JP6499595B2 - Photosensitive resin composition, method for producing cured film, cured film, touch panel, and display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a method for producing a cured film, a cured film, a touch panel, and a display device.

  Flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used. In recent years, capacitive touch panels have attracted attention with the spread of smartphones and tablet terminals. The sensor substrate of the capacitive touch panel has a transparent electrode (ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) etc.) and a metal electrode (silver, copper, molybdenum, titanium, aluminum, etc.) on glass or film, and Such a laminated body and an alloy thereof have a patterned wiring, and in addition, a structure having a protective film for protecting an insulating film, ITO, and metal at a crossing portion of the wiring is general.

  As a conventional photosensitive resin composition, Patent Document 1 discloses (A) a monomer having a carboxyl group and / or a repeating unit (a1) derived from a monomer having a phenolic hydroxyl group, the following general formula 2-1 and / or A positive photosensitive resin composition containing a copolymer having a repeating unit (a2) represented by general formula 2-2 and (B) a radiation-sensitive acid generating compound is described.

In General Formula 2-1, R ¹ represents a hydrogen atom, a methyl group, —CH ₂ OH, or —CH ₂ CH ₂ OH. A represents a divalent linking group. R ^a represents a hydrogen atom or a methyl group.

In General Formula 2-2, R ² represents a hydrogen atom, a hydroxyl group, —CH ₂ OH, —CH ₂ CH ₂ OH, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. One of R ³ and R ⁴ represents a hydrogen atom, a hydroxyl group, —CH ₂ OH, —CH ₂ CH ₂ OH, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and the other is It is a hydrogen atom. R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydroxyl group, —CH ₂ OH, —CH ₂ CH ₂ OH, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, At least one of R ⁵ and R ⁶ is a hydrogen atom. A represents a divalent linking group. R ^a represents a hydrogen atom or a methyl group.

JP 2013-76939 A

  The problem to be solved by the present invention is a photosensitive resin composition excellent in the storage stability of a photosensitive resin composition and the corrosion resistance of a cured film obtained using the photosensitive resin composition, and the above photosensitive property. It is providing the manufacturing method of the cured film using a resin composition, the cured film which hardened the said photosensitive resin composition, and the touchscreen and display apparatus using the said cured film.

The above-described problems of the present invention have been solved by means described in the following <1>, <9>, <10>, <12>, <14> or <15>. It is described below together with <2> to <8>, <11> and <13> which are preferred embodiments.
<1> Contains a polymer component containing a polymer satisfying at least one of the following a1 and a2, a quinonediazide compound, a solvent, and a structural unit d1 represented by the following formula 1 and a structural unit d2 having a carboxylic anhydride structure. The molar ratio of the structural unit d1 and the structural unit d2 in the polymer D is in the range of d1: d2 = 3: 1 to 8: 1, and the acid anhydride value of the polymer D is 1. It is 00-3.00 mmol / g, and content of the polymer D is 0.5-15 mass% with respect to content of the polymer which has a structural unit which has an acid group in the said polymer component. Photosensitive resin composition,
a1: A polymer having a structural unit having an acid group and a structural unit having a crosslinkable group a2: A polymer having a structural unit having an acid group and a polymer having a structural unit having a crosslinkable group

In Formula 1, each R ¹ independently represents a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, a carboxy group, or a halogen atom, R ² represents a hydrogen atom, an alkyl group, or an aryl group, and n is 0 to 0 Represents an integer of 5,
<2> The photosensitive property according to <1>, wherein the content of the polymer D is 0.5 to 10% by mass with respect to the content of the polymer having a structural unit having an acid group in the polymer component. Resin composition,
<3> The photosensitive resin composition according to <1> or <2>, further containing inorganic particles,
<4> The photosensitive resin composition according to <3>, wherein the content of the inorganic particles is 10 to 80% by mass with respect to the content of the polymer having a structural unit having an acid group in the polymer component. object,
<5> The photosensitive resin composition according to <3> or <4>, wherein the number average primary particle size of the inorganic particles is 10 to 200 nm.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the structural unit d2 is a structural unit including a 5-membered cyclic carboxylic acid anhydride structure,
<7> Any one of <1> to <6>, wherein the structural unit d2 includes a structural unit represented by the following formula d2-1 and / or a structural unit represented by the following formula d2-2. A photosensitive resin composition according to claim 1,

  <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the structural unit d2 includes a structural unit represented by the following formula d2-1.

<9> A method for producing a cured film comprising at least steps a to d in this order,
Step a: Application step of applying the photosensitive resin composition according to any one of <1> to <8> on a substrate Step b: Solvent removal step of removing the solvent from the applied photosensitive resin composition Step c: Exposure step of exposing at least a part of the photosensitive resin composition from which the solvent has been removed with actinic rays Step d: Heat treatment step of heat-treating the photosensitive resin composition <10> At least Step 1 to Step 5 in this order A method for producing a cured film, comprising:
Process 1: Application | coating process which apply | coats the photosensitive resin composition as described in any one of <1>-<8> on a board | substrate Process 2: The solvent removal process which removes a solvent from the apply | coated photosensitive resin composition Step 3: An exposure step of exposing at least a part of the photosensitive resin composition from which the solvent has been removed with actinic rays Step 4: A development step of developing the exposed photosensitive resin composition with an aqueous developer Step 5: developed Heat treatment step for heat-treating the photosensitive resin composition <11> The method for producing a cured film according to <10>, wherein the heat treatment temperature in Step 5 is 80 to 150 ° C.
<12> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <8>,
<13> The cured film according to <12>, which is an interlayer insulating film or an overcoat film,
<14> A touch panel having the cured film according to <12> or <13>,
<15> A display device having the cured film according to <12> or <13>.

  According to the present invention, the photosensitive resin composition excellent in the storage stability of the photosensitive resin composition and the corrosion resistance of the cured film obtained using the photosensitive resin composition, the photosensitive resin composition The manufacturing method of the used cured film, the cured film which hardened the said photosensitive resin composition, and the touch panel and display apparatus using the said cured film were able to be provided.

1 is a conceptual diagram illustrating a configuration of an example of an organic EL (Electroluminescence) display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 1 is a conceptual diagram illustrating a configuration of an example of a liquid crystal display device having a touch panel function. FIG. 5 shows a conceptual diagram of a configuration of another example of a liquid crystal display device having a touch panel function.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
Further, “structural unit d1 represented by the following formula 1” or the like is also simply referred to as “structural unit d1” or the like.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention (hereinafter also simply referred to as “composition”) includes a polymer component containing a polymer that satisfies at least one of the following a1 and a2, a quinonediazide compound, a solvent, and the following formula 1. The polymer D containing the structural unit d1 represented and the structural unit d2 which has a carboxylic anhydride structure is contained, and the molar content ratio of the structural unit d1 and the structural unit d2 in the polymer D is d1: d2 = 3: 1. Is in the range of ˜8: 1, the acid anhydride value of the polymer D is 1.00 to 3.00 mmol / g, and the content of the polymer D has a structural unit having an acid group in the polymer component. It is characterized by being 0.5 to 15% by mass with respect to the content of the polymer.
a1: A polymer having a structural unit having an acid group and a structural unit having a crosslinkable group a2: A polymer having a structural unit having an acid group and a polymer having a structural unit having a crosslinkable group

In Formula 1, each R ¹ independently represents a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, a carboxy group, or a halogen atom, R ² represents a hydrogen atom, an alkyl group, or an aryl group, and n is 0 to 0 Represents an integer of 5.

With the increase in size and power saving of touch panel display devices, it is required to reduce the resistance of the wiring of the sensor substrate of the capacitive touch panel. Specifically, the use and examination of metals having low resistance values (silver, copper, molybdenum, titanium, aluminum, etc., and their laminates and alloys) are in progress.
However, the present inventors have found that when a normal cured film is used as a protective film for a touch panel using the above metal electrode, the wiring corrodes with discoloration due to long-term use, resulting in an increase in resistance value or metal wiring. I found the problem that it might break. It is presumed that the discoloration of the wiring occurs, for example, when the user's sweat or salt in the sweat contacts the wiring through the protective film and the wiring corrodes. In the present invention, suppression of such wiring corrosion by the cured film is referred to as corrosion resistance of the cured film.
As a result of intensive studies, the present inventors have found that a polymer component containing a polymer satisfying at least one of the above a1 and a2, a quinonediazide compound, a solvent, and the structural unit d1 and the carboxylic acid anhydride structure represented by the above formula 1 And a molar content ratio of the structural unit d1 and the structural unit d2 in the polymer D is in the range of d1: d2 = 3: 1 to 8: 1, and the polymer D The acid anhydride value of 1.00 to 3.00 mmol / g, and the content of the polymer D is 0.5 to the content of the polymer having a structural unit having an acid group in the polymer component. The photosensitive resin composition characterized by being 15% by mass is found to be excellent in the storage stability of the photosensitive resin composition and the corrosion resistance of the cured film obtained using the photosensitive resin composition. It was.
Although the detailed mechanism is unknown, it is speculated that the above effect is obtained by the concerted action of the above components.
Hereinafter, each component which the photosensitive resin composition of this invention contains is demonstrated.

<Polymer component containing a polymer satisfying at least one of a1 and a2>
The photosensitive resin composition of the present invention contains a polymer component that satisfies at least one of the following a1 and a2.
a1: A polymer having a structural unit having an acid group and a structural unit having a crosslinkable group a2: A polymer having a structural unit having an acid group and a polymer having a structural unit having a crosslinkable group The coalescence component as a whole has an acid group and a crosslinkable group, so that a curing reaction is possible.

The polymer component is preferably a polymer component satisfying the a1.
Moreover, the photosensitive resin composition of this invention may contain polymers other than the polymer shown to said a1 and a2.
The polymer contained in the polymer component preferably has an acid anhydride value of less than 1.00, and more preferably does not have an acid anhydride structure.
When the polymer component contains a plurality of polymers, the acid anhydride value is preferably less than 1.00 for all the polymers, and more preferably has no acid anhydride structure.
The acid anhydride value of the polymer can be measured in the same manner as the acid anhydride value of polymer D described later.

Each polymer in the polymer component is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. Further, “(meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.
The polymer having a structural unit having an acid group preferably has an acid value of 50 mgKOH / g or more and 500 mgKOH / g or less from the viewpoint of imparting appropriate solubility in a developer and easily obtaining a desired pattern shape. / G or more and 300 mgKOH / g or less is more preferable. The acid value of the polymer having a structural unit having an acid group can be measured according to the method described in JIS K2501 (2003).
Hereinafter, the structural unit having an acid group, the structural unit having a crosslinkable group, and other structural units contained in the polymer in a1 or a2 will be described.

[Structural unit having an acid group]
The polymer component contains at least a polymer having a structural unit having an acid group.
When the polymer component contains a polymer having a structural unit having an acid group, the solubility in an alkaline developer is improved, the developability is improved, and the sensitivity is further improved, and further after development. Excellent adhesion.
The structural unit having an acid group is preferably a structural unit having at least one selected from the group consisting of a carboxy group, a phenolic hydroxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, and a sulfonylimide group. A structural unit having at least one selected from the group consisting of a group and a phenolic hydroxyl group is more preferred, and a structural unit having a carboxy group is more preferred.
The acid group in the structural unit having an acid group may be a group formed by neutralization to form a salt structure. Although there is no restriction | limiting in particular as said salt, An alkali metal salt, alkaline-earth metal salt, ammonium salt, and organic ammonium salt can illustrate preferably.

-Structural unit having a carboxy group-
Specific examples of the structural unit having a carboxy group include a structural unit derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule.
Examples of the unsaturated carboxylic acid used for forming the structural unit having a carboxy group include those listed below.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Examples include hexahydrophthalic acid and 2- (meth) acryloyloxyethyl phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be its acid anhydride, but is preferably not an acid anhydride. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.

  Especially, as a structural unit which has a carboxy group, the structural unit derived from methacrylic acid (the structural unit represented by the following formula a1-1) or the structural unit derived from acrylic acid (the structural unit represented by the following formula a1-2) The structural unit derived from methacrylic acid (the structural unit represented by the following formula a1-1) is more preferable.

In formula a1-1 and formula a1-2, R ^a each independently represents a hydrogen atom, an alkali metal cation, an alkaline earth metal cation, an ammonium ion, or an organic ammonium ion.
Among them, Ra is preferably ^a hydrogen atom.

-Structural unit having phenolic hydroxyl group-
Specific examples of the structural unit having a phenolic hydroxyl group include structural units derived from a phenolic hydroxyl group-containing unsaturated compound described in paragraphs 0029 to 0043 of JP2012-88459A, and a copolymerization reaction. O-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene and the like are preferable from the viewpoints of solubility, solubility in an alkaline aqueous solution, and availability.

In one polymer, the structural unit having an acid group can be used alone or in combination of two or more.
1-80 mol% is preferable with respect to the structural unit of all the polymer components, as for content of the structural unit which has an acid group, 10-65 mol% is more preferable, and 20-55 mol% is the most preferable.
In the present invention, when the content of the “structural unit” is defined in terms of molar ratio, the “structural unit” is synonymous with the “monomer unit”. In the present invention, the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

[Structural unit having a crosslinkable group]
The polymer component contains at least a polymer having a structural unit having a crosslinkable group.
The structural unit having the crosslinkable group is not particularly limited as long as it is a group that causes an effective reaction by heating. However, the structural unit having an epoxy group and / or oxetanyl group, (—NH—CH ₂ —O—R) A structural unit having a group represented (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), and a structural unit having an ethylenically unsaturated group, and an epoxy group and / or an oxetanyl group. And a group represented by (—NH—CH ₂ —O—R) (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), an epoxy group and / or an oxetanyl group. The structural unit having

-Structural unit having an epoxy group and / or an oxetanyl group-
A 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group.
The structural unit having the epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one or more oxetanyl groups, It may have two or more epoxy groups or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups. Alternatively, it is more preferable to have one or two oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic epoch Such compounds may be mentioned containing shea skeleton, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Acid esters, and the like, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having the epoxy group and / or oxetanyl group include a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure. It is preferable.

  Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyl) Preferred is oxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

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

_{- (- NH-CH 2 -O} -R) structural unit having a group represented by -
As the structural unit having a group represented by (—NH—CH ₂ —O—R), a structural unit described in paragraph 0023 of International Publication No. 2014/156873 is preferable.

-Structural unit having an ethylenically unsaturated group-
As the structural unit having an ethylenically unsaturated group, the structural unit described in paragraph 0022 of International Publication No. 2014/156873 is preferable.

In one polymer, the structural unit having a crosslinkable group can be used alone or in combination of two or more.
The content of the structural unit having a crosslinkable group is preferably from 5 to 90 mol%, more preferably from 20 to 80 mol%, still more preferably from 30 to 70 mol%, based on the structural units of all polymer components.

[Other structural units]
In the present invention, the polymer contained in the polymer component may have other structural units in addition to the above-described structural unit having an acid group and the structural unit having a crosslinkable group. Good.
There is no restriction | limiting in particular as a monomer which forms other structural units, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Examples thereof include dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, and unsaturated aromatic compounds.
The monomer which forms another structural unit can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the other structural units include styrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid (3 -Methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Examples of the structural unit include 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, and ethylene glycol monoacetoacetate mono (meth) acrylate. In addition, compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  As other structural units, styrenes or structural units derived from monomers having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.

In one polymer, other structural units can be used alone or in combination of two or more.
The content of other structural units is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, based on the structural units of all polymer components. As a lower limit, although 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

[Molecular weight of polymer]
The molecular weight of each polymer in the polymer component is independently polystyrene-converted weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and 10,000 to 20,000. Is more preferable. Various characteristics are favorable in the said range. The ratio of the number average molecular weight Mn to the weight average molecular weight Mw (dispersity, Mw / Mn) is preferably 1.0 to 5.0, and more preferably 1.5 to 3.5.
In addition, it is preferable to measure the weight average molecular weight and the number average molecular weight in the present invention by a gel permeation chromatography (GPC) method. The measurement by the gel permeation chromatography method in the present invention uses HLC-8020GPC (manufactured by Tosoh Corporation), and TSKgel Super HZ M-H, TSK gel Super HZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation), 4.6 mmID. It is preferable to use THF (tetrahydrofuran) as an eluent.

[Production method of polymer]
Various methods are also known for the synthesis of the above-mentioned polymer. For example, a radical polymerizable monomer containing a radical polymerizable monomer used to form each structural unit is exemplified. It can be synthesized by polymerizing the mixture in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

It is preferable that content of the said polymer component in the photosensitive resin composition of this invention is 20-95 mass% with respect to the total organic solid of a photosensitive resin composition, and is 50-93 mass%. More preferably, it is more preferably 55 to 90% by mass. When the content is within this range, an organic film having good curability can be obtained.
The total solid content of the photosensitive resin composition refers to all components excluding the solvent, and the total organic solid content of the photosensitive resin composition excludes inorganic components such as inorganic particles and the solvent described later. It means all ingredients.

<Quinonediazide compound>
The photosensitive resin composition of the present invention contains a quinonediazide compound.
As said quinonediazide compound, the 1, 2- quinonediazide compound which generate | occur | produces carboxylic acid by irradiation of actinic light can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, the description of paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2. -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably. Further, 4,4 ′-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Mol)), 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.44 mol), etc. It may be used.

These quinonediazide compounds can be used singly or in combination of two or more.
The content of the quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass with respect to 100 parts by mass of the total organic solid content in the photosensitive resin composition. 10-25 mass parts is still more preferable. By setting the blending amount of the quinonediazide compound within the above range, the difference in solubility between the irradiated portion of the actinic ray and the unirradiated portion with respect to the alkaline aqueous solution as the developer is large, the patterning performance is improved, and the resistance of the cured film obtained is improved Good solvent properties.

<Solvent>
The photosensitive resin composition of the present invention contains a solvent.
The photosensitive resin composition of the present invention comprises the polymer component and the quinonediazide compound, which are essential components, the polymer D described below, and an optional component, the polymer component, the quinonediazide compound, and the polymer D being It is preferable to prepare the photosensitive resin composition as a liquid in which these components are dissolved and / or dispersed using a dissolving organic solvent.
As the solvent, known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol. Monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, alcohols , Esters, ketones, amides, lactones, etc. . As specific examples of these organic solvents, reference can be made to paragraph 0062 of JP-A-2009-098616.

  Preferable specific examples include propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol diacetate, methoxypropyl acetate, cyclohexanol acetate, propylene glycol diacetate, tetrahydrofluoro Examples include furyl alcohol.

The boiling point of the solvent is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C, from the viewpoint of applicability.
The solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferred to use solvents having different boiling points in combination.
The content of the solvent in the photosensitive resin composition of the present invention is 100 to 3,000 parts by mass per 100 parts by mass of the total organic solid content of the photosensitive resin composition from the viewpoint of adjusting the viscosity to be suitable for coating. It is preferable that it is 200 to 2,000 parts by mass, and more preferably 250 to 1,000 parts by mass.
As solid content concentration of the photosensitive resin composition of this invention, 3-50 mass% is preferable, and it is more preferable that it is 10-40 mass%.
The viscosity of the photosensitive resin composition is preferably 1 to 200 mPa · s, more preferably 2 to 100 mPa · s, and most preferably 3 to 800 mPa · s. The viscosity is preferably measured at 25 ± 0.2 ° C. using, for example, a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed during measurement is preferably 100 rpm for less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 10 rpm for 30 mPa · s or more.

<Polymer D Containing Structural Unit d1 Represented by Formula 1 and Structural Unit d2 Having Carboxylic Anhydride Structure>
The photosensitive resin composition of the present invention includes a polymer D (hereinafter also simply referred to as “polymer D”) containing the structural unit d1 represented by the formula 1 and the structural unit d2 having a carboxylic anhydride structure. contains.
The weight average molecular weight of the polymer D is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, and still more preferably 3,000 to 50,000.
The polymer D preferably has an acid value of less than 500 mgKOH / g, and more preferably less than 300 mgKOH / g. The minimum of the said acid value is not specifically limited, What is necessary is just 0 mgKOH / g or more. The acid value of the polymer D can be measured according to the method described in JIS K2501 (2003).

[Structural unit d1]
The structural unit d1 is a structural unit represented by the following formula 1.
The structural unit d1 represented by Formula 1 is preferably a structural unit derived from a styrene compound.
Examples of the styrene compound include styrene, p-methylstyrene, α-methylstyrene, α, p-dimethylstyrene, p-ethylstyrene, pt-butylstyrene, 1,1-diphenylethylene, and styrene, α- Methyl styrene is preferred, and styrene is more preferred. In addition, a styrene compound may be used individually by 1 type, and may use 2 or more types together.

In Formula 1, each R ¹ independently represents a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, a carboxy group, or a halogen atom, R ² represents a hydrogen atom, an alkyl group, or an aryl group, and n is 0 to 0 Represents an integer of 5.
R ¹ independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxy group, an F atom, a Cl atom, a Br atom, or an I atom. Preferably, it is an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a Cl atom, or a Br atom.
R ² is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A methyl group or an ethyl group is more preferable, and a hydrogen atom is particularly preferable.
n is preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0.

  The content of the structural unit d1 in the polymer D is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, and 40 to 80% by mass with respect to the total mass of the polymer D. More preferably it is.

[Structural unit d2]
The structural unit d2 is a structural unit having a carboxylic anhydride structure.
The structural unit d2 is preferably a structural unit having only one carboxylic anhydride structure.
As the carboxylic acid anhydride structure, both chain and cyclic structures can be used, but a cyclic carboxylic acid anhydride structure is preferable. The number of ring members in the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 5-membered ring.
Further, other ring structures may be condensed or bonded to the cyclic carboxylic acid anhydride structure to form a polycyclic structure, but it is preferable that no polycyclic structure is formed. When other ring structures are condensed or bonded, other ring structures are condensed to form a bicyclo structure, or bonded to other ring structures to form a spiro structure. It is preferable that the number of condensed ring or other ring structures bonded is preferably 1 to 5, and more preferably 1 to 3. Examples of other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms and a heterocyclic group having 3 to 20 carbon atoms. Although it does not specifically limit as a heterocyclic group, The group or aromatic heterocyclic group in which one or more of the atoms which comprise an aliphatic ring is a hetero atom is mentioned. Moreover, as a heterocyclic group, a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is especially preferable. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.

  In addition, the carboxylic anhydride structure used in the present invention may or may not have a substituent, but preferably does not have a substituent. Although it does not specifically limit as a substituent, For example, a C1-C8 alkyl group, a C3-C7 cycloalkyl group, a C1-C8 alkoxy group, a C2-C8 alkoxycarbonyl group, A carboxy group, a halogen atom, a hydroxyl group, a cyano group, etc. are mentioned. More preferably, they are a C1-C4 alkyl group and a cyano group. As the alkyl group, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms is preferable. 1-3 alkyl groups are more preferred. When the carboxylic acid anhydride structure has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2. When the carboxylic anhydride structure used in the present invention has a plurality of substituents, the plurality of substituents may be the same as or different from each other. Further, when another ring structure is condensed to the carboxylic acid anhydride structure, the other ring structure may have a substituent.

  The structural unit having a carboxylic acid anhydride structure used in the present invention preferably includes a partial structure represented by the following formula 2.

In Formula 2, R ^A1a represents a substituent, and n ^1a R ^{A1a s} are independent and may be the same or different. Z ^1a represents a divalent group that forms a ring containing —C (═O) —O—C (═O) —. n ^1a represents an integer of 0 or more.
In Formula 2, R ^A1a represents a substituent, and n ^1a R ^{A1a s} are independent and may be the same or different. R ^A1a has the same meaning as the substituent that the carboxylic anhydride structure described above may have, and the preferred range is also the same.
In Formula 2, Z ^1a represents a divalent group that forms a ring containing —C (═O) —O—C (═O) —. Z ^1a preferably represents an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms.
The above partial structure may be bonded to another ring structure in a form forming a bicyclo structure, or may be bonded to another ring structure in a form forming a spiro structure, Preferably they are not bonded. The other ring structures are synonymous with the other ring structures described above, and the preferred ranges are also the same.
In Formula 2, n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0. When n ^1a represents an integer of 2 or more, a plurality of substituents may be the same as or different from each other. A plurality of substituents may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
The structural unit d2 is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, and an unsaturated aliphatic cyclic carboxylic acid. More preferably, it is a structural unit derived from an acid anhydride, more preferably a structural unit derived from maleic anhydride or itaconic anhydride, and particularly preferably a structural unit derived from maleic anhydride. .

Specific examples of the structural unit d2 are given below, but the structural unit d2 in the polymer D used in the present invention is not limited to these. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group, or a CF ₃ group, and Me represents a methyl group.

The structural unit d2 preferably contains a structural unit represented by at least one formula selected from the group consisting of the formulas d2-1 to d2-21, and the formula d2-1 to the formula d2-21. It is more preferable that it is a structural unit represented by either.
Among the specific examples, the structural unit d2 preferably contains a structural unit represented by the formula a2-1 and / or a structural unit represented by the formula d2-2, and is represented by the formula d2-1. It is more preferable to contain a unit.
The structural unit d2 is preferably a structural unit represented by the formula d2-1 and / or a structural unit represented by the formula d2-2, and is preferably a structural unit represented by the formula d2-1. More preferred.

The content of the structural unit d2 in the polymer D is preferably 5 to 60% by mass, more preferably 5 to 40% by mass, and 10 to 35% by mass with respect to the total mass of the polymer D. More preferably it is.
The total content of the structural unit d1 and the structural unit d2 in the polymer D is preferably 70% by mass or more, more preferably 90% by mass or more, based on the total mass of the polymer D. More preferably, it is 95 mass% or more. The upper limit of the total content is not particularly limited and may be 100% by mass or less.

[Structural unit d3]
The polymer D may contain a structural unit d3 in addition to the structural unit d1 and the structural unit d2.
From the viewpoint of reducing the acid value of the polymer D, the structural unit d3 preferably does not contain an acid group.
Although it does not specifically limit as structural unit d3, The structural unit derived from a monofunctional ethylenically unsaturated compound is mentioned. As the monofunctional ethylenically unsaturated compound, known compounds can be used without any particular limitation. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meta ) Acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid derivatives such as epoxy (meth) acrylate, N-vinyl such as N-vinylpyrrolidone, N-vinylcaprolactam Compounds, derivatives of allyl compounds such as allyl glycidyl ether are preferably used.

  The content of the structural unit d3 in the polymer D is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and 0 to 2% by mass with respect to the total mass of the polymer D. More preferably it is.

[Characteristics of Polymer D]
-Content-
It is preferable that content of the polymer D in the photosensitive resin composition of this invention is 0.5-8 mass% with respect to the total solid of the photosensitive resin composition, and it is 1-7 mass%. More preferably, it is further preferably 2 to 6% by mass. If it is the said range, it is excellent by the corrosion resistance of the hardened | cured material obtained.
Moreover, content of the polymer D in the photosensitive resin composition of this invention is 0.5-15 mass% with respect to content of the polymer which has a structural unit which has an acid group in the above-mentioned polymer component. 0.5 to 10% by mass is preferable, and 1 to 9% by mass is more preferable. If it is the said range, it is excellent in the storage stability of the photosensitive resin composition, and the photosensitive resin composition excellent in the corrosion resistance of the hardened | cured material obtained is obtained.

-Ratio of structural unit d1 and structural unit d2-
The molar content ratio of the structural unit d1 and the structural unit d2 in the polymer D is d1: d2 = 3: 1 to 8: 1, and preferably d1: d2 = 3.5: 1 to 8: 1. It is more preferable that d1: d2 = 4: 1 to 8: 1. If it is the said range, it is excellent in the storage stability of the photosensitive resin composition, and the photosensitive resin composition excellent in the corrosion resistance of the cured film obtained is obtained.

-Acid anhydride value-
The acid anhydride value of the polymer D is 1.00 to 3.00 mmol / g, preferably 1.00 to 2.80 mmol / g, and more preferably 1.10 to 2.60 mmol / g. preferable.
The acid anhydride value of the polymer D can be calculated, for example, by measuring the reaction amount of octylamine and acid anhydride. Specifically, the methods described below are listed.
Solution A and solution B having the following composition are prepared, and solution B is stirred at room temperature (25 ° C.) for 2 hours to complete the reaction. The solution A and the solution B are titrated with a 0.5 mol / l hydrochloric acid aqueous solution, and the valence A (mmol / g) of the amine of the solution A and the valence B (mmol / g) of the amine of the solution B are calculated. Furthermore, the acid anhydride value of the polymer D can be calculated from the following formula.
Acid anhydride amount of solution B (mmol)
= Amine valence A of solution A × weighed value of solution A used for preparation of solution B (g) −Amine valence B of solution B × (weighing value of solution A used for preparation of solution B (g ) + Weighed value of polymer D used for preparation of solution B (g))
Acid anhydride value of polymer D (mmol / g)
= Acid anhydride amount of solution B ÷ Weighed value of polymer D used for preparation of solution B Solution A: 10% by mass MFG (methylpropylene glycol) solution of octylamine Solution B: Mixture of polymer D and amine solution A The mixing ratio of the polymer D and the solution A used for the preparation of the solution B is such that, for example, the acid amount of the polymer D in the solution B and the amine amount of the solution A are approximately the same, or the amine amount of the solution A is excessive. Can be adjusted. The acid amount of the polymer D means the total acid amount in a state where the acid anhydride of the polymer D is hydrolyzed, and the polymer D in a state where the acid anhydride of the polymer D is hydrolyzed. It can be determined from the product of the total acid value of the polymer and the weighed value of the polymer D. The amine amount of the solution A can be determined from the product of the valence of the amine of the solution A and the measured value of the solution A.

<Inorganic particles>
The photosensitive resin composition of the present invention contains inorganic particles. By containing the inorganic particles, the adhesion of the cured film and the pencil hardness are further improved.

The number average primary particle size of the inorganic particles used in the present invention is preferably 10 to 200 nm, more preferably 10 to 150 nm, still more preferably 10 to 100 nm, and particularly preferably 10 to 50 nm. The number average primary particle size refers to an arithmetic average obtained by measuring the particle size of 200 arbitrary particles with an electron microscope. If the particle shape is not spherical, the equivalent circle diameter calculated from the projected area is taken as the diameter.
Further, from the viewpoint of the hardness of the cured film, the porosity of the inorganic particles is preferably less than 10%, more preferably less than 3%, and most preferably no void. The term “void” as used herein means a portion that becomes a hole inside the particle, which is seen when a cross section of the particle is observed. The porosity of the particle is an arithmetic average of 200 of the area ratio between the void portion of the cross-sectional image obtained by an electron microscope and the entire particle.

  Examples of the inorganic particles include metal particles, metal oxide particles, and mica particles from the viewpoints of particle stability, cured film hardness, transparency, and refractive index adjustability.

[Metal particles]
As the metal particles, any of transition metal elements and typical metal elements can be applied. For example, iron, cobalt, nickel, ruthenium, rhodium, palladium belonging to Group VIII of the periodic table, which are widely used for various purposes. Application of osmium, iridium, platinum, copper, silver, gold, etc. belonging to Group IB of the periodic table is preferred. Among these, gold, silver, platinum, palladium, copper, and nickel, which are excellent in conductivity, are preferable, copper, silver, and nickel are more preferable, and silver is more preferable. These are not limited to one type, but may be a combination of two or more types, or may be an alloy.

[Metal oxide particles]
As the metal oxide particles, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B Metal oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Silicon oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide Antimony / tin oxide is more preferable, silicon oxide, titanium oxide, titanium composite oxide, and zirconium oxide are more preferable, and silicon oxide, titanium oxide, and zirconium oxide are particles stability, availability, and hardness of the cured film. From the viewpoints of transparency, refractive index adjustment and the like, it is particularly preferable.

As a silicon oxide, a silica is mentioned preferably and a silica particle is mentioned more preferably.
The silica particles are not particularly limited as long as they are inorganic oxide particles containing silicon dioxide, and particles containing silicon dioxide or a hydrate thereof as a main component (preferably 80% by mass or more) are preferable. The said particle | grains may contain the aluminate as a minor component (for example, less than 5 mass%). Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate. The silica particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. Colloidal silica is exemplified as an example of such a compound.
There is no restriction | limiting in particular as a dispersion medium of colloidal silica, Any of water, an organic solvent, and these mixtures may be sufficient. These may be used individually by 1 type and can also use 2 or more types together.

[Mica particles]
As the mica particles, mica particles described in paragraph 0067 of International Publication No. 2015/076160 can be preferably used.

  Commercially available products can be used as the inorganic particles, and PMA-ST (manufactured by Nissan Chemical Industries, Ltd.), MIBK-ST I L (manufactured by Nissan Chemical Industries, Ltd.), TTO-51 (Ishihara Sangyo Co., Ltd.) Product), silver nanoparticles (manufactured by Adachi Shin Sangyo Co., Ltd.) and the like.

  In the present invention, the inorganic particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill. In the photosensitive resin composition of the present invention, it is not essential that the colloidal silica is present in a colloidal state.

When blending inorganic particles, the content of the inorganic particles is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more based on the total solid content of the photosensitive resin composition from the viewpoint of hardness. Is more preferable. Moreover, 80 mass% or less is preferable, 60 mass% or less is more preferable, 40 mass% or less is further more preferable, and 35 mass% or less is especially preferable.
In addition, the content of the inorganic particles is preferably 10 to 80% by mass and more preferably 15 to 70% by mass with respect to the content of the polymer having a structural unit having an acid group in the polymer component. Preferably, it is 20 to 60% by mass.
One type of inorganic particles may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

<Adhesion promoter>
The photosensitive resin composition of the present invention preferably contains an adhesion promoter.
As the adhesion promoter, a known adhesion promoter can be used, and an alkoxysilane compound is preferable. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved.
The alkoxysilane compound is not particularly limited as long as it has at least one group in which an alkoxy group is directly bonded to a silicon atom, but may be a compound having a dialkoxysilyl group and / or a trialkoxysilyl group. Preferably, it is a compound having a trialkoxysilyl group.
The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention includes a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, molybdenum, titanium, and aluminum, and a cured film. It is preferable that it is a compound which improves adhesiveness. Specifically, a known silane coupling agent or the like is also effective. A silane coupling agent having an ethylenically unsaturated bond is preferred.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxypropyl. Trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane It is done. Of these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, and γ-glycidoxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
Examples of commercially available products include KBM-403, KBM-402 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd., and Silquest A-187SILANE manufactured by Momentive Performance Materials.

The adhesion promoter may contain only one type or two or more types.
The content of the adhesion promoter in the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 2 to 20% by mass, based on the total organic solid content of the photosensitive resin composition. More preferred is ˜15% by mass. When two or more types of adhesion promoters are included, the total amount is preferably within the above range.

<Surfactant>
The photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. As the surfactant, nonionic surfactants are preferable, and fluorine-based surfactants are more preferable.
As the surfactant that can be used in the present invention, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780 are commercially available. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-1 05, the same SC-106 (Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (Mitsubishi Materials Electronics Chemical Co., Ltd.), and Footent 250 (Neos Co., Ltd.). . In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), MegaFuck (manufactured by DIC Corporation) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

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

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

<Sensitizer>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to accelerate the decomposition in combination with the quinonediazide compound.
The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the quinonediazide compound, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the quinonediazide compound undergoes a chemical change to generate an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (For example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (for example, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (Eg, merocyanine, carbomerocyanine), rhodocyanins, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridineo , Chloroflavin, acriflavine), acridones (for example, acridone, 10-butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), styryls, base styryls ( For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (eg, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2, 3, 6 , 7-tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11-non).

A sensitizer may be used individually by 1 type and can also use 2 or more types together.
The content of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the quinonediazide compound of the photosensitive resin composition. More preferably, it is more preferably 50 to 200 parts by mass.

<Crosslinking agent>
The photosensitive resin composition of the present invention may contain a crosslinking agent.
The crosslinking agent is preferably a crosslinking agent having a molecular weight of 1,000 or less.
The crosslinking agent can be used without limitation as long as a crosslinking reaction is caused by heat (however, the polymer and the alkoxysilyl compound are excluded). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, a compound having two or more blocked isocyanate groups in the molecule (a compound having a protected isocyanate group), and two in the molecule It is preferable to include at least one compound selected from the group consisting of the above-mentioned compound having an alkoxymethyl group and a compound having at least one ethylenically unsaturated group, and two or more epoxy groups in the molecule Or it is more preferable that at least 1 sort (s) chosen from the group which consists of a compound which has an oxetanyl group, and two or more blocked isocyanate compounds in a molecule | numerator is included.

It is preferable that content of the crosslinking agent in the photosensitive resin composition of this invention is 0-30 mass% with respect to the total organic solid content of the photosensitive resin composition, and it is more preferable that it is 1-20 mass%. preferable.
The said crosslinking agent can also use multiple types together, In that case, addition amount is calculated by the total content which added all the crosslinking agents.
Below, the crosslinking agent preferably used in this invention is demonstrated.

[Compounds having two or more epoxy groups or oxetanyl groups in the molecule]
Examples of the compound having two or more epoxy groups or oxetanyl groups in the molecule include polyfunctional 3- and / or 4-membered cyclic ether compounds. That is, it means a compound having two or more epoxy groups and / or oxetanyl groups in one molecule. The molecular weight of this compound is preferably 1,000 or less. A small amount of an oligomer having a molecular weight of more than 1,000 and less than 5,000, or a polymer having a molecular weight of 5,000 or more may be used in combination with this low-molecular crosslinking agent.

Specific examples of the compound having two or more epoxy groups in the molecule include aliphatic epoxy compounds.
These are available as commercial products. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321 , EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX -920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301 DLC-402 (manufactured by Nagase ChemteX Corporation), Celoxide 2021P, 2081, 3000, EHPE3 50, Epolead GT400, Serubinasu B0134, B0177 (or, Ltd. Daicel), and the like.
These can be used alone or in combination of two or more.

  As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.

  In addition, the compound containing two or more oxetanyl groups in the molecule is preferably used alone or mixed with a compound containing two or more epoxy groups in the molecule.

[Compound having two or more blocked isocyanate groups in the molecule]
In the photosensitive resin composition of the present invention, as the component D, a compound having two or more blocked isocyanate groups in the molecule (also simply referred to as “block isocyanate compound”) can be preferably employed. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group in which the isocyanate group is chemically protected. The blocked isocyanate compound also uses a compound having a molecular weight of 1,000 or less as a crosslinking agent.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said blocked isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic. Polyisocyanate may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate In addition, a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the block isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

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

  The blocked isocyanate compound that can be used in the present invention is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, Nippon Polyurethane Industry Co., Ltd.) Manufactured), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, Mitsui Chemicals, Inc.), Duranate 17B-60PX 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, Asahi Kasei Chemicals Corporation) Manufactured), Death Module BL1100, BL12 5 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) Can do.

[Compounds having two or more alkoxymethyl groups in the molecule]
As the compound having two or more alkoxymethyl groups in the molecule, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of outgas generation amount, A methyl group is particularly preferred.
Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
The alkoxymethyl group-containing crosslinking agent also uses a compound having a molecular weight of 1,000 or less in the photosensitive resin composition.
These compounds having two or more alkoxymethyl groups in the molecule are commercially available, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272. , 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

[Compound having at least one ethylenically unsaturated group]
As the compound having at least one ethylenically unsaturated group, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. it can.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the tri- or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.
Moreover, when adding the compound which has at least 1 ethylenically unsaturated double bond, it is preferable to add the below-mentioned thermal radical generator.

<Basic compound>
The photosensitive resin composition of the present invention may contain a basic compound.
The basic compound is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of JP2011-221494A.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene, butane-1,2,3,4-tetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
Among these, a heterocyclic amine is preferable, and N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea is particularly preferable.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
It is preferable that content of the basic compound in the photosensitive resin composition of this invention is 0.001-3 mass% with respect to the total organic solid content in the photosensitive resin composition, 0.05-0 More preferably, it is 5 mass%.

<Antioxidant>
The photosensitive resin composition of the present invention preferably contains an antioxidant.
As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing film thickness, with phenol-based antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, the contents of which are incorporated herein.

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

It is preferable that content of the antioxidant in the photosensitive resin composition of this invention is 0.1-10 mass% with respect to the total organic solid of a photosensitive resin composition, 0.2-5 mass% It is more preferable that it is 0.5-4 mass%. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
Further, as additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives” (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators and the like are used as photosensitive resin compositions. You may add to.

<Other ingredients>
In addition to the above components, the photosensitive resin composition of the present invention includes, as necessary, an ultraviolet absorber, a metal deactivator, an acid proliferator, a development accelerator, a plasticizer, a polymerization inhibitor, a thermal radical. Known additives such as a generator, a thermal acid generator, a thickener, and an organic or inorganic suspending agent can be added. Moreover, as these compounds, the description of Paragraph 0201-0224 of Unexamined-Japanese-Patent No. 2012-88459, and Unexamined-Japanese-Patent No. 2014-238438 can also be considered, for example, These content is integrated in this-application specification.
<Characteristics of photosensitive composition>
[Acid value]
In the photosensitive resin composition of the present invention, the acid value relative to the total solid content of the composition is preferably 0 mgKOH / g or more and 200 mgKOH / g or less, more preferably 5 mgKOH / g or more and 120 mgKOH / g or less, More preferably, it is 5 mgKOH / g or more and 40 mgKOH / g or less.
The acid value with respect to the total solid content of the photosensitive composition is determined by using a potentiometric automatic titrator (AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) and using a 0.1 mol / L sodium hydroxide / ethanol solution as a titration reagent. The acid value can be measured by potentiometric titration based on JIS K2501 (2003).

(Method for producing cured film)
The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. Moreover, it is preferable that the hardened | cured material of this invention is a cured film. The cured film of the present invention is preferably a cured film obtained by the method for producing a cured film of the present invention.
The method for producing a cured film of the present invention is not particularly limited as long as it is a method for producing a cured film by curing the photosensitive resin composition of the present invention, but includes the following steps a to d in this order. Is preferred.
Step a: Application step of applying the photosensitive resin composition of the present invention onto the substrate Step b: Solvent removal step of removing the solvent from the applied photosensitive resin composition Step c: Photosensitive resin composition from which the solvent has been removed Exposure step of exposing at least a part of the product with actinic rays Step d: Heat treatment step of heat-treating the photosensitive resin composition Further, the method for producing a cured film of the present invention includes the following steps 1 to 5 in this order. It is preferable.
Step 1: Application step of applying the photosensitive resin composition of the present invention onto a substrate Step 2: Solvent removal step of removing the solvent from the applied photosensitive resin composition Step 3: Photosensitive resin composition from which the solvent has been removed Exposure step of exposing at least a part of the product with actinic rays Step 4: Development step of developing the exposed photosensitive resin composition with an aqueous developer Step 5: Heat treatment step of heat-treating the developed photosensitive resin composition

  In the method for producing a cured film including steps a to d, the development step is an optional step, and examples include cases where patterning is not required, for example, when a protective film is provided on one surface of a substrate. .

In the application step, the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin composition to the substrate, the substrate can be cleaned such as alkali cleaning or plasma cleaning. Furthermore, the substrate surface can be treated with hexamethyldisilazane or the like after cleaning the substrate. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
Resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic From synthetic resins such as aromatic ethers, maleimide-olefin copolymers, cellulose and episulfide resins. Board, and the like. These substrates are rarely used in the above-described form, and usually, a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.
In the case of an on-cell touch panel or the like, the photosensitive resin composition of the present invention is applied to an LCD (liquid crystal display) cell or an OLED (organic light-emitting diode) cell that has been once completed as a panel. You can also.

  Since the photosensitive resin composition of the present invention has good adhesion to a metal film or metal oxide formed by sputtering, the substrate preferably includes a metal film formed by sputtering. The metal is preferably titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium and oxides or alloys thereof, molybdenum, titanium, aluminum, copper and More preferably, these alloys are used. In addition, a metal and a metal oxide may be used individually by 1 type, or may use multiple types together.

The coating method on the substrate is not particularly limited. For example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, an ink jet method, a printing method (flexo, gravure, screen, etc.) ) Etc. can be used. The ink jet method and the printing method are preferable because the composition can be placed in a necessary position and the composition can be saved.
The wet film thickness when applied is not particularly limited and can be applied with a film thickness according to the application, but is preferably in the range of 0.05 to 10 μm.
Furthermore, before applying the photosensitive resin composition of the present invention to the substrate, a so-called prewetting method as described in JP-A-2009-145395 can be applied.

In the solvent removing step, it is preferable that the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. Moreover, in the said solvent removal process, it is not necessary to remove the solvent in the photosensitive resin composition completely, and at least one part should just be removed.
In addition, the said application | coating process and the said solvent removal process may be performed in this order, may be performed simultaneously, or may be repeated alternately. For example, after all of the inkjet application in the application step is completed, the solvent removal step may be performed, or the substrate is heated and the photosensitive resin composition is discharged by the inkjet application method in the application step. Solvent removal may be performed.

In the exposure step, it is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm to 450 nm in a predetermined pattern.
As an exposure light source that can be used in the exposure process, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, an LED (light emitting diode) light source, an excimer laser generator, and the like can be used, i-line (365 nm), Actinic rays having a wavelength of from 300 nm to 450 nm, such as h-line (405 nm) and g-line (436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
As the exposure amount in the exposure step is not particularly limited, it is preferably from 1~3,000mJ / cm ^2, more preferably 1 to 500 mJ / cm ^2.
Moreover, the exposure in the said exposure process should just be performed to at least one part of the photosensitive resin composition from which the solvent was removed, for example, may be whole surface exposure or pattern exposure.
Further, after the exposure step, post-exposure heat treatment (Post Exposure Bake (hereinafter also referred to as “PEB”)) can be performed. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 120 ° C. or lower, and particularly preferably 50 ° C. or higher and 110 ° C. or lower.
The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and is preferably about 20 to 120 minutes in other cases. If it is this temperature range, it can heat without damage to a board | substrate and an apparatus.

In the development step, the uncured photosensitive resin composition is developed and removed using an aqueous developer to form a positive image. The developer used in the development step is preferably an alkaline aqueous developer.
The developer used in the development step preferably contains a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0]- Alicyclic amines such as 5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
As a preferred developing solution, a 0.4 to 2.5% by mass aqueous solution of tetramethylammonium hydroxide can be mentioned.
The pH of the developer is preferably 10.0 to 14.0. The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dip method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.
For pattern exposure and development, a known method or a known developer can be used. For example, the pattern exposure method and the development method described in JP 2011-186398 A and JP 2013-83937 A can be suitably used.

It is preferable that the manufacturing method of the cured film of this invention includes the process (post-baking) of heat-processing the developed photosensitive resin composition after the said image development process. By performing the heat treatment after developing the photosensitive resin composition of the present invention, a cured film having higher strength can be obtained.
As heat processing temperature in the said heat processing process, 180 degrees C or less is preferable, 150 degrees C or less is more preferable, and 130 degrees C or less is still more preferable. As a lower limit, 80 degreeC or more is preferable and 90 degreeC or more is more preferable. The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and is preferably about 20 to 120 minutes in other cases. If it is the said temperature range, it can harden | cure, suppressing the damage to a board | substrate and an apparatus.
In addition, the heat treatment step can be performed after baking at a relatively low temperature before the heat treatment step (post-bake) (addition of a middle bake step). When performing middle baking, it is preferable to heat-treat at a temperature of 100 ° C. or higher after heating at 80 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages. The shape of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Moreover, it is preferable to include the post-exposure process which further irradiates light to the developed photosensitive resin composition from a viewpoint of film | membrane hardness improvement after a image development process and before a heat processing process.
In the post-exposure step, it is preferable to expose the entire surface of the developed photosensitive resin composition. By post-baking after the post-exposure, it is possible to generate an initiation species from the photopolymerization initiator remaining in the exposed portion and to function as a catalyst for accelerating the crosslinking step, and to promote the film curing reaction. In the post-exposure process, it is preferable to perform energy exposure of about 50 to 3,000 mJ / cm ² with a mercury lamp or an LED lamp.

(Cured film)
The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film (insulating film) or an overcoat film (protective film), more preferably used as an overcoat film for a touch panel, and as an overcoat film for an on-cell structure touch panel. Further preferably used. The on-cell touch panel is synonymous with an on-cell touch panel display device described later. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention.
By the photosensitive resin composition of the present invention, a cured film having sufficient hardness even when cured at a low temperature, for example, a cured film having a hardness of H or more can be obtained. Since the protective film formed by curing the photosensitive resin composition of the present invention is excellent in cured film properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
Especially, the cured film of this invention can be used suitably as a protective film for touchscreen wiring, and can be used more suitably as a protective film for wiring in an on-cell structure touchscreen.

  Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, a cured product or resist pattern obtained by curing the photosensitive resin composition of the present invention as a structural member of a device for MEMS (Micro Electro Mechanical Systems). Is used as a partition wall or as a part of a mechanical drive part. Examples of such MEMS devices include SAW (Surface Acoustic Wave) filters, BAW (Bulk Acoustic Wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, Examples include parts such as biochips and sealants. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP2011-107476A, JP2010-2010A. Partition wall (12) and planarization film (102) described in FIG. 4A of JP-A-9793, and bank layer (221) and third interlayer insulating film (FIG. 10 of JP 2010-27591A). 216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4 (a) of Japanese Patent Laid-Open No. 2009-128577, and FIG. 3 of Japanese Patent Laid-Open No. 2010-182638. It can also be used to form a planarization film (12), a pixel isolation insulating film (14), and the like. In addition, spacers for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, color filters for the liquid crystal display device, color filter protective films, facsimiles, electronic copying machines, imaging of on-chip color filters such as solid-state image sensors It can also be suitably used for a microlens of an optical system or an optical fiber connector.

(Display device and touch panel)
The display device of the present invention has the cured film of the present invention.
Examples of the display device of the present invention include various display devices such as an organic EL display device, a liquid crystal display device, and a touch panel display device.

The organic EL display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 1 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing film 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix type in which two electrodes are formed, sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and TFTs 1 for driving the organic EL elements are connected. An organic EL display device is obtained.

The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has an overcoat film (protective film) formed using the photosensitive resin composition of the present invention, a planarizing film, and an interlayer insulating film. A known liquid crystal display device having a structure can be given.
For example, as specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention, amorphous silicon TFT, low temperature polysilicon TFT, oxide semiconductor TFT (for example, indium gallium zinc oxide, so-called, IGZO) and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane-Switching) method, FFS (Fringe Field Switching) method, OCB (OCB) method. Optically Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of Japanese Patent Laid-Open No. 2005-284291, -346054 can be used as the organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer alignment may be supported by the PSA (Polymer Sustained Alignment) technique described in JP2003-149647A or JP2011-257734A.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to a planarization film and an interlayer insulating film, it is suitable for a protective film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, etc. Can be used.

FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, white LED, multicolor LED such as blue, red, and green, fluorescent lamp (cold cathode tube), organic EL, and the like can be mentioned.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type (touch panel display device). Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP2011-145686A or the interlayer insulating film (520) described in JP2009-258758A. Can do.

The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or protective layer is made of a cured product of the photosensitive resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. The touch panel of the present invention may be any known method such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, or the like. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of Japanese Patent Publication No. 2012-517051), a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2012-43394). 14, International Publication No. 2012/141148, FIG. 2 (b)), OGS (One Glass Solution) type, TOL (Touch on Lens) type, and other configurations (for example, FIG. 6 of JP2013-164871A) Can be mentioned.
FIG. 3 is a conceptual diagram illustrating an example of a touch panel display device.
For example, the cured film of the present invention is preferably applied to the protective film between the layers in FIG. 3, and is also preferably applied to an interlayer insulating film that separates the detection electrodes of the touch panel. In addition, as a detection electrode of a touch panel, it is preferable that they are silver, copper, aluminum, titanium, molybdenum, and these alloys.
In FIG. 3, reference numeral 110 denotes a pixel substrate, 140 denotes a liquid crystal layer, 120 denotes a counter substrate, and 130 denotes a sensor unit. The pixel substrate 110 includes a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in order from the lower side of FIG. The counter substrate 120 includes an alignment film 121, a color filter 122, and a transparent substrate 123 in order from the lower side of FIG. The sensor unit 130 includes a retardation film 124, an adhesive layer 126, and a polarizing plate 127. In FIG. 3, reference numeral 125 denotes a sensor detection electrode. The cured film of the present invention includes an insulating layer (114) (also referred to as an interlayer insulating film) in the pixel substrate portion, various protective films (not shown), various protective films (not shown) in the pixel substrate portion, and a counter substrate portion. Can be used for various protective films (not shown), various protective films (not shown) for the sensor portion, and the like.

  In addition, a statically driven liquid crystal display device can display a pattern with high designability by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A No. 2001-125086.

FIG. 4 is a conceptual diagram of the configuration of another example of the touch panel display device.
A lower display panel 200 corresponding to a thin film transistor display panel provided with a thin film transistor (TFT) 440, and a color filter display panel provided with a plurality of color filters 330 on the surface facing the lower display panel 200 and facing the lower display panel 200. And the liquid crystal layer 400 formed between the lower display panel 200 and the upper display panel 300. The liquid crystal layer 400 includes liquid crystal molecules (not shown).

  The lower display panel 200 is disposed on the first insulating substrate 210, the thin film transistor (TFT) disposed on the first insulating substrate 210, the insulating film 280 formed on the upper surface of the thin film transistor (TFT), and the insulating film 280. A pixel electrode 290 is included. The thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260 and 262, a source electrode 270, and a drain electrode 272. A contact hole 282 is formed in the insulating film 280 so that the drain electrode 272 of the thin film transistor (TFT) is exposed.

  The upper display panel 300 is disposed on one surface of the second insulating substrate 310, on the light shielding members 320 arranged in a matrix, the alignment film 350 disposed on the second insulating substrate 310, and the alignment film 350. A color filter 330 to be disposed, and a common electrode 370 disposed on the color filter 330 and corresponding to the pixel electrode 290 of the lower display panel 200 to apply a voltage to the liquid crystal layer 400 are included.

  In the touch panel display device shown in FIG. 4, a sensing electrode 410, an insulating film 420, a drive electrode 430, and an insulating film (protective film) 280 are disposed on the other surface of the second insulating substrate 310. As described above, in the manufacture of the liquid crystal display device shown in FIG. 4, when the upper display panel 300 is formed, the sensing electrode 410, the insulating film 420, the drive electrode 430, and the like, which are constituent elements of the touch screen, are formed together. be able to. In particular, a cured film obtained by curing the photosensitive resin composition of the present invention can be suitably used for the insulating film 280 and the insulating film 420.

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

  Hereinafter, details of the abbreviations used in the examples are as follows.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
St: Styrene (Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
αMHSt: α-methyl-p-hydroxystyrene CHM: N-cyclohexylmaleimide THFM: tetrahydrofurfuryl methacrylate LM: lauryl methacrylate V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical) Manufactured by Kogyo Co., Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (Methoxypropyl acetate manufactured by Showa Denko KK)

<Synthesis Example 1: Synthesis of Resin A-1>
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 parts by mass of propylene glycol monomethyl ether acetate. . Subsequently, 25 parts by mass of styrene, 20 parts by mass of methacrylic acid, 45 parts by mass of glycidyl methacrylate, and 10 parts by mass of dicyclopentanyl methacrylate were charged and replaced with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the resin A-1. In addition, solid content concentration of the obtained polymer solution was adjusted so that it might become 40 mass%.

<Synthesis Examples 2-7: Synthesis of Resins A-2 to A-7>
The monomers were changed as shown in Table 1 below, and the resins A-2 to A-7 were synthesized by the same method as that for the resin A-1.

  The unit of the numerical value in each monomer component and polymerization initiator of Table 1 is a mass part. In addition, “-” in the table indicates that the corresponding compound was not used.

  Moreover, the detail of the various components used in the Example and the comparative example other than the said resin A-1 to A-7 is shown below.

<Quinonediazide compound>
B-1: NQD of 4- [4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl] phenol skeleton, esterification rate 66%, Toyo Gosei Co., Ltd.
B-2: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide- Condensate with 5-sulfonic acid chloride (3.0 mol) B-3: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5 Condensate with sulfonic acid chloride (2.0 mol) B-4: 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride ( 2.44 mol) condensate

<Solvent>
C-1: Propylene glycol monomethyl ether acetate (PGMEA)

<Surfactant>
・ Megafac F-554, 2% PGMEA solution of perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation

<Polymer D>
SMA-3000P: styrene-maleic anhydride copolymer, d1: d2 = 3: 1, Mw = 9,500, manufactured by Cray Valley Inc. SMA-EF-40: styrene-maleic anhydride copolymer, d1: d2 = 4: 1, Mw = 10,500, manufactured by CrayValley, SMA-EF-60: styrene-maleic anhydride copolymer, d1: d2 = 6: 1, Mw = 11,500, manufactured by CrayValley, SMA- EF-80: styrene-maleic anhydride copolymer, d1: d2 = 8: 1, Mw = 14,400, manufactured by Cray Valley, Inc. D-1: the following synthetic product D-1, d1: d2 = 3: 1
D-2: the following synthetic product D-2, d1: d2 = 4: 1
D-3: the following synthetic product D-3, d1: d2 = 5: 1
SMA-1000P: styrene-maleic anhydride copolymer, d1: d2 = 1: 1, Mw = 5,500, manufactured by Cray Valley, comparative example SMA-2000P: styrene-maleic anhydride copolymer, d1: d2 = 2: 1, Mw = 7,500, manufactured by Cray Valley, comparative example SMA-2625: styrene-maleic anhydride copolymer half ester, d1: d2 = 2: 1, Mw = 9,000, Cray Valley, comparative example

<Inorganic particles>
PMA-ST: Silica particles, manufactured by Nissan Chemical Industries, Ltd., number average primary particle size of 10 to 15 nm
MIBK-ST-L: Organosilica sol, manufactured by Nissan Chemical Industries, Ltd., number average primary particle size 40-50 nm
E-3: TTO-51, titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., number average primary particle size 20 nm
E-4: Silver nanoparticles, manufactured by Adachi Shin Sangyo Co., Ltd., number average primary particle size 200 nm
E-5: Particle E-6 prepared by the following preparation method, number average primary particle size 300 nm

<Adhesion promoter>
· KBM-403: 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. · KBM-402: 3-glycidoxypropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. · A-187: Sil Quest A-187SILANE, γ-glycidoxypropyltrimethoxysilane, manufactured by Momentive Performance Materials Co., Ltd.

<Synthesis of D-1>
Propylene glycol monomethyl ether acetate (119.9 g) was placed in a three-necked flask and heated to 85 ° C. in a nitrogen atmosphere. Methacrylic acid (22.3 g: amount to be 11.2% by mass in all monomer components), methyl methacrylate (41.8 g: amount to be 20.9% by mass in all monomer components), styrene (99.9 g: equivalent to 50.0% by mass in all monomer components), V-601 (11.17 g) (manufactured by Wako Pure Chemical Industries, Ltd.), 4-methoxyphenol (0.01 g), A solution to which propylene glycol monomethyl ether acetate (15.0 g) was added was prepared to give dropwise solution 1, and itaconic anhydride (35.8 g: equivalent to 17.9% by mass in all monomer components), propylene glycol monomethyl A solution in which ether acetate (236.3 g) and 4-methoxyphenol (0.01 g) were added was prepared to prepare Drop 2.
Into a three-necked flask solution maintained at 85 ° C. ± 1 ° C., the dropping liquid 1 was dropped over 2 hours, and the dropping liquid 2 was dropped over 2 hours and 15 minutes after 15 minutes from the start of dropping of the dropping liquid 1.
After completion of the dropwise addition of the dropping liquid 2, the mixture was stirred at 85 ° C. ± 1 ° C. for 1 hour and 30 minutes, V-601 (4.50 g) was added, and the mixture was further stirred at 85 ° C. ± 1 ° C. for 4 hours. The polymer D-1 (Solid content concentration 35.0 mass%, Mw = 13,000) was obtained by cooling this to room temperature.

<Synthesis of D-2>
Except for changing the amount of styrene to 124.9 g, the amount of methyl methacrylate to 19.0 g, and the amount of itaconic anhydride to 33.6 g, the same as in the case of the polymer D-1, Polymer D-2 (solid content concentration 35.0 mass%, Mw = 12,000) was obtained.

<Synthesis of D-3>
A polymer except that the amount of methacrylic acid used was changed to 17.2 g, the amount of styrene used was changed to 145.7 g, the amount of methyl methacrylate used was changed to 5.6 g, and the amount of itaconic anhydride was changed to 31.4 g. In the same manner as in the case of D-1, a polymer D-3 (solid content concentration 35.0% by mass, Mw = 11,200) was obtained.

<Preparation of E-5>
480 parts by mass of methanol was added to 100 parts by mass of Seahoster KE-P30 (amorphous silica particles, manufactured by Nippon Shokubai Co., Ltd., average particle size 0.3 μm), and the mixture was stirred in a mixing tank to obtain a 20 mass silica dispersion.
Furthermore, 20 parts by mass of acryloyloxypropyltrimethoxysilane and 1.5 parts by mass of diisopropoxyaluminum ethyl acetate were added and mixed, and then 9 parts by mass of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 mass parts of acetylacetone. The solvent was replaced by distillation under reduced pressure while adding methyl ethyl ketone so that the total liquid volume was almost constant.
Finally, a dispersion E-5 was prepared by adjusting the solid content to 20% by mass.

(Examples 1-68 and Comparative Examples 1-12)
<Preparation of photosensitive resin composition>
Each component listed in Tables 2 to 4 below, surfactant Megafac F-554, and solvent C-1 were blended and stirred to obtain a solvent solution and / or dispersion liquid. It filtered with the filter made from a fluoroethylene, and obtained each photosensitive resin composition of Examples 1-68 and Comparative Examples 1-12. The compounding amount of the solvent C-1 was adjusted so that the solid content of each photosensitive resin composition was 20%.
The unit of the addition amount of each component of the following Table 2-Table 4 is a mass part of an active ingredient.
Moreover, the example described as "-" in the column of "content" of each component in a table | surface means that the applicable component is not contained.
In the column “d1: d2”, “the molar content ratio of the structural unit d1 and the structural unit d2 in the polymer D” is described, and in the “acid anhydride value (mmol / g)” column, the above-mentioned The acid anhydride value of the polymer D measured by the method is described.
In the case where the composition does not contain the polymer D, “-” is written in the column “d1: d2”, and when the composition does not contain a polymer component containing a polymer satisfying at least one of a1 and a2, The column of the content (% by mass) of polymer D relative to the content of the polymer having a structural unit having an acid group in the coalescence component, and the content of the polymer having a structural unit having an acid group in the polymer component In the column of the content (mass%) of the inorganic particles, “-” is described.

  In Examples 1 to 23 and Comparative Examples 1 to 6, the obtained photosensitive resin compositions were used to evaluate corrosion resistance and storage stability as follows. The evaluation results are shown in Table 2.

<Evaluation of corrosion resistance (saline resistance)>
The photosensitive resin composition obtained in each Example and Comparative Example was spin-coated on a glass substrate on which a 10 μm-wide copper wiring was formed, prebaked at 90 ° C. for 120 seconds, and a film thickness of 2.0 μm. A coating film was obtained.
Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was prepared by baking at 120 ° C. for 60 minutes in an oven to obtain a sample for corrosion resistance evaluation.
Next, referring to the JIS standard (Z 2371: 2000), using the salt spray tester (STP-90V2 manufactured by Suga Test Instruments Co., Ltd.), the above sample was placed in the test tank, and the concentration was 50 g / L. Of salt water (pH = 6.7) was sprayed for 48 hours at a test bath temperature of 35 ° C. and a spray amount of 1.5 mL / h.
After spraying, the salt water was wiped off, the surface state of the sample for evaluation was observed, and evaluation was performed according to the following scores. 3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
5: No change on the surface of the protective film 4: A slight trace is visible on the surface of the protective film, but copper is unchanged 3: Traces are visible on the surface of the protective film, but copper is unchanged 2: Traces on the surface of the protective film Yes, and copper turns a little blue 1: There is a trace on the surface of the protective film, and copper turns blue abruptly

<Evaluation of storage stability (liquid storage stability)>
The viscosity of the photosensitive resin composition immediately after preparation (initial viscosity) and the viscosity of the photosensitive resin composition after storage for 2 weeks at 30 ° C. ). The temperature during the viscosity measurement was 24 ° C.
From the obtained viscosity measurement results, the amount of change (%) in the viscosity with time when the initial viscosity was 100% was calculated according to the following formula, and evaluated according to the following ratings. 3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
Amount of change in viscosity with time when initial viscosity is 100% (%) = | 1−viscosity / initial viscosity | × 100
5: Change amount (%) of the viscosity with time when the initial viscosity is 100% is less than 5% 4: Change amount (%) of the viscosity with time when the initial viscosity is 100% is 5% or more and 10% Less than 3: The amount of change with time (%) when the initial viscosity is 100% is 10% or more and less than 15% 2: The amount of change with time when the initial viscosity is 100% (%) 15% or more and less than 20% 1: The amount of change (%) in viscosity with time when the initial viscosity is 100% is 20% or more

  In Examples 24 to 68 and Comparative Examples 7 to 12, the obtained photosensitive resin compositions were used to evaluate corrosion resistance, storage stability, pencil hardness, transparency and adhesion as follows. . The evaluation results are shown in Tables 3-4.

<Evaluation of corrosion resistance (artificial sweat resistance)>
Each photosensitive resin composition was spin-coated on a sputtered copper substrate and pre-baked at 90 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm.
Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was prepared by baking at 120 ° C. for 60 minutes in an oven to obtain a sample for corrosion resistance evaluation.
Subsequently, acidic artificial sweat was prepared with reference to JIS standards (JIS L0848: 2004). 30 μl of the artificial sweat was dropped on the surface of the evaluation sample, and then the sweat was naturally dried over 24 hours.
The dried sample for evaluation was allowed to stand for 72 hours under high temperature and high humidity (85 ° C. RH 85%).
Copper corrosion progresses concentrically around the point where sweat is dripped and dried. Observation of the surface state of the substrate for evaluation, and the distance at which corrosion progressed from the center were measured and evaluated according to the following scores.
3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
5: No change on the surface of the protective film 4: Very little trace is visible on the surface of the protective film, and the corroded distance is less than 0.5 mm 3: Traces are visible on the surface of the protective film, and the corroded distance is 0. 5 mm or more and less than 10 mm 2: The surface of the protective film has a trace of blue discoloration of copper, and the corroded distance is 10 mm or more and less than 20 mm 1: The surface of the protective film has a trace of intense blue discoloration of copper and corroded Distance is 20mm or more

<Evaluation of storage stability>
Evaluation similar to the said Examples 1-23 and Comparative Examples 1-6 was performed.

<Evaluation of pencil hardness>
Each photosensitive resin composition prepared above was spin-coated on a glass substrate and pre-baked at 90 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and further, baking was performed in an oven at 120 ° C. for 60 minutes to prepare a cured film.
The obtained cured film was subjected to a pencil hardness test by a method (load 750 g) based on JIS K5600: 1999 to evaluate the film hardness. 4H or more is a practical range, 5H or more is preferable, and 6H or more is more preferable.

<Evaluation of transparency>
Each photosensitive resin composition prepared above was spin-coated on a glass substrate and pre-baked at 90 ° C. for 120 seconds to obtain a coating film having a thickness of 2.0 μm. Next, light irradiation of 500 mJ / cm ² (i-line conversion) was performed with a high-pressure mercury lamp, and a cured film was formed by baking at 120 ° C. for 60 minutes in an oven.
The total light transmittance was measured with respect to the obtained cured film using Hazemeter NDH7000 (made by Nippon Denshoku Industries Co., Ltd.).
3, 4, and 5 are practical levels, preferably 4 or 5, and more preferably 5.
The evaluation criteria are as follows: 5: Total light transmittance is 98% or more 4: Total light transmittance is 95% or more and less than 98% 3: Total light transmittance is 90% or more and less than 95% Yes 2: Total light transmittance is 80% or more and less than 90% 1: Total light transmittance is less than 80%

<Adhesion evaluation>
Each photosensitive resin composition was spin-coated on a glass substrate on which a Cu (copper) thin film was formed, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness was 3.0 μm. The photosensitive resin composition layer was formed. Subsequently, exposure is performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount is 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then the substrate is heated in an oven at 230 ° C./30 minutes. Thus, a cured film was obtained.
Using a cutter on the cured film, cuts were made at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600: 1999) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. As a numerical value, the smaller the area of the transferred cured film is, the more preferable.
6: The transferred area is less than 1% 5: The transferred area is 1% or more and less than 5% 4: The transferred area is 5% or more and less than 10% 3: The transferred area is 10% or more and less than 30% 2 : The transferred area is 30% or more and less than 50% 1: The transferred area is 50% or more

<Production of display device>
In the display device shown in FIG. 4, each of the display devices was manufactured using the photosensitive resin composition obtained in each example of the present invention as a touch detection electrode protective film (insulating film 420). Specifically, the protective film (420) was slit-coated with the photosensitive resin composition obtained in each example, pre-baked at 90 ° C. for 120 seconds, and 500 mJ / cm ² (i-line) with a high-pressure mercury lamp. (Conversion) was performed, followed by baking in an oven at 120 ° C. for 60 minutes. The other part of the display device was manufactured according to the manufacturing method described in FIG. 19 in JP 2013-168125 A. The produced display device was excellent in display performance and touch detection performance.

<Manufacture of touch panels>
The following resist composition was applied, exposed and developed on a polyethylene terephthalate (PET) substrate (100 mm × 100 mm) on which a copper film was formed with a thickness of 200 nm, and the resist layer was patterned. Here, the pattern of the resist layer was patterned so as to have a pattern corresponding to a mesh-like touch sensor portion, a lead wiring portion having a width of 0.02 mm to 0.05 mm, and a connection terminal.
Then, after etching with a copper etchant (CleanEtch SE-07, manufactured by Hishoe Chemical Co., Ltd., 7-fold diluted product), the resist was removed to prepare a substrate made of a copper wiring layer. This wiring layer has a touch sensor part having a copper wiring pattern having a line width of 5 μm, a wiring film thickness of 200 nm, and a wiring pitch of 1: 600, a lead-out wiring part, and a pattern part corresponding to the connection terminal.
The substrate was slit coated with the photosensitive resin composition obtained in each Example, pre-baked at 90 ° C. for 120 seconds, and irradiated with light of 500 mJ / cm ² (i-line conversion) with a high-pressure mercury lamp. Furthermore, the 1st touch panel member was formed by baking at 120 degreeC for 60 minute (s) in oven. Moreover, the 2nd touch panel member was formed by the method similar to the above, and the 1st and 2nd touch panel member was bonded together. The pattern part corresponding to the connection terminal in the first and second touch panel members was connected to a driving IC (integrated circuit) with a flexible printed circuit board (FPC) to manufacture a touch panel.
And in the said touch panel, the change of the electrostatic capacitance produced when there was touch operation was measured, and the presence or absence of touch operation was confirmed. In addition, it was tested whether the touch position could be detected when a touch operation was performed.
It was confirmed that the touch panel operates without any problems.

[Resist composition]
The following components were dissolved and mixed, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain a resist composition.
-PHS-EVE (1-ethoxyethyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%), the following structure): 71.4 parts-Acrylic polymer: 28.6 Part ・ IRGACURE PAG103 (manufactured by BASF): 2.7 parts ・ dibutoxyanthracene: 2.7 parts ・ epoxy resin (JER157S65, manufactured by Japan Epoxy Resin Co., Ltd.): 2.7 parts ・ solvent PGMEA (propylene glycol monomethyl ether) Acetate): The non-volatile content was adjusted to 10% by mass with respect to the entire composition.

  In addition, the number on the lower right of the parenthesis in each structural unit of the acrylic polymer represents a molar ratio.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12 : Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 110: Pixel substrate, 111: Polarizing plate 112: transparent substrate, 113: common electrode, 114: insulating layer, 115: pixel electrode, 116: alignment film, 120: counter substrate, 121: alignment film, 122: color filter, 123: transparent substrate, 124: phase difference Film: 125: Detection electrode for sensor, 126: Adhesive layer, 127: Polarizing plate, 130: Sensor part, 140: Liquid crystal layer, 200: Lower display panel, 210: First insulating substrate, 20: gate electrode, 240: gate insulating film, 250: semiconductor layer, 260, 262: ohmic contact layer, 270: source electrode, 272: drain electrode, 280: insulating film, 282: contact hole, 290: pixel electrode, 300 : Upper display board, 310: second insulating substrate, 320: light shielding member, 330: color filter, 350: alignment film, 370: common electrode, 400: liquid crystal layer, 410: sensing electrode, 420: insulating film, 430: driving Electrode, 440: TFT

Claims (15)

A polymer component containing a polymer satisfying at least one of the following a1 and a2;
Quinonediazide compounds,
Solvent, and
A polymer D containing a structural unit d1 represented by the following formula 1 and a structural unit d2 having a carboxylic anhydride structure;
The molar content ratio of the structural unit d1 and the structural unit d2 in the polymer D is in the range of d1: d2 = 3: 1 to 8: 1,
The acid anhydride value of the polymer D is 1.00 to 3.00 mmol / g,
Content of polymer D is 0.5-15 mass% with respect to content of the polymer which has a structural unit which has an acid group in the said polymer component, The photosensitive resin composition characterized by the above-mentioned.
a1: A polymer having a structural unit having an acid group and a structural unit having a crosslinkable group a2: A polymer having a structural unit having an acid group and a polymer having a structural unit having a crosslinkable group

In Formula 1, each R ¹ independently represents a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, a carboxy group, or a halogen atom, R ² represents a hydrogen atom, an alkyl group, or an aryl group, and n is 0 to 0 Represents an integer of 5.   The photosensitive resin composition of Claim 1 whose content of the polymer D is 0.5-10 mass% with respect to content of the polymer which has a structural unit which has an acid group in the said polymer component. .   The photosensitive resin composition of Claim 1 or 2 which further contains an inorganic particle.   The photosensitive resin composition of Claim 3 whose content of the said inorganic particle is 10-80 mass% with respect to content of the polymer which has a structural unit which has an acid group in the said polymer component.   The photosensitive resin composition of Claim 3 or 4 whose number average primary particle size of the said inorganic particle is 10-200 nm.   The photosensitive resin composition of any one of Claims 1-5 whose said structural unit d2 is a structural unit containing the cyclic carboxylic anhydride structure of a 5-membered ring. The photosensitivity of any one of Claims 1-6 in which the said structural unit d2 contains the structural unit represented by the following formula d2-1, and / or the structural unit represented by the following formula d2-2. Resin composition.

The photosensitive resin composition of any one of Claims 1-7 in which the said structural unit d2 contains the structural unit represented by the following formula d2-1.

A method for producing a cured film, comprising at least step a to step d in this order.
Step a: Application step of applying the photosensitive resin composition according to any one of claims 1 to 8 on the substrate Step b: Solvent removal step of removing the solvent from the applied photosensitive resin composition Step c : An exposure step of exposing at least a part of the photosensitive resin composition from which the solvent has been removed with actinic rays; step d: a heat treatment step of heat-treating the photosensitive resin composition. A method for producing a cured film, comprising at least Step 1 to Step 5 in this order.
Process 1: Application | coating process which apply | coats the photosensitive resin composition of any one of Claims 1-8 on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated photosensitive resin composition Process 3 : Exposure step of exposing at least a part of the photosensitive resin composition from which the solvent has been removed with actinic rays Step 4: development step of developing the exposed photosensitive resin composition with an aqueous developer Step 5: developed photosensitivity Heat treatment process for heat-treating the conductive resin composition   The manufacturing method of the cured film of Claim 10 whose heat processing temperature in the process 5 is 80-150 degreeC.   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-8.   The cured film according to claim 12, which is an interlayer insulating film or an overcoat film.   A touch panel having the cured film according to claim 12.   A display device comprising the cured film according to claim 12.

Images