1.7 parts

Surfactant W1 (nonionic surfactant containing perfluoroalkyl group, F-554, manufactured by DIC Corporation): 0.08 part

Dispersion P: 181.7 parts

The following compound L1: 0.2 part

&Lt; Examples 29 to 110 &gt;

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer was changed to the polymer shown in Tables 4 to 6, a photoacid generator, a sensitizer, a solvent, a heat crosslinking agent, a surfactant, and / or other additives. The addition amounts of the respective component amounts in Tables 4 to 6 indicate parts by mass. The evaluation results are shown in Tables 7 to 9 below.

Details of the abbreviations used for the respective compounds used in Examples and Comparative Examples other than those described above are as follows.

<Polymer>

C1 to C10: Polymers synthesized according to Synthesis Example

C11: Joncryl 67 (alkali soluble acrylic resin, weight average molecular weight: 12,500, acid value: 213 mgKOH / g, manufactured by BASF)

&Lt;

D1: The structure shown below (a synthesis example will be described later)

D2: A structure shown below (a synthesis example will be described later)

D3: The structure shown below (synthesized according to the method described in paragraph 0108 of Japanese Patent Publication No. 2002-528451)

D4: PAG-103 (trade name, the structure shown below, manufactured by BASF)

D5: GSID-26-1, triarylsulfonium salt (manufactured by BASF)

<Synthesis of D1>

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 캜 for reaction for 2 hours. A 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution under ice-cooling, and ethyl acetate (50 mL) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 占 폚 for 1 hour. 2N HCl aqueous solution (60 mL) was added thereto to separate the layers. The organic layer was concentrated, and the crystals were reslurried with diisopropyl ether , Filtered and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 mass% hydroxylamine aqueous solution (8.0 g) were added to the resulting suspension of the ketone compound (3.0 g) and methanol (30 ml), and the mixture was heated to reflux. After cooling, 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 Lt; / RTI &gt; Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered out and then slurry was rinsed with methanol (20 mL), followed by filtration and drying to obtain a compound of D1 (2.3 g).

In addition, ¹ H-NMR spectrum of D1 (300MHz, CDCl ₃₎ is δ = 8.3 (d, 1H) , 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

<Synthesis of D2>

4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 16 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) ), 4.9 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was heated at 120 캜 for 2 hours under a nitrogen atmosphere. After cooling, water and ethyl acetate were added to the reaction mixture, and the mixture was separated. The organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain residue D2A. The residue D2A was purified by silica gel column chromatography to obtain 1.7 g of Intermediate D2A.

D2A (1.7 g) and p-xylene (6 mL) were mixed, and 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 占 폚 for 2 hours. After cooling, water and ethyl acetate were added to the reaction mixture, and the mixture was separated. The organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain residue D2B.

(THF) (2 mL) and the total amount of residue D2B were mixed, 6.0 mL of a 2 M hydrochloric acid / THF solution was added dropwise under ice-cooling, and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) After the temperature was raised to room temperature, the mixture was stirred for 2 hours. Water and ethyl acetate were added to the reaction mixture to separate the layers. The organic layer was washed with water, dried over magnesium sulfate, filtered, and concentrated to obtain an intermediate residue D2C.

The entire amount of the intermediate residue D2C was mixed with acetone (10 mL), and then triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (1.2 g), p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) under ice-cooling. (1.4 g) was added, the mixture was heated to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture, and the mixture was separated. The organic phase was dried over magnesium sulfate, filtered, and concentrated to obtain residue D2. Residue D2 was slurried with cold methanol, filtered and dried to obtain D2 (1.2 g).

The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of D2 showed δ = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7.6 , 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H).

&Lt; Heat crosslinking agent &

F1: jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Holdings Corporation)

F2: jER157S65 (novolak type epoxy resin, manufactured by Mitsubishi Chemical Holdings Corporation)

F3: jER1007 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Holdings Corporation)

<Increase / decrease>

G1: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Chemicals)

<Alkoxysilane compound>

H1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

&Lt; Basic compound &gt;

I1: Compound of the following structure (manufactured by TOYO KASEI CO., LTD., CMTU)

<Surfactant>

W1: Perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation)

J1: PIONIN D-6112-W (polyoxyalkylene polystyryl phenyl ether, manufactured by TAKEMOTO OIL & FAT Co., Ltd.)

J2: PIONIN D-6512 (polyoxyethylene monostyryl phenyl ether, manufactured by TAKEMOTO OIL & FAT Co., Ltd.)

<Other additives>

L1: Compound of the following structure (heterocyclic compound having two or more nitrogen atoms)

L2: Compound of the following structure (heterocyclic compound having two or more nitrogen atoms)

L3: Compound of the following structure (heterocyclic compound having two or more nitrogen atoms)

L4: Compound of the following structure (heterocyclic compound having two or more nitrogen atoms)

L5: Compound of the following structure (heterocyclic compound having two or more nitrogen atoms)

&Lt; Evaluation of inkjet dischargeability &

Ink jet application device: Dimatix Material Printer DMP-2831 (manufactured by FUJIFILM Dimatix, Inc., driving voltage 16V, frequency 5 kHz)

The obtained photosensitive resin composition was subjected to 50 inkjet application onto a 100 mm x 100 mm glass substrate (trade name: XG, produced by Corning) in the apparatus. After completion of application to 50 sheets, all 16 discharge nozzle tips were observed to confirm clogging of the tip of the nozzle. In addition, the lines depicting the application were confirmed. The evaluation was carried out based on the following criteria. 3 or more is a practical range.

5: There is no nozzle clogging and there is no bending of the description line.

4: Nozzle clogging is 1 or 2, and there is no bending of the description line.

3: There are 3 to 5 nozzle clogging, and there is no bending of the description line.

2: There are 6 to 10 nozzle clogging, or bending of the description line.

1: There are more than 10 nozzle clogging, or bending of the description line.

&Lt; Evaluation of dryness &

The photosensitive resin composition thus obtained was coated on a 100 mm x 100 mm glass substrate (trade name: XG, produced by Corning) in the inkjet coating apparatus so as to have a dry film thickness of 2.0 m and dried on a hot plate at each temperature for 120 seconds Baked) to obtain a coating film. Thereafter, the coated film was touched with a finger to confirm drying. The evaluation criteria are as follows. 3 or more is a practical range.

5: The prebake was dried at a temperature of 80 캜 or lower.

4: The prebake temperature exceeded 80 캜 and was dried at 85 캜.

3: The prebake temperature exceeded 85 캜 and dried at 90 캜.

2: The prebake temperature exceeded 90 캜 and was dried at 100 캜.

1: No drying at 100 占 폚 pre-bake temperature.

&Lt; Evaluation of Developability (Resolution) &gt;

The obtained photosensitive resin composition was coated on the 100 mm x 100 mm glass substrate (trade name: XG, produced by Corning) treated with hexamethyldisilazane (HMDS) for 3 minutes in the ink jet application device so as to have a film thickness of 2.0 m , And dried (prebaked) on a hot plate at 90 DEG C for 120 seconds.

Subsequently, exposure was carried out using a ghi line high pressure mercury lamp exposer at a luminance of 20 mW / cm 2 and a luminance of 200 mJ / cm 2 through a 1% to 60% line-and-space mask with a line and space of 1: 1.

Subsequently, the resist film was developed with a 0.5% KOH aqueous solution at 23 DEG C for 15 seconds by a dipping puddle method, and further rinsed with ultrapure water for 10 seconds. And then heated at 220 DEG C for 45 minutes to obtain a pattern. This pattern was observed with an optical microscope.

This operation was started from the width of the line and space of the mask of 50 mu m, and the minimum width at which the pattern was produced with 5 mu m by 10 mu m and 10 mu m or less by narrowing the width by 1 mu m . 3 or more is a practical range.

5: The resolution was 5 탆 or less.

4: The resolution was more than 5 탆 and not more than 10 탆.

3: The resolution was more than 10 탆 and not more than 15 탆.

2: The resolution was more than 15 탆 and not more than 50 탆.

1: The pattern could not be formed with a line-and-space width of 50 mu m in the mask.

&Lt; Evaluation of haze (transparency) &gt;

The photosensitive resin composition thus obtained was coated on a 100 mm x 100 mm glass substrate (trade name: XG, produced by Corning) with the above-described ink-jet coating apparatus so as to have a dry film thickness of 1.5 탆 and dried on a hot plate at 80 캜 for 120 seconds Baked). Further, the coating film was subjected to heat treatment (post-baking) in an oven at 220 캜 for 15 minutes, and haze after post-baking was measured by NIPPON DENSHOKU INDUSTRIES Co., LTD. The opacity (haze value) was measured in accordance with the plastic product test method (JIS K7136, JIS K7361, ASTM D1003) with the film surface up with NDH-5000 manufactured.

The haze value refers to a value expressed by a ratio (%) of diffuse transmission light to the total light transmission light. The smaller the haze value, the higher the transparency.

The evaluation criteria are as follows. 3 or more is a practical range.

5: Haze value was less than 0.5%.

4: The haze value was 0.5% or more and less than 0.7%.

3: The haze value was 0.7% or more and less than 1.0%.

2: The haze value was 1.0% or more and less than 2.0%.

1: Haze value was 2.0% or more.

<Evaluation of storage stability>

After the obtained photosensitive resin composition was stored at 30 DEG C for 7 days, evaluation of developability and evaluation of haze were carried out. The criterion is based on the evaluation of developability and haze. 3 or more is a practical range.

5: Developability after storage for 7 days at 30 ℃, and haze value together 5.

4: Average of haze value after storage for 7 days at 30 ° C is 4 or more and less than 5.

3: Average of haze value after 3 days at 30 ℃ after 7 days storage is 3 or more and less than 4.

2: The average of the developability and haze value after storage for 7 days at 30 ° C is 2 or more and less than 3.

After storage at 1: 30 ℃ for 7 days, the average of the developing performance and haze value is less than 2.

<Overall evaluation>

5: Each evaluation is 5.

4: Each evaluation exceeds 2, and the average of each evaluation is 4 or more.

3: Each evaluation exceeds 2, and the average of each evaluation is 3 or more and less than 4.

2: Each evaluation exceeds 2, and the average of each evaluation is 2 or more and less than 3.

1: The average of each evaluation is less than 2.

However, if there is 2 or less in each item in each evaluation, take a value from negative evaluation point to negative evaluation point. 3 or more is a practical range.

As is clear from the results shown in Tables 3 and 7 to 9, the photosensitive resin composition for ink jet application of the present invention was excellent in dischargeability, dryness, transparency, developability and storage stability, and excellent in overall performance. On the other hand, it was found that the performance balance in the photosensitive resin composition of the comparative example deteriorates.

(Example 111)

In the active matrix type liquid crystal display device shown in Fig. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as described below, and a liquid crystal display device of Example 111 was obtained. That is, after the photosensitive resin composition of Example 1 was spin-coated on the substrate and prebaked (90 DEG C / 120 seconds) on a hot plate, i-line (365 nm) was irradiated from above the mask to 45 mJ / (Illuminance of 20 mW / cm 2), developed with an aqueous alkaline solution to form a pattern, and subjected to heat treatment at 230 ° C for 30 minutes to form a cured film 17 as an interlayer insulating film.

As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

(Example 112)

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 with the TFT 1 covered. Subsequently, a contact hole (not shown) was formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole was formed on the insulating film 3 . The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

In order to planarize the irregularities formed by the formation of the wirings 2, the planarization film 4 was formed on the insulating film 3 in a state in which irregularities due to the wirings 2 were embedded. The planarizing film 4 was formed on the insulating film 3 by applying the photosensitive resin composition of Example 2 on a substrate, pre-baking (90 DEG C / 120 seconds) on a hot plate, (365 nm) was irradiated with 45 mJ / cm 2 (illuminance: 20 mW / cm 2), and then developed with an aqueous alkali solution to form a pattern and subjected to heat treatment at 230 ° C. for 30 minutes.

The coating properties upon application of the photosensitive resin composition were favorable, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Subsequently, a bottom-emission organic EL device was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, the resist was applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using the ITO etchant. Thereafter, the resist pattern was peeled off at 50 占 폚 using a resist stripping solution (Remover 100, manufactured by AZ Electronic Materials). The thus obtained first electrode 5 corresponds to the anode of the organic EL element.

Then, an insulating film 8 having a shape covering the peripheral edge of the first electrode 5 was formed. The insulating film 8 was formed using the photosensitive resin composition of Example 2 in the same manner as described above. By forming the insulating film 8, a short circuit can be prevented between the first electrode 5 and the second electrode formed in the subsequent step.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially deposited in a vacuum deposition apparatus through a desired pattern mask. Then, a second electrode made of Al was formed on the entire surface above the substrate. The obtained substrate was taken out from the evaporator, and sealed by bonding the glass plate for sealing and the ultraviolet curable epoxy resin to each other.

An organic EL display device of the active matrix type in which the TFTs 1 for driving the organic EL elements were connected to the organic EL elements as described above was obtained. As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibits good display characteristics and is highly reliable.

(Example 113)

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

&Lt; Formation of first transparent electrode pattern &gt;

[Formation of transparent electrode layer]

A front plate of a tempered glass (300 mm x 400 mm x 0.7 mm) having a mask layer formed therein was introduced into a vacuum chamber and an ITO target (indium: tin = 95: 5 (molar ratio)) having a SnO ₂ content of 10 mass% An ITO thin film having a thickness of 40 nm was formed by DC magnetron sputtering (conditions: substrate temperature: 250 占 폚, argon pressure: 0.13 Pa, oxygen pressure: 0.01 Pa) to obtain a front plate having a transparent electrode layer. The surface resistance of the ITO thin film was 80? / ?.

Then, a commercially available etching resist was coated on ITO and dried to form an etching resist layer. After a pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i line) with a distance between the surface of the exposure mask (a quartz exposure mask having a transparent electrode pattern) and the etching resist layer set at 100 m, Lt; 0 &gt; C for 30 minutes to obtain a front plate having a transparent electrode layer and a photo-sensitive resin layer pattern for etching formed thereon.

The front plate on which the transparent electrode layer and the photo-sensitive resin layer pattern for etching were formed was dipped in an etching bath containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 占 폚) for 100 seconds, The transparent electrode layer in the exposed region was dissolved and removed to obtain a front plate having a transparent electrode layer pattern with an etching resist layer pattern.

Subsequently, a front plate with a transparent electrode layer pattern with an etching resist layer pattern was immersed in a special resist stripper, and a photo-sensitive resin layer for etching was removed to obtain a front plate having a mask layer and a first transparent electrode pattern formed thereon.

[Formation of insulating layer]

The photosensitive resin composition of Example 1 was applied and dried (film thickness 1 占 퐉, 90 占 폚 for 120 seconds) on the front plate on which the mask layer and the first transparent electrode pattern were formed to obtain a photosensitive resin composition layer. A pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i line) by setting a distance between the exposure mask (quartz exposure mask having an insulating layer pattern) surface and the photosensitive resin composition layer to 30 μm.

Subsequently, the resist film was developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 占 폚 for 15 seconds by a dipping puddle method, and further rinsed with ultrapure water for 10 seconds. Subsequently, post-baking treatment was performed at 220 캜 for 45 minutes to obtain a front plate having a mask layer, a first transparent electrode pattern, and an insulating layer pattern formed thereon.

&Lt; Formation of second transparent electrode pattern &gt;

[Formation of transparent electrode layer]

The front plate formed up to the insulating layer pattern in the same manner as the formation of the first transparent electrode pattern was subjected to DC magnetron sputtering (conditions: base temperature: 50 캜, argon pressure: 0.13 Pa, oxygen pressure: 0.01 Pa) A thin film was formed to obtain a front plate having a transparent electrode layer formed thereon. The surface resistance of the ITO thin film was 110? / ?.

A commercially available etching resist was used in the same manner as the formation of the first transparent electrode pattern, and a first transparent electrode pattern, an insulating layer pattern formed using the photosensitive resin composition of Example 82, a transparent electrode layer, (Post bake treatment; at 130 占 폚 for 30 minutes).

The mask layer, the first transparent electrode pattern, the insulating layer pattern formed by using the photosensitive resin composition of Example 82, and the second transparent electrode pattern were formed by etching in the same manner as the formation of the first transparent electrode pattern, Was obtained.

&Lt; Formation of a conductive element different from the first and second transparent electrode patterns &

The front plate on which the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 82, and the second transparent electrode pattern were formed in the same manner as in the formation of the first and second transparent electrode patterns was formed as a DC magnetron And a front plate having an aluminum (Al) thin film having a thickness of 200 nm was obtained by sputtering.

A commercially available etching resist was used in the same manner as the formation of the first and second transparent electrode patterns and the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 82, , And a front plate on which an etching resist pattern was formed (post baking treatment: 130 DEG C for 30 minutes).

The mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 82 were removed by etching (30 占 폚 for 50 seconds) and removing the etching resist layer (45 占 폚 for 200 seconds) A second transparent electrode pattern, and a front plate on which conductive elements different from those of the first and second transparent electrode patterns were formed were obtained.

&Lt; Formation of transparent protective layer &

The photosensitive resin composition of Example 60 was coated and dried (film thickness 1 占 퐉, 90 占 폚 for 120 seconds) on the front plate having the conductive elements other than the first and second transparent electrode patterns formed in the same manner as the formation of the insulating layer Thereby obtaining a photosensitive resin composition film. The mask layer, the first transparent electrode pattern, and the second transparent electrode pattern were subjected to a front exposure with an exposure dose of 50 mJ / cm 2 (i line) without passing through an exposure mask and development, post exposure (1,000 mJ / cm 2) The insulating layer pattern formed using the photosensitive resin composition, the second transparent electrode pattern, and the insulating layer formed using the photosensitive resin composition of Example 60 (a transparent Protective layer) was laminated thereon.

&Lt; Fabrication of Image Display Device (Touch Panel)

An image display device having a capacitive input device as a constituent element was manufactured by bonding a front plate prepared in advance to a liquid crystal display element manufactured by the method described in JP-A-2009-47936.

<Evaluation of Front Panel 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 the conductive elements different therefrom. On the other hand, since the first transparent electrode pattern and the second transparent electrode pattern have insulating property, Display characteristics were obtained. Further, the first and second transparent electrode patterns were hardly visually observed, and thus an image display apparatus 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 Curing 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 connecting portion 34 second transparent electrode pattern
35 insulating layer 36 conductive element
37 transparent protective layer 38 opening

Claims (16)

(Component A) An inorganic particle,
(Component B) Solvent,
(Component C) a polymer comprising a constituent unit having an acid group protected by an acid-decomposable group, and
(Component D) containing a photoacid generator,
Wherein the component B comprises a non-alcoholic solvent having a boiling point of 177 DEG C or higher and 227 DEG C or lower and an I / O value of 0.50 or more and 1.00 or less. The method according to claim 1,
Wherein the non-alcoholic solvent is at least one selected from the group consisting of an alkylene glycol monoalkyl ether acylate, a dialkylene glycol monoalkyl ether acylate, a dialkylene glycol dialkyl ether, and a trialkylene glycol dialkyl ether By weight based on the total weight of the photosensitive resin composition. 3. The method according to claim 1 or 2,
Wherein the component A is a metal oxide particle. 4. The method according to any one of claims 1 to 3,
Wherein the component A is a titanium oxide particle or a zirconium oxide particle. 5. The method according to any one of claims 1 to 4,
(Component E) a dispersing agent. 6. The method according to any one of claims 1 to 5,
(Component F) a thermal cross-linking agent. A method for producing a heat-treated product, comprising at least steps (a) to (c).
(a) a coating step of coating the photosensitive resin composition for inkjet coating according to any one of claims 1 to 6 onto a substrate by an ink-jet coating method
(b) a solvent removing step of removing the solvent from the applied resin composition
(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed A method for producing a resin pattern, comprising at least steps (1) to (5).
(1) A coating process for coating the photosensitive resin composition for inkjet coating according to any one of claims 1 to 6 on a substrate by an ink-jet coating method
(2) a solvent removing step of removing the solvent from the applied resin composition
(3) an exposure step of exposing the resin composition from which the solvent has been removed to a pattern shape by an actinic ray
(4) a developing step of developing the exposed resin composition with an aqueous developing solution
(5) Heat treatment process for heat-treating the developed resin composition A heat-treated product characterized by being obtained by the method for producing a heat-treated product according to claim 7 or the method for producing a resin pattern according to claim 8. A heat-treated product obtained by heat-treating the photosensitive resin composition for ink-jet application according to any one of claims 1 to 6. 11. The method of claim 10,
Wherein the insulating film is an interlayer insulating film. A liquid crystal display device having the heat-treated product according to claim 10 or 11. An organic EL display device having the heat-treated product according to claim 10 or claim 11. A manufacturing method of a touch panel having a transparent substrate, an ITO electrode, and an insulating layer,
A process for coating the photosensitive resin composition for inkjet application according to any one of claims 1 to 6 by an inkjet coating method so as to contact with an ITO electrode,
A step of laminating a mask having an opening pattern of a predetermined shape on the resin composition,
A step of developing the resin composition after exposure, and
And heating the resin composition after development to produce an insulating layer. Wherein all or a part of the insulating layer is made of the heat-treated product of the photosensitive resin composition for ink-jet application according to any one of claims 1 to 6. A touch panel display device comprising the heat-treated product according to claim 10 or 11, or the touch panel according to claim 15.

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