JP6426563B2 - Photosensitive composition, method of producing cured film, method of producing liquid crystal display device, method of producing organic electroluminescence display device, and method of producing touch panel - Google Patents

Description

  The present invention relates to a photosensitive composition. More specifically, it is suitable for forming a planarizing film, a protective film, an interlayer insulating film and the like of an electronic component such as a liquid crystal display device, an image display device such as an organic electroluminescent display device, a touch panel, an integrated circuit element, and a solid state imaging device. It relates to a photosensitive composition. In addition, the present invention relates to a method of manufacturing a cured film, a method of manufacturing a liquid crystal display device, a method of manufacturing an organic electroluminescence display device, and a method of manufacturing a touch panel.

  In many cases, pattern-formed interlayer insulating films are provided in liquid crystal display devices, image display devices such as organic electroluminescent display devices, and input devices such as touch panels. In the formation of the interlayer insulating film, a photosensitive composition is widely used because the number of steps for obtaining the required pattern shape is small and sufficient flatness can be obtained.

  The interlayer insulating film in the above device may be formed, for example, using a negative photosensitive composition containing a compound having two or more groups having an ethylenically unsaturated bond, a photopolymerization initiator, and a solvent. It is tried (refer patent document 1).

International Publication 2014/208647 Publication

  The photosensitive composition often uses a surfactant to improve the coatability. From the viewpoint of coatability, a fluorine-based surfactant is often used as the surfactant. However, the fluorine-based surfactant may be unevenly distributed on the surface of the coating film after application. When a cured film produced using such a photosensitive composition is used as a permanent film, various layers are often laminated on the cured film. At this time, if the fluorinated surfactant is unevenly distributed on the film surface, the adhesion between the upper layer laminated on the cured film and the cured film may be lowered. For this reason, ashing treatment etc. may be performed to the surface layer of a cured film, and the film surface layer which uneven distribution of fluorine type surfactant was removed. Thus, conventionally, the cured film may require a process such as ashing, which may increase the number of processes. In recent years, it has been desired to reduce the number of processes to simplify the processes and reduce the manufacturing cost.

  Therefore, an object of the present invention is to provide a photosensitive composition which has good coatability and can produce a cured film excellent in adhesion to the upper layer laminated on the cured film. Another object of the present invention is to provide a method of producing a cured film, a method of producing a liquid crystal display device, a method of producing an organic electroluminescence display device, and a method of producing a touch panel.

Under these circumstances, as a result of investigations by the present inventors, coating is carried out by incorporating the compound S having a structure represented by the following formula S1 and a structure represented by the following formula S2 in a photosensitive composition. It has been found that it is possible to produce a cured film excellent in adhesiveness and excellent in adhesion to the upper layer laminated on the cured film without undergoing a process such as ashing, and the present invention has been completed. That is, the present invention provides the following.
<1> Compound S Having a Structure Represented by a Structure Represented by a Structure Represented by a Structure Represented by a Structure Represented by a Structure Represented by a Structure Represented by the Following Formula S1 A photosensitive composition comprising;
In the formula, a wavy line represents a bonding position with a group constituting the compound S,
R ¹ represents an alkyl group,
R ² represents a hydrogen atom or an alkyl group,
L ¹ represents a single bond or a divalent linking group, and when L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring,
Rf represents a fluoroalkyl group having three or more fluorine atoms,
L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30,
When n is 0, R ¹⁰⁰ represents a hydroxy group,
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, and R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. It may be good or different.
The photosensitive composition as described in <1> which contains 0.001-20 mass parts of compounds S with respect to 100 mass parts of a compound which has 2 or more of groups which have a <2> ethylenic unsaturated bond.
<3> The compound S is a polymer having a structural unit S1-1 having a structure represented by formula S1 in a side chain and a structural unit S2-1 having a structure represented by formula S2 in a side chain The photosensitive composition as described in <1> or <2>.
<4> In any one of <1> to <3>, the compound S is a polymer having a constitutional unit represented by the following formula S1-2 and a constitutional unit represented by the following formula S2-2. The photosensitive composition described;
In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ¹² represents an alkyl group,
R ¹³ represents a hydrogen atom or an alkyl group,
L ¹⁰ represents a single bond or a divalent linking group, and when L ¹⁰ represents a divalent linking group, R ¹² may combine with L ¹⁰ to form a ring,
Rf represents a fluoroalkyl group having three or more fluorine atoms,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
n1 represents an integer of 0 to 30,
When n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n1 is 2 to 30, the plurality of L ¹⁰¹ may be the same or different.
<5> In any one of <1> to <4>, the compound S is a polymer having a constitutional unit represented by the following formula S1-3 and a constitutional unit represented by the following formula S2-3 The photosensitive composition described;
In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ²² represents an alkyl group having 1 to 3 carbon atoms,
R ²³ represents a hydrogen atom,
L ²⁰ represents an alkylene group having 1 to 12 carbon atoms,
R f ¹ represents a C 3-6 perfluoroalkyl group,
R ²² may combine with L ²⁰ to form a ring,
L ²⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ²⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
n2 represents an integer of 1 to 20, and when n2 is 2 to 20, a plurality of L ²⁰¹ may be the same or different.
<6> The compound S is a polymer containing the structural unit S1-1 and the structural unit S2-1 at 70% by mass or more of the total structural units of the compound S, and the structural unit S1-1 and the structure The photosensitive composition in any one of <3>-<5> whose mass ratio with unit S2-1 is structural unit S1-1: structural unit S2-1 = 5: 95-95: 5.
The photosensitive composition in any one of <1>-<6> whose weight average molecular weights of <7> compound S are 100-100000.
<8> The photosensitive composition according to any one of <1> to <7>, further including an alkali-soluble resin.
The photosensitive composition as described in <8> whose <9> alkali-soluble resin is 1 or more types chosen from an acrylic resin, a styrene resin, polybenzoxazole resin, a polyimide resin, a cycloolefin resin, and a siloxane resin.
The process of apply | coating the photosensitive composition in any one of <10><1>-<9> on a board | substrate, the process of removing a solvent from the apply | coated photosensitive composition, the photosensitive composition which removed the solvent Exposing the object in a pattern, developing the unexposed area of the photosensitive composition exposed in a pattern to form a pattern, and heating the photosensitive composition after development Method of producing a cured film.
The manufacturing method of the liquid crystal display device containing the manufacturing method of the cured film as described in <11><10>.
The manufacturing method of the organic electroluminescent display apparatus containing the manufacturing method of the cured film as described in <12><10>.
The manufacturing method of a touch panel including the manufacturing method of the cured film as described in <13><10>.

  It has become possible to provide a photosensitive composition capable of producing a cured film having good coatability and excellent adhesion with the upper layer laminated on the cured film without passing through steps such as ashing. . In addition, it has become possible to provide a method for producing a cured film, a cured film and an apparatus.

FIG. 2 is a conceptual diagram of an example of a liquid crystal display device. It is the schematic which shows an example of the liquid crystal display device which has a function of a touch panel. It is the schematic which shows an example of the liquid crystal display device which has a function of a touch panel.

Hereinafter, the contents of the present invention will be described in detail. Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments. In addition, in this specification, "-" is used in the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.
In the notation of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "(meth) acrylate" represents "acrylate" and "methacrylate", "(meth) acrylic" represents "acrylic" and "methacrylic", and "(meth) acryloyl" Represents "acryloyl" and "methacryloyl", and "(meth) allyl" represents "allyl" and "methallyl".
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values determined by gel permeation chromatography (GPC).

<Photosensitive composition>
The photosensitive composition of the present invention is represented by a compound having two or more groups having an ethylenically unsaturated bond, a photopolymerization initiator, a solvent, a structure represented by formula S1 described later, and a formula S2 And a compound S having a structure.

According to the present invention, by using the photosensitive composition having the above-described structure, the coating property is good, and the adhesion to the upper layer laminated on the cured film is excellent without passing through a process such as ashing. A cured film can be produced. The mechanism of the effects of the present invention is presumed as follows.
That is, the structure represented by Formula S1 described later is excellent in hydrophobicity since it has a fluoroalkyl group, and the structure represented by Formula S2 is excellent in hydrophilicity because it has a hydrophilic group. It is presumed that the compound S having the structure of both functions as a surfactant, and it becomes possible to obtain excellent coatability. Further, in the structure represented by the formula S1 possessed by the compound S, since the fluoroalkyl group is bonded via an acetal bond, the acetal bond is broken when heating or the like, and the fluoroalkyl group part is eliminated to volatilize It is thought that it is easy to do, and it is hard to unevenly distribute a fluorine in the surface layer of a cured film. For this reason, it is presumed that it has become possible to produce a cured film excellent in adhesion to the upper layer laminated on the cured film without undergoing a process such as ashing.
The present invention will be described in detail below.

<< Compound Having Two or More Groups Having Ethylenically Unsaturated Bond (Polymerizable Compound) >>
The photosensitive composition of the present invention contains a compound having two or more groups having an ethylenically unsaturated bond (hereinafter, also referred to as a polymerizable compound). As a group which has an ethylenically unsaturated bond which a polymeric compound has, a vinyl group, a (meth) allyl group, a (meth) acryloyl group etc. are mentioned, A (meth) acryloyl group is preferable.

  In the present invention, the polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, polymers and the like. Monomers and / or polymers are preferred. The polymerizable compound of the monomer type preferably has a molecular weight of 100 to 3,000. The polymerizable compound of the polymer type preferably has a weight average molecular weight of 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4,000 or more, more preferably 5,000 or more.

  The polymerizable compound is preferably a (meth) acrylate compound. The (meth) acrylate compound is preferably a compound having two or more (meth) acryloyl groups in one molecule, and more preferably a compound having three or more (meth) acryloyl groups. The upper limit of the number of (meth) acryloyl groups is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 6 or less. As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-29760A, and paragraph Nos. 0254 to 0257 of JP2008-292970A. The contents of which are incorporated herein by reference.

  The polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd.) Made in Japan) dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; A) D-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues (for example, commercially available from Sartomer, SR454, SR499) are preferred. These oligomer types can also be used. Moreover, KAYARAD RP-1040, DPCA-20 (made by Nippon Kayaku Co., Ltd.), M-321 (made by Toagosei Co., Ltd.) can also be used.

  The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g. When the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the developability is good, and when it is 40 mg KOH / g or less, it is advantageous in terms of production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent. As a commercial item of the polymeric compound which has an acidic radical, M-305, M-510, M-520 etc. are mentioned, for example as a polybasic acid modified | denatured acrylic oligomer made from Toagosei Co., Ltd. product.

  As a polymerizable compound, a compound having a caprolactone structure is also a preferable embodiment. The polymerizable compound which has a caprolactone structure is marketed as Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, for example, and DPCA-20, DPCA-30, DPCA-60, DPCA-120 etc. are mentioned.

  As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups (meta More preferred are acrylate compounds. As a commercial item of the polymerizable compound having an alkyleneoxy group, for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentylene oxy groups manufactured by Nippon Kayaku Co., Ltd. Examples include DPCA-60, which is a hexafunctional acrylate having one, and TPA-330, a trifunctional acrylate having three isobutylene oxy groups.

  Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable. As commercially available products, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Gokusaku Pulp Co., Ltd.), U-15 HA, U-6 LPA, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan) Kayaku Co., Ltd. product, UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha) etc. are mentioned.

  The polymerizable compound is also preferably a polymer having a group having an ethylenically unsaturated bond in a side chain (hereinafter, also referred to as a polymerizable polymer). In the polymerizable polymer, the content of a constituent unit having a group having an ethylenically unsaturated bond in a side chain is preferably 5 to 100% by mass of all constituent units. As for a minimum, 10 mass% or more is more preferable, and 15 mass% or more is still more preferable. As for the upper limit, 95 mass% or less is more preferable, and 90 mass% or less is still more preferable.

  The polymerizable polymer may contain other structural unit positions in addition to the structural unit having a group having an ethylenically unsaturated bond in a side chain. The other constituent unit may contain a functional group such as an acid group or may not contain a functional group. As an acid group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group are illustrated. Only one type of acid group may be contained, or two or more types may be contained. Other functional groups include development accelerating groups such as lactones, acid anhydrides, amides and cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, maleimide groups, amino groups, etc. And can be introduced as appropriate.

  The polymerizable polymer preferably contains a structural unit having an acid group. It is preferable that the ratio of the structural unit which has an acidic radical is 1-50 mass% of all the structural units which comprise a polymeric polymer. The lower limit is more preferably 2% by mass or more and still more preferably 3% by mass or more. 35 mass% or less is more preferable, and, as for an upper limit, 30 mass% or less is still more preferable. When the polymerizable polymer contains a structural unit having an acid group, the acid value of the polymerizable polymer is preferably 10 to 150 mg KOH / g. The lower limit is preferably 20 mg KOH / g or more, and more preferably 30 mg KOH / g or more. The upper limit is preferably 140 mg KOH / g or less, and more preferably 130 mg KOH / g or less.

  Commercial products of the polymerizable polymer include Diamond NR series (made by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (containing COOH containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.,), Biscoat R-264, KS Resist 106 (any one) Also, Osaka Organic Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA 230 AA), Plaxel CF 200 series (all of which are Daicel Chemical Industries, Ltd.), Ebecryl 3800 (Daicel UBC Co., Ltd.), Acricle Cure RD-F8 Nippon Catalyst Co., Ltd.) and the like.

  The content of the polymerizable compound in the photosensitive composition of the present invention is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30 parts by mass or more with respect to 100 parts by mass of the total solid components of the photosensitive composition. Is more preferred. The upper limit is, for example, more preferably 99 parts by mass or less. The photosensitive composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<< photoinitiator >>
The photosensitive composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light rays visible from the ultraviolet region are preferable. The photopolymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 within the range of about 300 nm to 800 nm (330 nm to 500 nm is more preferable).

  As the photopolymerization initiator, for example, acyl phosphine compounds, alkyl phenone compounds, α-amino ketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds Compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, metallocene compounds, organic boron salt compounds, disulfone compounds, thiol compounds and the like can be mentioned. From the viewpoint of sensitivity, oxime compounds and alkylphenone compounds are preferred. As a photoinitiator, the description of Paragraph No. 0061-0073 of Unexamined-Japanese-Patent No. 2011-186398 can be considered, for example, and this content is integrated in this-application specification.

  As an oxime compound, IRGACURE OXE-01 (made by BASF Corporation) which is a commercial item, IRGACURE OXE-02 (made by BASF Corporation), TR-PBG-304 (made by Changzhou strong electronic new materials Co., Ltd. company), Adeka ARKules NCI -831 (made by ADEKA), Adeka ARKRUZ NCI-930 (made by ADEKA), etc. can be used.

  In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. As specific examples of the oxime compound having a fluorine atom, a compound described in JP-A-2010-262028, a compound 24 described in JP-A-2014-500852, a compound described in JP-A-2013-164471 ( C-3) and the like. This content is incorporated herein by reference.

  Examples of the alkylphenone compounds include hydroxyalkylphenone compounds and aminoalkylphenone compounds. As the hydroxyalkyl phenone compound, commercially available products IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade names: all manufactured by BASF, Inc.) can be used. As the aminoalkylphenone compound, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 EG (trade names: all manufactured by BASF Corp.) can be used.

  As an acyl phosphine compound, IRGACURE 819 and DAROCUR-TPO (brand name: all are BASF Corporation make) which are commercial items can be used.

  The content of the photopolymerization initiator is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, and still more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound. is there. Within this range, better sensitivity and pattern formability can be obtained. The photosensitive composition may contain only one type of photopolymerization initiator, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<< solvent >>
The photosensitive composition of the present invention contains a solvent. The photosensitive composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. As the solvent, those which dissolve essential components and optional components and do not react with each component are preferable.
In the present invention, as the solvent C, known solvents can be used. For example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol mono alkyl ether acetates, propylene glycol mono alkyl ethers, propylene glycol dialkyl ethers, propylene glycol mono alkyl ether acetates, diethylene glycol dialkyl ethers (eg, Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc.), diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides And lactones etc. Kill. Further, the solvents described in paragraphs [0174] to [0178] of JP-A-2011-221494, the solvents described in paragraphs [0167] to [0168] of JP-A-2012-194290 can also be mentioned, and the contents thereof are incorporated in the present specification. . Specific examples of preferable solvents include propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, γ-butyrolactone, N-methyl pyrrolidone, and 1,3-butylene glycol diacetate.

  The content of the solvent in the photosensitive composition of the present invention is preferably 50 to 95 parts by mass with respect to 100 parts by mass of all the components in the photosensitive composition. The lower limit is more preferably 60 parts by mass or more. The upper limit is more preferably 90 parts by mass or less. The solvent may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount becomes the said range.

<< Compound S >>
The photosensitive composition of the present invention comprises a compound S having a structure represented by the following formula S1 and a structure represented by the following formula S2. Hereinafter, the structure represented by S1 is also referred to as structure S1. Further, the structure represented by the formula S2 is also referred to as a structure S2.
In the formula, a wavy line represents a bonding position with a group constituting the compound S,
R ¹ represents an alkyl group,
R ² represents a hydrogen atom or an alkyl group,
L ¹ represents a single bond or a divalent linking group, and when L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring,
Rf represents a fluoroalkyl group having three or more fluorine atoms,
L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30,
When n is 0, R ¹⁰⁰ represents a hydroxy group,
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, and R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. It may be good or different.

First, the structure S1 will be described.
In formula S1, R ¹ represents an alkyl group. 1-10 are preferable, 1-6 are more preferable, 1-3 are still more preferable, 1 or 2 are especially preferable, and, as for carbon number of an alkyl group, 1 is most preferable. The alkyl group may be linear, branched or cyclic, but linear or branched is preferable, and linear is more preferable.
When L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring. Examples of the ring formed by combining R ¹ and L ¹ include tetrahydrofuranyl and tetrahydropyranyl.

In formula S1, R ² represents a hydrogen atom or an alkyl group. Examples of the alkyl group include the alkyl groups described for R ¹ , and preferred ranges are also the same. R ² is preferably a hydrogen atom.

In Formula S1, L ¹ represents a single bond or a divalent linking group.
As a bivalent coupling group, the group which combines an alkylene group, an arylene group, and these is mentioned.
1-12 are preferable, as for carbon number of an alkylene group, 1-10 are more preferable, 1-6 are more preferable, and 1-4 are especially preferable. The alkylene group is preferably linear or cyclic, and more preferably linear. The alkylene group may be linked via one or more types of bonds selected from ether bonds, ester bonds and amide bonds, and may not have these bonds. The alkylene group preferably does not have the aforementioned bond. The alkylene group may be unsubstituted or may have a substituent, but is preferably unsubstituted. A halogen atom can be illustrated as a substituent. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, and a fluorine atom is preferable.
6-20 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable. The arylene group may be unsubstituted or may have a substituent. No substitution is preferred. A halogen atom can be illustrated as a substituent. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, and a fluorine atom is preferable.
L ¹ is preferably a single bond or an alkylene group, and more preferably an alkylene group.

In formula S1, Rf represents a fluoroalkyl group having three or more fluorine atoms. The carbon number of the fluoroalkyl group is preferably 1 to 12. The lower limit is preferably 3 or more, more preferably 4 or more. The upper limit is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.
The fluoroalkyl group represented by Rf may be linear, branched or cyclic, preferably linear or cyclic, and more preferably linear. According to this aspect, the coatability can be improved. Furthermore, the adhesiveness with the upper layer laminated | stacked on a cured film can be improved more.
In the present invention, Rf is preferably a perfluoroalkyl group. 3-6 are preferable and, as for carbon number of a perfluoroalkyl group, 4-6 are more preferable. According to this aspect, the coatability can be improved. Furthermore, the adhesiveness with the upper layer laminated | stacked on a cured film can be improved more.
In the present invention, a fluoroalkyl group means an alkyl group in which at least a part of hydrogen atoms of the alkyl group is substituted with a fluorine atom. That is, the fluoroalkyl group is an alkyl group having a fluorine atom as a substituent. The perfluoroalkyl group is a kind of fluoroalkyl group, and means an alkyl group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

In the formula S1, preferred specific examples of the combination of L ¹ and R f include the following. _{CF 3 CH 2 CH 2 -,} CF 3 CF 2 CH 2 CH 2 -, CF 3 (CF 2) 2 CH 2 CH 2 -, CF 3 (CF 2) 3 CH 2 CH 2 -, CF 3 (CF 2) ₄ CH ₂ CH _2- , CF ₃ (CF ₂ ) ₅ CH ₂ CH _2- , CF ₃ (CF ₂ ) ₆ CH ₂ CH _2- , CF ₃ (CF ₂ ) ₇ CH ₂ CH _2- , (CF ₃ ) ₃ CCH ₂ CH _2- and the like. Among these, CF ₃ (CF ₂ ) ₃ CH ₂ CH _2- , CF ₃ (CF ₂ ) ₄ CH ₂ CH _2- , CF ₃ (CF ₂ ) ₅ CH ₂ CH _2- , (CF ₃ ) ₃ CCH ₂ CH ₂ -is preferred, and CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ -is particularly preferred.

Next, the structure S2 will be described.
In the formula S2, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30.

In formula S2, the number of carbon atoms of the alkylene radical L ¹⁰⁰ represents preferably 1 to 12, more preferably 1 to 6, 2 to 4 is more preferable. The alkylene group represented by L ¹⁰⁰ is preferably linear or branched, more preferably branched. Number of branches of the alkylene group L ¹⁰⁰ represents the 1-2 is preferred, and more preferably 1. The alkylene group represented by L ¹⁰⁰ may have a substituent, but is preferably unsubstituted.
In formula S2, the number of carbon atoms in the alkyl group R ¹⁰⁰ represents preferably 1 to 12, more preferably 1 to 6, 1 to 3 is more preferable. The alkyl group represented by R ¹⁰⁰ is preferably linear or branched, and more preferably linear. The alkyl group represented by R ¹⁰⁰ may have a substituent, but is preferably unsubstituted.

In formula S2, n represents an integer of 0 to 30. The lower limit is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The upper limit is preferably 20 or less, more preferably 15 or less.
In addition, although n represents the integer of 0-30, the photosensitive composition of this invention may contain two or more things in which n in the compound S differs. Therefore, the average value of n of the compound S contained in the photosensitive composition of the present invention may not be an integer. In the present invention, n in one compound S is preferably an integer of 0 to 30.

In formula S2, when n is 0, R ¹⁰⁰ represents a hydroxy group,
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, and R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. It may be good or different.
According to this aspect, excellent hydrophilicity is easily obtained. In particular, from the viewpoint of improving hydrophilicity, the following embodiments (1) to (3) are preferable, the embodiment (2) or (3) is more preferable, and the embodiment (3) is further preferable.
(1) A structure in which n is 0 and R ¹⁰⁰ is a hydroxy group.
(2) A structure in which n is 1 and L ¹⁰⁰ represents an alkylene or carbonyl group having 1 to 12 carbon atoms, and R ¹⁰⁰ represents a hydrogen atom. (3) n is 2 to 30, L ¹⁰⁰ has 1 to 1 carbon atoms A structure in which R ¹⁰⁰ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, which is an alkylene group of 12;

The compound S may have only one structure S1, or two or more. Moreover, when it has two or more structures S1, the same structure may be sufficient and a different structure may be sufficient.
In addition, the compound S may have only one structure S2, or two or more. Moreover, when it has two or more structures S2, the same structure may be sufficient and a different structure may be sufficient.

  The photosensitive composition of the present invention preferably contains Compound S in an amount of 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound. 0.005 mass part or more is preferable, and, as for a lower limit, 0.01 mass part or more is more preferable. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 2 parts by mass or less.

  In the present invention, the compound S may be a low molecular weight compound or a polymer. From the viewpoint of coatability, the compound S is preferably a polymer.

(When the compound S is a low molecular weight compound)
When the compound S is a low molecular weight compound, the compound S is preferably a compound represented by the following formula S-100.
R ¹ represents an alkyl group,
R ² represents a hydrogen atom or an alkyl group,
L ¹ represents a single bond or a divalent linking group, and when L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring,
Rf represents a fluoroalkyl group having three or more fluorine atoms,
L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30,
When n is 0, R ¹⁰⁰ represents a hydroxy group,
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, and R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. Good or different,
A represents a single bond or a (p + q) -valent linking group,
p and q each independently represent an integer of 1 or more,
A represents a single bond, and p and q each represent 1 when a single bond is a single bond.

In formula S-100, R ¹ , R ² , L ¹ , Rf, L ¹⁰⁰ , R ¹⁰⁰ and n have the same meanings as the ranges described for formulas S1 and S2 described above.

In formula S-100, A represents a single bond or a (p + q) -valent linking group.
As the (p + q) -valent linking group, 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Included are groups consisting of 0 to 20 sulfur atoms.
As a specific example of the (n + k) -valent linking group, the following structural units or a group formed by combining two or more of the following structural units (may form a ring structure) can be mentioned .

  In Formula S-100, p and q each independently represent an integer of 1 or more. The upper limit of the total number of p and q is not particularly limited, but may be 10 or less, or 6 or less. The lower limit is 2 or more.

  When the compound S is a low molecular weight compound, the molecular weight of the compound S is preferably 100 to 1000. The lower limit is preferably 120 or more, more preferably 150 or more. The upper limit is preferably 500 or less, more preferably 400 or less. In addition, the molecular weight of a low molecular weight compound is a theoretical value calculated | required from Structural formula, when it can calculate from Structural formula, When it can not calculate from Structural formula, the polystyrene by the GPC measurement based on the method as described in the Example mentioned later It is a weight average molecular weight by a conversion value.

The following compounds may be mentioned as specific examples of the low molecular weight compound. In the following, Rf ^a represents a linear or branched perfluoroalkyl group having 3 to 8 carbon atoms. Rf ^a is preferably perfluoroalkyl group linear 4 to 6 carbon atoms.

(When the compound S is a polymer)
When the compound S is a polymer, the compound S is preferably a polymer having a structural unit S1-1 having a structure S1 in a side chain and a structural unit S2-1 having a structure S1 in a side chain.

The main chain structure of the structural unit S1-1 and the structural unit S2-1 may, for example, be acrylic, styrenic or cycloolefin, with acrylic being preferred. As an acryl-type main chain structure, the structure represented by following P1 is mentioned, for example. As a styrenic main chain structure, for example, a structure represented by the following P2 can be mentioned. As a cycloolefin main chain structure, for example, a structure represented by the following P3 can be mentioned. Wherein, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, * represents a bonding position of the side chain.

As a specific example in which the structural unit S1-1 is an acrylic main chain structure, for example, a structure represented by the following S1-2 can be mentioned. As a specific example in which the structural unit S1-1 is a styrene-based main chain structure, for example, a structure represented by the following S1-100 can be mentioned. Specific examples of the structural unit S1-1 having a cycloolefin main chain structure include, for example, a structure represented by the following S1-200.
Moreover, as a specific example in which the structural unit S2-1 is an acrylic main chain structure, for example, a structure represented by the following S2-2 can be mentioned. As a specific example in which the structural unit S2-1 is a styrene-based main chain structure, for example, a structure represented by the following S2-100 can be mentioned. Specific examples of the structural unit S2-1 having a cycloolefin main chain structure include, for example, a structure represented by S2-200 below.
In formulas S1-1, S1-100 and S1-200,
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group,
R ¹³ represents a hydrogen atom or an alkyl group,
L ¹⁰ represents a single bond or a divalent linking group, and when L ¹⁰ represents a divalent linking group, R ¹² may combine with L ¹⁰ to form a ring,
Rf represents a fluoroalkyl group having three or more fluorine atoms.
In formula S2-2,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
n1 represents an integer of 0 to 30,
When n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n1 is 2 to 30, the plurality of L ¹⁰¹ may be the same or different.
In formulas S2-100 and S2-200,
L ¹¹⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹¹⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n10 represents an integer of 0 to 30,
When n10 is 0, R ¹¹⁰ represents a hydroxy group,
When n10 is 1, L ¹¹⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, and R ¹¹⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n10 is 2 to 30, L ¹¹⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹¹⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹¹⁰ may be the same. It may be good or different.

In the present invention, the compound S may further have a structural unit (other structural unit) other than the structural unit S1-1 and the structural unit S2-1.
Examples of other structural units include structural units having a crosslinkable group. Examples of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), and an ethylenic group Examples include structural units that include at least one selected from the group consisting of unsaturated groups. The crosslinkable group is preferably at least one selected from an epoxy group, an oxetanyl group, and a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). , An epoxy group and / or an oxetanyl group is more preferable.
30 mass% or less is preferable with respect to all the structural units of a polymer, and, as for content of another structural unit, 20 mass% or less is more preferable. The lower limit can also be, for example, 1% by mass. Moreover, it can also contain substantially no other structural unit. The content of the other constituent unit is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, based on the total constituent units of the polymer, as substantially not containing the other constituent unit It is more preferable not to contain other structural units.

In the present invention, the compound S includes a constitutional unit represented by the following formula S1-2 (hereinafter also referred to as a constitutional unit S1-2) and a constitutional unit represented by the following formula S2-2 (hereinafter referred to as a constitutional unit S2- It is preferable that it is a polymer which has 2).
In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ¹² represents an alkyl group,
R ¹³ represents a hydrogen atom or an alkyl group,
L ¹⁰ represents a single bond or a divalent linking group, and when L ¹⁰ represents a divalent linking group, R ¹² may combine with L ¹⁰ to form a ring,
Rf represents a fluoroalkyl group having three or more fluorine atoms,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
n1 represents an integer of 0 to 30,
When n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n1 is 2 to 30, the plurality of L ¹⁰¹ may be the same or different.

In Formula S1-2, R ¹² , R ¹³ , L ¹⁰ and Rf have the same meanings as R ¹ , R ² , L ¹ and Rf described in the above-mentioned Formula S1.

In Formula S1-2 and Formula S2-2, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group.

In formula S2-2, L ¹⁰¹ represents a C 1-12 alkylene group. 1-12 are preferable, as for carbon number of an alkylene group, 1-6 are more preferable, and 2-4 are still more preferable. The alkylene group is preferably linear or branched, more preferably branched. 1-2 are preferable and, as for the branch number of an alkylene group, 1 is more preferable. The alkylene group may have a substituent, but is preferably unsubstituted.

In formula S2-2, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Number of carbon atoms of the alkyl group R ¹⁰¹ represents preferably 1 to 12, more preferably 1 to 6, 1 to 3 is more preferable. The alkyl group represented by R ¹⁰¹ is preferably linear or branched, and more preferably linear. The alkyl group represented by R ¹⁰¹ may have a substituent, but is preferably unsubstituted. R ¹⁰¹ is preferably a hydrogen atom.

n1 represents an integer of 0 to 30. The lower limit is preferably 1 or more. The upper limit is preferably 20 or less, more preferably 15 or less. When n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when n1 is 2 to 30, a plurality of L ¹⁰¹ may be identical.
In addition, although n1 represents the integer of 0-30, the photosensitive composition of this invention may contain two or more things in which n1 in compound S differs. Therefore, the average value of n1 of the compounds S contained in the photosensitive composition of the present invention may not be an integer.

In the present invention, in the compound S, the total content of the structural unit S1-1 and the structural unit S2-1 is preferably 70% by mass or more of the total constituent units of the compound S, and is 75% by mass or more It is more preferable that it is 80 mass% or more. If it is the said range, coating property is favorable and it is easy to form the cured film excellent in adhesiveness with the upper layer laminated | stacked on a cured film. The mass ratio of the structural unit S1-1 to the structural unit S2-1 is preferably structural unit S1-1: structural unit S2-1 = 5: 95 to 95: 5, and 10:90 to 90. 10 is more preferable, and 15: 85 to 85: 15 is more preferable.
In the present invention, the compound S preferably has the structural unit S1-1 and the structural unit S2-1 at least 60 mol%, and more preferably at least 70 mol%, of the total structural units of the compound S. It is more preferable to contain 80 mol% or more. If it is the said range, coating property is favorable and it is easy to form the cured film excellent in adhesiveness with the upper layer laminated | stacked on a cured film. Moreover, it is preferable that it is structural unit S1-1: structural unit S2-1 = 95: 5-5: 95, and the molar ratio of structural unit S1-1 and structural unit S2-1 is 80: 20-10. : 90 is more preferable, and 70:30 to 10:90 is more preferable.

In the present invention, the compound S may have one or more types of structures in which n1 is represented by 0 and n1 is represented by 1 or more as the structural unit S2-2.
That is, the compound S is represented by the structural unit S1-2, a structural unit represented by the following formula S2-2-1 (also referred to as a structural unit S2-2-1), or the following formula S2-2-2. At least one structural unit selected from a structural unit (also referred to as structural unit S2-2-2) and a structural unit represented by the following formula S2-2-3 (also referred to as structural unit S2-2-3); It may be a polymer having one.
Especially, the polymer which has structural unit S1-2, structural unit S2-2-1, and / or structural unit S2-2-2 is preferable.
5 mass% or more is preferable, and, as for sum total content of structural unit S2-2-1 and structural unit S2-2-2 in all the structural units of a polymer, 10 mass% or more is more preferable, and 20 mass% or more Is more preferable, and 40% by mass or more is particularly preferable. 95 mass% or less is preferable, for example, 90 mass% or less is more preferable, and, as for the upper limit, 85 mass% or less is still more preferable.
Moreover, 1 mass% or more is preferable, as for content of structural unit S2-2-1 in all the structural units of a polymer, 10 mass% or more is more preferable, 20 mass% or more is still more preferable, 40 mass% or more. Is particularly preferred. 95 mass% or less is preferable, for example, 90 mass% or less is more preferable, and, as for the upper limit, 85 mass% or less is still more preferable.
Moreover, 1-20 mass% is preferable with respect to all the structural units of a polymer, and, as for content of structural unit S2-2-2 in all the structural units of a polymer, 1-15 mass% is more preferable, 1-10 mass% is still more preferable, and 1-5 mass% is especially preferable.
Moreover, 30 mass% or less is preferable, as for content of structural unit S2-2-3 in all the structural units of a polymer, 20 mass% or less is more preferable, 10 mass% or less is still more preferable, and 1 mass% or less Is particularly preferred. Moreover, it is also preferable not to contain structural unit S2-2-3 substantially. The content of the structural unit S2-2-3 is preferably 0.5% by mass or less with respect to all the structural units of the polymer that the structural unit S2-2-3 is not substantially contained. % Or less is more preferable, and it is further more preferable not to contain structural unit S2-2-3. According to this aspect, it is easy to obtain excellent coatability.
In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
R ¹⁰³ represents an alkyl group having 1 to 6 carbon atoms,
n1a represents an integer of 1 to 30,
When n1a is 1, R ¹⁰² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n1a is 2 to 30, the plurality of L ¹⁰¹ may be the same or different.

R ¹¹ , L ¹⁰¹ and R ¹⁰² have the same meanings as R ¹¹ , L ¹⁰¹ and R ^{101 of} S2-2.
Number of carbon atoms of the alkyl group R ¹⁰³ represents is 1 to 6 preferably 1 to 3 is more preferable. The alkyl group is preferably linear or branched, more preferably linear. The alkyl group may have a substituent, but is preferably unsubstituted.

In the present invention, the compound S includes a constitutional unit represented by the following formula S1-3 (hereinafter also referred to as a constitutional unit S1-3) and a constitutional unit represented by the following formula S2-3 (hereinafter referred to as a constitutional unit S2- It is preferable that it is a polymer which has (3).
In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ²² represents an alkyl group having 1 to 3 carbon atoms,
R ²³ represents a hydrogen atom,
L ²⁰ represents an alkylene group having 1 to 12 carbon atoms,
R f ¹ represents a C 3-6 perfluoroalkyl group,
R ²² may combine with L ²⁰ to form a ring,
L ²⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ²⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
n2 represents an integer of 1 to 20, and when n2 is 2 to 20, a plurality of L ²⁰¹ may be the same or different.

In Formula S1-3 and Formula S2-3, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group.

In Formula S1-3, R ²² represents an alkyl group having 1 to 3 carbon atoms, and R ²³ represents a hydrogen atom. Number of carbon atoms of the alkyl group R ²² represents is preferably 1 or 2, and more preferably 1.
R ²² may combine with L ²⁰ to form a ring. Examples of the ring formed by combining R ²² and L ²⁰ include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantyl and tetrahydropyranyl.

In Formula S1-3, L ²⁰ represents a C 1-12 alkylene group. 1-12 are preferable, as for carbon number of an alkylene group, 1-10 are more preferable, and 1-6 are more preferable. The alkylene group is preferably linear or cyclic, and more preferably linear. The alkylene group may have one or more bonds selected from ether bonds, ester bonds and amide bonds, and may not have these bonds. The alkylene group preferably does not have the aforementioned bond. The alkylene group may be unsubstituted or may have a substituent. No substitution is preferred.

In formula S1-3, Rf ¹ represents a C 3-6 perfluoroalkyl group. 3-6 are preferable and, as for carbon number of a perfluoroalkyl group, 4-6 are more preferable. The perfluoroalkyl group may be linear, branched or cyclic, preferably linear or cyclic, and more preferably linear.

In Formula S2-3, the number of carbon atoms of the alkylene radical L ²⁰¹ represents the 1 to 12 preferably 1 to 6 is more preferable. The alkylene group represented by L ²⁰¹ is preferably linear or branched, and more preferably branched. Number of branches of the alkylene group L ²⁰¹ represents the 1-2 is preferred, and more preferably 1. The alkylene group represented by L ²⁰¹ may have a substituent, but is preferably unsubstituted.
In Formula S2-3, the carbon number of the alkyl group represented by R ²⁰¹ is more preferably 1 to 6, and still more preferably 1 to 3. The alkyl group represented by R ²⁰¹ is preferably linear or branched, and more preferably linear. The alkyl group represented by R ²⁰¹ may have a substituent, but is preferably unsubstituted. R ²⁰¹ is preferably a hydrogen atom.

  In formula S2-3, n2 represents an integer of 1 to 20. The lower limit is preferably 2 or more, more preferably 3 or more. The upper limit is preferably 15 or less. Although n2 represents an integer of 1 to 20, the photosensitive composition of the present invention may contain a plurality of compounds in which n2 in the compound S is different. Therefore, the average value of n2 of the compounds S contained in the photosensitive composition of the present invention may not be an integer. In the present invention, n2 in one compound S is preferably an integer of 1 to 20.

In the present invention, the compound S may further have the above structure S2-2-2 and / or the above structure S2-2-3 in addition to the structural unit S1-3 and the structural unit S2-3. The other structural unit is preferably the structural unit S2-2-2. According to this aspect, the coatability and the adhesion to the upper layer can be made better.
The content of the structural unit S2-2-2 is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, still more preferably 1 to 10% by mass, based on all the constituent units of the polymer. 5% by weight is particularly preferred.
30 mass% or less is preferable with respect to all the structural units of a polymer, 20 mass% or less is more preferable, 10 mass% or less is still more preferable, and content of structural unit S2-2-3 is 1 mass% or less. Particularly preferred. Moreover, it is also preferable that a polymer does not contain structural unit S2-2-3 substantially. The content of the structural unit S2-2-3 is preferably 0.5% by mass or less with respect to all the structural units of the polymer that the structural unit S2-2-3 is not substantially contained. % Or less is more preferable, and it is further more preferable not to contain structural unit S2-2-3. According to this aspect, it is easy to obtain excellent coatability.

In the present invention, when the compound S is a polymer, the weight average molecular weight of the compound S is preferably 100 to 100,000. The lower limit is preferably 300 or more, and more preferably 1000 or more. The upper limit is preferably 30000 or less, more preferably 10000 or less, and particularly preferably 5000 or less. When the molecular weight of the compound S is in the above range, the coatability is good.
1.0-5.0 are preferable and, as for the dispersion degree (Mw / Mn) of compound S, 1.2-3.0 are more preferable.

Specific examples of the compound S include, for example, the structures shown below and the structures shown in the examples described later. In the following, R represents a hydrogen atom or a methyl group, n100 represents an integer of 1 to 20, and Rf ^b represents a linear or branched perfluoroalkyl group having 3 to 8 carbon atoms. n100 is preferably an integer of 2 to 20. Rf ^b is preferably a C4 to C6 linear perfluoroalkyl group.

<< Alkali-soluble resin >>
The photosensitive composition of the present invention preferably contains an alkali-soluble resin. By containing the alkali-soluble resin, developability and patternability are improved.
In the present invention, the alkali-soluble resin is a component different from the compound S described above. That is, a polymer having the structure S1 and the structure S2 described above corresponds to the compound S.
In the present invention, the alkali-soluble resin is a component different from the above-described polymerizable compound (compound having two or more groups having an ethylenically unsaturated bond). That is, a polymer having two or more groups having an ethylenically unsaturated bond and an alkali-soluble group such as an acid group is considered to be a polymerizable compound.

  When the photosensitive composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 0.5 to 80% by mass in the total solid content of the photosensitive composition. The lower limit is more preferably 1% by mass or more. 70 mass% or less is more preferable, and, as for the upper limit, 60 mass% or less is particularly preferable.

  The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 1,000 to 1,000,000, and more preferably 1,000 to 200,000. . The alkali-soluble resin may be a linear organic polymer, and can be appropriately selected from alkali-soluble resins having at least one group that promotes alkali solubility in the molecule.

Examples of groups promoting alkali solubility (hereinafter, also referred to as acid groups) include, for example, a carboxyl group, a phosphate group, a sulfonic acid group, a phenolic hydroxyl group, and a silanol group. Those which can be developed with an aqueous solution are preferred, and a carboxyl group is particularly preferred. These acid groups may be of only one type, or of two or more types.
As for the acid value of alkali-soluble resin, 30-500 mgKOH / g is preferable. The lower limit is more preferably 50 mg KOH / g or more, and still more preferably 70 mg KOH / g or more. The upper limit is more preferably 400 mg KOH / g or less, still more preferably 200 mg KOH / g or less, particularly preferably 150 mg KOH / g or less, and even more preferably 120 mg KOH / g or less.

  The type of alkali-soluble resin is preferably one or more selected from acrylic resin, styrene resin, polybenzoxazole resin, polyimide resin, cycloolefin resin and siloxane resin, and acrylic resin, styrene resin, polybenzoxazole resin It is more preferable that it is 1 or more types chosen from polyimide resin and cycloolefin resin. In the present invention, the acrylic resin refers to a resin containing, in a mass ratio, the largest number of structural units whose main chain structure is (meth) acrylic, among all the structural units constituting the resin. Also, for example, the structural units having a main chain structure of (meth) acrylic and the structural units having a main chain structure of styrene in the same amount, and among these all the structural units constituting the resin, When it is a resin containing a large amount, it is also referred to as a (meth) acrylic resin and also as a styrene resin. The same applies to other resins.

(Acrylic resin, styrene resin)
In the present invention, the acrylic resin as the alkali-soluble resin preferably has a structural unit represented by the following (X-1). Moreover, it is preferable that the styrene resin as alkali-soluble resin has a structural unit represented by following (X-2). It is preferable to contain 5 mass% or more of following (X-1) in all the structural units, and, as for an acrylic resin, it is more preferable to contain 10 mass% or more. It is preferable to contain 5 mass% or more of following (X-2) in all the structural units, and, as for a styrene resin, it is more preferable to contain 10 mass% sulfur. The upper limit may be 100% by mass, may be 80% by mass or less, and may be 50% by mass or less.

In formulas (X-1) and (X-2), R ^x1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^x1 is preferably a hydrogen atom or a methyl group. L ^X1 represents a single bond or a divalent linking group. The divalent linking group is selected from an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 12 carbon atoms, and -CO-, -OCO-, -O-, -NH- and -SO _2- And groups each of which is combined with one of the above.

  The acrylic resin and the styrene resin may further contain a structural unit derived from an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound or the like. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, police Ren macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, N- phenylmaleimide, mention may be made of N- cyclohexyl maleimide and the like. These other monomers copolymerizable with (meth) acrylic acid may be only one type, or two or more types.

  The weight average molecular weight of the acrylic resin and the styrene resin is preferably 5,000 to 100,000.

(Polyimide resin, polybenzoxazole resin)
In the present invention, the polyimide resin and the polybenzoxazole resin as the alkali-soluble resin preferably have a structural unit represented by the following (X-3). In the formula (X-3), a resin having a structural unit in which m is 0 and n is 2 is a polyimide resin. In the formula (X-3), a resin having a constitutional unit in which n is 0 and m is 2 is a polybenzoxazole resin.
The polyimide resin and the polybenzoxazole resin preferably contain 10 mol% or more, and more preferably 20 mol% or more, of the structural units represented by (X-3) in all the structural units. The upper limit may be 100 mol%, may be 95 mol% or less, and may be 90 mol% or less.

In formula (X-3), X ¹ and Y ¹ each independently represent a divalent or tetravalent organic group having 2 to 60 carbon atoms, m represents 0 or 2, n is 0 Or 2 and m + n represents 2;

The divalent and tetravalent organic groups represented by X ¹ and Y ¹ include groups having 2 to 60 carbon atoms. The divalent and tetravalent organic groups represented by X ¹ include residues remaining after removal of the amino group of diamine. Examples of the divalent organic group represented by Y ¹ include residues remaining after removal of the carboxyl group of dicarboxylic acid. Examples of the tetravalent organic group represented by Y ¹ include residues remaining after removal of the anhydride group from tetracarboxylic acid dianhydride.

Examples of the divalent and tetravalent organic groups include a chain aliphatic group, a cyclic aliphatic group, an aromatic ring group, a heterocyclic group, and a group formed by combining two or more of these groups via a single bond or a linking group. Can be mentioned. The linking group, e.g., -O -, - S -, - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - NHCO- and include groups composed of combinations thereof. In the present invention, a linear aliphatic group means a linear or branched hydrocarbon group. In addition, the cyclic aliphatic group means a cyclic hydrocarbon group.

2-60 are preferable, as for carbon number of a chain | strand-shaped aliphatic group, 2-40 are more preferable, 2-30 are still more preferable, and 2-20 are especially preferable. The linear aliphatic group may have a substituent or may be unsubstituted. The substituent includes a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group and the like.
3-60 are preferable, as for carbon number of a cyclic aliphatic group, 3-40 are more preferable, 3-30 are still more preferable, and 3-20 are especially preferable. The cyclic aliphatic group may have a substituent or may be unsubstituted. The substituent includes a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group and the like.
6-60 are preferable, 6-40 are more preferable, 6-30 are still more preferable, and, as for carbon number of an aromatic ring group, 6-20 are especially preferable. In the present invention, the aromatic ring group means an aromatic hydrocarbon group. The aromatic ring group may have a substituent or may be unsubstituted. As a substituent, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group and the like can be mentioned.
The heterocyclic group includes groups having a 5-, 6- or 7-membered heterocyclic ring. The heterocyclic group is preferably a group having a 5- or 6-membered heterocyclic ring. As a hetero atom which comprises a heterocyclic ring, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The heterocyclic group may have a substituent or may be unsubstituted. As a substituent, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group and the like can be mentioned.

In the present invention, at least ^one of X ¹ and Y ¹ preferably has at least one or more (more preferably 1 to 10, more preferably 1 to 5) cyclic structures. According to this aspect, it is easy to obtain a cured film having excellent heat resistance.

  The cyclic structure may be any of an aromatic ring, a heterocycle, and an aliphatic ring, preferably an aromatic ring or a heterocycle, more preferably an aromatic ring. The aromatic ring, the heterocyclic ring and the aliphatic ring may be a single ring or may be a fused ring. In addition, the aliphatic ring may have a crosslinked structure.

As a specific example of an aromatic ring, a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring etc. are mentioned, for example.
Specific examples of the heterocyclic ring include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazan ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring Etc.
Examples of the aliphatic ring include, for example, the structures shown below.

It is preferable that the polyimide resin and the polybenzoxazole resin have a structure in which the end is sealed with a monofunctional acid chloride. According to this aspect, it is easy to obtain a cured film with good transmittance. Examples of monofunctional acid chlorides include acetyl chloride, butyryl chloride, propionic acid chloride, 2-ethylhexanoic acid chloride, cyclohexanecarboxylic acid chloride, benzoyl chloride, naphthoyl chloride, acrylic acid chloride, heptanoic acid chloride, isobutyryl Chloride, isononanoyl chloride, neodecanoyl chloride, octanoyl chloride, pivaloyl chloride, valeroyl chloride, methoxyacetyl chloride, acetoxyacetyl chloride, phenylacetyl chloride, cinnamoyl chloride, methacrylic acid chloride, 2-furoyl chloride , 3-chloropropionyl chloride, 4-chlorobutyryl chloride, 5-chlorovaleryl chloride, diethylcarbamoyl chloride, methyl chloroformate, ethyl chloroforme N, propyl chloroformate, n-butyl chloroformate, sec-butyl chloroformate, pentyl chloroformate, n-hexyl chloroformate, n-octyl chloroformate, 2-ethylhexyl chloroformate, cyclohexyl chloroformate Mate, 4-tert-butylcyclohexyl chloroformate, cetyl chloroformate, benzyl chloroformate, 2-chloroethyl chloroformate, allyl chloroformate and the like.
From the viewpoint of solvent solubility, acid chlorides having 3 or more carbon atoms are preferred. From the viewpoint of solvent resistance, acid chlorides having 12 or less carbon atoms are preferred.

In the present invention, the polyimide resin and the polybenzoxazole resin preferably have a group represented by the general formula (b1) at one end or both ends, and a group represented by the general formula (b1) It is more preferable that
General formula (b1)
In the general formula (b1), Z represents a single bond, a carbon atom or a sulfur atom, R ³⁰ represents a monovalent organic group, n represents 0 or 1, and when Z is a single bond, a is 0 And when Z is a carbon atom, a is 1; when Z is a sulfur atom, a is 2; and when n is 0, two R ³⁰ may be bonded to each other to form a ring Good.

Z represents a single bond, a carbon atom or a sulfur atom, and a single bond or a carbon atom is preferable.
R ³⁰ represents a monovalent organic group. Although there is no restriction | limiting in particular as monovalent organic group, The group of formula weight per molecule is 15-500 is illustrated. The atom constituting the monovalent organic group is preferably selected from carbon atom, oxygen atom, nitrogen atom, hydrogen atom and sulfur atom, and is selected from carbon atom, oxygen atom, nitrogen atom and hydrogen atom Is more preferred.
Specifically, an alkyl group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenyl group (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), an alkynyl group (preferably Preferably, it has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, an aryl group (preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), and an alkoxy group (preferably 1 to 10 carbon atoms) More preferably, it has 1 to 6 carbon atoms, a carboxyl group, a crosslinkable group, and an oxygen atom, a carbonyl group, a sulfonyl group, an arylene group (preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), alkylene Groups (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), alkenylene groups (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), and alkynylenes From the combination of (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) and an alkenyl group, an alkynyl group, an aryl group, a carbonyl group, a carboxyl group, an oxygen atom, an alkylene group, an alkynylene group or an arylene group It is more preferred that
These groups may have a substituent, and examples of the substituent include a hydroxy group, an alkyl group, a halogen atom, a cyano group, an amido group, a sulfonylamide group and the like.

  Specific examples of the group represented by formula (b1) include the structures described in paragraph 0050 of WO 2015/087831. This content is incorporated herein by reference.

The polyimide resin and the polybenzoxazole resin may further contain a structural unit other than the formula (X-3) (hereinafter, also referred to as another structural unit).
As another structural unit, the structural unit represented by following formula a1-a3 is illustrated, for example. 60 mol% or less of all the structural units which a polyimide resin or polybenzoxazole resin has is preferable, 50 mol% or less is more preferable, 40 mol% or less is still more preferable, and 30 mol% or less is especially preferable.

In formula a1, X ¹⁰ and Y ¹⁰ each independently represent a divalent or tetravalent organic group having 2 to 60 carbon atoms. R ^A10 and R ^A11 each independently represent an alkyl group. m represents 0 or 2, n represents 0 or 2, and m + n represents 2. When m is 2, two R ^A11 may be the same or different. When n is 2, two R ^A10 may be the same or different.

Examples of the divalent or tetravalent organic group represented by X ¹⁰ and Y ^{10 in the} formula a1 include, for example, a chain aliphatic group, a cyclic aliphatic group, an aromatic ring group, a heterocyclic group and a single bond or a linkage thereof Groups formed by combining two or more groups are included. The linking group, e.g., -O -, - S -, - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - NHCO- and include groups composed of combinations thereof. As these details, groups described for X ¹ and Y ¹ in formula (X-3) can be mentioned.
The alkyl group represented by R ^A10 and R ^A11 of the formula a1 may be linear, branched or cyclic. In the case of a linear alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. In the case of a branched alkyl group, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 15, and still more preferably 3 to 10. In the case of a cyclic alkyl group, 3 to 15 are preferable, 5 to 15 are more preferable, and 5 to 10 are more preferable.

In formula a2, X ¹¹ and Y ¹¹ each independently represent a divalent organic group having 2 to 60 carbon atoms. Examples of the divalent organic group represented by X ¹¹ and Y ¹¹ of the formula a2 include, for example, a chain aliphatic group, a cyclic aliphatic group, an aromatic ring group, a heterocyclic group, and these via a single bond or a linking group Groups formed by combining two or more can be mentioned. The linking group, e.g., -O -, - S -, - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - NHCO- and include groups composed of combinations thereof. As these details, groups described for X ¹ and Y ¹ in formula (X-3) can be mentioned.

In formula a3, Y ¹² represents a divalent organic group having 2 to 60 carbon atoms, and X ¹² represents a group containing a silicon atom. Examples of the divalent organic group represented by Y ^{12 in} formula a3 include a chain aliphatic group, a cyclic aliphatic group, an aromatic ring group, a heterocyclic group, and a combination of two or more of these via a single bond or a linking group Groups can be mentioned. The linking group, e.g., -O -, - S -, - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - NHCO- and include groups composed of combinations thereof. With respect to these details, the groups described in X ¹ and Y ¹ of Formula A can be mentioned.
Represents X ¹² of formula a3, group containing a silicon atom is preferably a group represented by the following.
R ²⁰ and R ²¹ each independently represent a divalent organic group, and R ²² and R ²³ each independently represent a monovalent organic group.

The divalent organic group represented by R ²⁰ and R ²¹ is not particularly limited, and examples thereof include a chain aliphatic group, a cyclic aliphatic group, an aromatic ring group, a heterocyclic group, and a single bond or a linkage thereof Groups formed by combining two or more groups are included. The linking group, e.g., -O -, - S -, - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - NHCO- and include groups composed of combinations thereof. About these details, the bivalent organic group demonstrated by X < ¹ >, Y < ¹ > of Formula (X-3) is mentioned.

  The weight average molecular weight of the polyimide resin and the polybenzoxazole resin is preferably 3,000 to 200,000. The lower limit is more preferably 4,000 or more, and still more preferably 5,000 or more. The upper limit is more preferably 100,000 or less, still more preferably 50,000 or less. Moreover, as for a number average molecular weight (Mn), 1,000-50,000 are preferable. The lower limit is more preferably 2,000 or more, and still more preferably 3,000 or more. The upper limit is more preferably 40,000 or less, still more preferably 30,000 or less. In addition, the degree of dispersion (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.5 to 3.5, and still more preferably 1.5 to 3.0. Within this range, the lithography performance and the physical properties of the cured film can be made excellent.

(Siloxane resin)
The siloxane resin preferably has at least one structural unit selected from the following (X-4) to (X-6), and the structural unit represented by the following (X-4) or (X-5) It is more preferable to have.
Moreover, it is preferable that a siloxane resin contains 10 mass% or more in at least 1 sort (s) of structural units chosen from the following (X-4)-(X-6), and 20 mass% or more in all the structural units. It is more preferable to do. The upper limit may be 100% by mass, may be 80% by mass or less, and may be 70% by mass or less.

In formulas (X-4) to (X-6), R ^x2 represents an alkyl group, an aryl group or an aralkyl group, and a represents 0 or 1.
1-10 are preferable, as for carbon number of the alkyl group which ^Rx2 represents, 1-8 are more preferable, and 1-6 are more preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic.
6-20 are preferable, as for carbon number of the aryl group which ^Rx2 represents, 6-14 are more preferable, and 6-10 are more preferable. The aryl group may have a substituent.
The aralkyl group represented by R ^x2 is preferably a group in which part of hydrogen atoms of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms. The aralkyl group may have a substituent. The alkyl group constituting the aralkyl group may be linear, branched or cyclic.
Examples of the substituent which the alkyl group, the aryl group and the aralkyl group may have include an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, a halogen atom And chlorine atom, bromine atom, iodine atom) and the like.
From the viewpoint of solvent resistance and heat resistance, R ^X2 is preferably a methyl group, a phenyl group, a propyl group, a butyl group or a hexyl group, and more preferably a methyl group or a phenyl group.

In formula (X-5), R ^x3 represents an alkyl group or a halogen atom, and q represents an integer of 0 to 4.
As an alkyl group which ^Rx3 represents, a C1-C4 alkyl group is preferable. As a halogen atom which ^Rx3 represents, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

In formulas (X-4) and (X-5), L ^X1 represents a single bond or a divalent linking group. The divalent linking group is selected from an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 12 carbon atoms, and -CO-, -OCO-, -O-, -NH- and -SO _2- And groups each of which is combined with one of the above.

  A siloxane resin can contain other structural units other than Formula (X-4)-(X-6). As another structural unit, a structural unit represented by the following formula a2-1, a structural unit represented by the following formula a2-2, a structure represented by the following formula a4-1, etc. may be mentioned.

In formulas a2-1 and a2-2, a represents 0 or 1, R ^5A represents an alkyl group, an aryl group or an aralkyl group, R ^y represents an alkyl group or a halogen atom, and L ^3A is a single atom Represents a bond or a divalent linking group, n represents 0 or 1, m2 represents an integer of 0 to 2 when n is 0, and an integer of 0 to 3 when n is 1 M3 represents an integer of 0 to 6;
In formula a4-1, a1 represents an integer of 0 to 3, and b1 represents an integer of 0 to 3. However, 0 ≦ a1 + b1 ≦ 3. R ^7A and R ^8A each independently represent an alkyl group, an aryl group or an aralkyl group.

The alkyl group, aryl group and aralkyl group represented by R ^5A , R ^7A and R ^8A are the same as the ranges described for R ^X2 in the above-mentioned formulas (X-4) to (X-6), and preferred ranges are also the same. It is. As a bivalent coupling group which ^L3A represents, it is the same as the range ^demonstrated by L ^<X1> of Formula (X-4) and (X-5), and its preferable range is also the same. As an alkyl group and a halogen atom which R ^y represents, it is the same as the range ^demonstrated by ^Rx3 of (X-5) mentioned above, and its preferable range is also the same.
In formula a2-1, n represents 0 or 1, preferably 0. m2 represents an integer of 0 to 2 when n is 0, and represents an integer of 0 to 3 when n is 1. m2 is preferably 0.
In formula a2-2, m3 represents an integer of 0 to 6, and 0 is preferable.

  The siloxane resin has the number of moles of the structural unit represented by the formulas (X-4) to (X-6) (the number of moles of the total when including a plurality of structural units), the formula a2-1 and / or the formula a The ratio of the number of moles of the constitutional unit represented by -2 (the number of moles of the total when including a plurality of constitutional units) is preferably 10:90 to 90:10, and preferably 30:70 to 70:30. It is more preferable that it is 40:60 to 60:40. If the ratio of the number of moles of each structural unit is in the above range, a cured film having excellent solvent resistance is easily formed.

  1,000-200,000 are preferable and, as for the weight average molecular weight of siloxane resin, 2,000-50,000 are more preferable.

(Cycloolefin resin)
In the present invention, the cycloolefin resin is a resin having a structural unit derived from an olefin monomer containing an alicyclic structure (hereinafter referred to as "cycloolefin monomer"). It is preferable that the cycloolefin resin as alkali-soluble resin used by this invention contains the structural unit derived from the cycloolefin monomer which has an acidic radical. As an acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group are mentioned, and a carboxyl group is preferable.

  The alicyclic structure possessed by the cycloolefin monomer may be a single ring or a multiple ring (a condensed multiple ring, a bridged ring, a combination of these, etc.). From the viewpoint of mechanical strength, heat resistance, etc., the alicyclic structure is preferably a polycyclic ring. Although the number of carbon atoms constituting the alicyclic structure is not particularly limited, 4 to 30 are preferable, 5 to 20 are more preferable, and 5 to 15 are more preferable. Within this range, the balance of various properties such as heat resistance and pattern shape is good.

  In the cycloolefin resin, the proportion of structural units derived from cycloolefin monomers having an acid group is preferably 10 to 100 mol% with respect to all the constituent units. The upper limit may be 95 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. 15 mol% or more is preferable and 20 mol% or more of an upper limit is still more preferable.

  The cycloolefin resin may be a copolymer obtained by copolymerizing a cycloolefin monomer having an acid group and a monomer copolymerizable therewith. As such a copolymerizable monomer, a cycloolefin monomer having a polar group other than an acid group, a cycloolefin monomer having no polar group, a monomer other than a cycloolefin may be mentioned.

  The cycloolefin resin is, for example, (i) ring-opened polymer of cycloolefin monomer, (ii) hydrogenated product of ring-opened polymer of cycloolefin monomer, (iii) addition polymer of cycloolefin monomer, (iv) cyclocycloolefin resin Addition polymers of olefin monomers and vinyl compounds, (v) single ring cycloalkene polymers, (vi) alicyclic conjugated diene polymers, (vii) vinyl based alicyclic hydrocarbon polymers, (v iii) vinyl based systems The hydrogenated substance of an alicyclic hydrocarbon polymer, the aromatic ring hydrogenated substance of (ix) aromatic olefin polymer, etc. are mentioned. Among these, ring-opened polymers of cycloolefin monomers and their hydrogenated products, addition polymers of cyclo-olefin monomers, and addition polymers of cycloolefin monomers and vinyl compounds are preferred, and hydrogen of ring-opened polymers of cycloolefin monomers Additives are further preferred. In addition, these polymers include not only homopolymers but also copolymers. The cycloolefin resins can be used alone or in combination of two or more.

The method for obtaining the cycloolefin resin is not particularly limited. For example, bicyclo [2.2.1] hept-2-ene, according to a conventional method described in JP-A-11-52574, JP-A-2002-363263, International Publication WO 01/79325, etc. Tricyclo [4.3.0.12,5] deca-3,7-diene, tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-ethylidenetetracyclo [4. 4.0.12, 5.17, 10] dodec-3-ene, cyclopentadiene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12, 5.17, 10] dodeca-3- En, 5-hydroxyethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycar Nirubishikuro [2.2.1] hept-2-ene, 9-hydroxycarbonyl tetracyclo [6.2.1.1 ^{3, 6.} Addition polymerization or opening of cycloolefin monomers such as 0 ^2,7 ] dodec-4-ene and N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide It can be obtained by ring polymerization, hydrogenation of the unsaturated bond part if necessary, and addition, if necessary, to a modification reaction or the like in which a compound having an acid group such as maleic anhydride is added (grafted). It can also be obtained by copolymerizing a cycloolefin monomer and a monomer copolymerizable therewith (for example, ethylene etc.). About the detail of these, the description of Unexamined-Japanese-Patent No.2012-211988, Paragraph 0038-0078 can be considered into consideration, This content shall be integrated in this-application specification.
Examples of the cycloolefin monomer used for the synthesis of the cycloolefin resin include, for example, the monomers described in paragraphs 0008 to 0015 of JP-A-11-52574, and the monomers described in paragraphs 0019 to 0035 of JP-A-2012-211988. be able to. This content is incorporated herein by reference.

  In addition, a ring-opening polymer of cycloolefin monomer is produced by ring-opening metathesis polymerization of a cycloolefin monomer having an acid group and a copolymerizable monomer optionally used, in the presence of a metathesis reaction catalyst. Can. The metathesis reaction catalyst is a Group 3-11 transition metal compound of the periodic table, and a compound described in Olefin Metathesis and Metathesis Polymerization (KJ Ivin and JC MoI, Academic Press, San Diego 1997). It can be used. For example, (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride and the like can be mentioned. About the detail of a metathesis reaction catalyst, the description of Unexamined-Japanese-Patent No.2012-211988, Paragraph 0043-0063 can be considered into consideration, This content shall be integrated in this-application specification.

  In addition to this, the cycloolefin resin is obtained by hydrogenating the aromatic ring of a polymer obtained by addition polymerization of an aromatic olefin such as styrene, α-methylstyrene, divinylbenzene, vinyl naphthalene, vinyl toluene, etc. You may form the same structural unit as the structural unit derived from a mer.

In the cycloolefin resin, — (CH ₂ ) _k COOR (wherein k is an integer of 0 or 1 to 4 and R is a hydrocarbon group having 1 to 12 carbon atoms or a fluorine-substituted hydrocarbon group) Hydrolyzate of a ring-opened polymer of a norbornene-based monomer containing a polar group such as.) Or hydrolyzate of a hydrogenated product of the ring-opened polymer is also preferable. They have good alkali solubility, are easy to develop with an alkali developer, and have good sensitivity. Hydrolysis hydrolyzes the polar group such as the above-mentioned ester group, thereby improving the alkali solubility of the ring-opened polymer and the hydrogenated substance thereof, and the sensitivity of the photosensitive composition can be improved. In order to hydrolyze the hydrolyzate of the ring-opened polymer of the norbornene-based monomer or the hydrogenated product of the ring-opened polymer, a method of performing hydrolysis using an alkali or acid in a solvent according to a conventional method is adopted can do. The hydrolysis rate can be controlled by adjusting the reaction temperature, reaction time, amount of acid or alkali, and the like.

<< Alkoxysilane Compound >>
The photosensitive composition of the present invention may further contain an alkoxysilane compound. The alkoxysilane compound is preferably a compound having an alkoxysilane structure and at least one member selected from the group consisting of an epoxy group, a group having ethylenic unsaturation, an alkyl group substituted with a chloro group and a mercapto group. By blending such a compound, the sensitivity can be further improved, and the adhesion to the substrate at the time of curing of the photosensitive composition can be further improved.
The alkoxysilane compound may contain only one kind, or two or more kinds.
The molecular weight of the alkoxysilane compound is not particularly limited, but is preferably less than 1000, and more preferably 500 or less. The lower limit value of the molecular weight of the alkoxysilane compound is not particularly limited, but is preferably 100 or more, and more preferably 200 or more.

Specific examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxy Propyltrialkoxysilane, γ-methacryloxypropyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane It can be mentioned.
Examples of commercially available products include KBM-403, KBE-503, KBM-5103, KBM-303, and KBM-803 manufactured by Shin-Etsu Silicone Co., Ltd.

  When the photosensitive composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.05 to 10% by mass in the total solid content of the photosensitive composition. The lower limit is more preferably 0.1% by mass or more and particularly preferably 0.5% by mass or more. The upper limit is more preferably 8% by mass or less and particularly preferably 6% by mass or less.

<< Compound Having Crosslinkable Group >>
The photosensitive composition of the present invention may contain a compound having a crosslinkable group (hereinafter, also referred to as "crosslinking agent"). By containing a crosslinking agent, a harder cured film can be obtained. In the present invention, the molecular weight of the crosslinking agent is preferably 200 to 1,000.

The crosslinking agent is not particularly limited as long as the crosslinking reaction occurs by heat. For example, compounds having two or more epoxy groups or oxetanyl groups in the molecule, blocked isocyanate compounds, alkoxymethyl group-containing compounds and the like can be mentioned. In the present invention, the crosslinking agent is a compound other than the above-described polymerizable compound.
The crosslinking agent is preferably a compound having two or more epoxy groups and / or oxetanyl groups in the molecule. When a compound having two or more epoxy groups and / or oxetanyl groups is blended in the molecule, a cured film having particularly excellent heat resistance is easily obtained. The details of the crosslinking agent are described in paragraphs 0138 to 0147 of JP-A 2014-238438, paragraphs 0082 to 0104 of WO 2015/087831, and paragraphs 0120 to 0144 of WO 2015/087829. The description can be referred to, the contents of which are incorporated herein.

  Examples of compounds having two or more epoxy groups or oxetanyl groups in the molecule include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, aliphatic epoxy resin, etc. Can. These are commercially available. For example, as compounds having two or more epoxy groups in the molecule, JER 152, JER 157 S70, JER 157 S 65, JER 806, JER 828, JER 1007 (manufactured by Mitsubishi Chemical Corporation), etc. can be used in paragraph 0189 of JP 2011-221494A. The commercial item of description etc. are mentioned.

The blocked isocyanate compound is not particularly limited, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the block isocyanate group in this invention is group which can produce | generate an isocyanate group by heat, for example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can be illustrated preferably. Moreover, it is preferable that the said block isocyanate group is group which can produce | generate an isocyanate group by the heat | fever of 90 degreeC-250 degreeC.

  The skeleton of the blocked isocyanate compound is not particularly limited, and may be any one having two isocyanate groups in one molecule, and an aliphatic, alicyclic or aromatic polyisocyanate. It may be. For a specific example of the skeleton, the description in paragraph 0144 of JP-A-2014-238438 can be referred to, and the contents thereof are incorporated herein.

Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, an imide compound and the like. be able to. Among these, blocking agents selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds and pyrazole compounds are particularly preferable. As a specific example of the blocking agent, the description in JP-A-2014-238438, paragraph 0146 can be referred to, and the contents thereof are incorporated herein.

  As the alkoxymethyl group-containing compound, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These are each obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril or methylolated urea into an alkoxymethyl group. The type of alkoxymethyl group is not particularly limited, and examples thereof include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group and the like, but from the viewpoint of the amount of outgassing, methoxy Methyl is particularly preferred. Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine and alkoxymethylated glycoluril are mentioned as preferable compounds, and from the viewpoint of transparency, alkoxymethylated glycoluril is particularly preferable.

  When the photosensitive composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound, and 0.1 to 30 It is more preferable that it is a mass part, and it is further more preferable that it is 0.5-25 mass parts. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. The crosslinking agent may contain only one type, or two or more types. When two or more types are contained, the total amount is preferably in the above range.

<< polymerization inhibitor >>
In the photosensitive composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the photosensitive composition.
As a polymerization inhibitor, hydroquinone, phenothiazine, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine cerous salt and the like.
When the photosensitive composition of this invention contains a polymerization inhibitor, as for content of a polymerization inhibitor, 0.01-5 mass% is preferable with respect to the total solid of a photosensitive composition. The photosensitive composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<< Antioxidant >>
The photosensitive composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, it is possible to prevent coloring of the cured film, or to reduce a decrease in film thickness due to decomposition, and also have an advantage of being excellent in heat-resistant transparency.
Examples of the antioxidant include phosphorus-based antioxidants, amides, hydrazides, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, saccharides, nitrites, and sulfites. Salts, thiosulfates, hydroxylamine derivatives and the like can be mentioned. Among them, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur antioxidants from the viewpoint of coloring of the cured film and reduction in film thickness. Agents are preferred, and phenolic antioxidants are most preferred. These may be used singly or in combination of two or more.
Specific examples thereof include compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, and compounds described in paragraphs 0106 to 0116 of JP-A-2011-227106, and the contents thereof are Incorporated herein.
Preferred commercially available products include Adekastab AO-20, Adekastab AO-60, Adekastab AO-80, Adekastab LA-52, Adekastab LA-81, Adekastab AO-412S, Adekastab PEP-36 (all manufactured by ADEKA), Irga Knox 1035, Irganox 1098, Tinuvin 144 (all from BASF) can be mentioned.
The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive composition. It is particularly preferable that it is 4% by mass. By setting this range, it is easy to form a film having excellent transparency. Furthermore, the sensitivity at the time of pattern formation also becomes good.

<< Pigment >>
The photosensitive composition of the present invention may contain a pigment. As the pigment, various known inorganic pigments or organic pigments can be used. For example, the pigment as described in stage 0062-0064 of Unexamined-Japanese-Patent No. 2011-257722 can be mentioned. When the photosensitive composition of the present invention contains a pigment, the content thereof is preferably 5 to 80% by mass and 10 to 60% by mass with respect to the total solid content of the photosensitive composition. Is more preferred.

<< Dyes >>
The photosensitive composition of the present invention may contain a dye. As the dye, various conventionally known dyes can be used. For example, a dye described in paragraph 0074 of JP-A-2011-257722 can be mentioned. When the photosensitive composition of the present invention contains a dye, the content thereof is preferably 5 to 60% by mass and 10 to 40% by mass with respect to the total solid content of the photosensitive composition. Is more preferred.

<Other ingredients>
The photosensitive composition of the present invention comprises, if necessary, a sensitizer (9,10-dibutoxyanthracene), a thermal radical generator, a thermal acid generator, an acid multiplier, a development accelerator, an ultraviolet light absorber, and a thickener Well-known additives, such as an agent, an organic or inorganic precipitation inhibitor, can be added independently 1 type or 2 types or more, respectively. Moreover, trimellitic acid can also be used as an additive. Moreover, surfactant other than the said compound S can further be included. As these compounds, for example, compounds described in paragraphs [0145] to [0172] of JP-A-2013-120233 can be used, and the contents thereof are incorporated in the present specification.
Moreover, the thermal radical generating agent as described in Paragraph No. 0120-0121 of Unexamined-Japanese-Patent No. 2012-8223, the nitrogen-containing compound as described in WO2011 / 136074 A1, and a thermal acid generator can also be used, and these contents are this specification. Incorporated into

<Method of Preparing Photosensitive Composition>
The photosensitive composition of the present invention can be prepared by mixing and stirring the respective components in a predetermined ratio and in any method. The prepared photosensitive composition can also be used after filtration using, for example, a filter with a pore diameter of 0.2 μm. The pore size of the filter can be appropriately adjusted according to the target purity etc., and in addition to 0.2 μm, examples of 0.05 μm, 0.1 μm, 0.3 μm, 0.5 μm and the like can be mentioned.

The photosensitive composition of the present invention can adjust the solid concentration, viscosity and surface tension according to the purpose.
In the case of slit coating, the solid content concentration of the photosensitive composition is preferably 2 to 40% by mass, more preferably 3 to 30% by mass, and still more preferably 4 to 20% by mass. The viscosity in the case of slit coating is preferably 1 to 40 mPa · s, more preferably 2 to 25 mPa · s, and most preferably 3 to 20 mPa · s.
The surface tension of the photosensitive composition is preferably 10 to 100 mN / m, preferably 15 to 80 mN / m, and most preferably 20 to 50 mN / m from the viewpoint of coatability. In the present invention, the viscosity is a value at 25 ° C.

<Method for producing cured film>
It is preferable that the manufacturing method of the cured film of this invention includes the process of the following (1)-(5).
(1) A step of applying the photosensitive composition of the present invention on a substrate.
(2) removing the solvent from the applied photosensitive composition.
(3) A step of exposing the photosensitive composition from which the solvent has been removed in a pattern.
(4) A step of developing a non-exposed portion of the photosensitive composition exposed in a pattern to form a pattern.
(5) A step of heating (post-baking) the photosensitive composition after development.
Each step will be described in order below.

  In the step (1), it is preferable to apply the photosensitive composition of the present invention on a substrate to form a wet film (photosensitive composition layer) containing a solvent.

In the step (1), the substrate may be washed with alkali, plasma or the like before the photosensitive composition is applied to the substrate. In addition, the substrate surface may be treated with hexamethyldisilazane or the like on the substrate after cleaning. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate in hexamethyldisilazane vapor.
Examples of the substrate include an inorganic substrate, a resin substrate, a resin composite material substrate and the like.
Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and a composite substrate in which molybdenum, titanium, aluminum, copper or the like is vapor-deposited on a substrate such as them.
As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamide imide, polyether imide, Fluorinated resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, cross-linked fumaric acid diester, cyclic polyolefin, It consists of synthetic resin such as aromatic ether, maleimido olefin, cellulose, episulfide compound etc. Plate, and the like. When a resin substrate is used, a so-called roll-to-roll process can be used.
These substrates are rarely used as they are in the above-mentioned form, and a multilayer laminate structure such as a thin film transistor (TFT) element may be formed depending on the form of the final product.

The size of the substrate is not particularly limited. Productivity, the area of the substrate from the viewpoint of coating property is preferably 10000 mm ² or more 10000000Mm ² or less. For example, a size of 300 mm × 400 mm square and a size of 1000 mm × 1100 mm can be exemplified.

The method for applying the photosensitive composition to the substrate is not particularly limited. For example, methods such as slit coating, spraying, roll coating, spin coating, cast coating, and slit and spin may be used. .
In the case of the slit coating method, it is preferable to set the relative moving speed between the substrate and the slit die to 50 to 120 mm / sec. Slit coating is preferred in that it can be applied efficiently to a large substrate and is excellent in productivity. And large substrate refers to a substrate area of 300000Mm ² more 10000000Mm ² or less.
The wet film thickness when the photosensitive composition is applied is not particularly limited, and can be applied with a film thickness according to the application. For example, 0.5 to 10 μm is preferable.
Before applying the photosensitive composition of the present invention to a substrate, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.

  In the step (2), it is preferable to form a dry film on the substrate by removing the solvent from the above-mentioned wet film formed by applying the photosensitive composition by reducing pressure (vacuum) and / or heating. . The heating conditions of the solvent removal step are preferably about 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern tends to be better and the residue can be further reduced. The film thickness of the dry film can be selected according to the application and is not particularly limited. From the viewpoint of ease of solvent removal, 0.01 to 20 μm is preferable, 0.1 to 10 μm is more preferable, and 0.1 to 5.0 μm is the most preferable.

In the step (3), the dried film (photosensitive composition) formed on the substrate is exposed in a pattern. For example, the dry film formed on the substrate can be pattern-exposed by exposing the dry film through a mask having a predetermined mask pattern using an exposure apparatus. Thereby, the exposed portion can be cured.
As a light source of actinic light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator etc. can be used, i ray (365 nm), h ray (405 nm), An actinic ray having a wavelength of 300 nm or more and 450 nm or less such as g-line (436 nm) can be preferably used. In addition, it is also possible to adjust the irradiation light through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed. The exposure dose is preferably 1 to 500 mJ / cm ² .
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, a laser exposure, and the like can be used. It is also possible to carry out exposure using a so-called super resolution technique. As the super resolution technique, multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, an annular illumination method and the like can be mentioned. The use of these super resolution techniques makes it possible to form patterns with higher definition, which is preferable.

In the step (4), the unexposed area of the dried film (photosensitive composition) on the substrate is removed by development to form a pattern. The development removal of the unexposed part of a dry film can be performed using a developing solution. As a result, the unexposed area in the dried film after exposure is dissolved in the developer, and only the photocured area remains, and a pattern (negative image) is obtained.
The developing solution used in the developing step preferably contains an aqueous solution of a basic compound. Examples of the basic compound include the compounds described in paragraph 0171 of WO 2015/087829, and sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrapropylammonium hydroxide. Butyl ammonium hydroxide and choline (2-hydroxyethyl trimethyl ammonium hydroxide) are preferred. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above-mentioned alkalis can also be used as a developer.
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 deposition method (paddle method), a shower method, a dip method and the like.
The development is preferably rinsed (cleaned) with pure water or the like. The rinse method can use a well-known method. For example, shower rinse and dip rinse can be mentioned.

In the step (5), by heating (post-baking) the obtained pattern, it is possible to remove the remaining solvent component or accelerate the curing of the polymerizable compound or the like to form a cured film.
This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 400 ° C., for a predetermined time, for example, 5 to 90 minutes on a hot plate, or 30 to 120 minutes for an oven. It is preferable to process. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Before post-baking, post-baking can also be performed after baking at a relatively low temperature (addition of a middle-baking step). When middle baking is performed, it is preferable to perform post baking at a high temperature of 200 ° C. or higher after heating at 90 to 180 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be divided into three or more stages and heated. The taper angle of the pattern can be adjusted by means of such middle baking and post baking. The heating may be performed using a known heating method such as a hot plate, an oven, or an infrared heater.

The curing reaction of the film can be promoted by post-baking after re-exposure (post-exposure) to the entire surface of the substrate on which the pattern is formed by active light prior to post-baking. As a preferable exposure amount in the case of including a post-exposure step, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  The cured film obtained from the photosensitive composition of the present invention can be used as a permanent film, but can also be used as a dry etching resist.

<Cured film>
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive composition of the present invention. The cured film of the present invention can be suitably used as an interlayer insulating film.
The cured film of the present invention is excellent in the adhesion of the upper layer. For this reason, after a cured film of a predetermined pattern is formed on the substrate by the method of (1) to (5) described above, the photosensitive composition of the present invention is further coated on the cured film, It is suitable for forming a cured film of a predetermined pattern by overlapping by the method of 1) to (5). As described above, by laminating the photosensitive composition of the present invention to form a pattern, a more complicated pattern (for example, a pattern having unevenness) can be formed. In addition, the process of (1)-(5) can be repeated 3 times or more, and a still more complicated pattern can also be formed.
By forming the interlayer insulating film with such a stacked structure, the aperture ratio can be improved and various functional composites can be achieved.

<Liquid Crystal Display Device and Method of Manufacturing the Same>
The liquid crystal display device of the present invention has the cured film of the present invention. Further, the method for producing a liquid crystal display device of the present invention includes the method for producing a cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a planarization film and an interlayer insulating film formed using the photosensitive composition of the present invention, and known liquid crystal display devices having various structures are used. It can be mentioned.
For example, as a specific example of the TFT (thin film transistor) included in the liquid crystal display device of the present invention, amorphous silicon, low temperature polysilicon, an oxide semiconductor, and the like can be given. As an oxide semiconductor, so-called IGZO (a semiconductor composed of indium, gallium, zinc, oxygen) can be exemplified. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs. With regard to a liquid crystal display device, the description in paragraph 0176 of WO 2015/087829 can be referred to, and the contents thereof are incorporated herein.

Moreover, the liquid crystal display device shown in FIG. 1 is also mentioned. FIG. 1: is a liquid crystal display device of FIG. 1 of Unexamined-Japanese-Patent No. 2007-328210.
In FIG. 1, reference numeral SUB1 denotes a glass substrate, and includes a plurality of scanning signal lines and a plurality of video signal lines intersecting the plurality of scanning signal lines. In the vicinity of each intersection, a TFT (thin film transistor) is provided.
Over the glass substrate SUB1, a base film UC, a semiconductor film PS, a gate insulating film GI, a gate electrode GT of a TFT, and a first interlayer insulating film IN1 are formed in order from the bottom. On the first interlayer insulating film IN1, a drain electrode SD1 of the TFT and a source electrode SD2 of the TFT are formed.
The drain electrode SD1 is connected to the drain region of the TFT via a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1. The source electrode SD2 is connected to the source region of the TFT via a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1.
A second interlayer insulating film IN2 is formed on the drain electrode SD1 and the source electrode SD2. An organic insulating film PAS is formed on the second interlayer insulating film IN2. The organic insulating film PAS can be formed using the photosensitive composition of the present invention.
The counter electrode CT and the reflective film RAL are formed on the organic insulating film PAS.
A third interlayer insulating film IN3 is formed on the counter electrode CT and the reflective film RAL. The pixel electrode PX is formed on the third interlayer insulating film IN3. The pixel electrode PX is connected to the source electrode SD2 of the TFT through the contact hole formed in the second interlayer insulating film IN2 and the third interlayer insulating film IN3.
The first interlayer insulating film IN1, the second interlayer insulating film IN2, and the third interlayer insulating film IN3 can also be formed using the photosensitive composition of the present invention.
The details of the liquid crystal display device shown in FIG. 1 can be referred to the description of JP-A-2007-328210, the contents of which are incorporated herein.

<Organic Electroluminescent Display Device and Method of Manufacturing the Same>
The organic electroluminescent (organic EL) display device of the present invention has the cured film of the present invention. Moreover, the manufacturing method of the organic electroluminescence display of this invention includes the manufacturing method of the cured film of this invention.
The organic EL display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the photosensitive composition of the present invention, and known organic EL displays having various structures. An apparatus can be mentioned. As for the organic EL display device, the description in paragraph [017] of WO 2015/087829 can be referred to, and the contents thereof are incorporated herein.
As another embodiment of the organic EL display device, the pixel separation film (19) and the flattening film (17) described in FIG. 1 of JP 2012-203121 A are formed using the photosensitive composition of the present invention Can. Further, the photosensitive composition of the present invention has the high resistance layer (18), the interpixel insulating film (16), the interlayer insulating film (14) and the interlayer insulating film (12c) described in FIG. 1 of JP-A-2013-196919. It can be formed using a material.

  The photosensitive composition of the present invention can also be used to form a barrier of a MEMS (Micro Electro Mechanical Systems) device. Examples of MEMS devices include parts such as surface acoustic wave (SAW) filters, bulk acoustic wave (BAW) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, sealants and the like. Be More specific examples are illustrated in JP-A-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  The photosensitive composition of the present invention is, for example, the bank layer (16) and the flattening film (57) described in FIG. 2 of JP-A-2011-107476, and FIG. 4 (a) of JP-A-2010-9793. Partition wall (12) and planarizing film (102) described in JP-A-2010-27591, bank layer (221) and third interlayer insulating film (216b) described in FIG. The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A, and the planarization film (12) and the pixel isolation insulating film described in FIG. 3 of JP-A-2010-182638. It can also be used to form (14) and the like. In addition, the spacer for maintaining the thickness of the liquid crystal layer in the liquid crystal display device, the imaging optical system of an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state imaging device or a microlens of an optical fiber connector It can be used suitably.

<Touch panel, touch panel display device and manufacturing method thereof>
The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or the protective layer is a cured product of the photosensitive 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. Moreover, the manufacturing method of the touch panel of this invention and a touch-panel display apparatus includes the manufacturing method of the cured film of this invention.
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 of known methods such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, and an electromagnetic induction method. Among them, the capacitance method is preferable. The touch panel display device of the present invention may be a touch panel display device in which all or part of the insulating layer and / or the protective layer of the touch panel or the display device is made of the cured product of the photosensitive composition of the present invention.
As a capacitive touch panel, those disclosed in JP 2010-28115 A and those disclosed in WO 2012/057165 can be mentioned.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7, FIG. 8 of JP-A-2012-517051), a so-called on-cell type (for example, a diagram of JP-A 2013-168125) 19), OGS (One Glass Solution) type, TOL (Touch on Lens) type, and other configurations (for example, FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871, FIG. 1 of WO2013 / 141056, and Japanese Patent No. 5673782 2) and various out-cell types (so-called GG method, G1 method / G2 method, GFF method, GF2 method, GF1 method, G1F method, etc.).
As a touch panel, the description in paragraphs 0288 to 0296 of JP-A-2015-103102 and FIGS. 7 to 9 can be referred to, and the contents thereof are incorporated in the present specification.

  The touch panel display device equipped with a capacitive touch panel and a capacitive touch panel as constituent elements is the "latest touch panel technology" (issued on July 6, 2009, Techno Times), supervised by Yuji Mitani, "Touch panel The configurations disclosed in Technology and Development, CMC Publishing (2004, 12), "FPD International 2009 Forum T-11 Lecture Textbook", "Cypress Semiconductor Corporation Application Note AN2292" and the like can be applied.

FIG. 2 shows a conceptual diagram of an example of a liquid crystal display device having a touch panel function.
The cured film of the present invention is preferably applied to the protective film between the layers in FIG. 2 and is also preferably applied to an interlayer insulating film which separates the detection electrodes of the touch panel. In addition, as a detection electrode of a touch panel, a transparent electrode (ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), etc.) and a metal electrode (silver, copper, molybdenum, titanium, aluminum etc., and their laminates and alloys) Etc.) or a laminate of these.
In FIG. 2, 110 indicates a pixel substrate, 140 indicates a liquid crystal layer, 120 indicates an opposite substrate, and 130 indicates a sensor portion. 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 this 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. 2, reference numeral 125 denotes a sensor detection electrode. The cured film of the present invention includes the insulating layer (114) (also referred to as interlayer insulating film) of the pixel substrate portion, various protective films (not shown), various protective films (not shown) of the pixel substrate portion, and the opposing substrate portion Can be used as various protective films (not shown) of the above, various protective films (not shown) of a sensor part, etc.

  Furthermore, even in a static drive liquid crystal display device, it is possible to 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 Japanese Patent Application Laid-Open No. 2001-125086.

  Moreover, FIG. 3 is a configuration conceptual diagram of another example of the liquid crystal display device having a touch panel function. A lower display panel 200 corresponding to a thin film transistor array panel provided with a thin film transistor (TFT) 440, a color filter display panel provided with a plurality of color filters 330 on the surface facing the lower display panel 200 facing the lower display panel 200. And a 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, a thin film transistor (TFT) disposed on the first insulating substrate 210, an insulating film 280 formed on the top surface of the thin film transistor (TFT), and the insulating film 280. A pixel electrode 290 is included. The thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260 and 262, a source electrode 270, and a drain electrode 272. A contact hole 282 is formed in the insulating film 280 so as to expose the drain electrode 272 of the thin film transistor (TFT).

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

  In the liquid crystal display device illustrated in FIG. 3, the touch sensing electrode 410, the insulating film 420, the touch driving electrode 430, and the protective film 600 are disposed on the other surface of the second insulating substrate 310. In the liquid crystal display device, when the upper display panel 300 is formed, the sensing electrode 410, the insulating film 420, the touch driving electrode 430, and the like which are components of the touch screen can be formed together.

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references. Also, NMR is an abbreviation of nuclear magnetic resonance.

<Measurement of Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)>
Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions.
Column type: TSK gel Super (Tosoh)
Developing solvent: tetrahydrofuran Column temperature: 40 ° C
Flow rate (sample injection volume): 10 μl
Device name: HLC-8220GPC (Tosoh Corporation)
Calibration curve based resin: polystyrene resin

Synthesis Example of Compound S
(Synthesis of S-1)
In a four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet, 56.0 g (0.65 mol) of methacrylic acid, 0.13 g of sulfuric acid, and 111 g of toluene were placed. While maintaining the liquid temperature at 23 ° C. in a nitrogen atmosphere and stirring, 50.7 g (0.13 mol) of 2- (perfluorohexyl) ethyl vinyl ether (CHEMINOX FAVE-6, manufactured by Unimatec Co., Ltd., structure (A) below) Was added over 2 hours, and after the addition was completed, it was further stirred for 4.5 hours. The reaction solution was added to 345 g of a 10% by mass aqueous sodium carbonate solution and stirred. The organic layer was separated, washed three times with 110 g of a 10% by mass aqueous sodium carbonate solution and twice with 112 g of pure water, and then concentrated under reduced pressure. The concentrate was further purified by distillation under reduced pressure to obtain 2- (perfluorohexyl) ethyl methacrylate (the following structure (B)).
Next, 33 g of diethylene glycol ethyl methyl ether (MEDG) was introduced into a separable flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen inlet tube, and the temperature was raised to 65 ° C.
Next, 2.0 g of 2- (perfluorohexyl) ethyl methacrylate (the following structure (B)), 8.0 g of hexabutylene glycol methacrylate (the following structure (C)), and 2,2'-azobis (2) And a solution obtained by mixing 0.40 g of 68 mg of MEDG with the above mixture of 0.40 g of MEDG, and 4-dimethyl valeronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name “V-65”) It dripped over 6 hours in the flask. It ripened for 2 hours after dripping.
The resulting reaction solution was added dropwise to 700 g of heptane, and the precipitated polymer was recovered with a Nutche.
The obtained polymer was dried under reduced pressure to obtain the target S-1. The weight average molecular weight (Mw) of S-1 was 1900, and the degree of dispersion (Mw / Mn) was 1.74.

(Synthesis of S-2 to S-33)
S-2 to S-33 were synthesized in the same manner as S-1, except that the raw materials were appropriately changed so that the polymers described in the following table could be produced.

<Preparation of Photosensitive Composition>
The materials shown in the following table are mixed, stirred, dissolved into a solution, filtered with a polyethylene filter with a pore size of 0.4 μm, and further filtered with a polytetrafluoroethylene filter with a pore size of 0.1 μm to obtain a photosensitive composition. Obtained. The numerical value which does not attach a unit in particular in a table | surface is a mass part. In addition, the polymeric compound and alkali-soluble resin were added so that solid content might become the quantity as described in the table. That is, when obtained as a solid, the solid content was added in the amount shown in the table, and when obtained as a solution, the solution was added so that the solid content became the amount described in the table.

The detail of the symbol which shows each compound used for the Example and the comparative example is as follows.
(Polymerizable compound)
A-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., polyfunctional (meth) acrylate)
A-2: M-321 (manufactured by Toagosei Co., Ltd., polyfunctional (meth) acrylate)
A-3: Multifunctional (meth) acrylate of the following structure
A-4: U-15 HA (manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional (meth) acrylate)
A-5: U-6LPA (manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional (meth) acrylate)
A-6: 3 g of 2,2′-azobis (isobutyronitrile) and 50.0 g of PGMEA (propylene glycol methyl ether acetate) were charged in a 500 mL flask of a polyfunctional (meth) acrylate synthesized below. After that, 30.0 g (0.349 mol) of methacrylic acid and 22.48 g (0.216 g of styrene)
mol), 35.0 g (0.149 mol) of tricyclo [5.2.1.02,6] decan-8-yl methacrylate is charged, and after stirring for a while at room temperature, the inside of the flask is replaced with nitrogen, and then 5 at 70 ° C. Heated and stirred for time. Next, 15.00 g (0.106 mol) of glycidyl methacrylate, 1.00 g of dimethylbenzylamine, 0.200 g of p-methoxyphenol and 100 g of PGMEA are added to the obtained solution, and heating is carried out at 90 ° C. for 4 hours. Stir to obtain an acrylic resin solution. Reprecipitation and drying gave A-6. The weight average molecular weight of A-6 was 16000, and the acid value was 118 mg KOH / g.

(Compound S)
S-1 to S-33 shown above were used.

(Photopolymerization initiator)
B-1: IRGACURE OXE-01 (manufactured by BASF)
B-2: IRGACURE OXE-02 (manufactured by BASF)
B-3: IRGACURE 907 (manufactured by BASF)

(solvent)
C-1: Diethylene glycol ethyl methyl ether C-2: Propylene glycol monomethyl ether acetate C-3: γ-butyrolactone C-4: 1, 3-butylene glycol diacetate

(Alkali-soluble resin)
X-1: Alkali-soluble resin (acrylic resin) obtained by the following method
In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were charged. Subsequently, 25 parts by mass of styrene, 16 parts by mass of methacrylic acid, 18 parts by mass of dicyclopentanyl methacrylate and 45 parts by mass of glycidyl methacrylate were charged, and after replacing with nitrogen, stirring was gradually started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a solution containing the alkali-soluble resin X-1. Reprecipitation and drying gave an alkali-soluble resin (acrylic resin) X-1. The weight average molecular weight of the alkali-soluble resin (acrylic resin) X-1 was 24,000.

X-2: Alkali-soluble resin (polybenzoxazole resin) obtained by the following method
73.2 g (0.20 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Bis-AP) in a three-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube -AF, made by Central Glass Co., Ltd., 31 g (0.40 mol) of pyridine and 290 g of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to -16 ° C with a dry ice / methanol bath. In this solution, while maintaining the reaction temperature at −5 ° C. to −16 ° C., a 30 mass% NMP solution of 30.1 g (0.14 mol) of 1,4-cyclohexanedicarboxylic acid dichloride, 3.83 g (0. A mixed solution of 016 mol) of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of NMP was dropped. After the addition was complete, the resulting mixture was stirred at room temperature for 16 hours.
Next, this reaction solution is cooled to -5 ° C or less by an ice / methanol bath, and 9.59 g (0.090 mol) of butyryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) while maintaining the reaction temperature at -0 ° C or less. ) And 34.5 g of NMP were dropped. After the addition was completed, the mixture was further stirred for 16 hours.
The reaction was diluted with 550 g of NMP, poured into a vigorously stirred 4 L mixture of deionized / methanol (80/20 by volume), the precipitated white powder collected by filtration and washed with deionized water. The polymer was dried at 50 ° C. for 2 days under vacuum to obtain an alkali-soluble resin (polybenzoxazole resin) X-2. The weight average molecular weight of the alkali-soluble resin (polybenzoxazole resin) X-2 was 27,000.

X-3: Alkali-soluble resin (polyimide resin) obtained by the following method
After adding 80 g of propylene glycol monoethyl ether acetate (PGMEA) as a polymerization solvent to the reaction vessel, the diamine and the tetracarboxylic acid dianhydride are polymerized solvent so that the solid content concentration becomes 20 mass% with respect to the total 80 g of the polymerization solvent. I added it inside. At this time, 90 mol parts of tetracarboxylic acid dianhydride was added to 100 mol parts of the total amount of diamine. In this synthesis example, 2,2′-bis (4-aminophenyl) hexafluoropropane is used as a diamine compound, which is then dissolved and then 2,3,5-tricarboxy as a tetracarboxylic acid dianhydride. Cyclopentylacetic acid dianhydride was charged. The mixture was then allowed to react at 65 ° C. for 3 hours. The amine ends were capped by further adding acetyl chloride and reacting at 23 ° C. for 24 hours. Reprecipitation and drying were performed to obtain an alkali-soluble resin (polyimide resin) X-3. The weight average molecular weight of alkali-soluble resin (polyimide resin) X-3 was 15,000.

X-4: Alkali-soluble resin (siloxane resin) obtained by the following method
In a container equipped with a stirrer, 100 parts by mass of propylene glycol monomethyl ether are charged, followed by 1.36 parts by mass of methyltrimethoxysilane, 1.98 parts by mass of phenyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic acid. 10.4 parts by mass of an acid anhydride and 9.44 parts by mass of glycidoxypropyltrimethoxysilane were charged, and the solution was heated until the solution temperature reached 60.degree.
After the solution temperature reached 60 ° C., 0.1 parts by mass of phosphoric acid and 9 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 2 hours. After cooling to 45 ° C., 20 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Furthermore, the solution temperature was brought to 40 ° C., and evaporation was carried out while maintaining the temperature to remove ion-exchanged water and methanol generated by hydrolysis condensation. Re-precipitation and drying gave an alkali-soluble resin (siloxane resin) X-4. The alkali-soluble resin (siloxane resin) X-4 had a weight average molecular weight (Mw) of 4,000 and a degree of dispersion (Mw / Mn (number average molecular weight)) of 2.0.
As a result of conducting FT-IR (Fourier transform infrared spectroscopy) analysis of alkali-soluble resin (siloxane resin) X-4, a broad absorption band by OH group derived from carboxyl group in the vicinity of 2500 cm ^{-1 to} 3000 cm ^-1 is confirmed From the result, it was confirmed that the succinic acid residue derived from 3-trimethoxysilylpropylsuccinic acid was hydrolyzed to have a carboxyl group.

X-5: Alkali-soluble resin (cycloolefin resin) obtained by the following method
9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 60.0 parts by mass of 0 ^2,7 ] dodec-4-ene and 40 parts by mass of N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI) 2.8 parts by mass of 1,5-hexadiene, 0.05 parts by mass of (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, and diethylene glycol ethyl methyl ether 400 The mass part was charged into a nitrogen-substituted pressure resistant glass reactor, and a polymerization reaction was carried out at 80 ° C. for 4 hours while stirring to obtain a polymerization reaction solution containing a ring-opening metathesis polymer. Then, the obtained polymerization reaction solution is put into an autoclave and stirred for 5 hours at 150 ° C. under a hydrogen pressure of 4 MPa to carry out a hydrogenation reaction, and a polymer solution containing an alkali soluble resin (cycloolefin resin) X-5 Obtained. The polymerization conversion ratio of the alkali-soluble resin (cycloolefin resin) X-5 was 99.8%, the weight average molecular weight was 5,100, the number average molecular weight was 3,200, and the hydrogenation rate was 99.9%.

(Alkoxysilane compound)
KBE-503: KBE-503, Shin-Etsu Silicone Co., Ltd. KBM-5103: KBM-5103, Shin-Etsu Silicone Co., Ltd.

(Other ingredients)
PH: phenothiazine HQ: hydroquinone JER: JER 157 S60 (manufactured by Mitsubishi Chemical Corporation, crosslinker)
TA: trimellitic acid DBA: 9, 10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)
S′-1: the following structure (structural unit S′-1-1: structural unit S′-1-2 = 20: 80 (mass ratio), Mw = 2600)
S′-2: the following structure (structural unit S′-2-1: structural unit S′-2-2 = 20: 80 (mass ratio), Mw = 2600)

<Evaluation>
(Applicability)
Each photosensitive composition was applied at a coating speed of 90 mm / sec by a slit die on a 1,500 mm × 1,800 mm Cr-deposited glass substrate (glass: EAGLE 2000, Corning) treated with HMDS (hexamethyldisilazane). The coating was applied to a dry film thickness of 2.8 μm while adjusting the coating flow rate under the conditions of a gap of 90 μm, and vacuum drying was performed in a reduced pressure drying chamber to an ultimate vacuum of 0.05 kPa (0.4 Torr). The dried substrate was dried on a hot plate at 90 ° C. for 120 seconds, then observed in the dark using a Na lamp, a white lamp and a green lamp, and coating streaks and drying unevenness were evaluated according to the following criteria: .
1 to 4 is a practical range.
1: There are no coating streaks and coating unevenness.
2: There is no coating streak, but there is slight coating unevenness.
3: The coating streaks were only slightly at the periphery of the substrate, and there were slight coating irregularities.
4: The coating streaks are slightly at the center of the substrate, and the coating unevenness is slight.
5: Coating streaks and / or coating unevenness are present on the entire surface of the substrate.

<Upper layer adhesion>
The substrate produced in the same manner as in the coating property evaluation was heated at 250 ° C. for 60 minutes in a nitrogen atmosphere. An ITO (Indium Tin Oxide) film was formed to a film thickness of 45 nm using an ULVAC sheet-fed type sputtering apparatus SMD-2400C, and heated at 200 ° C. for 30 minutes in a nitrogen atmosphere. On this substrate, a cross cut test was conducted by cutting slits at intervals of 1 mm in accordance with JIS K5600-5-6: 1999, and the adhesion between the cured film of the present invention and ITO was evaluated. 1 to 4 is a practical range.
1: Total area of ITO film peeled off from the surface of the cured film is less than 2% 2: Total area of ITO film peeled off from the surface of the cured film is 2% or more and less than 5% 3: Total area of ITO film peeled off from the surface of the cured film 5% or more and less than 10% 4: The total area of ITO films peeled off from the surface of the cured film is 10% or more and less than 15% 5: The total area of ITO films peeled off from the surface of the cured film is 15% or more

<Patternability>
About the photosensitive composition of Examples 1-235, the negative pattern of a 12-micrometer hole was exposed using MPA-7800 + (made by Canon Inc.) for the board | substrate produced similarly to coating property evaluation. Next, it was covered with a 21% by mass aqueous solution (developing solution) of FHD-5 (manufactured by Fuji Film Electronics Materials Co., Ltd.), and was rested for 60 seconds. After standing, pure water was sprayed on the shower to wash away the developer, and then it was naturally dried. Furthermore, the substrate after drying was heated at 250 ° C. for 60 minutes, and then the shape of the pattern was observed with an optical microscope (magnification of 300 ×) and a scanning electron microscope (SEM) (magnification of 5000 ×). It was confirmed that the hole pattern had a good resolution without residue and a clear hole pattern.

As shown in the above table, in the examples, the coatability was good, and the obtained cured film was excellent in the adhesion to the upper layer. Furthermore, heat resistance and pattern formability were also excellent.
On the other hand, in the comparative example, at least one of the coatability and the adhesion to the upper layer was inferior.

<Production of Display Device>
(Example 1001)
JP-A-2012-203121 discloses that the display device shown in FIG. 1 is produced by using the photosensitive composition of Example 1 and the pixel separation film (19) and the flattening film (17). It produced according to the 2012-203121 gazette. The display was excellent in display characteristics.
(Examples 1002 to 1235)
A display was produced in the same manner as in Example 1001 except that the photosensitive composition of Example 1 was changed to the photosensitive compositions of Examples 2 to 235 in Example 1001. The display was excellent in display characteristics.

(Example 2001)
JP-A-2013-196919 discloses that the display device shown in FIG. 1 is produced using the photosensitive composition of Example 1 with the inter-pixel insulating film (16) and the interlayer insulating film (14). It produced according to the 2013-196919 gazette. The display was excellent in display characteristics.
(Examples 2002 to 2235)
A display was produced in the same manner as in Example 2001 except that the photosensitive composition of Example 1 was changed to the photosensitive compositions of Examples 2 to 235 in Example 2001. The display was excellent in display characteristics.

(Example 3001)
The liquid crystal display device shown in FIG. 1 of JP 2007-328210 A was manufactured according to JP 2007-328210 A except that the organic insulating film PAS was manufactured using the photosensitive composition of Example 1. . The display was excellent in display characteristics.
(Examples 3002 to 3235)
A display was produced in the same manner as in Example 3001 except that the photosensitive composition of Example 1 was changed to the photosensitive compositions of Examples 2 to 235 in Example 3001. The display was excellent in display characteristics.

(Example 4001)
JP-A-2007-328210 except that the liquid crystal display device shown in FIG. 1 of JP-A-2007-328210 was produced as follows using the photosensitive composition of Example 1 as the organic insulating film PAS. It manufactured according to a gazette. The display was excellent in display characteristics.
In accordance with JP 2007-328210 A, up to IN2 was manufactured. Thereafter, the composition of Example 1 is slit-coated, solvent-removed, hole-shaped pattern exposure, 0.5 mass of tetramethyl ammonium hydroxide (TMAH) so that the film thickness after heat curing becomes half of the predetermined film thickness % Developed with a paddle for 60 seconds, heated at 180 ° C. for 30 minutes in a nitrogen atmosphere, and further heated at 250 ° C. for 60 minutes to form a cured film having a thickness of half of the predetermined thickness.
Similarly, a cured film having a half thickness of a predetermined film thickness was formed with the composition of Example 1 on the above cured film. By these, PAS which is a laminated body of a cured film (laminated structure of a cured film having a half thickness) was formed. Thereafter, a liquid crystal display device was manufactured according to Japanese Patent Application Laid-Open No. 2007-328210.

(Examples 4002 to 4235)
A display was produced in the same manner as in Example 4001 except that the photosensitive composition of Example 1 was changed to the photosensitive compositions of Examples 1 to 235 in Example 4001. The display was excellent in display characteristics.

  110: pixel substrate, 111: polarizing plate, 112: transparent substrate, 113: common electrode, 114: insulating layer, 115: pixel electrode, 116: alignment film, 120: opposing substrate, 121: alignment film, 122: color filter, 123: transparent substrate, 124: retardation film, 126: adhesive layer, 127: polarizing plate, 130: sensor unit, 200: lower display panel, 210: insulating substrate, 220: gate electrode, 240: gate insulating film, 250: Semiconductor layer, 260: ohmic contact layer, 270: source electrode, 272: drain electrode, 280: insulating film, 282: contact hole, 290: pixel electrode, 300: upper display panel, 310: 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: touch drive electrode, 600: protective film, CT: counter electrode, GI: gate insulating film, GT: gate electrode, IN1: first interlayer insulating film, IN2: second interlayer insulating film, IN3: Third interlayer insulating film, PAS: organic insulating film, PS: semiconductor film, PX: pixel electrode, RAL: reflective film, SD1: drain electrode, SD2: source electrode, SUB1: glass substrate, UC: base film

Claims (10)

A compound having two or more groups having an ethylenically unsaturated bond, a photopolymerization initiator, a solvent, a compound S having a structure represented by the following formula S1 and a structure represented by the following formula S2, an alkali soluble A photosensitive composition comprising a resin and
A photosensitive composition, wherein the alkali-soluble resin is one or more selected from an acrylic resin, a styrene resin, a polybenzoxazole resin, a polyimide resin, a cycloolefin resin and a siloxane resin ;
In the formula, a wavy line represents a bonding position with a group constituting the compound S,
R ¹ represents an alkyl group,
R ² represents a hydrogen atom or an alkyl group,
L ¹ represents a single bond or a divalent linking group, and when L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring,
Rf represents a fluoroalkyl group having three or more fluorine atoms,
L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30,
When n is 0, R ¹⁰⁰ represents a hydroxy group,
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, and R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. It may be good or different.   The photosensitive composition of Claim 1 which contains 0.001-20 mass parts of said compounds S with respect to 100 mass parts of a compound which has 2 or more of groups which have the said ethylenically unsaturated bond.   The compound S is a polymer having a structural unit S1-1 having a structure represented by the formula S1 in a side chain and a structural unit S2-1 having a structure represented by the formula S2 in a side chain The photosensitive composition according to claim 1 or 2. The compound according to any one of claims 1 to 3, wherein the compound S is a polymer having a constitutional unit represented by the following formula S1-2 and a constitutional unit represented by the following formula S2-2. Photosensitive composition;
In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ¹² represents an alkyl group,
R ¹³ represents a hydrogen atom or an alkyl group,
L ¹⁰ represents a single bond or a divalent linking group, and when L ¹⁰ represents a divalent linking group, R ¹² may combine with L ¹⁰ to form a ring,
Rf represents a fluoroalkyl group having three or more fluorine atoms,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
n1 represents an integer of 0 to 30,
When n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n1 is 2 to 30, the plurality of L ¹⁰¹ may be the same or different. The constitutional unit represented by the formula S1-2 is a constitutional unit represented by the following formula S1-3, and the constitutional unit represented by the formula S2-2 is a constitutional unit represented by the following formula S2-3 there, photosensitive composition according to claim 4;
In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ²² represents an alkyl group having 1 to 3 carbon atoms,
R ²³ represents a hydrogen atom,
L ²⁰ represents an alkylene group having 1 to 12 carbon atoms,
R f ¹ represents a C 3-6 perfluoroalkyl group,
R ²² may combine with L ²⁰ to form a ring,
L ²⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ²⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
n2 represents an integer of 1 to 20, and when n2 is 2 to 20, a plurality of L ²⁰¹ may be the same or different. The compound S is a polymer containing the structural unit S1-1 and the structural unit S2-1 in an amount of 70% by mass or more of the total structural units of the compound S, and the structural unit S1-1, The photosensitive composition of Claim 3 whose mass ratio with the said structural unit S2-1 is structural unit S1-1: structural unit S2-1 = 5: 95-95: 5. Applying the photosensitive composition according to any one of claims 1 to 6 on a substrate;
Removing the solvent from the applied photosensitive composition;
Exposing the photosensitive composition from which the solvent has been removed in the form of a pattern;
Developing the unexposed area of the photosensitive composition exposed in a pattern to form a pattern;
Heating the photosensitive composition after development;
A method of producing a cured film comprising: The manufacturing method of a liquid crystal display device containing the manufacturing method of the cured film of Claim 7 . The manufacturing method of the organic electroluminescent display apparatus containing the manufacturing method of the cured film of Claim 7 . The manufacturing method of a touch panel containing the manufacturing method of the cured film of Claim 7 .