JP6385852B2 - Photosensitive resin composition, method for producing cured film, cured film, touch panel, touch panel display device, liquid crystal display device, and organic EL 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, a touch panel display device, a liquid crystal display device, and an organic EL display device.

Flat panel displays such as liquid crystal display devices and organic EL 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 wiring in which ITO (Indium Tin Oxide) or metal (silver, molybdenum, aluminum, etc.) is patterned on glass, and in addition, an insulating film, ITO and A structure having a protective film for protecting a metal is common.
As a conventional protective film for touch panel wiring, those described in Patent Documents 1 and 2 are known.

JP 2013-200891 A JP2013-76821A

The present inventor has found that “reworkability” and “skirting characteristics” are important characteristics required for a protective film for touch panel wiring.
Reworkability means that when a polarizing plate is pasted onto the protective film using glue or adhesive, the polarizing plate is removed due to misalignment, the surface of the protective film is cleaned, and the polarizing plate is removed again. It is a characteristic of whether it can be re-applied.
When peeling off a polarizing plate, high adhesiveness is calculated | required so that a protective film may not peel from an electrode substrate. In addition, when the surface of the protective film is cleaned, high hardness and chemical resistance are required because physical and / or chemical cleaning is performed in order to remove glue and adhesive.
These comprehensive characteristics including adhesion, hardness and chemical resistance are reworkability.

  The skirting is a phenomenon in which a film is cured to a region not originally irradiated with an actinic ray when a negative material is exposed and patterned by photolithography. If tailing occurs, the photomask pattern cannot be formed correctly. Therefore, it is preferable that tailing does not occur. Since negative materials with excellent hardness and chemical resistance are highly reactive, tailing due to light leaking from photomasks is likely to occur, resulting in trade-off performance.

The problem to be solved by the present invention is to provide a photosensitive resin composition that is excellent in reworkability and tailing characteristics at the time of development, and that can provide a cured film with little film loss at the time of development.
In addition, other problems to be solved by the present invention include a method for producing a cured film using the photosensitive resin composition and a cured film, and a touch panel, a touch panel display device, a liquid crystal display device using the cured film, and the like. An organic EL display device is provided.

The above-described problems of the present invention have been solved by means described in the following <1>, <7>, <8>, or <12> to <15>. It describes below with <2>-<6> and <9>-<11> which are preferable embodiments.
<1> As component A, a polymer having a (meth) acryloyl group and an acid group, as component B, a trifunctional or higher functional ethylenically unsaturated compound, as component C, as a photopolymerization initiator, and as component D, A compound having a phosphate ester structure and an ethylenically unsaturated group, wherein the content of component D relative to the total organic solid content in the composition is 0.01 to 5% by mass. Resin composition,
<2> The photosensitive resin composition according to <1>, wherein the total content of component A and component B with respect to the total organic solid content in the composition is 50 to 99 mass%.
<3> The photosensitive resin composition according to <1> or <2>, wherein the content of component D with respect to the total organic solid content in the composition is 0.5 to 2% by mass,
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the component D includes a compound having a P—OH structure,
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the total content of component A and component B with respect to the total organic solid content in the composition is 70 to 99% by mass. object,
<6> The photosensitive resin composition according to any one of <1> to <5>, further including inorganic particles,
<7> A method for producing a cured film including at least Step 1 to Step 3 in this order,
Process 1: Application | coating process which apply | coats the photosensitive resin composition as described in any one of <1>-<6> on a board | substrate Process 2: At least one part of the apply | coated photosensitive resin composition is actinic light. Exposure step for exposure Step 3: Development step for developing the exposed photosensitive resin composition with an aqueous developer <8><1> to <6> The photosensitive resin composition according to any one of <1> to <6> is cured. Cured film,
<9> The cured film according to <8>, which is an interlayer insulating film or a protective film,
<10> The cured film according to <8> or <9>, which is a protective film for touch panel wiring,
<11> The cured film according to any one of <8> to <10>, which is a protective film for wiring in an on-cell structure touch panel,
<12> A touch panel having the cured film according to any one of <8> to <11>,
<13> A touch panel display device having the cured film according to any one of <8> to <11>,
<14> A liquid crystal display device having the cured film according to <8> or <9>,
<15> An organic EL display device having the cured film according to <8> or <9>.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is excellent in rework property and the bottoming characteristic at the time of image development, and can obtain the cured film with little film loss at the time of image development can be provided.
Moreover, according to this invention, the manufacturing method and cured film of a cured film using the said photosensitive resin composition, and the touch panel using the said cured film, an organic electroluminescent display device, a liquid crystal display device, and a touch panel display device are provided. can do.

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

  In the present invention, for the polymer component, the molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention (hereinafter also simply referred to as “photosensitive resin composition” or “composition”) is a polymer having a (meth) acryloyl group and an acid group as Component A, Component B. A trifunctional or higher functional ethylenically unsaturated compound, component C as a photopolymerization initiator, and component D as a compound having a phosphate ester structure and an ethylenically unsaturated group, Content of the component D with respect to organic solid content is 0.01-5 mass%, It is characterized by the above-mentioned.
The photosensitive resin composition of the present invention may further contain other components such as inorganic particles and alkoxysilane compounds.
The photosensitive resin composition of the present invention is preferably capable of patterning by photolithography using an alkaline developer. In addition, when the photosensitive resin composition of the present invention is subjected to patterning by photolithography with an alkaline developer, the resulting pattern is a negative pattern in which the photosensitive portion remains as a pattern.
In the present invention, the “solid content” in the photosensitive resin composition means a component excluding volatile components such as a solvent. “Organic solid content” means a component obtained by removing a volatile component such as a solvent and an inorganic component such as inorganic particles from the photosensitive resin composition.
Specifically, a composition containing the following components is exemplified as a specific embodiment.

As a result of intensive studies, the inventor has the components A to D described above, and the photosensitive resin composition in which the content of the component D is in a specific range with respect to the total organic solid content is reworked and developed. The present inventors have found that a cured film having excellent tailing characteristics and little film loss during development can be obtained, and the present invention has been completed.
Although the mechanism of action of the present invention is not clear, it is presumed as follows. By containing component D, it is presumed that the tailing characteristics at the time of development are excellent, components A to D are contained, and the content of component D is in a specific range with respect to the total organic solid content. Therefore, it is presumed that the rework property, which is a comprehensive property including adhesion, hardness and chemical resistance, is excellent.
Hereinafter, each component which the photosensitive resin composition of this invention contains is demonstrated.

Component A: Polymer having (meth) acryloyl group and acid group The photosensitive resin composition of the present invention contains, as Component A, a polymer having a (meth) acryloyl group and an acid group.
The weight average molecular weight of component A is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 12,000 or more. The weight average molecular weight of Component A is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

Examples of the acid group that component A has include a carboxyl group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group thereof, and a phenolic hydroxy group. A carboxyl group, an anhydride group of a carboxylic acid, and a phenolic hydroxy group include Preferably, a carboxyl group is particularly preferable.
Component A preferably has a structural repeating unit having an acid group, and more preferably has a structural repeating unit having a carboxyl group.
Examples of the monomer for introducing an acid group into Component A include (meth) acrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, fumaric acid, crotonic acid, 1,4-cyclohexenedicarboxylic acid, o-, m -, P-vinylbenzoic acid, (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropionic acid, 2- (meth) acryloyloxypropionic acid, 4- (meth) acryloyloxybutanoic acid, 4- (meth) Acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 2- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxyphthalic acid, 3- (meth) acryloyloxyphthalic acid, 4- (meth) Examples include acryloyloxyisophthalic acid and 5- (meth) acryloyloxyisophthalic acid. Door can be. Among these, (meth) acrylic acid is particularly preferable. That is, component A particularly preferably has a repeating unit derived from (meth) acrylic acid.

Component A is a polymer having a (meth) acryloyl group, and is preferably a polymer having a methacryloyl group. Component A is preferably a polymer having a (meth) acryloyloxy group.
The method for introducing the (meth) acryloyl group into the component A is not particularly limited. For example, even when a compound having a (meth) acryloyl group is introduced by polymer reaction, the precursor group of the (meth) acryloyl group is used as a resin. It may be introduced at the time of polymerization and converted to a (meth) acryloyl group. Among them, a polymer having an acid group is synthesized, and a cyclic ether group such as an epoxy group and a (meth) acryloyl group are synthesized as part of the acid group. It is preferable to introduce a (meth) acryloyl group by reacting the compound having
Examples of the compound having a cyclic ether group and a (meth) acryloyl group include glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, α-n-propylglycidyl (meth) acrylate, and (meth) acrylic. Examples include acid α-n-butylglycidyl, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate, and the like. be able to. From the viewpoint of pattern processability and improved hardness of the cured film, glycidyl (meth) acrylate is preferred. Two or more of these may be used.

Examples of component A include acrylic resins, polysiloxanes, vinyl ether resins, polyhydroxystyrenes, novolac resins, polyimides and polyamides having a (meth) acryloyl group and an acid group. Among these polymers, acrylic resin, polysiloxane, vinyl ether resin, and polyhydroxystyrene are preferable, and acrylic resin is more preferable because of the ease of introduction of (meth) acryloyl group.
Moreover, the photosensitive resin composition of this invention may contain the component A individually by 1 type, or may contain 2 or more types.

Component A preferably has a benzene ring structure, more preferably a structural repeating unit having a benzene ring structure, from the viewpoint of the heat resistance of the cured film.
The benzene ring structure is preferably a phenyl group.
Examples of the monomer that introduces a benzene ring structure into Component A include styrene, α-, o-, m- or p-methylstyrene, benzyl (meth) acrylate, and the like. Of these, styrene, α-methylstyrene, and benzyl (meth) acrylate are preferable, and benzyl (meth) acrylate is more preferable from the viewpoint of heat resistance of the cured film and solubility in an alkali developer. Two or more of these monomers may be used.

Component A preferably has an alicyclic hydrocarbon group, more preferably a structural repeating unit having an alicyclic hydrocarbon group, from the viewpoint of transparency of the cured film.
The alicyclic hydrocarbon group is preferably an isobornyl group, a tricyclodecanyl group or a tetracyclodecanyl group, more preferably a tricyclodecanyl group or a tetracyclodecanyl group, A cyclodecanyl group is more preferable, and a tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group is particularly preferable.
Examples of the monomer for introducing an alicyclic hydrocarbon group into Component A include cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, (meth ) 4-methoxycyclohexyl acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, 2-cyclohexyloxycarbonylethyl (meth) acrylate, (meth) acrylic acid 2-cyclohexenyloxycarbonylethyl, 2- (4-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, ( Data) acrylic acid tetra tricyclodecanyl, and (meth) acrylic acid dicyclopentenyl (meth) adamantyl acrylate, (meth) acrylic acid adamantylmethyl, (meth) 1-methyl-adamantyl acrylic acid. Of these, cyclopropyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclo (meth) acrylate Decanyl and adamantyl (meth) acrylate are preferred. From the viewpoint of further improving the water absorption of the cured film and the adhesiveness during development with an inorganic substance having no Si atom, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclo (meth) acrylate Decanyl is more preferred. Two or more of these monomers may be used.

Component A may have a constitutional repeating unit other than those described above.
Examples of monomers that may be copolymerized when preparing component A include, for example, butadiene, 2,3-dimethylbutadiene, N, N-dimethylacrylamide, N, N-dipropylacrylamide, (meth) acrylonitrile, acrolein, vinyl chloride. , Vinylidene chloride, N-vinylpyrrolidone, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, t-butyl (meth) acrylate, and the like. From the viewpoint of adjusting the molecular weight, butadiene, methyl (meth) acrylate, and ethyl (meth) acrylate are preferred. Two or more of these monomers may be used.

The acid equivalent of Component A is preferably 150 to 1,000 g / mol, more preferably 300 to 800 g / mol, and still more preferably 400 to 600 g / mol. It is excellent in a sensitivity as it is the said range, and is excellent by rework property.
Moreover, it is preferable that the acid equivalent of the said component A is a carboxylic acid equivalent.

There is no restriction | limiting in particular in the manufacturing method of the component A, For example, it can manufacture by the method mentioned above.
Examples of the solvent used in producing component A include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; cyclic ethers such as tetrahydrofuran and dioxane; aromatic carbonization such as benzene, toluene and xylene. Hydrogen; Aprotic polar solvents such as dimethylformamide (DMF) and N-methylpyrrolidone (NMP); Acetic esters such as ethyl acetate and butyl acetate; Glycol ethers such as diethylene glycol dimethyl ether and propylene glycol monomethyl ether; Propylene glycol Examples include glycol ether esters such as monomethyl ether acetate; cellosolv esters such as methyl cellosolve acetate, and the like.
The amount of these reaction solvents used is preferably 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.
Examples of the polymerization initiator used in producing Component A include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′- Azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1,1-bis (t-butylperoxy) cyclohexane, etc. An organic peroxide, hydrogen peroxide, etc. can be mentioned. When a peroxide is used as an initiator, it may be combined with a reducing agent as a redox initiator.

  The content of component A in the photosensitive resin composition of the present invention is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application, but with respect to the total organic solid content in the photosensitive resin composition, It is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass.

Component B: Trifunctional or higher functional ethylenically unsaturated compound The photosensitive resin composition of the present invention contains, as Component B, a trifunctional or higher functional ethylenically unsaturated compound.
Component B is a compound other than Component A, and the molecular weight of Component B (when having a molecular weight distribution, the weight average molecular weight) is preferably less than 5,000, more preferably less than 3,000. Preferably, it is less than 1,000.
Component B preferably has no acid group, and when it has an acid group, the molecular weight is preferably less than 5,000.
Furthermore, it is preferable that the component B does not have a phosphate ester structure.

The number of ethylenically unsaturated groups that Component B has is preferably 3 to 15, more preferably 3 to 10, still more preferably 3 to 7, and particularly preferably 4 to 6. It is excellent in hardness and reactivity as it is the said range, and is excellent by rework property.
Examples of the ethylenically unsaturated group in Component B include a (meth) acryloyl group, a vinyl group, an allyl group, a styryl group, a vinyl ether group, and a vinyl ester group, and a (meth) acryloyl group is preferable. More preferred is a (meth) acryloyloxy group. In the above embodiment, the hardness and reactivity are excellent, and the reworkability is excellent.

As the component B, a compound applied to this type of composition can be appropriately selected and used. For example, the component described in paragraph 0011 of JP-A-2006-23696, or JP-A-2006-64921 Among the components described in paragraphs 0031 to 0047, those having three or more (meth) acryloyl groups in the molecule can be given, and these descriptions are incorporated in the present specification.
Component B is preferably exemplified by (meth) acrylic acid esters of polyhydroxy compounds, specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ethylene oxide (EO) modified product, dipentaerythritol hexa ( Examples include meth) acrylate modified EO.

As the component B, commercially available products may be used. For example, Aronix (registered trademark) M-309, M-400, M-405, M-450, M-7100, M -8030, M-8060, TO-1382, TO-1450 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA- 120 (manufactured by Nippon Kayaku Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.).
In addition, even if it is a compound applicable to the component B, what corresponds to the alkoxysilane compound mentioned later shall be an alkoxysilane compound.

In the present invention, urethane (meth) acrylate may be used as component B.
Examples of the urethane (meth) acrylate that can be used in the present invention include urethane addition polymerizable compounds produced by using an addition reaction of an isocyanate and a hydroxyl group. Examples include urethane acrylates as described in Japanese Patent No. 32293 and Japanese Patent Publication No. 2-16765, and these descriptions are incorporated in the present specification.
The molecular weight of urethane (meth) acrylate is preferably from 500 to less than 5,000, more preferably from 650 to less than 5,000, and still more preferably from 800 to 3,000, from the viewpoint of cured film hardness.

The (meth) acryloxy group in the urethane (meth) acrylate may be either an acryloxy group or a methacryloxy group or both, but is preferably an acryloxy group.
The number of (meth) acryloxy groups in the urethane (meth) acrylate is preferably 3 or more, and more preferably 6 or more. The effect of this invention is more effectively exhibited as it is the said aspect.
The upper limit of the number of the (meth) acryloxy groups is not particularly limited, but is preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
The photosensitive resin composition of the present invention may contain only one type of urethane (meth) acrylate, or may contain two or more types.

The number of urethane bonds in the urethane (meth) acrylate is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, still more preferably 2 to 10, and 2 to 5 Is particularly preferred, and 2 or 3 is most preferred.
The urethane (meth) acrylate is preferably an aliphatic urethane (meth) acrylate.
The urethane (meth) acrylate preferably has an isocyanuric ring structure.
The urethane (meth) acrylate is preferably a compound comprising a core portion having one or more urethane bonds and a terminal portion bonded to the core portion and having one or more (meth) acryloxy groups. More preferably, the compound is a compound in which two or more of the terminal portions are bonded to the portion, more preferably a compound in which 2 to 5 of the terminal portions are bonded to the core portion, Particularly preferred is a compound in which two or three of the above terminal moieties are bonded.

The urethane (meth) acrylate is preferably a compound having at least a group represented by the following formula Ae-1 or Ae-2, and preferably a compound having at least a group represented by the following formula Ae-1. More preferred. The urethane (meth) acrylate is more preferably a compound having two or more groups selected from the group consisting of a group represented by the following formula Ae-1 and a group represented by the formula Ae-2.
Moreover, it is preferable that the said terminal part in urethane (meth) acrylate is group represented by the following formula Ae-1 or Formula Ae-2.

  In formula Ae-1 and formula Ae-2, R represents an acrylic group or a methacryl group each independently, and a wavy line part represents a bonding position with another structure.

The urethane (meth) acrylate is preferably a compound having at least a group represented by the following formula Ac-1 or formula Ac-2, and is a compound having at least a group represented by the following formula Ac-1. It is more preferable.
Moreover, it is preferable that the said core part in urethane (meth) acrylate is group represented by the following formula Ac-1 or formula Ac-2.

In Formula Ac-1 and Formula Ac-2, L ^{1 to} L ⁴ each independently represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and the wavy line represents a bonding position with another structure.
L ^{1 to} L ⁴ are each independently preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and an alkylene group having 4 to 8 carbon atoms. Is more preferable. The alkylene group may have a branched or ring structure, but is preferably a linear alkylene group.
The urethane (meth) acrylate is 2 or 3 selected from the group consisting of a group represented by Formula Ac-1 or Formula Ac-2 and a group represented by Formula Ae-1 and Formula Ae-2. It is particularly preferable that the compound is bonded to the above group.

  Hereinafter, urethane (meth) acrylates preferably used in the present invention will be exemplified, but it goes without saying that the present invention is not limited to these.

  Examples of the urethane (meth) acrylate that can be used in the present invention include urethane addition polymerizable compounds produced by using an addition reaction between an isocyanate and a hydroxyl group. Examples of the urethane acrylates are described in JP-A-2-32293 and JP-B-2-16765, and these descriptions are incorporated in the present specification.

  As commercially available products of urethane (meth) acrylate, U-6HA, UA-1100H, U-6LPA, U-15HA, U-6H, U-10HA, U-10PA, available from Shin-Nakamura Chemical Co., Ltd. UA-53H, UA-33H (both are registered trademarks), UA-306H, UA-306T, UA-306I, UA-510H available from Kyoeisha Chemical Co., Ltd., Lamarer UA-9048 available from BASF , UA-9050, PR9052, EBECRYL 220, 5129, 8301, KRM8200, 8200AE, 8452 and the like available from Daicel Ornex Corporation.

Component B may be used alone or in combination of two or more.
The content of Component B is preferably 20 to 85% by mass, more preferably 30 to 70% by mass, and 35 to 60% by mass with respect to the total organic solid content of the photosensitive resin composition. More preferably it is.

In the photosensitive resin composition of the present invention, the total content of Component A and Component B with respect to the total organic solid content in the composition is preferably 50 to 99% by mass, and preferably 70 to 99% by mass. More preferably, it is more preferably 70 to 95% by mass, and particularly preferably 75 to 95% by mass. In the above embodiment, the developability is excellent and the reworkability is excellent.
The mass ratio of component A to component B in the photosensitive resin composition of the present invention is preferably component A: component B = 1.5: 1 to 1: 1.5, and component A: component B = 1.3: 1 to 1: 1.3 is more preferable, and component A: component B = 1: 1 to 1: 1.3 is still more preferable. Within the above range, film loss during development can be further suppressed.
Furthermore, it is preferable that the content of the component B is larger in terms of mass than the content of the component A in the photosensitive resin composition of the present invention. Within the above range, film loss during development can be further suppressed.

Component C: Photopolymerization initiator The photosensitive resin composition of the present invention contains a photopolymerization initiator as Component C.
The photopolymerization initiator preferably contains a radical polymerization initiator.
The photopolymerization initiator that can be used in the present invention is a compound that can initiate and accelerate polymerization by light. Among these, a photo radical polymerization initiator is more preferable.
The “light” is not particularly limited as long as it is an active energy ray capable of imparting energy capable of generating a starting species from the component C by irradiation, and is widely limited to α rays, γ rays, X rays, ultraviolet rays. (UV), visible light, electron beam, and the like. Among these, light containing at least ultraviolet rays is preferable.

  Examples of the photopolymerization initiator include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocenes. Examples include compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity, and oxime ester compounds are more preferable.

  Examples of the oxime ester compound include JP 2000-80068, JP 2001-233842, JP 2004-534797, JP 2007-231000, JP 2009-134289, and international publication. The compounds described in paragraphs 0046 to 0059 of 2012/057165 can be used.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, and Japanese Examined Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and particularly, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Examples include various compounds described in the specification.

  Examples of the acylphosphine (oxide) compound include a monoacylphosphine oxide compound and a bisacylphosphine oxide compound. Specific examples include Irgacure 819, Darocur 4265, and Darocur TPO manufactured by BASF.

A photoinitiator can be used 1 type or in combination of 2 or more types.
It is preferable that content of the photoinitiator in the photosensitive resin composition of this invention is 0.5-30 mass parts with respect to 100 mass parts of total solids in a composition, 1-20 mass parts It is more preferable that it is 1-10 mass parts, and it is especially preferable that it is 1.5-5 mass parts.

Component D: Compound having a phosphate ester structure and an ethylenically unsaturated group The photosensitive resin composition of the present invention contains, as Component D, a compound having a phosphate ester structure and an ethylenically unsaturated group. Content of the component D with respect to the total organic solid content in a thing is 0.01-5 mass%.
The phosphate ester structure in component D may be a phosphate monoester structure, a phosphate diester structure, or a phosphate triester structure, but a phosphate monoester structure or a phosphate diester structure It is preferable that That is, component D preferably contains a compound having a P—OH structure.
Examples of the ethylenically unsaturated group in Component D include a (meth) acryloyl group, a vinyl group, an allyl group, a styryl group, a vinyl ether group, and a vinyl ester group, and a (meth) acryloyl group is preferable. More preferred is a (meth) acryloyloxy group. It is excellent in sclerosis | hardenability and reactivity as it is the said aspect, and is excellent by rework property.
The number of ethylenically unsaturated groups in Component D is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.
The molecular weight of component D is preferably less than 1,000.
Component D is preferably a compound represented by Formula D-1.

In Formula D-1, R ^D each independently represents a hydrogen atom or a methyl group, L ^D each independently represents a divalent linking group, and n represents 1 to 3.

^RD is preferably a methyl group.
L ^D is preferably independently an alkylene group or a group in which two or more alkylene groups are combined with a bond selected from the group consisting of one or more ether bonds and ester bonds, and is an alkylene group. Is more preferable, and an ethylene group is further preferable.
The number of carbon atoms in L ^D is preferably 2 to 40, more preferably 2 to 20, still more preferably 2 to 8, and particularly preferably 2.
n is preferably 1 to 2. In addition, when n is not an integer, it represents that it is a 2 or more types of mixture which n takes the value as an average value.

  Specific examples of component D include those shown below, but it goes without saying that they are not limited to these.

  As commercial products of these compounds, JPA-514 (manufactured by Johoku Chemical Industry Co., Ltd.), Light acrylate P-1A (N), P-1M, P-2M (manufactured by Kyoeisha Chemical Co., Ltd.), KAYAMER PM-2 , PM-21 (manufactured by Nippon Kayaku Co., Ltd.), MR-200, MR-260 (manufactured by Daihachi Chemical Industry Co., Ltd.) and the like.

Component D may be contained singly or in combination of two or more.
In the photosensitive resin composition of the present invention, the content of component D with respect to the total organic solid content in the photosensitive resin composition is 0.01 to 5% by mass, and 0.05 to 4.5% by mass. It is preferably 0.1 to 4% by mass, more preferably 0.3 to 3% by mass, and particularly preferably 0.5 to 2% by mass. Within the above range, it is possible to obtain a cured film that is more excellent in tailing characteristics at the time of development and has less film loss at the time of development.

Component E: Inorganic particles The photosensitive resin composition of the present invention preferably contains inorganic particles as Component E. By containing the inorganic particles, the hardness of the cured film becomes more excellent.
The average particle size of the inorganic particles used in the present invention is preferably 1 to 200 nm, more preferably 5 to 100 nm, and still more preferably 5 to 50 nm. The average particle diameter is an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.
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 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.
As inorganic particles, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al Metal oxide particles containing atoms such as 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, or zirconium oxide is particle stability, availability, and hardness of 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.
In the present invention, the 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 exists 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, 50 mass% or less is more preferable, 40 mass% or less is further more preferable, and 30 mass% or less is especially preferable.
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.

Component F: Blocked isocyanate compound The photosensitive resin composition of the present invention preferably contains a blocked isocyanate compound as Component F. By containing the component F, it is excellent in reworkability. The mechanism of action is not clear, but it is considered that the blocked isocyanate group of component F is deprotected by the heat treatment after photocuring. In the cured film, it is presumed that the work of the isocyanate group derived from the component F improves the adhesiveness with the substrate, or the isocyanate group interacts with moisture and salts, so that the reworkability is excellent.
The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. The upper limit of the number of blocked isocyanate groups is not particularly defined, but is preferably 6 or less.

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-tetrazine Methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-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 , Hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. Products, multimers thereof, and prepolymer type skeleton compounds derived from these compounds can be suitably used. Among these, blocked isocyanate compounds that protect a compound selected from the group consisting of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and multimers thereof. A blocked isocyanate compound in which a compound selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and multimers thereof is protected is more preferable.
The isocyanate compound multimer is not particularly limited as long as it is a dimer or higher multimer, and examples thereof include biuret bodies, isocyanurate bodies, and adduct bodies, and biuret bodies are preferred.

Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, or pyrazole compounds are preferable, oxime compounds and lactam compounds are more preferable, oxime compounds are more preferable, and methyl ethyl ketone oxime is more preferable. Particularly preferred.

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 thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

  The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60P, 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P , K6000 (above, manufactured by Asahi Kasei Chemicals Corporation) Modules BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumijour BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) and the like are preferable Can be used.

Component F may be contained singly or in combination of two or more.
It is preferable that content of the block isocyanate compound in the photosensitive resin composition of this invention is 0.1-20 mass% with respect to the total solid of the photosensitive resin composition, and is 0.5-10 mass%. More preferably, it is more preferably 1 to 5% by mass.
Moreover, it is preferable that content of the block isocyanate compound in the photosensitive resin composition of this invention is 0.1-20 mass% with respect to the total organic solid content of the photosensitive resin composition, 0.5-10 More preferably, it is 1 mass%, and it is still more preferable that it is 1-5 mass%.
It is preferable for the content of component F to be in the above range since a cured film having excellent reliability can be obtained.

-Other ingredients-
The photosensitive resin composition of the present invention may contain other components in addition to the components described above. As other components, known components can be used, and the following components can be preferably exemplified.

<Solvent>
The photosensitive resin composition of the present invention may contain a solvent. The photosensitive resin composition of the present invention is preferably prepared as a composition in which components A to D, which are essential components, and optional components described above and below are dissolved and / or dispersed in a solvent.
As the solvent, an organic solvent is preferable. As the organic solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol mono Alkyl 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 and the like. As specific examples of these organic solvents, reference can be made to paragraph 0062 of JP-A-2009-098616.

  Specifically, propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol diacetate, cyclohexanol acetate, propylene glycol diacetate, and tetrahydrofurfuryl alcohol are preferable.

The boiling point of the organic solvent is preferably 100 ° C to 300 ° C, more preferably 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 preferably 100 to 3,000 parts by mass per 100 parts by mass of the total solid content of the composition from the viewpoint of adjusting the viscosity to be suitable for coating. 200 to 2,000 parts by mass is more preferable, and 250 to 1,000 parts by mass is even more preferable.
As solid content concentration of the photosensitive resin composition, 3-50 mass% is preferable, and it is more preferable that it is 20-40 mass%.

  The viscosity of the photosensitive resin composition is preferably 1 to 200 mPa · s, more preferably 2 to 100 mPa · s, and still more preferably 3 to 80 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.

<Alkoxysilane compound>
The photosensitive resin composition of the present invention preferably contains an alkoxysilane compound. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved.
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 present invention improves the adhesion between a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, molybdenum, titanium, or aluminum and a cured film. It is preferable that it is a compound to be made. 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-glycidoxypropyltriacoxysilane are more preferable. These can be used alone or in combination of two or more.
Examples of commercially available products include KBM-403 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.

  The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 2 to 20% by mass, and more preferably 3 to 10% with respect to the total solid content of the photosensitive resin composition. More preferred is mass%. Only one type of alkoxysilane compound may be used, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

<Surfactant>
The photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. As the surfactant, 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 described in Paragraph 0119-0123 of Unexamined-Japanese-Patent No. 2014-238438 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% by mass, and 0.01 to 2.0%, based on the total solid content of the composition. The 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.

<Antioxidant>
The photosensitive resin composition of this invention may contain antioxidant other than said component.
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 phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, hydroxyls. An amine derivative etc. can be mentioned. Among these, hindered phenolic antioxidants and phosphorus antioxidants are particularly preferable from the viewpoints of coloring of the cured film and reduction in film thickness, and hindered phenolic antioxidants are most preferable. These may be used individually by 1 type and may mix 2 or more types.
As a preferable commercial item, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (above, the product made from BASF) can be mentioned.
Although there is no restriction | limiting in particular in content of antioxidant, It is preferable that it is 0.1-10 mass% with respect to the total solid of the photosensitive resin composition, and it is 0.2-5 mass% Is more preferable, and it is still more preferable that it is 0.5-4 mass%.

  The photosensitive resin composition of the present invention may contain other compounds (for example, an alkoxymethyl group-containing compound) other than those described above without departing from the gist of the present invention. Examples of the alkoxymethyl group-containing compound include those described in paragraphs 0192 to 0194 of JP2011-221494A.

<Polymerization inhibitor>
The photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the polymerization reaction due to light leakage is suppressed, and the developability is excellent.
A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation), etc. to the polymerization initiation radical component generated from the polymerization initiator by exposure or heat. Is a substance that plays a role in deactivating polymerization initiation radicals and inhibiting polymerization initiation. For example, compounds described in paragraphs 0154 to 0173 of JP2007-334322A can be used.
Although there is no restriction | limiting in particular in content of the polymerization inhibitor in the photosensitive resin composition of this invention, It is preferable that it is 0.005-0.5 mass% with respect to the total solid of the photosensitive resin composition. More preferably, the content is 0.01 to 0.5% by mass. By adjusting the blending amount of the polymerization inhibitor, the patterning property can be improved without impairing the sensitivity.

<Binder polymer>
The photosensitive resin composition of the present invention may contain a binder polymer other than Component A from the viewpoints of resolution and film property improvement.
There is no restriction | limiting in particular as binder polymers other than the component A, Although a well-known thing can be used, It is preferable to use a linear organic polymer. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or Copolymerized resin, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half esterified or half amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and examples of the monomer having an acid anhydride include maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
The content of the binder polymer other than Component A in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0 to 40% by mass with respect to the total solid content of the photosensitive resin composition. 0 to 30% by mass, more preferably 0 to 20% by mass, particularly preferably 0 to 10% by mass, and most preferably 0 to 5% by mass.
Moreover, it is preferable that content of binder polymers other than the component A in the photosensitive resin composition of this invention is smaller than content of the component A.

[Other ingredients]
In the photosensitive resin composition of the present invention, if necessary, in addition to those described above, a sensitizer, a compound having an epoxy group, a compound having an oxetanyl group, a plasticizer, a thermal acid generator, and an acid proliferation Other components such as an agent can be added. Regarding these components, for example, paragraphs 0102 to 0104 of JP2014-235216A, paragraphs 0106 to 0108 of JP2014235216A, JP2009-98616A, and JP2009-244801A are disclosed. The thing of description and other well-known things can be used. In addition, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators and the like may be added to the curable composition of the present invention.

<Curing film, cured product and production method thereof>
The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. The cured product is preferably a cured film. 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.
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 1 to 3 in this order. Is preferred.
Process 1: Application | coating process which apply | coats the photosensitive resin composition of this invention on a board | substrate Process 2: The exposure process which exposes at least one part of the apply | coated photosensitive resin composition with an actinic ray Process 3: Exposed photosensitive property Development Step of Developing Resin Composition with Aqueous Developer Further, the method for producing a cured film of the present invention more preferably includes the following step 4 following the following step 3.
Step 4: Heat treatment step of heat-treating the developed photosensitive resin composition Further, the method for producing a cured film of the present invention may include the following step 3 ′ following step 3 and before step 4. Further preferred.
Step 3 ′: a step of further irradiating the developed photosensitive resin composition with actinic rays

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 obtained by depositing molybdenum, titanium, aluminum, copper, or the like on such a substrate.
The 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 Synthetic trees such as aromatic polyether resins, maleimide-olefin copolymers, cellulose, episulfide resins, etc. A substrate made of, 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 can also be applied on an LCD cell or an OLED cell that has been completed as a panel.

  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 alloys thereof are more preferable. 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 method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or a printing method may be used. it can.

In addition, when the photosensitive resin composition of the present invention contains a solvent, the method for producing a cured film of the present invention removes the solvent from the applied photosensitive resin composition after step 1 and before step 2. It is preferable to include a solvent removing step.
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 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. In this step, the polymerizable monomer is polymerized and cured by the action of the photopolymerization initiator.
As an exposure light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used. Actinic rays having a wavelength of from 300 nm to 450 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.
Further, even if 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.
The exposure in the exposure step is preferably performed in a state where oxygen is blocked from the viewpoint of curing acceleration. Examples of means for blocking oxygen include exposure in a nitrogen atmosphere and provision of an oxygen blocking film.
Moreover, the exposure in the said exposure process should just be performed to at least one part of the curable composition from which the solvent was removed, for example, may be whole surface exposure or pattern exposure. In this invention, it is preferable that an exposure process is pattern exposure, and it is more preferable that it is a process exposed through a photomask.
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. Within this range, the substrate and the apparatus can be heated without damage.

In the development step, the uncured portion of the photosensitive resin composition exposed in a pattern is developed and removed using an aqueous developer to form a negative image. The developer used in the development step is preferably an alkaline aqueous developer.
The developer used in the development step is preferably an aqueous solution of 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 the development step. 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.

Moreover, it is preferable to include the process (post-exposure) which further irradiates the developed photosensitive resin composition to a developed photosensitive resin composition from a viewpoint of film | membrane hardness improvement after a image development process and before a heat processing process.
In this case, it is preferable to perform energy exposure of about 50 to 3,000 mJ / cm ² with a mercury lamp or an LED lamp. Moreover, it is preferable that the post-exposure is performed on the entire surface.
By performing the post exposure, the curing reaction of the film can be further promoted, and the film hardness is improved.

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.
The heat treatment temperature is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 130 ° C. or lower. 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. Within this range, the substrate and the device can be cured without damage.
Moreover, the curing by light and / or heat in the method for producing a cured film of the present invention may be performed continuously or sequentially.
In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
From the viewpoint of adjusting the shape after heating, 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). For example, a method of first heating at 90 ° C. for 30 minutes (middle baking) and then heating at 120 ° C. for 30 minutes (post baking) can be exemplified. Further, middle baking and post baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.

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 overcoat film (protective film) or an interlayer insulating film. 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.
With the photosensitive resin composition of the present invention, a cured film having sufficient hardness can be obtained even when cured at a low temperature. For example, a cured film having a pencil hardness of 2H or more is 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 such as touch panels, touch panel display devices, organic EL display devices, and liquid crystal display devices. Especially, it is preferable that the cured film of this invention is a protective film for touchscreen wiring, and it is especially preferable that it is 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 characteristics, the cured product or resist pattern obtained by curing the photosensitive resin composition of the present invention is used as a partition as a structural member of a MEMS device, or is mechanically driven. Used as part of the part. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

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

<Organic EL display device>
The organic EL display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 1 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is 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.

<Liquid crystal display device>
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 a protective film, a planarizing film, and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and is known in various structures. The liquid crystal display device can be mentioned.
In addition, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Vertical Alignment) method, an IPS (In-Plane-Switching) method, an FFS (Fringe Field Switching) method, an OCB (OCB) (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 JP-A-2005-284291, or JP-A-2005 -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 orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to 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. 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.

<Touch panel and touch panel display device>
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 curable 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 the touch panel, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7 and 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP 2013-168125 A). 19 of FIG. 19, those described in FIG. 1 and FIG. 5 of JP 2012-89102 A, OGS type, TOL type (for example, those described in FIG. 2 of JP 2013-54727 A, 2, 3, 4, and 5 of JP-A-2015-15042), other configurations (for example, those described in FIG. 6 of JP-A-2013-164871), various out-cell types (So-called GG, G1 · G2, GFF, GF2, GF1, G1F, etc.).

FIG. 3 is a conceptual diagram illustrating an example of a liquid crystal display device having a touch panel function.
For example, the cured film of the present invention is preferably applied to a 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.

A known adhesive layer composition can be used for the adhesive layer 126 and the polarizing plate 127.
As specific examples of the polarizing plate and the adhesive layer, the polarizing plate with an adhesive layer described in Example 1, Example 7 or Example 13 of JP 2014-152319 A, Example 1 of JP 2014-191005 A, Polarizing plate with adhesive layer described in Example 3 or Example 6, polarized light with adhesive layer described in Example 1, Example 3, Example 6, Example 11 or Example 14 of JP2013-1000038 The adhesive layer described in Example 1, Example 2, Example 3, or Example 4 of JP, 2013-163783, A can be mentioned.
The adhesive layer preferably contains an antistatic agent for preventing static charge.
As the antistatic agent, known ones can be used. For example, ionic compounds such as metal particles, metal oxides, conductive polymers, quaternary ammonium salts and lithium salts can be used.
Specific examples of the antistatic agent include those described in paragraphs 0107 to 0115 of JP-A-2014-191005, those described in paragraphs 0046 to 0054 of JP-A-2013-1003006, and JP-A-2014-515046. In paragraphs 0027 to 0047.

  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 a liquid crystal display device having a touch panel function.
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. 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, the light shielding members 320 arranged in a matrix, the alignment film 350 disposed on the second insulating substrate 310, and the alignment film. And a common electrode 370 that is disposed on the color filter 330 and applies a voltage to the liquid crystal layer 400 in correspondence with the pixel electrode 290 of the lower display panel 200.

In the liquid crystal display device illustrated in FIG. 4, a sensing electrode 410, an insulating film 420, a driving electrode 430, and a 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.
In addition, an adhesive layer in the polarizing plate with an adhesive layer exemplified for the adhesive layer 126 and the polarizing plate 127 can be attached to the protective film 280.

  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.

<Method of measuring carboxylic acid equivalent>
A potentiometric titration method based on JIS K2501 (2003) using an automatic potentiometric 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. Was used to measure the acid value, and the carboxylic acid equivalent was calculated.

<Synthesis Example 1: Synthesis of acrylic resin solution A-1>
The flask was charged with 1 part of 2,2′-azobis (isobutyronitrile) and 50 parts of PGMEA (propylene glycol methyl ether acetate). Thereafter, 23.0 parts of methacrylic acid, 31.5 parts of benzyl methacrylate, and 32.8 parts of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged at room temperature (25 ° C., below) The same was carried out for a while and the inside of the flask was sufficiently purged with nitrogen by bubbling, and then heated and stirred at 70 ° C. for 5 hours. Next, 12.7 parts of glycidyl methacrylate, 1 part of dimethylbenzylamine, 0.2 part of p-methoxyphenol and 100 parts of PGMEA are added to the resulting solution, and the mixture is heated and stirred at 90 ° C. for 4 hours. An acrylic resin solution A-1 containing an acrylic resin A-1 having a methacryloyl group was obtained. The weight average molecular weight of the acrylic resin A-1 was 30,000, and the carboxylic acid equivalent was 560 g / mol.

<Synthesis Example 2: Synthesis of acrylic resin solution A-2>
The flask was charged with 2 parts of 2,2′-azobis (isobutyronitrile) and 50 parts of PGMEA (propylene glycol methyl ether acetate). Thereafter, 26.5 parts of methacrylic acid, 21.3 parts of styrene, and 37.7 parts of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred at room temperature for a while. The inside was sufficiently purged with nitrogen by bubbling, and then heated and stirred at 70 ° C. for 5 hours. Next, 14.6 parts of glycidyl methacrylate, 1 part of dimethylbenzylamine, 0.2 part of p-methoxyphenol and 100 parts of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours. An acrylic resin solution A-2 containing an acrylic resin A-2 having a methacryloyl group was obtained. The weight average molecular weight of acrylic resin A-2 was 13,000, and the carboxylic acid equivalent was 490 g / mol.

<Synthesis Example 3: Synthesis of acrylic resin solution A-3>
The flask was charged with 3 parts of 2,2′-azobis (isobutyronitrile) and 50 parts of PGMEA. Then, 29.4 parts of methacrylic acid, 26.7 parts of styrene, and 25.7 parts of methyl methacrylate were charged, stirred at room temperature for a while, and the inside of the flask was sufficiently purged with nitrogen by bubbling, and then heated at 70 ° C. for 5 hours. Stir. Next, 18.2 parts of glycidyl methacrylate, 1 part of dimethylbenzylamine, 0.2 part of p-methoxyphenol and 100 parts of PGMEA are added to the resulting solution, and the mixture is heated and stirred at 90 ° C. for 4 hours. An acrylic resin solution A-3 containing an acrylic resin A-3 having a methacryloyl group was obtained. The weight average molecular weight of the acrylic resin A-3 was 20,000, and the carboxylic acid equivalent was 470 g / mol.

<Synthesis Example 4: Synthesis of Acrylic Resin Solution J-4>
The flask was charged with 2 parts of 2,2′-azobis (isobutyronitrile) and 300 parts of PGMEA. Thereafter, 20 parts of methacrylic acid, 30 parts of styrene and 50 parts of methyl methacrylate were added and stirred for a while at room temperature. After the atmosphere in the flask was sufficiently replaced with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours. Acrylic resin solution J-4 containing -4 was obtained. The weight average molecular weight of the acrylic resin J-4 was 17,000, and the carboxylic acid equivalent was 250 g / mol.

<Synthesis Example 5: Synthesis of Compound 1 (C-1)>
[Synthesis of Compound A]
Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C., aluminum chloride (70.3 g, 0.527 mol) was added. Subsequently, o-toluoyl chloride (81.5 g, 0.527 mol) was added dropwise over 40 minutes, the temperature was raised to room temperature (25 ° C., the same applies hereinafter), and the mixture was stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) was added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) was added dropwise over 40 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of 35 mass% hydrochloric acid aqueous solution and 392 ml of distilled water was cooled to 0 ° C., and the reaction solution was added dropwise. The precipitated solid was filtered with suction, washed with distilled water and methanol, and recrystallized from acetonitrile to obtain Compound A having the following structure (yield 164.4 g, yield 77%).

[Synthesis of Compound B]
Compound A (20.0 g, 47.9 mmol) obtained above was dissolved in 64 ml of tetrahydrofuran (THF), and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4. 79 mmol). Subsequently, sodium hydroxide (2.0 g, 50.2 mmol) was added to the reaction solution, and the mixture was refluxed for 2 hours. Next, after cooling to 0 ° C., SM-28 (11.1 g, 57.4 mmol, sodium methoxide 28% methanol solution, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 20 minutes, and the temperature was raised to room temperature. And stirred for 2 hours. Next, after cooling to 0 ° C., isopentyl nitrite (6.73 g, 57.4 mmol) was added dropwise over 20 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was diluted with 120 ml of acetone and added dropwise to a 0.1N hydrochloric acid aqueous solution cooled to 0 ° C. The precipitated solid was filtered with suction and washed with distilled water. Subsequently, recrystallization was performed with acetonitrile to obtain Compound B having the following structure (yield 17.0 g, yield 64%).

[Synthesis of Compound 1]
Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml N-methylpyrrolidone (NMP) and triethylamine (Et ₃ N, 3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (AcCl, 3.05 g, 38.9 mmol) was added dropwise over 20 minutes, and then the mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then compound 1 (yield 19.5 g, yield 99%). )

Moreover, the structure of the obtained compound 1 was identified by NMR.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.81 ( d, 1H, J = 8.0 Hz), 7.51-7.24 (m, 10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2.36 (s, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4 Hz).

Each component used in Examples and Comparative Examples is as follows.
<Component A>
A-1: Acrylic resin A-1 of Synthesis Example 1
A-2: Acrylic resin A-2 of Synthesis Example 2
A-3: Acrylic resin A-3 of Synthesis Example 3
<Component B>
B-1: Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), hexafunctional B-2: Pentaerythritol tetraacrylate (A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), tetrafunctional B- 3: Trimethylolpropane triacrylate (M309, manufactured by Toagosei Co., Ltd.), trifunctional B-4: NK oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), 15 functional B-5: UA-306H ( Kyoeisha Chemical Co., Ltd.), 6 functional B'-1: Aronix M-5300 (manufactured by Toagosei Co., Ltd.), 1 functional B'-2: 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), bifunctional <component C>
C-1: Compound 1 (synthetic product, see above), oxime ester compound C-2: IRGACURE OXE-01 (manufactured by BASF), oxime ester compound, following structure C-3: IRGACURE OXE-02 (manufactured by BASF) , Oxime ester compound, following structure

<Component D>
D-1: Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd., phosphate ester compound whose main component is the following compound)
D-2: Light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd., phosphate ester compound whose main component is the following compound)
D-3: KAYAMER PM-21 (Nippon Kayaku Co., Ltd., mixture satisfying the following composition)
D-4: JPA-514 (manufactured by Johoku Chemical Industry Co., Ltd., the following two kinds of mixtures)
D-5: MR-260 (manufactured by Daihachi Chemical Industry Co., Ltd., the following compound)

<Component E>
E-1: PMA-ST (manufactured by Nissan Chemical Industries, Ltd.), silica particles, average particle size of 10 to 15 nm
E-2: MIBK-ST-L (Nissan Chemical Industry Co., Ltd.), silica particles, average particle size of 40-50 nm
<Component F>
F-1: Takenate B870N (Mitsui Chemicals, Inc.)
F-2: Death Module BL3575 / 1 PMA / SN (manufactured by Sumika Bayer Urethane Co., Ltd.)
F-3: Death Module BL4265 (manufactured by Sumika Bayer Urethane Co., Ltd.)
F-4: Duranate SBN-70D (manufactured by Mitsui Chemicals, Inc.)
<Alkoxysilane compound>
SC-1: KBM-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
SC-2: KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
<Surfactant>
W-1: MegaFuck F554 (manufactured by DIC Corporation), fluorosurfactant)
<Additives>
J-1: ADK STAB AO-60 (hindered phenol-based antioxidant, manufactured by ADEKA Corporation)
J-2: Irganox 1035 (hindered phenol-based antioxidant, manufactured by BASF)
J-3: Karenz MT-PE-1 (thiol compound, manufactured by Showa Denko KK)
J-4: Acrylic resin J-4 of Synthesis Example 4
<Solvent>
Y-1: Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation)
Y-2: Methyl ethyl diglycol (manufactured by Daicel Corporation)
Y-3: 1,3-butylene glycol diacetate

(Examples 1-42 and Comparative Examples 1-5)
<Preparation of photosensitive resin composition>
As shown in Table 2 or Table 3 below, each component was blended and stirred to form a solvent solution and / or dispersion, filtered through a polytetrafluoroethylene filter having a pore size of 0.3 μm, and Examples 1-42 And each photosensitive resin composition of Comparative Examples 1-5 was obtained. The unit of the addition amount of each component of the following Table 2 and Table 3 is a mass part.
The following evaluation was performed using each obtained photosensitive resin composition. The evaluation results are shown in Tables 2 and 3.

<Evaluation of reworkability>
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, irradiation with light 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.
Next, a polarizing plate with an acrylic pressure-sensitive adhesive prepared according to Example 1 of JP-A-7-33210 is cut into a width of 20 mm and a length of 100 mm under an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH. The pressure-sensitive adhesive layer surface of the polarizing plate was attached to the cured film by one reciprocating 2 kg roller.
Furthermore, after curing for 30 minutes in an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH, the end of the sample for evaluation is pinched by the evaluator's hand, the peeling angle is 100 to 120 ° in the direction of 100 mm in length, and the pulling speed is 100 mm. It peeled at / min-500mm / min.
Finally, in order to clean the surface of the cured film, the surface was wiped by the evaluator's hand using a nonwoven fabric containing acetone.
The cured film after wiping was observed and judged as follows.
5: The cured film is not damaged and the film thickness does not change.
4: Minor scratches that do not affect display quality occur in the cured film, or a film thickness change of less than 1% occurs.
3: Scratches slightly affecting the display quality occur in the cured film, or a film thickness change of 1% or more and less than 3% occurs.
2: Conspicuous scratches that greatly affect display quality occur in the cured film, or a film thickness change of 3% or more occurs.
1: The cured film is peeled off from the substrate.

<Evaluation of hemming>
A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated and then 90 ° C./120 seconds. Pre-baking was performed on a hot plate to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a mask having a hole pattern with a mask diameter of 50 μm using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. By these operations, the optimum i-line exposure amount (Eopt) when resolving a hole diameter of 50 μm at a point of 1.5 μm in the film thickness direction from the substrate side was defined as sensitivity.
About the hole pattern with a mask diameter of 50 micrometers, it exposed by the said optimal i line | wire exposure amount, and evaluated the hole diameter at the time of producing a permanent film. In the subsequent evaluation, the actual hole pattern diameter was defined by the size of the bottom (bottom) of the resist. The smaller the difference between the hole diameter and the mask diameter, that is, the smaller the skirting, the easier the panel design becomes, and this is preferable.
-Evaluation criteria-
5: Ratio of mask diameter to actual hole pattern diameter is within ± 10% 4: Ratio of mask diameter to actual hole pattern diameter exceeds ± 10% and within ± 20% 3: Mask diameter to actual hole Pattern diameter ratio exceeds ± 20% and within ± 30% 2: Ratio of mask diameter to actual hole pattern diameter exceeds ± 30% and within ± 40% 1: Mask diameter and actual hole The pattern diameter ratio exceeds ± 40%, or there is a residual film and the bottom does not resolve

<Evaluation of development film reduction>
A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated and then 90 ° C./120 seconds. Pre-baking was performed on a hot plate to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was irradiated with light of 100 mJ / cm ² (i-line conversion) using a high-pressure mercury lamp. The exposed photosensitive resin composition layer was developed with an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The film thickness before and after the development treatment was measured to evaluate the development film reduction rate.
-Evaluation criteria-
5: Film reduction rate of less than 3% 4: Film reduction rate of 3% to less than 8% 3: Film reduction rate of 8% to less than 15% 2: Film reduction rate of 15% to less than 30% 1: Film reduction rate 30% 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.

  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: image 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)

As component A, a polymer having a (meth) acryloyl group and an acid group,
As component B, a trifunctional or higher functional ethylenically unsaturated compound,
As component C, a photopolymerization initiator ,
As component D, a compound having a phosphate structure and an ethylenically unsaturated group, and
Component F includes a blocked isocyanate compound ,
Content of the component D with respect to the total organic solid content in a composition is 0.01-5 mass%, The photosensitive resin composition characterized by the above-mentioned. The photosensitive resin composition of Claim 1 whose total content of the component A with respect to the total organic solid content in a composition and the component B is 50-99 mass%. Content of the component D with respect to the total organic solid content in a composition is 0. 6 is to 2 wt%, the photosensitive resin composition according to claim 1 or 2. The photosensitive resin composition of any one of Claims 1-3 whose compound which has the said phosphate ester structure and an ethylenically unsaturated group is a compound which has a P-OH structure . The photosensitive resin composition of any one of Claims 1-4 whose total content of the component A with respect to the total organic solid content in a composition and the component B is 70-99 mass%.   The photosensitive resin composition of any one of Claims 1-5 which further contains an inorganic particle. A method for producing a cured film comprising at least Step 1 to Step 3 in this order.
Process 1: Application | coating process which apply | coats the photosensitive resin composition of any one of Claims 1-6 on a board | substrate Process 2: Exposing at least one part of the apply | coated photosensitive resin composition with actinic light. Exposure step Step 3: Development step of developing the exposed photosensitive resin composition with an aqueous developer   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-6.   The cured film of Claim 8 which is an interlayer insulation film or a protective film.   The cured film according to claim 8 or 9, which is a protective film for touch panel wiring. 11. The protective film for wiring in an on-cell touch panel, according to any one of claims 8 to 10.
The cured film as described in the item.   The touch panel which has a cured film of any one of Claims 8-11.   The touch panel display device which has a cured film of any one of Claims 8-11.   A liquid crystal display device having the cured film according to claim 8.   An organic EL display device having the cured film according to claim 8.

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