Transfer film, method for manufacturing a laminate, method for manufacturing circuit wiring

Abstract

The present invention provides a transfer film excellent in pattern formability and also excellent in peelability, a method for manufacturing a laminate, and a method for manufacturing a circuit wiring. The transfer film of the present invention sequentially has a temporary support, a photosensitive composition layer disposed on the temporary support, and a protective film. Among them, the temporary support has a temporary support main body, a first layer disposed on one surface of the temporary support main body, and a second layer disposed on the other surface of the temporary support main body. In the first layer and the second layer, the first layer is disposed on the side of the photosensitive composition layer. The first layer contains first organic particles having an average particle diameter of 100 to 1000 nm and first inorganic particles having an average particle diameter of 70 nm or less. The kurtosis Rku of the surface of the first layer in contact with the photosensitive composition layer is 2.0 to 100. The second layer contains second inorganic particles having an average particle diameter of 70 nm or less or does not contain inorganic particles.

Description

Technical Field

[0001] The present invention relates to a transfer film, a method for manufacturing a laminate, and a method for manufacturing circuit wiring. Background Art

[0002] Since the number of steps for obtaining a predetermined pattern is small, a method is widely used in which a photosensitive composition layer is disposed on a transfer object such as a substrate using a transfer film, and the photosensitive composition layer is exposed through a mask and then developed.

[0003] For example, Patent Document 1 discloses a polyester film for an ultra-fine line photoresist, which contains predetermined particles on the surface of the laminate polyester film on the side opposite to the resist layer side.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2006-327158 Summary of the Invention

[0007] Technical Problem to be Solved by the Invention

[0008] In recent years, when using a transfer film, excellent pattern formation properties have been required. Specifically, it is required that the line width deviation of the pattern obtained by exposing and developing the photosensitive composition layer of the transfer film is small. Hereinafter, in the present specification, the case where the line width deviation of the pattern is small is also referred to as excellent pattern formation properties.

[0009] In addition, excellent peelability of the transfer film has also been required. Specifically, first, the protective film is peeled off when using the transfer film. When peeling off the protective film, it is required that the photosensitive composition layer is not easily left on the surface of the protective film. And, after the photosensitive composition layer of the transfer film is attached to the transfer object, the temporary support is peeled off. When peeling off the temporary support, it is required that the photosensitive composition layer is not easily left on the surface of the temporary support. That is, when peeling off the protective film and when peeling off the temporary support, it is required that the photosensitive composition layer is not easily left on the surface of the temporary support and the surface of the protective film. Hereinafter, in the present specification, the case where the photosensitive composition layer is not easily left on the surfaces of the temporary support and the protective film during peeling and peeling is also referred to as excellent peelability.

[0010] As a result of the present inventors' research on the characteristics of conventional transfer films having a temporary support such as Patent Document 1, it has been found that the pattern formation properties and peelability of the transfer film cannot be achieved at the same time.

[0011] Therefore, an object of the present invention is to provide a transfer film having excellent pattern formation properties and excellent peelability.

[0012] Further, an object of the present invention is to provide a method for manufacturing a laminate using a transfer film and a method for manufacturing a circuit wiring.

[0013] Means for Solving the Technical Problem

[0014] As a result of intensive studies on the above problems by the present inventors, it has been found that the above problems can be solved by the following configuration.

[0015] 〔1〕A transfer film having, in this order, a temporary support, a photosensitive composition layer disposed on the temporary support, and a protective film,

[0016] The temporary support has a temporary support body, a first layer disposed on one surface of the temporary support body, and a second layer disposed on the other surface of the temporary support body,

[0017] In the first layer and the second layer, the first layer is disposed on the side of the photosensitive composition layer,

[0018] The first layer contains first organic particles having an average particle diameter of 100 to 1000 nm and first inorganic particles having an average particle diameter of 70 nm or less, and the kurtosis Rku of the surface of the first layer in contact with the photosensitive composition layer is 2.0 to 100.

[0019] The second layer contains second inorganic particles having an average particle diameter of 70 nm or less or does not contain inorganic particles.

[0020] 〔2〕The transfer film according to 〔1〕, wherein

[0021] The first organic particles contain polystyrene resin particles.

[0022] 〔3〕The transfer film according to 〔1〕 or 〔2〕, wherein

[0023] The average particle diameter of the first organic particles is 350 to 800 nm.

[0024] 〔4] The transfer film according to any one of 〔1〕 to 〔3〕, wherein

[0025] At least one of the first inorganic particles and the second inorganic particles contains at least one selected from a silicon atom and an aluminum atom.

[0026] 〔5〕The transfer film according to any one of 〔1〕 to 〔4〕, wherein

[0027] At least one of the first inorganic particles and the second inorganic particles contains alumina.

[0028] 〔6〕The transfer film according to any one of 〔1〕 to 〔5〕, wherein

[0029] The average particle diameter of the first inorganic particles and the average particle diameter of the second inorganic particles are 10 to 50 nm.

[0030] 〔7〕The transfer film according to any one of 〔1〕 to 〔6〕, wherein

[0031] The thickness of the temporary support body main body is 6.0 to 30.0 μm,

[0032] The thicknesses of the first layer and the second layer are 0.8 to 3.0 μm.

[0033] 〔8〕The transfer film according to any one of 〔1〕 to 〔7〕, wherein

[0034] The average particle diameter of the first organic particles is 350 to 800 nm,

[0035] The first inorganic particles contain alumina,

[0036] The average particle diameter of the first inorganic particles is 10 to 50 nm.

[0037] 〔9〕The transfer film according to any one of 〔1〕 to 〔8〕, wherein

[0038] The second layer contains second organic particles with an average particle diameter of 350 to 800 nm,

[0039] The second inorganic particles contain alumina,

[0040] The average particle diameter of the second inorganic particles is 10 to 50 nm.

[0041] 〔10〕The transfer film according to any one of 〔1〕 to 〔9〕, wherein

[0042] The kurtosis Rku of the surface of the first layer is 2.5 to 10.

[0043] 〔11〕The transfer film according to any one of 〔1〕 to 〔10〕, wherein

[0044] The kurtosis Rku of the surface of the first layer is 3.0 to 5.0, and the first inorganic particles and the second inorganic particles contain alumina.

[0045] 〔12〕The transfer film according to any one of 〔1〕 to 〔11〕, wherein

[0046] The photosensitive composition layer contains a binder polymer, a polymerizable compound, and a polymerization initiator.

[0047] 〔13〕The transfer film according to any one of 〔1〕 to 〔12〕, wherein

[0048] An index matching layer is further provided between the photosensitive composition layer and the protective film.

[0049] 〔14〕The transfer film according to any one of 〔1〕 to 〔13〕, wherein,

[0050] The photosensitive composition layer is used to form an electrode protective film for a touch panel.

[0051] 〔15〕A method for manufacturing a laminate, comprising:

[0052] A bonding step of peeling off the protective film from the transfer film according to any one of 〔1〕 to 〔14〕 and bonding the surface on the side opposite to the temporary support to a substrate having a conductive layer, to obtain a substrate with a photosensitive composition layer having a conductive layer, a photosensitive composition layer, and a temporary support in sequence,

[0053] An exposure step of performing pattern exposure on the photosensitive composition layer; and

[0054] A development step of developing the exposed photosensitive composition layer to form a pattern;

[0055] The method for manufacturing a laminate further includes:

[0056] A peeling step of peeling off the temporary support from the substrate with a photosensitive composition layer between the bonding step and the exposure step or between the exposure step and the development step.

[0057] 〔16〕A method for manufacturing a circuit wiring, comprising:

[0058] A bonding step of peeling off the protective film from the transfer film according to any one of 〔1〕 to 〔14〕 and bonding the surface on the side opposite to the temporary support to a substrate having a conductive layer, to obtain a substrate with a photosensitive composition layer having a conductive layer, a photosensitive composition layer, and a temporary support in sequence,

[0059] An exposure step of performing pattern exposure on the photosensitive composition layer;

[0060] A development step of developing the exposed photosensitive composition layer to form a pattern;

[0061] An etching step of etching the conductive layer in the area where no pattern is disposed; and

[0062] A peeling step of further peeling off the temporary support from the substrate with a photosensitive composition layer between the bonding step and the exposure step or between the exposure step and the development step.

[0063] Advantages of the Invention

[0064] According to the present invention, it is possible to provide a transfer film having excellent pattern formability and excellent peelability. Further, according to the present invention, it is also possible to provide a method for manufacturing a laminate and a method for manufacturing a circuit wiring using the transfer film. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 FIG. is a schematic view showing an example of the structure of the transfer film according to the first embodiment.

[0066] Figure 2 FIG. is a schematic view showing an example of the structure of the transfer film according to the second embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0067] Hereinafter, the present invention will be described in detail.

[0068] In this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0069] In this specification, in a numerically defined range described stepwise, the upper limit value or the lower limit value described in a certain numerical range can be replaced by the upper limit value or the lower limit value of another numerically defined range described stepwise. In the numerical range described in this specification, the upper limit value or the lower limit value described in a certain numerical range can also be replaced by the value shown in the examples.

[0070] In this specification, the term "step" includes not only an independent step, but also includes cases where it cannot be clearly distinguished from other steps as long as it can achieve the purpose expected by the step.

[0071] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more.

[0072] In this specification, the average transmittance of visible light is a value measured with a spectrophotometer. For example, it can be measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0073] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values converted using the standard substance polystyrene measured as follows: using three TSK gel SuperHZM-N (manufactured by Tosoh Corporation) connected in series as the column, using THF (tetrahydrofuran) as the eluent, using a differential refractometer as the detector, using polystyrene as the standard substance, and measuring with a gel permeation chromatography (GPC) analyzer.

[0074] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight.

[0075] In this specification, unless otherwise specified, the ratio of the structural units of the polymer is a mass ratio.

[0076] In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

[0077] In this specification, “(meth)acrylic acid” is a concept encompassing both acrylic acid and methacrylic acid, “(meth)acrylate” is a concept encompassing both acrylate and methacrylate, and “(meth)acryloyloxy” is a concept encompassing both acryloyloxy and methacryloyloxy.

[0078] Furthermore, in this specification, an “organic group” refers to a group containing at least one carbon atom.

[0079] In this specification, when it is stated that “it may have a substituent”, there are no particular limitations on the type, position, or number of the substituent. The number of substituents may be, for example, 1, 2, 3, or more. Examples of the substituent include monovalent non-metal atomic groups other than a hydrogen atom, and for example, those that can be selected from the following substituent group T.

[0080] (Substituent group T)

[0081] Examples of the substituent group T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; acyloxy groups such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; acyl groups such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxyoxalyl group; alkylthio groups such as a methylthio group and a tert-butylthio group; arylthio groups such as a phenylthio group and a p-tolylthio group; an alkyl group; a cycloalkyl group; an aryl group; a heteroaryl group; a hydroxyl group; a carboxyl group; a formyl group; a sulfo group; a cyano group; a nitro group; an ether group; an alkylaminocarbonyl group; an arylaminocarbonyl group; a sulfonamide group; a silyl group; an amino group; a monoalkylamino group; a dialkylamino group; an arylamino group; and combinations thereof.

[0082] [Transfer film]

[0083] The transfer film sequentially has a temporary support, a photosensitive composition layer disposed on the temporary support, and a protective film. The temporary support has a temporary support main body, a first layer disposed on one surface of the temporary support main body, and a second layer disposed on the other surface of the temporary support main body. Among the first layer and the second layer, the first layer is disposed on the side of the photosensitive composition layer. That is, the transfer film sequentially has a second layer, a temporary support main body, a first layer, a photosensitive composition layer, and a protective film.

[0084] As a characteristic point of the transfer film of the present invention, as described below, it can be mentioned that the temporary support of the transfer film has a first layer and a second layer.

[0085] As described above, as a result of the inventors' research on conventional transfer films, it has been found that pattern formability and peelability cannot be achieved at the same time.

[0086] In contrast, in the present invention, when a temporary support including a first layer and a second layer is included, the desired effects can be obtained. Regarding the mechanism, the inventors presume as follows.

[0087] By controlling the first inorganic particles that each layer may contain to a specified average particle size, light scattering during exposure is suppressed, the exposure is uniform, and the line width deviation of the resin pattern is small. Also, it is presumed that by including organic particles having a specified particle size contained in the first layer, the kurtosis Rku is adjusted within a specified range, and the desired peelability can be imparted between the photosensitive composition layer and the temporary support and between the photosensitive composition layer and the protective film.

[0088] Hereinafter, in the present specification, a case where at least one of the effects of more excellent pattern formability of the transfer film and more excellent peelability of the transfer film can be obtained is also referred to as more excellent effects of the present invention.

[0089] Hereinafter, an example of the mode of the transfer film of the present invention is shown, but it is not limited thereto.

[0090] (1) "Temporary support / Photosensitive composition layer / Refractive index adjustment layer / Protective film"

[0091] (2) "Temporary support / Photosensitive composition layer / Protective film"

[0092] (3) "Temporary support / Intermediate layer / Photosensitive composition layer / Protective film"

[0093] (4) "Temporary support / Thermoplastic resin layer / Intermediate layer / Photosensitive composition layer / Protective film"

[0094] In addition, in each of the above structures, the photosensitive composition layer is preferably a negative photosensitive composition layer. Also, the photosensitive composition layer is preferably a colored resin layer.

[0095] As described below, the transfer film of the present invention can be used as a transfer film for a wiring protective film or as a transfer film for a resist.

[0096] When it is set as a transfer film for a wiring protective film, as the structure of the transfer film, the structures of (1) to (2) above are preferred. And when it is set as a transfer film for a resist, as the structure of the transfer film, the structures of (2) to (4) above are preferred.

[0097] Specifically, for example, the first embodiment and the second embodiment described later can be cited.

[0098] Hereinafter, an example of the embodiment of the transfer film of the first embodiment will be described.

[0099] Figure 1 The transfer film 10 shown has, in order, a temporary support 1, a composition layer 2 including a photosensitive composition layer 3 and a refractive index adjusting layer 5, and a protective film 7.

[0100] Moreover, Figure 1 The transfer film 10 shown is configured with the refractive index adjusting layer 5, but the refractive index adjusting layer 5 may not be provided.

[0101] Hereinafter, an example of an embodiment of the transfer film of the second embodiment will be described.

[0102] Figure 2 The transfer film 20 shown has, in order, a temporary support 11, a composition layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive composition layer 17, and a protective film 19.

[0103] Moreover, Figure 2 The transfer film 20 shown is configured with the thermoplastic resin layer 13 and the intermediate layer 15, but the thermoplastic resin layer 13 and the intermediate layer 15 may not be provided.

[0104] In the transfer film of the second embodiment, as the temporary support 11 and the protective film 17, the same temporary support and protective film as the temporary support 1 and the protective film 9 of the first embodiment described above can be cited.

[0105] Hereinafter, each structure of the transfer film will be described in detail.

[0106] <Temporary support>

[0107] The transfer film has a temporary support.

[0108] The temporary support has a temporary support main body, a first layer described later, and a second layer described later.

[0109] The temporary support is a member that supports the photosensitive composition layer and is finally removed by a peeling process.

[0110] Hereinafter, each component constituting the temporary support will be described in detail.

[0111] [Temporary support main body]

[0112] The temporary support has a temporary support main body.

[0113] The temporary support main body is a member disposed between the first layer and the second layer.

[0114] As the temporary support body main body, for example, a glass substrate and a film can be cited, and a resin film is preferred. Further, as the temporary support body main body, a film that does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heating and has flexibility is preferred.

[0115] As the above resin film, for example, polyester films such as polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film can be cited.

[0116] Among them, as the temporary support body main body, a polyester film is preferred, a biaxially stretched polyester film is more preferred, and a biaxially stretched PET film is further preferred. Further, the temporary support body main body preferably has no deformations such as wrinkles and scratches.

[0117] As the temporary support body main body, a biaxially stretched polyester film is preferred.

[0118] Biaxial stretching means that a biaxial stretching treatment is performed and molecular orientation is present in the biaxial directions.

[0119] The molecular orientation is measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Scientific Instruments Co., Ltd.). The angle formed in the biaxial directions is preferably 90° ± 5°, more preferably 90° ± 3°, and further preferably 90° ± 1°.

[0120] The above biaxially stretched polyester film preferably has molecular orientation in the length direction and the width direction.

[0121] The width direction refers to the direction orthogonal to the length direction. Further, when the width direction is unknown, the direction with the strongest degree of orientation in the degree of orientation measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Scientific Instruments Co., Ltd.) is taken as the width direction. Further, orthogonal does not necessarily mean strictly orthogonal, but also includes substantially orthogonal. Substantially orthogonal means intersecting at 90° ± 5°, preferably intersecting at 90° ± 3°, and more preferably intersecting at 90° ± 1°.

[0122] The biaxially stretched polyester film is a biaxially stretched polyester film containing polyester as the main polymer component. The main polymer component refers to the polymer with the highest content ratio (mass%) among all the polymers contained in the film, and polyester refers to a polymer having an ester bond in the main chain.

[0123] As the polyester, for example, well-known polyesters can be cited.

[0124] As the polyester, for example, polyethylene terephthalate (PET) and polyethylene 2,6-naphthalate (PEN) can be cited. Among them, as the polyester, PET is preferred.

[0125] The intrinsic viscosity of the polyester is preferably 0.50 dl / g or more and less than 0.80 dl / g, more preferably 0.55 dl / g or more and less than 0.70 dl / g.

[0126] The biaxially stretched polyester film may contain only one kind of polyester, or may contain two or more kinds.

[0127] The content of the polyester is preferably 85% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 98% by mass or more, based on the total mass of the polymers in the biaxially stretched polyester film. There is no particular limitation on the upper limit, and it is preferably 100% by mass or less based on the total mass of the polymers in the biaxially stretched polyester film.

[0128] The content of the polyester is preferably 85% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 98% by mass or more, based on the total mass of the biaxially stretched polyester film. There is no particular limitation on the upper limit, and it is preferably 100% by mass or less based on the total mass of the biaxially stretched polyester film.

[0129] When the biaxially stretched polyester film contains PET, the content of PET is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, further preferably 98 to 100% by mass, and particularly preferably 100% by mass, based on the total mass of the polyester in the biaxially stretched polyester film.

[0130] There is no particular limitation on the method for producing the polyester, and known methods can be cited.

[0131] As a method for producing the polyester, for example, the polyester can be produced by polycondensing at least one dicarboxylic acid compound and at least one glycol compound in the presence of a catalyst.

[0132] As the dicarboxylic acid compound, for example, an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, and an aromatic dicarboxylic acid compound can be cited.

[0133] As the glycol compound, for example, an aliphatic glycol compound, an alicyclic glycol compound, and an aromatic glycol compound can be cited.

[0134] As the catalyst, for example, an alkali metal compound, an alkaline earth metal compound, a zinc compound, a lead compound, a manganese compound, a cobalt compound, an aluminum compound, an antimony compound, a titanium compound, a germanium compound, and a phosphorus compound can be cited.

[0135] When producing the polyester, a known end-capping agent can be used as needed. As the end-capping agent, for example, an oxazoline-based compound, a carbodiimide compound, and an epoxy compound can be cited.

[0136] As a method for synthesizing polyester, known synthesis methods can be applied. For example, the methods described in paragraphs

[0033] to

[0070] of Japanese Patent No. 5575671 can be cited, and these are incorporated into this specification.

[0137] The haze of the temporary support body main body is preferably small.

[0138] Specifically, the haze of the temporary support is preferably less than 0.5%, more preferably 0.4% or less. The lower limit is not particularly limited, and preferably 0% or more.

[0139] In addition, the haze can be measured using a haze meter according to the method in accordance with JIS K 7105:1981. The haze described in this specification is the value measured using a haze meter (NDH-2000, manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.).

[0140] In the temporary support body main body, as L * a * b * The b value in the colorimetric system * is preferably 0 to 1, more preferably 0 to 0.8, still more preferably 0 to 0.6, and particularly preferably 0 to 0.4. By the L * a * b * The b value in the colorimetric system * is 0 to 1, the yellowness of the film can be reduced, and thus the hue of the film can be made close to colorless. As a result, for example, it can be preferably applied to uses that require high visual recognition (such as display devices).

[0141] The L * a * b * The b value in the colorimetric system * is measured by a spectrocolorimeter (for example, SE-2000, manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.) by the transmission method.

[0142] Regarding the thickness of the temporary support body main body, from the viewpoint of handling suitability (especially the handling suitability during lamination of the film), it is preferably 1.0 to 100.0 μm, more preferably 6.0 to 30.0 μm, still more preferably 10.0 to 30.0 μm. If the thickness of the temporary support body main body is 10.0 μm or more, good strength can be obtained and the operation in the processing process becomes easier. If it is 50.0 μm or less, a better haze value can be obtained.

[0143] If the dimensional change rate of the temporary support body main body is within the following range, generation of distortion and wrinkles due to thermal shrinkage in the DFR processing step can be suppressed, and thus it is preferable. The above-described dimensional change rate can be appropriately adjusted by adjusting conditions such as relaxation and heat treatment in the film-forming conditions using a known method. The dimensional change rate at 150°C is preferably less than 3% in the length direction and less than 2.5% in the width direction, more preferably 0.5% or more and less than 2% in the length direction and 1% or more and less than 2% in the width direction. Further, the dimensional change rates in the length direction and the width direction at 100°C are preferably less than 1%, more preferably less than 0.8%. When the dimensional change rate is within the above range, the planarity tends to become better when coating the photosensitive composition.

[0144] In the temporary support body main body, as the strength when the film is stretched by 5% in the length direction (hereinafter, also referred to as "F-5"), it is preferably 70 MPa or more and less than 150 MPa. When the F-5 in the length direction is less than 70 MPa, scratches or the like are generated due to insufficient strength, and thus the processing characteristics sometimes deteriorate. On the other hand, when the F-5 in the length direction is 150 MPa or more, it is sometimes difficult to balance the F-5 in the width direction. As the F-5 in the length direction, it is more preferably 80 MPa or more and less than 140 MPa, and further preferably 90 MPa or more and less than 130 MPa.

[0145] Further, as the F-5 in the width direction, it is preferably 80 MPa or more and less than 160 MPa.

[0146] When the F-5 in the width direction is within the above range, generation of scratches due to insufficient strength and the like is suppressed and the processing characteristics are prevented from deteriorating, and the F-5 in the length direction can also be balanced. It is more preferably 90 MPa or more and less than 150 MPa, and further preferably 100 MPa or more and less than 140 MPa.

[0147] As the breaking strength of the temporary support body main body in the length direction, it is preferably 200 MPa or more and less than 360 MPa, more preferably 220 MPa or more and less than 340 MPa. Further, as the breaking strength in the width direction, it is preferably 260 MPa or more and less than 420 MPa, more preferably 280 MPa or more and less than 400 MPa.

[0148] The F-5 and the breaking strength can be achieved by appropriately adjusting the stretching temperature and the stretching ratio in the longitudinal and transverse directions.

[0149] [First layer]

[0150] The temporary support has a first layer disposed on the photosensitive composition layer side.

[0151] The first layer contains first organic particles with an average particle size of 100 to 1000 nm and first inorganic particles with an average particle size of 70 nm or less, and the kurtosis Rku of the surface of the first layer in contact with the photosensitive composition layer is 2 to 100.

[0152] (Kurtosis Rku)

[0153] The kurtosis Rku of the surface of the first layer in contact with the photosensitive composition layer (hereinafter, also simply referred to as "kurtosis Rku") is preferably 2.5 to 80, more preferably 2.5 to 10, still more preferably 2.5 to 6.0, and particularly preferably 3.0 to 5.0.

[0154] In the measurement of kurtosis Rku, 10 sites randomly selected from the surface of the first layer in contact with the photosensitive composition layer (the surface on the side opposite to the temporary support body main body) are measured using New View 6000 manufactured by Zygo Corporation, and the average value of the obtained measurement values excluding the minimum value and the maximum value is set.

[0155] As a method for adjusting kurtosis Rku, a method of adjusting the types and contents of the first organic particles and the first inorganic particles described later can be cited.

[0156] (The first organic particles)

[0157] The average particle size of the first organic particles is 100 to 1000 nm. From the aspect of more excellent effects of the present invention, it is preferably 350 to 800 nm, more preferably 350 to 700 nm, and still more preferably 400 to 600 nm.

[0158] The average particle size of the first organic particles is obtained by arithmetically averaging the particle sizes of 50 first organic particles randomly selected from the image of a transmission electron microscope (TEM: Transmission Electron Microscope). Specifically, it can be obtained by the following method: After cutting out the cross-section of the temporary support, observe the cross-section of the temporary support with a TEM, randomly select 50 particles from the TEM observation image, and perform energy dispersive X-ray analysis (EDX: Energy dispersive X-ray spectroscopy) on the selected particles. According to the results of EDX, particles containing no inorganic elements are regarded as organic particles, and particles containing inorganic elements are regarded as inorganic particles, and the particle sizes of each particle are arithmetically averaged. And when each particle is not spherical, regarding the average particle size of each particle, the cross-sectional area of the organic particle or inorganic particle obtained from the TEM image of the cross-section of the temporary support is obtained, and the diameter when replaced with a circle having the same area as the cross-sectional area is used as the average particle size of each particle. In addition, the average particle size is the value obtained by arithmetically averaging the diameters in the TEM image of the cross-section.

[0159] As the first organic particle, resin particles are preferred.

[0160] As the resin particles, for example, polystyrene resin particles, acrylic resin particles, polyester resin particles, silicone organic particles, and styrene-acrylic organic particles can be mentioned, and polystyrene resin particles are preferred.

[0161] Moreover, the first organic particle preferably has a crosslinked structure.

[0162] The first layer may contain only one kind of the first organic particle or may contain two or more kinds.

[0163] The content of the first organic particle is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, still more preferably 0.1 to 1.0% by mass, and particularly preferably 0.1 to 0.3% by mass with respect to the total mass of the first layer.

[0164] (The first inorganic particle)

[0165] The average particle diameter of the first inorganic particle is 70 nm or less, and from the aspect of more excellent effects of the present invention, it is preferably 65 nm or less, and more preferably 50 nm or less. The lower limit is not particularly limited, and it is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 8 nm or more, and particularly preferably 10 nm or more.

[0166] The average particle diameter of the first inorganic particle can be measured by the measurement method of the average particle diameter of the above-mentioned organic particle.

[0167] The first inorganic particle preferably contains at least one selected from a silicon atom and an aluminum atom, and more preferably contains an aluminum atom.

[0168] As the first inorganic particle, for example, silica particles (silica particles), titanium dioxide particles (titanium oxide particles), calcium carbonate, barium sulfate, and alumina particles (alumina particles) can be mentioned. Among them, as the inorganic particle, from the aspects of haze and durability, alumina particles or silica particles are preferred, and alumina particles are more preferred.

[0169] As the silica particles, there is no particular limitation, and known silica particles can be mentioned.

[0170] As the silica particles, for example, fumed silica particles and colloidal silica particles can be mentioned.

[0171] As the fumed silica particles, for example, they can be obtained by reacting a silicon atom-containing compound with oxygen and hydrogen in the gas phase. As the silicon compound as a raw material, for example, silicon halide (for example, silicon chloride) can be mentioned.

[0172] As colloidal silica particles, for example, they can be synthesized by the sol-gel method of hydrolyzing and condensing raw material compounds. As raw material compounds for colloidal silica, for example, alkoxysilanes (e.g., tetraethoxysilane) and silane halide compounds (e.g., diphenyldichlorosilane) can be cited.

[0173] The morphology of the silica particles can be primary particles or aggregates of primary particles (aggregated silica particles).

[0174] The first layer may contain only one type of first inorganic particle or may contain two or more types.

[0175] The content of the first inorganic particle is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, still more preferably 0.1 to 1.0% by mass, and particularly preferably 0.2 to 0.5% by mass with respect to the total mass of the first layer.

[0176] In the first layer, the content of the first inorganic particle is preferably more than the content of the first organic particle. Specifically, the mass ratio of the content of the first inorganic particle to the content of the first organic particle (content of the first inorganic particle / content of the first organic particle) is preferably 1.0 or more, more preferably 2.0 or more. The upper limit is not particularly limited, preferably 10.0 or less, more preferably 5.0 or less, still more preferably 3.0 or less.

[0177] (Other components)

[0178] The first layer may contain other components other than the above components.

[0179] As other components, for example, resins, surfactants, crosslinking agents, and film-forming aids can be cited, and resins are preferred.

[0180] The first layer may contain only one type of other component or may contain two or more types.

[0181] -Resin-

[0182] Resin refers to a polymer having a weight-average molecular weight of 3000 or more.

[0183] The weight-average molecular weight of the resin can be measured by gel permeation chromatography (GPC).

[0184] As resins, olefin resins, resins constituting the above-mentioned temporary support body main body, and binder polymers contained in the photosensitive composition layer described later can be cited. Preferred are resins constituting the temporary support body main body or binder polymers, more preferably polyester resins, and still more preferably PET resins.

[0185] As the olefin resin, for example, known olefin resins can be cited. As the olefin resin, for example, polyethylene and polypropylene can be cited.

[0186] From the viewpoints of the durability of the first layer and the dispersibility of the particles, the content of the resin is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more, relative to the total mass of the first layer. The upper limit is not particularly limited, and is preferably 99.99% by mass or less, more preferably 99.9% by mass or less.

[0187] - Surfactant -

[0188] As the surfactant, for example, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be cited, and anionic surfactants or nonionic surfactants are preferred.

[0189] As the anionic surfactant, for example, RAPISOL (registered trademark) A - 90 (manufactured by NOF CORPORATION), SANDET BL (manufactured by Sanyo Chemical Industries., Ltd.), and NIKKOL SCS (manufactured by Nikko Chemicals Co., Ltd.) can be cited.

[0190] As the nonionic surfactant, for example, NAROACTY (registered trademark) CL95 (manufactured by Sanyo Chemical Industries., Ltd.) can be cited.

[0191] As the surfactant, in addition to the above, for example, surfactants described in the Surfactant Physical Property Data Book (Technical Information Association) can also be cited.

[0192] The content of the surfactant is preferably 10% by mass or less, more preferably 0.001 - 10% by mass, and further preferably 0.01 - 3% by mass, relative to the total mass of the first layer.

[0193] - Cross - linker -

[0194] As the cross - linker, for example, known cross - linkers such as carbodiimide compounds, oxazoline compounds, epoxy compounds, melamine compounds, and isocyanate compounds can be cited.

[0195] As the crosslinking agent, for example, CARBODILITE (registered trademark) V-02-L2 (manufactured by Nisshinbo Chemical Inc.), EPOCROS (registered trademark) WS-700 (manufactured by Nippon Shokubai Co., Ltd.), DENACOL (registered trademark) EX614B (manufactured by Nagase ChemteX Corporation), and Duranate (registered trademark) WM44 (manufactured by Asahi Kasei Corporation) can be cited.

[0196] The content of the crosslinking agent is preferably 1 to 50% by mass, more preferably 2 to 20% by mass, relative to the total mass of the first layer.

[0197] The thickness of the first layer is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. There is no particular limitation on the upper limit, and it is preferably 10.0 μm or less, more preferably 5.0 μm or less, further preferably 3.0 μm or less, particularly preferably 2.0 μm or less, and most preferably 1.0 μm or less.

[0198] [Second layer]

[0199] The second layer is a layer containing second inorganic particles with an average particle diameter of 70 nm or less or a layer containing no inorganic particles. In other words, the second layer contains second inorganic particles or does not contain inorganic particles of any average particle diameter. Among them, the second layer preferably contains second inorganic particles.

[0200] When the second layer contains second inorganic particles with an average particle diameter of 70 nm or less, from the aspect of more excellent effects of the present invention, the average particle diameter of the second inorganic particles contained in the second layer is preferably 65 nm or less, more preferably 50 nm or less. There is no particular limitation on the lower limit, and it is preferably 1 nm or more, more preferably 5 nm or more, further preferably 8 nm or more, and particularly preferably 10 nm or more.

[0201] The average particle diameter of the second inorganic particles can be measured by the measurement method of the average particle diameter of the first organic particles described above.

[0202] The second inorganic particles preferably contain at least one selected from silicon atoms and aluminum atoms, and more preferably contain aluminum atoms.

[0203] As the second inorganic particles, for example, silica particles, titanium dioxide particles (titanium oxide particles), calcium carbonate, barium sulfate, and alumina particles can be cited. Among them, as the inorganic particles, from the aspects of haze and durability, alumina particles or silica particles are preferred, and alumina particles are more preferred.

[0204] The morphology of the silica particles is as described above.

[0205] The second layer may contain only one type of second inorganic particle or two or more types.

[0206] The content of the second inorganic particle is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, further preferably 0.1 to 1.0% by mass, and particularly preferably 0.2 to 0.5% by mass relative to the total mass of the second layer.

[0207] When the second layer does not contain inorganic particles, the second layer does not contain inorganic particles of any average particle size.

[0208] The second layer may contain second organic particles having an average particle size of 100 to 1000 nm.

[0209] As the definition of the second organic particle, it has the same meaning as the first organic particle contained in the first layer above, and the preferred manner is also the same.

[0210] The second layer may contain only one type of second organic particle or two or more types.

[0211] The content of the second organic particle is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, further preferably 0.1 to 1.0% by mass, and particularly preferably 0.1 to 0.3% by mass relative to the total mass of the second layer.

[0212] (Other components)

[0213] The second layer may contain other components other than the above components.

[0214] As other components, it has the same meaning as the other components contained in the first layer above, and the preferred manner is also the same.

[0215] The thickness of the second layer is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. There is no particular limitation on the upper limit, and it is preferably 10.0 μm or less, more preferably 5.0 μm or less, further preferably 3.0 μm or less, particularly preferably 2.0 μm or less, and most preferably 1.0 μm or less.

[0216] The mode of the first layer and the mode of the second layer may be the same layer or different layers. Among them, from the aspect of more excellent effects of the present invention, the same layer is preferred. In addition, the same layer means a layer having the same components contained in the layer and the same thickness of the layer.

[0217] The first organic particles contained in the first layer and the second organic particles contained in the second layer may be the same organic particles or different organic particles. Among them, from the aspect of more excellent effects of the present invention, the same organic particles are preferred.

[0218] Moreover, the content of the first organic particles contained in the first layer and the content of the second organic particles contained in the second layer may be the same content or different contents. Among them, from the aspect of more excellent effects of the present invention, the same content is preferred.

[0219] The first inorganic particles contained in the first layer and the second inorganic particles contained in the second layer may be the same inorganic particles or different inorganic particles. Among them, from the aspect of more excellent effects of the present invention, the same inorganic particles are preferred.

[0220] Moreover, the content of the first inorganic particles contained in the first layer and the content of the second inorganic particles contained in the second layer may be the same content or different contents. Among them, from the aspect of more excellent effects of the present invention, the same content is preferred.

[0221] The thickness of the first layer and the thickness of the second layer may be the same thickness or different thicknesses. Among them, from the aspect of more excellent effects of the present invention, the same thickness is preferred.

[0222] [Physical property values of the temporary support]

[0223] The temporary support preferably has light transmittance.

[0224] When exposing the photosensitive composition layer, the photosensitive composition layer can be exposed through the temporary support. In this specification, having light transmittance means that the transmittance of light with the wavelength used in pattern exposure is 50% or more.

[0225] From the aspect of being able to perform pattern exposure through the temporary support, the transmittance of light with a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. There is no particular limitation on the upper limit, and it is preferably 100% or less.

[0226] In addition, the transmittance refers to the ratio of the intensity of the outgoing light that passes through the layer to be measured and exits to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface (thickness direction) of the layer to be measured. For example, the transmittance can be measured using the MCPD Series manufactured by Otsuka Flectronics Co., Ltd.

[0227] The haze of the temporary support is preferably small.

[0228] Specifically, the haze of the temporary support is preferably less than 0.5%, more preferably 0.4% or less. There is no particular limitation on the lower limit, and it is preferably 0% or more. When the haze of the temporary support is within the above range, during the exposure process, the scattering of light during the exposure of the photosensitive composition layer supported by the temporary support is effectively suppressed, and the distortion and loss of the resin pattern after the development process are suppressed. As a result, a resin pattern with a good wall surface state can be formed.

[0229] In addition, the haze can be measured using a haze meter according to the method in accordance with JIS K 7105:1981. The haze described in this specification is the value measured using a haze meter (NDH-2000, manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.).

[0230] The thickness of the temporary support can be determined, for example, based on the strength, light transmittance, material of the temporary support, and the flexibility required for the adhesion of the transfer film to the substrate.

[0231] There is no particular limitation on the thickness of the temporary support, and it is often 200.0 μm or less. From the aspect of more excellent effects of the present invention, it is preferably 100.0 μm or less, more preferably 40.0 μm or less, and further preferably 35.0 μm or less. There is no particular limitation on the lower limit, and it is preferably 1.0 μm or more, more preferably 5.0 μm or more, and further preferably 10.0 μm or more.

[0232] The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0233] As a preferred embodiment of the temporary support, for example, the descriptions in paragraphs

[0017] to

[0018] of Japanese Patent Application Laid-Open No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Application Laid-Open No. 2016-027363, paragraphs

[0041] to

[0057] of WO2012 / 081680A1, and paragraphs

[0029] to

[0040] of WO2018 / 179370A1 can be cited, and the contents of these publications are incorporated into this specification.

[0234] <Protective film>

[0235] The transfer film has a protective film.

[0236] By having a protective film, the surface of the layer in contact with the protective film (for example, the photosensitive composition layer) can be protected.

[0237] Examples of the protective film include a resin film and paper. From the viewpoints of strength and flexibility, a resin film is preferred.

[0238] As the resin film, for example, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film can be mentioned. Among them, as the resin film, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable, and a polyethylene terephthalate film is more preferable.

[0239] The thickness of the protective film is preferably 5 to 100 μm, more preferably 10 to 50 μm, and still more preferably 10 to 20 μm.

[0240] From the aspect of more excellent resolution, the arithmetic mean roughness Ra of the surface of the protective film on the side where the photosensitive composition layer is disposed is preferably 0.3 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less. By the arithmetic mean roughness Ra of the surface of the protective film on the side where the photosensitive composition layer is disposed being within the above range, the uniformity of the thickness of the photosensitive composition layer and the resin pattern formed is improved. The lower limit of the arithmetic mean roughness Ra is not particularly limited, and is preferably 0.001 μm or more. Regarding the arithmetic mean roughness Ra of the surface of the protective film on the side where the photosensitive composition layer is disposed, 10 portions randomly selected from the surface (the surface on the side opposite to the temporary support body) of the first layer in contact with the photosensitive composition layer are measured using New View 6000 manufactured by Zygo Corporation, and the average value excluding the minimum value and the maximum value among the obtained measurement values is set.

[0241] <Photosensitive composition layer>

[0242] The transfer film has a photosensitive composition layer disposed on the temporary support.

[0243] The photosensitive composition layer preferably contains an adhesive polymer, a polymerizable compound, and a polymerization initiator described later.

[0244] By transferring the photosensitive composition layer onto the object to be transferred and then performing exposure and development, a pattern can be formed on the object to be transferred.

[0245] As the photosensitive composition layer, it can be a positive-type photosensitive composition layer or a negative-type photosensitive composition layer. A positive-type photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer is increased by exposure. A negative-type photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer is decreased by exposure.

[0246] Among them, it is preferable to use a negative-type photosensitive composition layer. When the photosensitive composition layer is a negative-type photosensitive composition layer, the formed pattern corresponds to the protective film.

[0247] From the perspective of coatability, the thickness of the photosensitive composition layer is preferably 20.0 μm or less, more preferably 15.0 μm or less, and still more preferably 10.0 μm or less. The lower limit is not particularly limited, and is preferably 0.05 μm or more, more preferably 3.0 μm or more, still more preferably 4.0 μm or more, and particularly preferably 5.0 μm or more.

[0248] The thickness of the photosensitive composition layer is calculated as the average value of any five points measured by cross-sectional observation based on a scanning electron microscope (SEM).

[0249] The refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

[0250] The photosensitive composition layer is preferably colorless. The a * value of the photosensitive composition layer is preferably -1.0 to 1.0, and the b * value of the photosensitive composition layer is preferably -1.0 to 1.0.

[0251] The hue of the photosensitive composition layer can be measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

[0252] Hereinafter, each material constituting the photosensitive composition layer will be described.

[0253] [Binder polymer]

[0254] The photosensitive composition layer may contain a binder polymer.

[0255] Examples of the binder polymer include (meth)acrylic resins, styrene resins, epoxy resins, polyamide resins, polyamide epoxy resins, alkyd resins, phenolic resins, polyester resins, polyurethane resins, epoxy acrylate resins obtained by the reaction of an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of an epoxy acrylate resin with an acid anhydride.

[0256] As one preferred form of the binder polymer, from the aspect of excellent alkali developability and film-forming property, (meth)acrylic resins can be cited.

[0257] In addition, in this specification, the (meth)acrylic resin refers to a resin having a structural unit derived from a (meth)acrylic acid compound. The content of the structural unit derived from the (meth)acrylic acid compound is preferably 50% by mass or more, more preferably 70% by mass or more, relative to all the structural units of the (meth)acrylic resin.

[0258] (Meth)acrylic resins may be composed only of structural units derived from (meth)acrylic compounds, or may have structural units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of the structural units derived from (meth)acrylic compounds is preferably 100% by mass or less relative to all the structural units of the (meth)acrylic resin.

[0259] Examples of the (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylic esters, (meth)acrylamides, and (meth)acrylonitrile.

[0260] Examples of the (meth)acrylic esters include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred.

[0261] Examples of the (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0262] The alkyl group of the alkyl (meth)acrylate may be linear or branched. Specific examples include alkyl (meth)acrylates having an alkyl group with 1 to 12 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

[0263] As the (meth)acrylic ester, an alkyl (meth)acrylate having an alkyl group with 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0264] (Meth)acrylic resins may have structural units other than those derived from (meth)acrylic compounds.

[0265] As the polymerizable monomer for forming the above structural unit, there is no particular limitation as long as it is a compound other than the (meth)acrylic acid compound that can copolymerize with the (meth)acrylic acid compound. For example, styrene compounds that may have substituents at the α-position or on the aromatic ring such as styrene, vinyltoluene, and α-methylstyrene, vinyl esters such as acrylonitrile and vinyl n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid can be cited.

[0266] These polymerizable monomers can be used singly or in combination of two or more.

[0267] Furthermore, from the viewpoint of further improving the alkali developability, the (meth)acrylic resin preferably contains a structural unit having an acid group. As the acid group, for example, a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group can be cited.

[0268] Among them, the (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably has a structural unit derived from the above (meth)acrylic acid.

[0269] From the viewpoint of excellent developability, the content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more with respect to the total mass of the (meth)acrylic resin. And there is no particular limitation on the upper limit value. From the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0270] Furthermore, the (meth)acrylic resin more preferably has a structural unit derived from the above (meth)acrylic acid alkyl ester.

[0271] The content of the structural unit derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 1 to 90% by mass, more preferably 1 to 80% by mass, and further preferably 5 to 60% by mass with respect to all the structural units of the (meth)acrylic resin.

[0272] As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid alkyl ester is preferred, and a resin composed only of a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid alkyl ester is more preferred.

[0273] Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferred.

[0274] Further, from the aspect of more excellent effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate, and preferably has both the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate.

[0275] From the aspect of more excellent effects of the present invention, the total content of the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, relative to all the structural units of the (meth)acrylic resin. The upper limit is not particularly limited, preferably 100% by mass or less, more preferably 80% by mass or less.

[0276] Further, from the aspect of more excellent effects of the present invention, the (meth)acrylic resin also preferably has at least one selected from the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate and at least one selected from the structural unit derived from acrylic acid and the structural unit derived from an alkyl acrylate.

[0277] From the aspect of more excellent effects of the present invention, the total content of the structural unit derived from methacrylic acid and the structural unit derived from an alkyl methacrylate, relative to the total content of the structural unit derived from acrylic acid and the structural unit derived from an alkyl acrylate, is preferably 60 / 40 to 80 / 20 in terms of mass ratio.

[0278] From the aspect of excellent developability of the photosensitive composition layer after transfer, the (meth)acrylic resin preferably has an ester group at the terminal.

[0279] In addition, the terminal portion of the (meth)acrylic resin is composed of a site derived from a polymerization initiator used for synthesis. The (meth)acrylic resin having an ester group at the terminal is synthesized by using a polymerization initiator that generates a radical having an ester group.

[0280] Further, as another preferred form of the binder polymer, an alkali-soluble resin can be cited.

[0281] In addition, in the present invention, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more.

[0282] For example, from the aspect of developability, the binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more.

[0283] Further, for example, in terms of easily forming a firm film by heat-crosslinking with a crosslinking component through heating, the adhesive polymer is more preferably a resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing resin), and still more preferably a (meth)acrylic resin having a carboxyl group with an acid value of 60 mgKOH / g or more (so-called carboxyl group-containing (meth)acrylic resin).

[0284] When the adhesive polymer is a resin having a carboxyl group, for example, a thermosetting compound such as a blocked isocyanate compound is added for thermosetting, whereby the three-dimensional crosslinking density can be increased. Further, if the carboxyl group of the resin having a carboxyl group is dehydrated to be hydrophobized, the moisture and heat resistance can be improved.

[0285] As the carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more, as long as the above acid value conditions are satisfied, there is no particular limitation, and it can be appropriately selected from known (meth)acrylic resins.

[0286] For example, it is possible to preferably use a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph

[0025] of Japanese Patent Application Laid-Open No. 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs

[0033] to

[0052] of Japanese Patent Application Laid-Open No. 2010-237589, and the like.

[0287] As another preferred form of the adhesive polymer, a styrene-acrylic copolymer can be cited.

[0288] In addition, in the present invention, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound. The total content of the above structural unit derived from a styrene compound and the above structural unit derived from a (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, relative to all the structural units of the above copolymer. The lower limit is not particularly limited, and preferably 100% by mass or less.

[0289] Further, the content of the structural unit derived from a styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 5 to 80% by mass, relative to all the structural units of the above copolymer.

[0290] Further, the content of the structural unit derived from a (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20 to 95% by mass, relative to all the structural units of the above copolymer.

[0291] In terms of more excellent effects of the present invention, the adhesive polymer preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

[0292] As the monomer for forming the structural unit having an aromatic ring structure, monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.) can be cited. Among them, monomers having an aralkyl group or styrene are preferred.

[0293] As the aralkyl group, substituted or unsubstituted phenylalkyl (except benzyl) and substituted or unsubstituted benzyl, etc. can be cited, and substituted or unsubstituted benzyl is preferred.

[0294] As the monomer having a phenylalkyl group, phenethyl (meth)acrylate, etc. can be cited.

[0295] As the monomer having a benzyl group, (meth)acrylate having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol, etc. Among them, benzyl (meth)acrylate is preferred.

[0296] Furthermore, in terms of more excellent effects of the present invention, the adhesive polymer more preferably has a structural unit (structural unit derived from styrene) represented by the following formula (S).

[0297] [Chemical formula 1]

[0298]

[0299] When the adhesive polymer contains a structural unit having an aromatic ring structure, in terms of more excellent effects of the present invention, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and further preferably 20 to 60% by mass relative to all the structural units of the adhesive polymer.

[0300] Moreover, in terms of more excellent effects of the present invention, the content of the structural unit having an aromatic ring structure in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and further preferably 20 to 60 mol% relative to all the structural units of the adhesive polymer.

[0301] In addition, in terms of more excellent effects of the present invention, the content of the structural unit represented by the above formula (S) in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and further preferably 20 to 60 mol% relative to all the structural units of the adhesive polymer.

[0302] In addition, in the present invention, when the content of the "structural unit" is specified by a molar ratio, the meaning of the above "structural unit" is the same as that of the "monomer unit". Also, in the present invention, the above "monomer unit" can be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0303] From the aspect of more excellent effects of the present invention, the adhesive polymer preferably has a monocyclic aliphatic hydrocarbon ring structure or a polycyclic aliphatic hydrocarbon ring structure. That is, the adhesive polymer preferably contains a structural unit having a monocyclic or polycyclic aliphatic hydrocarbon ring structure. Among them, the adhesive polymer more preferably has a polycyclic aliphatic hydrocarbon ring structure, and further preferably has a ring structure formed by condensation of two or more aliphatic hydrocarbon rings.

[0304] As the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure, a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isophorone ring can be cited.

[0305] Among them, from the aspect of more excellent effects of the present invention, a ring formed by condensation of two or more aliphatic hydrocarbon rings is preferred, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 2，6 decane ring) is more preferred.

[0306] As the monomer for forming the structural unit having an aliphatic hydrocarbon ring structure, dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate can be cited.

[0307] Also, from the aspect of more excellent effects of the present invention, the adhesive polymer more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0308] [Chemical formula 2]

[0309]

[0310] In formula (Cy), R M represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure. Also, as the aliphatic hydrocarbon ring structure in R Cy of formula (Cy), it can be a monocyclic aliphatic hydrocarbon ring structure or a polycyclic aliphatic hydrocarbon ring structure.

[0311] R M in formula (Cy) is preferably a methyl group.

[0312] From the aspect of more excellent effects of the present invention, R CyPreferably a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms.

[0313] And, as R in formula (Cy) Cy Regarding the aliphatic hydrocarbon ring structure in, from the aspect of more excellent effects of the present invention, a monocyclic aliphatic hydrocarbon ring structure such as a cyclopentane ring structure, a cyclohexane ring structure or an isophorone ring structure, or a polycyclic aliphatic hydrocarbon ring structure such as a tetrahydrodicyclopentadiene ring structure or a norbornane ring structure is preferred, a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure is more preferred, and a tetrahydrodicyclopentadiene ring structure is still more preferred.

[0314] Moreover, from the aspect of more excellent effects of the present invention, R in formula (Cy) Cy Regarding the aliphatic hydrocarbon ring structure in, a polycyclic aliphatic hydrocarbon ring is preferred, a ring structure formed by condensing 2 or more aliphatic hydrocarbon rings is more preferred, and a ring formed by condensing 2 to 4 aliphatic hydrocarbon rings is still more preferred.

[0315] Moreover, from the aspect of more excellent effects of the present invention, R in formula (Cy) Cy is preferably an aliphatic hydrocarbon ring group in which the oxygen atom of -C(=O)O- in formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure (which may be monocyclic or polycyclic), more preferably a cyclohexyl group or a dicyclopentyl group, and still more preferably a dicyclopentyl group.

[0316] The adhesive polymer may have 1 type of structural unit having an aliphatic hydrocarbon ring structure alone, or may have 2 or more types.

[0317] When the adhesive polymer contains a structural unit having an aliphatic hydrocarbon ring structure, from the aspect of more excellent effects of the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass relative to all the structural units of the adhesive polymer.

[0318] And, from the aspect of more excellent effects of the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 60 mol% relative to all the structural units of the adhesive polymer.

[0319] Moreover, from the aspect of more excellent effects of the present invention, the content of the structural unit represented by the above formula (Cy) in the adhesive polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 60 mol% relative to all the structural units of the adhesive polymer.

[0320] When the binder polymer contains a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, from the aspect of more excellent effects of the present invention, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 30 to 75% by mass with respect to all the structural units of the binder polymer.

[0321] Moreover, from the aspect of more excellent effects of the present invention, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and further preferably 30 to 60 mol% with respect to all the structural units of the binder polymer.

[0322] Furthermore, from the aspect of more excellent effects of the present invention, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and further preferably 30 to 60 mol% with respect to all the structural units of the binder polymer.

[0323] Moreover, from the aspect of more excellent effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and further preferably satisfy the following formula (SCy-2).

[0324] 0.20 ≤ nS / (nS + nCy) ≤ 0.80 Formula (SCy)

[0325] 0.30 ≤ nS / (nS + nCy) ≤ 0.75 Formula (SCy-1)

[0326] 0.40 ≤ nS / (nS + nCy) ≤ 0.70 Formula (SCy-2)

[0327] From the aspect of more excellent effects of the present invention, the binder polymer preferably contains a structural unit having an acid group.

[0328] Examples of the above acid group include a carboxyl group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxyl group is preferred.

[0329] As the above structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0330] [Chemical formula 3]

[0331]

[0332] The binder polymer may contain one structural unit having an acid group alone, or may contain two or more.

[0333] When the binder polymer contains a structural unit having an acid group, from the aspect that the effects of the present invention are more excellent, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass relative to all the structural units of the binder polymer.

[0334] Moreover, from the aspect that the effects of the present invention are more excellent, the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and further preferably 15 to 40 mol% relative to all the structural units of the binder polymer.

[0335] Furthermore, from the aspect that the effects of the present invention are more excellent, the content of the structural unit derived from (meth)acrylic acid in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and further preferably 15 to 40 mol% relative to all the structural units of the binder polymer.

[0336] From the aspect that the effects of the present invention are more excellent, the binder polymer preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

[0337] As the reactive group, a radical polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. Moreover, when the binder polymer has an ethylenically unsaturated group, the binder polymer preferably contains a structural unit having an ethylenically unsaturated group in the side chain.

[0338] In the present invention, the "main chain" means the relatively longest bonding chain in the molecule of the high molecular compound constituting the resin, and the "side chain" means an atomic group branched from the main chain.

[0339] As the ethylenically unsaturated group, a (meth)acryloyl group is preferred, and a (meth)acryloyloxy group is more preferred.

[0340] As an example of the structural unit having a reactive group, the following examples are shown, but are not limited thereto.

[0341] [Chemical formula 4]

[0342]

[0343] The binder polymer may contain one structural unit having a reactive group alone, or may contain two or more.

[0344] When the binder polymer contains structural units having reactive groups, from the aspect of more excellent effects of the present invention, the content of the structural units having reactive groups is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass with respect to all the structural units of the binder polymer.

[0345] Moreover, from the aspect of more excellent effects of the present invention, the content of the structural units having reactive groups in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% with respect to all the structural units of the binder polymer.

[0346] As a method for introducing a reactive group into the binder polymer, methods of reacting a compound such as an epoxide compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a hydroxymethyl compound, and a carboxylic anhydride with a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group can be mentioned.

[0347] As a preferred example of the method for introducing a reactive group into the binder polymer, the following method can be mentioned: after synthesizing a polymer having a carboxyl group by a polymerization reaction, a part of the carboxyl groups of the obtained polymer is reacted with glycidyl (meth)acrylate by a polymer reaction, whereby a (meth)acryloyloxy group is introduced into the polymer. By this method, a binder polymer having a (meth)acryloyloxy group in the side chain can be obtained.

[0348] The above polymerization reaction is preferably carried out under a temperature condition of 70 to 100°C, more preferably under a temperature condition of 80 to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred. For example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferred. The above polymer reaction is preferably carried out under a temperature condition of 80 to 110°C. In the above polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0349] As the binder polymer, from the aspect of more excellent effects of the present invention, the following polymers are preferred. In addition, the content ratios (a to d) of the respective structural units shown below, the weight average molecular weight Mw, etc. can be appropriately changed according to the purpose.

[0350] The content ratio a of each structural unit shown below is preferably 20 to 60% by mass relative to all the structural units of the following binder polymer. b is preferably 10 to 50% by mass relative to all the structural units of the following binder polymer. c is preferably 5.0 to 25% by mass relative to all the structural units of the following binder polymer. d is preferably 10 to 50% by mass relative to all the structural units of the following binder polymer.

[0351] [Chemical formula 5]

[0352]

[0353] The content ratio a of each structural unit shown below is preferably 20 to 60% by mass relative to all the structural units of the following binder polymer. b is preferably 10 to 50% by mass relative to all the structural units of the following binder polymer. c is preferably 5.0 to 25% by mass relative to all the structural units of the following binder polymer. d is preferably 10 to 50% by mass relative to all the structural units of the following binder polymer.

[0354] [Chemical formula 6]

[0355]

[0356] The content ratio a of each structural unit shown below is preferably 30 to 65% by mass relative to all the structural units of the following binder polymer. b is preferably 1.0 to 20% by mass relative to all the structural units of the following binder polymer. c is preferably 5.0 to 25% by mass relative to all the structural units of the following binder polymer. d is preferably 10 to 50% by mass relative to all the structural units of the following binder polymer.

[0357] [Chemical formula 7]

[0358]

[0359] The content ratio a of each structural unit shown below is preferably 1.0 to 20% by mass relative to all the structural units of the following binder polymer. b is preferably 20 to 60% by mass relative to all the structural units of the following binder polymer. c is preferably 5.0 to 25% by mass relative to all the structural units of the following binder polymer. d is preferably 10 to 50% by mass relative to all the structural units of the following binder polymer.

[0360] [Chemical formula 8]

[0361]

[0362] Further, the binder polymer may contain a polymer (hereinafter, also referred to as "polymer X") that contains a structural unit having a carboxylic anhydride structure.

[0363] The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, preferably a cyclic carboxylic anhydride structure.

[0364] As the ring of the cyclic carboxylic anhydride structure, a 5- to 7-membered ring is preferred, a 5- or 6-membered ring is more preferred, and a 5-membered ring is further preferred.

[0365] The structural unit having a carboxylic anhydride structure is preferably a structural unit that contains a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain or a structural unit in which a monovalent group obtained by removing one hydrogen atom from the compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0366] [Chemical formula 9]

[0367]

[0368] In formula P-1, R A1a represents a substituent, and n 1a R A1a may be the same or different, Z 1a represents a divalent group that forms a ring containing -C(=O)-O-C(=O)-, and n 1a represents an integer of 0 or more.

[0369] Examples of the substituent represented by R A1a include an alkyl group.

[0370] As Z 1a , an alkylene group having 2 to 4 carbon atoms is preferred, an alkylene group having 2 or 3 carbon atoms is more preferred, and an alkylene group having 2 carbon atoms is further preferred.

[0371] n 1a represents an integer of 0 or more. When Z 1a represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and further preferably 0.

[0372] n 1a represents an integer of 2 or more, and multiple R A1a may be the same or different. Also, multiple R A1a may bond to each other to form a ring, but preferably do not bond to each other to form a ring.

[0373] As a structural unit having a carboxylic anhydride structure, a structural unit derived from an unsaturated carboxylic anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride is further preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0374] Hereinafter, specific examples of the structural unit having a carboxylic anhydride structure are given, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0375] [Chemical formula 10]

[0376]

[0377] [Chemical formula 11]

[0378]

[0379] The structural unit having a carboxylic anhydride structure in polymer X may be a single type or two or more types.

[0380] The total content of the structural unit having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, further preferably 10 to 35 mol% relative to all the structural units of polymer X.

[0381] The photosensitive composition layer may contain only one type of polymer X or two or more types.

[0382] When the photosensitive composition layer contains polymer X, from the aspect of more excellent effects of the present invention, the content of polymer X is preferably 0.10 to 30.00% by mass, more preferably 0.20 to 20.00% by mass, further preferably 0.20 to 5.00% by mass, and particularly preferably 0.50 to 1.50% by mass relative to the total mass of the photosensitive composition layer.

[0383] From the aspect of more excellent effects of the present invention, the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 10,000 to 30,000.

[0384] From the aspect of reducing development residues, the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the binder polymer is preferably 1.0 to 3.0, more preferably 2.0 to 3.0.

[0385] The acid value of the binder polymer is preferably from 10 to 200 mgKOH / g, more preferably from 60 to 200 mgKOH / g, still more preferably from 60 to 150 mgKOH / g, and particularly preferably from 60 to 110 mgKOH / g.

[0386] The acid value of the binder polymer is the value measured by the method described in JIS K0070:1992.

[0387] As the binder polymer, polymer A is also preferred.

[0388] When the binder polymer is polymer A, the photosensitive composition layer is preferably a negative photosensitive composition layer.

[0389] Polymer A is preferably an alkali-soluble resin.

[0390] From the viewpoint of more excellent resolution by suppressing the swelling of the photosensitive composition layer caused by the developer, the acid value of polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, still more preferably less than 190 mgKOH / g.

[0391] The lower limit of the acid value of polymer A is not particularly limited. From the viewpoint of more excellent developability, it is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, still more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more.

[0392] In addition, the acid value (mgKOH / g) means the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be calculated, for example, from the average content of acid groups in the compound.

[0393] The acid value of polymer A can be adjusted according to the types of structural units constituting polymer A and the content of structural units containing acid groups.

[0394] The weight-average molecular weight of Polymer A is preferably from 5,000 to 500,000. When the weight-average molecular weight is 500,000 or less, it is preferred from the viewpoints of improving resolution and developability. The weight-average molecular weight is more preferably 100,000 or less, and further preferably 60,000 or less. On the other hand, when the weight-average molecular weight is 5,000 or more, it is preferred from the viewpoints of controlling the properties of development aggregates and the properties of the unexposed film such as edge meltability and chippability when it is a negative photosensitive resin laminate. The weight-average molecular weight is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. Edge meltability means the ease of exudation of the photosensitive composition layer from the end face of the roll when the negative photosensitive resin laminate is wound in a roll. Chippability means the degree of easy scattering of chips when the unexposed film is cut with a knife. If such chips adhere to the upper surface of the negative photosensitive resin laminate, etc., it may be transferred to the mask in subsequent exposure processes, etc., and cause defective products. The dispersity of Polymer A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, further preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0395] In the photosensitive composition layer, from the viewpoint of suppressing the broadening of the line width or the decrease in resolution when the focus position deviates during exposure, Polymer A preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group. In addition, as such an aromatic hydrocarbon group, for example, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group can be mentioned. The content of the structural unit based on the monomer having an aromatic hydrocarbon group in Polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of Polymer A. As the upper limit, there is no particular limitation, and it is preferably 95% by mass or less, more preferably 85% by mass or less, based on the total mass of Polymer A. In addition, when a plurality of Polymer A are contained, the average value of the content of the structural unit based on the monomer having an aromatic hydrocarbon group is preferably within the above range.

[0396] As the monomer having an aromatic hydrocarbon group, for example, a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.) can be mentioned. Among them, a monomer having an aralkyl group or styrene is preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in Polymer A is styrene, the content of the structural unit based on styrene is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, further preferably 30 to 60% by mass, and particularly preferably 30 to 55% by mass, based on the total mass of Polymer A.

[0397] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl) and substituted or unsubstituted benzyl groups, etc., and substituted or unsubstituted benzyl groups are preferred.

[0398] Examples of the monomer having a phenylalkyl group include phenethyl (meth)acrylate.

[0399] Examples of the monomer having a benzyl group include benzyl group-containing (meth)acrylates, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Among them, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the structural unit based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, further preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, relative to the total mass of polymer A.

[0400] Polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one of the following-described first monomers and / or at least one of the following-described second monomers.

[0401] Polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the following-described first monomers, and more preferably by copolymerizing at least one first monomer with at least one of the following-described second monomers.

[0402] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half-ester. Among these, (meth)acrylic acid is preferred.

[0403] The content of the structural unit based on the first monomer in polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 10 to 30% by mass, relative to the total mass of polymer A.

[0404] From the viewpoints of showing good developability and controlling edge melting properties, etc., it is preferred to set the above content to 5% by mass or more. From the viewpoints of the high resolution and tailing shape of the resist pattern, and the chemical resistance of the resist pattern, it is preferred to set the above content to 50% by mass or less.

[0405] The second monomer is a non-acidic monomer having at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred.

[0406] The content of the structural unit based on the second monomer in Polymer A is preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and further preferably 20 to 45% by mass, relative to the total mass of Polymer A.

[0407] When Polymer A contains a structural unit based on a monomer having an aralkyl group and / or a structural unit based on a styrene monomer, it is preferred from the viewpoint of suppressing the thickening of the line width or the reduction in resolution when the focal position deviates during exposure. For example, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, etc. are preferred.

[0408] In one embodiment, Polymer A is preferably a polymer containing 25 to 55% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of a structural unit based on the first monomer, and 15 to 45% by mass of a structural unit based on the second monomer. And in another embodiment, it is preferably a polymer containing 70 to 90% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit based on the first monomer.

[0409] Polymer A may have a branched structure and / or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of Polymer A.

[0410] Specific examples of the monomer containing a group having a branched structure in the side chain include, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

[0411] As specific examples of the monomer containing a group having an alicyclic structure in the side chain, monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group can be cited. Further, (meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms can be cited. As more specific examples, (bicyclo[2.2.1]heptan-2-yl)-(meth)acrylate, 1-adamantyl-(meth)acrylate, 2-adamantyl-(meth)acrylate, 3-methyl-1-adamantyl-(meth)acrylate, 3,5-dimethyl-1-adamantyl-(meth)acrylate, 3-ethyladamantyl-(meth)acrylate, 3-methyl-5-ethyl-1-adamantyl-(meth)acrylate, 3,5,8-triethyl-1-adamantyl-(meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl-(meth)acrylate, 2-methyl-2-adamantyl-(meth)acrylate, 2-ethyl-2-adamantyl-(meth)acrylate, 3-hydroxy-1-adamantyl-(meth)acrylate, octahydro-4,7-mentanoinden-5-yl-(meth)acrylate, octahydro-4,7-mentanoinden-1-ylmethyl-(meth)acrylate, 1-menthyl-(meth)acrylate, tricyclodecyl (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl-(meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl-(meth)acrylate, (meth)acrylate (norbornene), isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate can be cited. Among these (meth)acrylates, cyclohexyl (meth)acrylate, (meth)acrylate (norbornene), isobornyl (meth)acrylate, 1-adamantyl-(meth)acrylate, 2-adamantyl-(meth)acrylate, fenchyl (meth)acrylate, 1-menthyl-(meth)acrylate, or tricyclodecyl (meth)acrylate is preferable, and cyclohexyl (meth)acrylate, (meth)acrylate (norbornene), isobornyl (meth)acrylate, 2-adamantyl-(meth)acrylate, or tricyclodecyl (meth)acrylate is more preferable.

[0412] Polymer A can be used alone as one kind, or two or more kinds can be used.

[0413] When using two or more kinds, it is preferred to use two kinds of polymer A containing structural units based on monomers having an aromatic hydrocarbon group in combination, or to use polymer A containing structural units based on monomers having an aromatic hydrocarbon group and polymer A not containing structural units based on monomers having an aromatic hydrocarbon group in combination. In the latter case, the proportion of polymer A containing structural units based on monomers having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of polymer A. The upper limit is not particularly limited and is preferably 100% by mass or less.

[0414] The synthesis of polymer A is preferably carried out by the following method: In a solution obtained by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone, and isopropyl alcohol, an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile is added and heated with stirring. Sometimes, a part of the mixture is dropped into the reaction solution while carrying out the synthesis. Sometimes, after the reaction is completed, a solvent is further added to adjust to a desired concentration. As the synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

[0415] The glass transition temperature Tg of polymer A is preferably 30 to 135 °C. By using polymer A having a Tg of 135 °C or lower, it is possible to suppress the broadening of the line width or the reduction in resolution when the focus position deviates during exposure. From this viewpoint, the Tg of polymer A is more preferably 130 °C or lower, further preferably 120 °C or lower, and particularly preferably 110 °C or lower. Also, from the viewpoint of improving the edge melting resistance, it is preferred to use polymer A having a Tg of 30 °C or higher. From this viewpoint, the Tg of polymer A is more preferably 40 °C or higher, further preferably 50 °C or higher, particularly preferably 60 °C or higher, and most preferably 70 °C or higher.

[0416] The photosensitive composition layer may contain other resins other than the above as polymer A.

[0417] Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0418] The photosensitive composition layer may contain only one kind of binder polymer or may contain two or more kinds.

[0419] From the aspect of more excellent effects of the present invention, the content of the binder polymer is preferably 10.00 to 90.00% by mass, more preferably 30.00 to 80.00% by mass, still more preferably 40.00 to 70.00% by mass, and particularly preferably 45.00 to 60.00% by mass, based on the total mass of the photosensitive composition layer.

[0420] [Polymerization initiator]

[0421] The photosensitive composition layer may contain a polymerization initiator.

[0422] There is no particular limitation on the polymerization initiator, and known polymerization initiators can be used. As the polymerization initiator, a photoinitiator or a thermal initiator is preferred.

[0423] The polymerization initiator may also be a radical polymerization initiator or a cationic polymerization initiator.

[0424] As the polymerization initiator, for example, photoinitiators having an oxime ester structure (hereinafter also referred to as "oxime-based photoinitiators"), photoinitiators having an α-aminoalkyl phenyl ketone structure (hereinafter also referred to as "α-aminoalkyl phenyl ketone-based photoinitiators"), photoinitiators having an α-hydroxyalkyl phenyl ketone structure (hereinafter also referred to as "α-hydroxyalkyl phenyl ketone-based polymerization initiators"), photoinitiators having an acylphosphine oxide structure (hereinafter also referred to as "acylphosphine oxide-based photoinitiators"), and photoinitiators having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine-based photoinitiators") can be cited.

[0425] Furthermore, from the viewpoints of photosensitivity, visual recognition of the exposed and unexposed portions, and resolution, the photosensitive composition layer preferably contains at least one selected from 2,4,5-triaryl imidazole dimers and their derivatives as a photo radical polymerization initiator. In addition, the two 2,4,5-triaryl imidazole structures in the 2,4,5-triaryl imidazole dimers and their derivatives may be the same or different.

[0426] As derivatives of the 2,4,5-triaryl imidazole dimer, for example, 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer can be cited.

[0427] The polymerization initiator preferably contains at least one selected from oxime-based photopolymerization initiators, α-aminoalkylbenzophenone-based photopolymerization initiators, α-hydroxyalkylbenzophenone-based polymerization initiators, and N-phenylglycine-based photopolymerization initiators, more preferably contains at least one selected from oxime-based photopolymerization initiators, α-aminoalkylbenzophenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and further preferably contains at least one selected from oxime-based photopolymerization initiators and α-aminoalkylbenzophenone-based photopolymerization initiators.

[0428] Examples of the polymerization initiator also include the polymerization initiators described in paragraphs

[0031] to

[0042] of Japanese Unexamined Patent Application Publication No. 2011-95716 and paragraphs

[0064] to

[0081] of Japanese Unexamined Patent Application Publication No. 2015-014783.

[0429] As polymerization initiators, for example, 1-[4-(phenylthio)]phenyl-1,2-octanedione-2-(O-benzoyl oxime) [trade name: IRGACURE® OXE-01, manufactured by BASF Corporation], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime) [trade name: IRGACURE® OXE-02, manufactured by BASF Corporation], 8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyl oxime) [trade name: IRGACURE® OXE-03, manufactured by BASF Corporation], 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methyl-1-pentanone-1-(O-acetyl oxime) [trade name: IRGACURE® OXE-04, manufactured by BASF Corporation], oxime ester compounds [trade name: Lunar® 6, manufactured by DKSH Japan K.K.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloximino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Flectronic Materials Co., Ltd.), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, manufactured by IGM Resins B.V.], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad® 907, manufactured by IGM Resins B.V.], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad® 127, manufactured by IGM Resins B.V.2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one [trade name: Omnifad® 369, manufactured by IGM Resins B.V.], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad® 1173, manufactured by IGM Resins B.V.], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad® 184, manufactured by IGM Resins B.V.], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: Omnirad 651, manufactured by IGM Resins B.V.], 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (trade name: APi-307, manufactured by Shenzhen UV-ChemTech Ltd.).

[0430] A photo cationic polymerization initiator (photo acid generator) is a compound that accepts actinic rays to generate an acid. As the photo cationic polymerization initiator, a compound that is sensitive to actinic rays with a wavelength of 300 nm or more (preferably a wavelength of 300 to 450 nm) and generates an acid is preferred, but its chemical structure is not limited. Further, even a photo cationic polymerization initiator that is not directly sensitive to actinic rays with a wavelength of 300 nm or more can be preferably used in combination with a sensitizer as long as it is sensitive to actinic rays with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.

[0431] As the photo cationic polymerization initiator, a photo cationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photo cationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photo cationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. The lower limit value of the pKa is not particularly limited, and for example, -10.0 or more is preferred.

[0432] Examples of the photo cationic polymerization initiator include ionic photo cationic polymerization initiators and non-ionic photo cationic polymerization initiators.

[0433] Examples of the ionic photo cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0434] As the ionic photo cationic polymerization initiator, the ionic photo cationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Laid-Open No. 2014-085643 can be used.

[0435] As nonionic photo cationic polymerization initiators, for example, trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds can be mentioned. As the trichloromethyl s-triazine compounds, diazomethane compounds, and imide sulfonate compounds, the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be used. And, as the oxime sulfonate compounds, the compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 can be used.

[0436] The photosensitive composition layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from 2,4,5-triaryl imidazole dimers and their derivatives.

[0437] The polymerization initiator can be used alone or two or more kinds can be used simultaneously.

[0438] The content of the polymerization initiator in the photosensitive composition layer is not particularly limited, and is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, relative to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, and is preferably 10.00% by mass or less, more preferably 5.00% by mass or less, relative to the total mass of the photosensitive composition layer.

[0439] [Polymerizable compound]

[0440] The photosensitive composition layer may contain a polymerizable compound.

[0441] The polymerizable compound is a compound having a polymerizable group. As the polymerizable group, for example, a radical polymerizable group and a cationic polymerizable group can be mentioned, and a radical polymerizable group is preferred.

[0442] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as "ethylenically unsaturated compound").

[0443] As the ethylenically unsaturated group, (meth)acryloyloxy is preferred.

[0444] In the present specification, the ethylenically unsaturated compound is a compound other than the above binder polymer, and the molecular weight is preferably less than 5,000.

[0445] As the polymerizable compound, a compound represented by the following formula (M) (hereinafter, also simply referred to as "compound M") is preferred.

[0446] Q 2 -R 1a -Q 1 Formula (M)

[0447] In formula (M), Q 1and Q 2 each independently represents a (meth)acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.

[0448] Regarding Q in formula (M) 1 and Q 2 , in terms of ease of synthesis, Q 1 and Q 2 are preferably the same group.

[0449] Moreover, in terms of reactivity, Q in formula (M) 1 and Q 2 are preferably acryloyloxy groups.

[0450] As R in formula (M) 1a , in order to achieve more excellent effects of the present invention, an alkylene group, an alkoxyalkylene group (-L 1 -O-L 1 -), or a polyalkoxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is further preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred.

[0451] It is sufficient that at least a part of the above hydrocarbon group has a chain structure, and there is no particular limitation on the part other than the above chain structure. For example, it can be branched, cyclic, or a linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or any combination thereof. An alkylene group or a group formed by combining two or more alkylene groups with one or more arylene groups is preferred, an alkylene group is more preferred, and a linear alkylene group is further preferred.

[0452] In addition, each of the above L 1 independently represents an alkylene group, preferably a vinyl group, a propenyl group, or a butenyl group, more preferably a vinyl group or a 1,2-propenyl group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

[0453] Moreover, in order to achieve more excellent effects of the present invention, the number of atoms in the shortest connecting chain between Q 1 and Q 2 in compound M is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

[0454] In the present invention, "the number of atoms in the shortest connecting chain between Q 1 and Q 2 " means the number of atoms from R 1 connected to Q 1The atom in is connected to Q 2 connected R 1 The shortest number of atoms up to the atom in.

[0455] As the compound M, for example, 1,3 - butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, 1,7 - heptanediol di(meth)acrylate, 1,8 - octanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate can be mentioned. The above ester monomers can also be used as a mixture.

[0456] Among them, from the aspect that the effects of the present invention are more excellent, as the compound M, at least one compound selected from 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate is preferred, and at least one compound selected from 1,6 - hexanediol di(meth)acrylate, 1,9 - nonanediol di(meth)acrylate, and 1,10 - decanediol di(meth)acrylate is more preferred, and at least one compound selected from 1,9 - nonanediol di(meth)acrylate and 1,10 - decanediol di(meth)acrylate is further preferred.

[0457] And, as the polymerizable compound, an ethylenically unsaturated compound having 2 or more functional groups is preferred.

[0458] In this specification, the "ethylenically unsaturated compound having 2 or more functional groups" means a compound having 2 or more ethylenically unsaturated groups in one molecule.

[0459] As the ethylenically unsaturated group in the ethylenically unsaturated compound, (meth)acryloyl is preferred.

[0460] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0461] As the difunctional ethylenically unsaturated compound, there is no particular limitation, and it can be appropriately selected from known compounds.

[0462] As the difunctional ethylenically unsaturated compound other than the above compound M, tricyclodecane dimethanol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate can be mentioned.

[0463] Examples of commercially available difunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK ESTER A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK ESTER DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK ESTER A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK ESTER A-HD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

[0464] There are no particular restrictions on ethylenically unsaturated compounds having three or more functional groups, and they can be appropriately selected from known compounds.

[0465] Examples of ethylenically unsaturated compounds having three or more functional groups include (meth)acrylate compounds having a dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and glycerol tri(meth)acrylate skeleton.

[0466] Herein, “(tri / tetra / penta / hexa)(meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra)(meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0467] As the polymerizable compound, for example, there may also be mentioned a caprolactone-modified compound of a (meth)acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.), an alkylene oxide-modified compound of a (meth)acrylate compound (KAYARAD (registered trademark) R-604 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), and ethoxylated glycerol triacrylate (NK ESTER A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.).

[0468] As the polymerizable compound, there may also be mentioned a urethane (meth)acrylate compound [preferably a urethane (meth)acrylate compound having 3 or more functional groups].

[0469] As the urethane (meth)acrylate compound having 3 or more functional groups, for example, there may be mentioned ACRIT 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), NK ESTER UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), NK ESTER UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

[0470] Further, as the urethane (meth) acrylate, a urethane (meth) acrylate having three or more functional groups can also be mentioned. As the lower limit of the number of functional groups, 6 or more functional groups are more preferable, and 8 or more functional groups are further preferable. In addition, as the upper limit of the number of functional groups, 20 or less functional groups are preferable. As the urethane (meth) acrylate having three or more functional groups, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), U-15HA (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), AH-600 (trade name) manufactured by KYOEISHA CHEMICAL CO., LTD., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.) can be mentioned.

[0471] As the polymerizable compound, an ethylenically unsaturated compound having an acid group is preferable.

[0472] As the acid group, for example, a phosphoric acid group, a sulfo group, and a carboxyl group can be mentioned.

[0473] Among them, as the acid group, a carboxyl group is preferable.

[0474] As the ethylenically unsaturated compound having an acid group, an ethylenically unsaturated compound having an acid group with 3 to 4 functional groups [obtained by introducing a carboxyl group into the pentaerythritol tri- and tetraacrylate (PETA) skeleton (acid value: 80 to 120 mgKOH / g)] and an ethylenically unsaturated compound having an acid group with 5 to 6 functional groups [obtained by introducing a carboxyl group into the dipentaerythritol penta- and hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mgKOH / g)] can be mentioned.

[0475] These ethylenically unsaturated compounds having an acid group with three or more functional groups can also be used in combination with an ethylenically unsaturated compound having an acid group with two functional groups as needed.

[0476] As the ethylenically unsaturated compound having an acid group, at least one selected from ethylenically unsaturated compounds having a carboxyl group with two or more functional groups and their carboxylic anhydrides is preferable.

[0477] If the ethylenically unsaturated compound having an acid group is at least one selected from ethylenically unsaturated compounds having a carboxyl group with two or more functional groups and their carboxylic anhydrides, the developability and film strength are further improved.

[0478] The polyfunctional olefinically unsaturated compound having a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0479] Examples of the polyfunctional olefinically unsaturated compound having a carboxyl group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.).

[0480] As the olefinically unsaturated compound having an acid group, a polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of Japanese Patent Application Laid-Open No. 2004-239942 is preferably used, and the content described in this publication is incorporated into the present specification.

[0481] Examples of the polymerizable compound also include compounds obtained by reacting a polyol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a compound containing a glycidyl group with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid-based compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, and (meth)acrylic acid alkyl esters.

[0482] These can be used alone or in combination of two or more.

[0483] Examples of the compound obtained by reacting a polyol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene glycol polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; trimethylolpropane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane ethoxytri(meth)acrylate; trimethylolpropane diethoxytri(meth)acrylate; trimethylolpropane triethoxytri(meth)acrylate; trimethylolpropane tetraethoxytri(meth)acrylate; trimethylolpropane pentaethoxytri(meth)acrylate; di(trimethylolpropane) tetraacrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; dipentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate; and dipentaerythritol hexa(meth)acrylate.

[0484] Among them, as the above-mentioned compound, an ethylenically unsaturated compound having a pentaerythritol structure or a trimethylolpropane structure is preferred, and pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferred.

[0485] Among them, as the polymerizable compound (particularly, ethylenically unsaturated compound), from the viewpoint of excellent developability of the photosensitive composition layer after transfer, it is also preferred to contain an ester bond.

[0486] As the ethylenically unsaturated compound containing an ester bond, as long as it contains an ester bond in the molecule, there is no particular limitation. From the viewpoint of excellent effects of the present invention, an ethylenically unsaturated compound having a pentaerythritol structure or a trimethylolpropane structure is preferred, and pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane) tetraacrylate is more preferred.

[0487] From the viewpoint of imparting reliability, as the ethylenically unsaturated compound, an ethylenically unsaturated compound having an aliphatic group with 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above-mentioned pentaerythritol structure or trimethylolpropane structure are preferred.

[0488] As an ethylenically unsaturated compound having an aliphatic structure with 6 or more carbon atoms, for example, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate can be cited.

[0489] As a polymerizable compound, for example, a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound) can be cited.

[0490] As the above polymerizable compound, a polymerizable compound having a ring structure formed by condensation of 2 or more aliphatic hydrocarbon rings (preferably a structure selected from a tricyclodecane structure and a tricyclodecene structure) is preferred, a bifunctional ethylenically unsaturated compound having a ring structure formed by condensation of 2 or more aliphatic hydrocarbon rings is more preferred, and tricyclodecane dimethanol di(meth)acrylate is further preferred.

[0491] As the above aliphatic hydrocarbon ring structure, from the aspect that the effects of the present invention are more excellent, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure is preferred.

[0492] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0493] With respect to the content of all polymerizable compounds contained in the photosensitive composition layer, the proportion of the content of the polymerizable compound having a molecular weight of 300 or less in the polymerizable compounds contained in the photosensitive composition layer is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

[0494] The lower limit of the proportion of the content of the polymerizable compound having a molecular weight of 300 or less is not particularly limited, and preferably 1.0% by mass or more.

[0495] The photosensitive composition layer preferably contains an ethylenically unsaturated compound having 2 or more functional groups, more preferably contains an ethylenically unsaturated compound having 3 or more functional groups, and further preferably contains a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0496] The photosensitive composition layer also preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an adhesive polymer containing a structural unit having an aliphatic hydrocarbon ring.

[0497] Further, the photosensitive composition layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxyl group, and still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0498] The photosensitive composition layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

[0499] The photosensitive composition layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a polyfunctional ethylenically unsaturated compound having three or more functional groups (preferably a polyfunctional (meth)acrylate compound having three or more functional groups).

[0500] In consideration of rust prevention properties, the photosensitive composition layer preferably contains compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure.

[0501] Further, in consideration of adhesion, suppression of development residues, and rust prevention properties, the photosensitive composition layer preferably contains compound M and an ethylenically unsaturated compound having an acid group, more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, still more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a polyfunctional ethylenically unsaturated compound having three or more functional groups, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a polyfunctional ethylenically unsaturated compound having three or more functional groups, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound.

[0502] Further, in consideration of adhesion, suppression of development residues, and rust prevention properties, the photosensitive composition layer preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxyl group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxyl group, still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate (A-DPH), and an ethylenically unsaturated compound having a carboxyl group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxyl group, and a urethane acrylate compound.

[0503] The photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0504] The content of the ethylenically unsaturated compound having two or more functional groups among the above-mentioned ethylenically unsaturated compounds is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass, relative to the total content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0505] (Polymerizable compound B1)

[0506] The photosensitive composition layer preferably further contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. Among the above-mentioned polymerizable compounds B, the polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule.

[0507] From the viewpoint of more excellent resolution, the proportion of the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds in the photosensitive composition layer is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit is not particularly limited, and from the viewpoint of peelability, it is preferably 100% by mass or less, more preferably 99% by mass or less, further preferably 95% by mass or less, particularly preferably 90% by mass or less, and most preferably 85% by mass or less.

[0508] Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocycles such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and their condensed rings. An aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred. In addition, the above-mentioned aromatic ring may have a substituent.

[0509] The polymerizable compound B1 may have only one aromatic ring or may have two or more aromatic rings.

[0510] From the viewpoint of improving the resolution by suppressing the swelling of the photosensitive composition layer caused by the developer, the polymerizable compound B1 preferably has a bisphenol structure.

[0511] Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). A bisphenol A structure is preferred.

[0512] As the polymerizable compound B1 having a bisphenol structure, for example, a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure can be mentioned.

[0513] Both ends of the bisphenol structure and the two polymerizable groups can be directly bonded or bonded through one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, ethenyloxy or propenyloxy is preferred, and ethenyloxy is more preferred. The number of added alkyleneoxy groups to the bisphenol structure is not particularly limited, and preferably 4 to 16 per molecule, more preferably 6 to 14.

[0514] Regarding the polymerizable compound B1 having a bisphenol structure, it is described in paragraphs

[0072] to

[0080] of Japanese Patent Laid-Open No. 2016-224162, and the content described in this publication is incorporated into this specification.

[0515] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0516] Examples of 2,2-bis(4-((meth)acryloxypolyalkoxyl)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), EO-modified bisphenol A dimethacrylate (FA-321M, manufactured by Hitachi Chemical Co., Ltd.), ethoxylated bisphenol A dimethacrylate (BPE-80N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), nonylphenoxypolyethylene glycol acrylate (FA-318AS, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ESTER A-BPE-10, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

[0517] As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0518] [Chemical formula 12]

[0519]

[0520] In the general formula B1, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 are each independently an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the structural units of -(A-O)- and -(B-O)- may be random or block. Moreover, in the case of a block, either -(A-O)- or -(B-O)- may be on the biphenyl side.

[0521] In one mode, n1 + n2 + n3 + n4 is preferably 2 to 20, more preferably 2 to 16, still more preferably 4 to 12. Further, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.

[0522] The polymerizable compound B1 can be used alone as one kind, or two or more kinds can be used.

[0523] From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, and from the viewpoints of transferability and edge melting (a phenomenon in which the photosensitive resin oozes out from the end of the transfer member), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0524] The polymerizable compound (especially, an ethylenically unsaturated compound) can be used alone as one kind, or two or more kinds can be used simultaneously.

[0525] The content of the polymerizable compound (especially, an ethylenically unsaturated compound) in the photosensitive composition layer is preferably 1.00 to 70.00% by mass, more preferably 10.00 to 70.00% by mass, still more preferably 15.0 to 50.0% by mass, and particularly preferably 20.0 to 40.0% by mass, relative to the total mass of the photosensitive composition layer.

[0526] [Heterocyclic compound]

[0527] The photosensitive composition layer may contain a heterocyclic compound.

[0528] The heterocycle possessed by the heterocyclic compound can be either a monocyclic or polycyclic heterocycle.

[0529] Examples of the heteroatom possessed by the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0530] Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, a pyrimidine, and a pyridine compound.

[0531] Among them, as the heterocyclic compound, it is preferably at least one compound selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyridine compounds, and more preferably at least one compound selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0532] The following shows preferred specific examples of the heterocyclic compound.

[0533] As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[0534] [Chemical formula 13]

[0535]

[0536] [Chemical formula 14]

[0537]

[0538] As the tetrazole compound, the following compounds can be exemplified.

[0539] [Chemical formula 15]

[0540]

[0541] [Chemical formula 16]

[0542]

[0543] As the thiadiazole compound, the following compounds can be exemplified.

[0544] [Chemical formula 17]

[0545]

[0546] As the triazine compound, the following compounds can be exemplified.

[0547] [Chemical formula 18]

[0548]

[0549] As the rhodanine compound, the following compounds can be exemplified.

[0550] [Chemical formula 19]

[0551]

[0552] As the thiazole compound, the following compounds can be exemplified.

[0553] [Chemical formula 20]

[0554]

[0555] As a benzothiazole compound, the following compounds can be exemplified.

[0556] [Chemical formula 21]

[0557]

[0558] As a benzimidazole compound, the following compounds can be exemplified.

[0559] [Chemical formula 22]

[0560]

[0561] [Chemical formula 23]

[0562]

[0563] As a benzoxazole compound, the following compounds can be exemplified.

[0564] [Chemical formula 24]

[0565]

[0566] As a pyridine compound, for example, (iso)nicotinic acid and (iso)nicotinamide can be cited.

[0567] The photosensitive composition layer may contain a single heterocyclic compound or two or more heterocyclic compounds.

[0568] When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.00% by mass, more preferably 0.10 to 10.00% by mass, still more preferably 0.10 to 5.00% by mass, and particularly preferably 0.10 to 1.00% by mass, based on the total mass of the photosensitive composition layer.

[0569] [Aliphatic thiol compound]

[0570] The photosensitive composition layer may contain an aliphatic thiol compound.

[0571] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having two or more functional groups) is preferred, and a polyfunctional aliphatic thiol compound is more preferred in terms of the adhesion of the formed pattern (especially, the adhesion after exposure).

[0572] In this specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0573] The molecular weight of the polyfunctional aliphatic thiol compound is preferably 100 or more, more preferably 100 to 1,500, and still more preferably 150 to 1,000.

[0574] As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, from the viewpoint of the adhesion of the formed pattern, it is preferably 2 to 10 functional groups, more preferably 2 to 8 functional groups, and still more preferably 2 to 6 functional groups.

[0575] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetra(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol bisthioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethyl mercaptan, meso-2,3-dimercaptosuccinic acid, and bis(mercaptoethyl) ether.

[0576] Among them, as the polyfunctional aliphatic thiol compound, at least one compound selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.

[0577] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0578] The photosensitive composition layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds.

[0579] When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, further preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, based on the total mass of the photosensitive composition layer.

[0580] [Thermally crosslinkable compound]

[0581] In view of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive composition layer preferably contains a thermally crosslinkable compound.

[0582] In addition, in the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is regarded as a thermally crosslinkable compound and not as an ethylenically unsaturated compound.

[0583] Moreover, the thermally crosslinkable compound is a compound different from the components (such as binder polymer, polymerization initiator, and polymerizable compound) contained in the above-mentioned photosensitive composition layer.

[0584] Examples of the thermally crosslinkable compound include an epoxy compound, an oxetane compound, a hydroxymethyl compound, and a blocked isocyanate compound.

[0585] Among them, in view of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, a blocked isocyanate compound is preferred.

[0586] Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when at least one of the binder polymer and the radical polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, there is a tendency that the hydrophilicity of the formed film decreases and the function as a protective film is enhanced.

[0587] In addition, the blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so-called masked) by a blocking agent".

[0588] (First blocked isocyanate compound)

[0589] The blocked isocyanate compound preferably contains a blocked isocyanate compound having a blocked isocyanate equivalent (hereinafter, also referred to as "NCO value") of 4.5 mmol / g or more (hereinafter, also referred to as "first blocked isocyanate compound"). Thereby, the bending resistance is more excellent, and the corrosion of the conductive layer can also be suppressed.

[0590] The NCO value of the first blocked isocyanate compound is 4.5 mmol / g or more, and from the aspect that the effects of the present invention are more excellent, it is more preferably 5.0 mmol / g or more, and further preferably 5.3 mmol / g or more.

[0591] From the aspect of more excellent effects of the present invention, the upper limit value of the NCO value of the first blocked isocyanate compound is preferably 6.0 mmol / g or less, more preferably less than 5.8 mmol / g, and further preferably 5.7 mmol / g or less.

[0592] The NCO value of the blocked isocyanate compound in the present invention refers to the number of millimoles of the blocked isocyanate group contained in 1 g of the blocked isocyanate compound, and can be calculated by the following formula.

[0593] Formula: NCO value of the blocked isocyanate compound = 1000×(number of blocked isocyanate groups contained in the molecule) / (molecular weight of the blocked isocyanate compound)

[0594] As the dissociation temperature of the first blocked isocyanate compound, it is preferably 100 to 160 °C, more preferably 110 to 150 °C.

[0595] In the present specification, the "dissociation temperature of the blocked isocyanate compound" refers to the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound when analyzed and measured by a differential scanning calorimeter through DSC (Differential Scanning Calorimetry). There is no particular limitation on the differential scanning calorimeter. For example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used.

[0596] As the blocking agent having a dissociation temperature of 100 to 160 °C, for example, active methylene compounds [(malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)) etc.], and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc., compounds having a structure represented by -C(=N-OH)- in the molecule) can be cited. Among the above, as the blocking agent having a dissociation temperature of 100 to 160 °C, from the aspect of storage stability, an oxime compound is preferred.

[0597] From the aspect of more excellent effects of the present invention, the first blocked isocyanate compound preferably has a ring structure. As the ring structure, an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring can be cited. From the aspect of more excellent effects of the present invention, an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring are preferred, and an aliphatic hydrocarbon ring is more preferred.

[0598] Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, and a cyclohexane ring is preferred.

[0599] Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and a benzene ring is preferred.

[0600] As a specific example of the heterocycle, an isocyanurate ring can be cited.

[0601] When the first blocked isocyanate compound has a ring structure, from the aspect that the effects of the present invention are more excellent, the number of rings is preferably 1 to 2, more preferably 1. In addition, when the first blocked isocyanate compound contains a fused ring, the number of rings constituting the fused ring is counted. For example, the number of rings in a naphthalene ring is counted as 2.

[0602] From the aspect that the strength of the formed pattern is excellent and the effects of the present invention are more excellent, the number of blocked isocyanate groups possessed by the first blocked isocyanate compound is preferably 2 to 5, more preferably 2 to 3, and further preferably 2.

[0603] From the aspect that the effects of the present invention are more excellent, the first blocked isocyanate compound is preferably a blocked isocyanate compound represented by formula Q.

[0604] B 1 -A 1 -L 1 -A 2 -B 2 Formula Q

[0605] In formula Q, B 1 and B 2 each independently represents a blocked isocyanate group.

[0606] As the blocked isocyanate group, there is no particular limitation. From the aspect that the effects of the present invention are more excellent, it is preferably a group in which the isocyanate group is blocked by an oxime compound, and more preferably a group in which the isocyanate group is blocked by methyl ethyl ketoxime (specifically, a group represented by *-NH-C(=O)-O-N=C(CH3)-C2H5. * represents the bonding position to A 1 or A 2 .).

[0607] B 1 and B 2 are preferably groups having the same structure.

[0608] In formula Q, A 1 and A 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.

[0609] The alkylene group can be linear, branched or cyclic, and is preferably linear.

[0610] The number of carbon atoms of the alkylene group is 1 to 10. From the aspect that the effects of the present invention are more excellent, it is preferably 1 to 5, more preferably 1 to 3, and further preferably 1.

[0611] A 1and A 2 Groups that are preferably of the same structure.

[0612] In formula Q, L 1 represents a divalent linking group.

[0613] As a specific example of the divalent linking group, a divalent hydrocarbon group can be cited.

[0614] As a specific example of the divalent hydrocarbon group, a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by linking two or more of these groups can be cited.

[0615] As the divalent saturated hydrocarbon group, it can be linear, branched, or cyclic. From the aspect of more excellent effects of the present invention, a cyclic structure is preferred. From the aspect of more excellent effects of the present invention, the number of carbon atoms of the divalent saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 10, and further preferably 5 to 8.

[0616] As the divalent aromatic hydrocarbon group, the number of carbon atoms is preferably 5 to 20. For example, a phenylene group can be cited. The divalent aromatic hydrocarbon group can have substituents (for example, alkyl groups).

[0617] Among them, as the divalent linking group, a linear, branched, or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms, and a group formed by linking a linear alkylene group having 1 to 3 carbon atoms are preferred. A divalent aromatic hydrocarbon group that can have substituents or a group formed by linking a divalent aromatic hydrocarbon group and a linear alkylene group having 1 to 3 carbon atoms is more preferred. A cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms or a phenylene group that can have substituents is further preferred. A cyclohexylene group or a phenylene group that can have substituents is particularly preferred, and a cyclohexylene group is especially preferred.

[0618] From the aspect of more excellent effects of the present invention, the blocked isocyanate compound represented by formula Q is preferably the blocked isocyanate compound represented by formula QA.

[0619] B 1a -A 1a -L 1a -A 2a -B 2a Formula QA

[0620] In formula QA, B 1a and B 2a each independently represent a blocked isocyanate group. B 1a and B 2a The preferred forms of 1 and B 2 are the same as those of B in formula Q.

[0621] In formula QA, A 1a and A 2aEach independently represents a divalent linking group. A 1a and A 2a The preferred forms of the divalent linking groups in 1a and A 2a are the same as those of A in formula Q

[0622] In formula QA, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.

[0623] L 1a The number of carbon atoms of the cyclic divalent saturated hydrocarbon group in

[0624] L 1a is preferably 5 to 10, more preferably 5 to 8, still more preferably 5 to 6, and particularly preferably 6. 1 The preferred form of the divalent aromatic hydrocarbon group in

[0625] L 1a is the same as that of L in formula QA.

[0626] Hereinafter, specific examples of the first blocked isocyanate compound are shown, but the first blocked isocyanate compound is not limited thereto.

[0627] [Chemical formula 25]

[0628]

[0629] The photosensitive composition layer may contain a single first blocked isocyanate compound or two or more first blocked isocyanate compounds.

[0630] The content of the first blocked isocyanate compound is preferably 0.50 to 25.00% by mass, more preferably 1.00 to 20.00% by mass, and still more preferably 1.50 to 5.00% by mass, based on the total mass of the photosensitive composition layer.

[0631] The first blocked isocyanate compound is obtained, for example, by reacting the isocyanate group of a compound having an isocyanate group (for example, B in the above formula Q 1 and B 2 is a compound having an isocyanate group) with the above blocking agent.

[0632] (Second blocked isocyanate compound)

[0633] The blocked isocyanate compound preferably contains a blocked isocyanate compound having an NCO value of less than 4.5 mmol / g (hereinafter, also referred to as "the second blocked isocyanate compound"). Thereby, after pattern exposure and development of the photosensitive composition layer, generation of development residues can be suppressed.

[0634] The NCO value of the second blocked isocyanate compound is less than 4.5 mmol / g, preferably 2.0 to 4.5 mmol / g, more preferably 2.5 to 4.0 mmol / g.

[0635] As the dissociation temperature of the second blocked isocyanate compound, it is preferably 100 to 160 °C, more preferably 110 to 150 °C.

[0636] Specific examples of the blocking agent having a dissociation temperature of 100 to 160 °C are as described above.

[0637] From the aspects of improving the brittleness of the film or increasing the adhesion to the transfer body, etc., the second blocked isocyanate compound preferably has an isocyanurate structure. The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration.

[0638] As the blocked isocyanate compound having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferably used from the following aspects: compared with a compound not having an oxime structure, it is easier to set the dissociation temperature within a preferred range and it is easier to reduce development residues.

[0639] From the aspect of the strength of the formed pattern, the second blocked isocyanate compound may have a polymerizable group. As the polymerizable group, a radical polymerizable group is preferred.

[0640] Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloyloxy, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as glycidyl group. Among the above, as the polymerizable group, from the aspects of the planar shape of the surface of the obtained pattern, development rate, and reactivity, an ethylenically unsaturated group is preferred, and (meth)acryloyloxy is more preferred.

[0641] Hereinafter, specific examples of the second blocked isocyanate compound are shown, but the second blocked isocyanate compound is not limited thereto.

[0642] [Chemical formula 26]

[0643]

[0644] As the second blocked isocyanate compound, commercially available products can be used. Examples of commercially available products of blocked isocyanate compounds include, for example, Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) AOI-BP, Karenz (registered trademark) MOI-BP, etc. (the above are manufactured by SHOWA DENKO K.K.), and blocked Duranate series [for example, Duranate (registered trademark) TPA-B80E, WT32-B75P, manufactured by Asahi Kasei Corporation).

[0645] The photosensitive composition layer may contain a single type of the second blocked isocyanate compound or may contain two or more types of the second blocked isocyanate compounds.

[0646] When the photosensitive composition layer contains the second blocked isocyanate compound, considering that the development residue can be further reduced, the content of the second blocked isocyanate compound is preferably 1.00 to 25.00% by mass, more preferably 1.00 to 20.0% by mass, and still more preferably 10.00 to 15.00% by mass with respect to the total mass of the photosensitive composition layer.

[0647] When the photosensitive composition layer contains the first blocked isocyanate compound and the second blocked isocyanate compound, considering the bending resistance and the reduction of moisture permeability, the mass ratio of the content of the first blocked isocyanate compound to the content of the second blocked isocyanate compound (the first blocked isocyanate compound / the second blocked isocyanate compound) is preferably 0.10 to 9.00, more preferably 0.18 to 2.35, and still more preferably 0.18 to 1.00.

[0648] The thermally crosslinkable compound may be used alone or two or more thereof may be used simultaneously.

[0649] When the photosensitive composition layer contains the thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1.00 to 50.00% by mass, more preferably 10.00 to 30.00% by mass, and still more preferably 10.00 to 20.00% by mass with respect to the total mass of the photosensitive composition layer.

[0650] [Surfactant]

[0651] The photosensitive composition layer may contain a surfactant.

[0652] As the surfactant, for example, the surfactants described in

[0017] of Japanese Patent No. 4502784 and

[0060] to

[0071] of Japanese Unexamined Patent Application Publication No. 2009-237362 are cited, and these contents are incorporated into the present specification.

[0653] As the surfactant, for example, fluorosurfactants, silicone surfactants, and nonionic surfactants can be mentioned. Fluorosurfactants or silicone surfactants are preferred, and fluorosurfactants are more preferred.

[0654] As commercially available products of fluorosurfactants, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-5650, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (the above are manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (the above are manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (the above are manufactured by AGC Inc.); PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (the above are manufactured by OMNOVA Solutions Inc.); Ftergent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, and 681 (the above are manufactured by Neos Corporation), etc.

[0655] Further, a fluorosurfactant can preferably be a acrylic compound as follows: having a molecular structure containing a functional group (the functional group contains a fluorine atom), and a part of the functional group containing a fluorine atom breaks when heated and the fluorine atom volatilizes. As such fluorosurfactants, those of the MEGAFACE DS series manufactured by DIC Corporation (The Chemical Dai ly Co., Ltd. on February 22, 2016, NIKKEI BUSINESS DAILY on February 23, 2016, for example, MEGAFAC DS-21) can be mentioned.

[0656] Further, a fluorosurfactant can preferably be a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl or fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

[0657] A fluorosurfactant can also be a block polymer. As a fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) can preferably be used.

[0658] A fluorosurfactant can also be a fluorine-containing polymer having a group containing an ethylenic unsaturated bond in the side chain. For example, MEGAFACE RS-101, RS-102, RS-718K and RS-72-K (the above are manufactured by DIC Corporation) can be mentioned.

[0659] As a fluorosurfactant, from the viewpoint of improving environmental adaptability, a surfactant which is a substitute material for a compound having a perfluoroalkyl group having 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) is preferred.

[0660] As a silicone surfactant, for example, a linear polymer composed of a siloxane bond and a modified silicone polymer having an organic group introduced into the side chain or the terminal can be mentioned.

[0661] Examples of commercially available silicone surfactants include DOWSIL 8032 ADDITIVE, TORAYSILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC1 1PA, TORAY SILICONESH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, and TORAY SILICONE SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive performance Materials Inc.); BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK33 1, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (all manufactured by BYK-Chemie GmbH).

[0662] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., propoxylated glycerin and ethoxylated glycerin, etc.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.

[0663] Examples of commercially available products of the nonionic surfactant include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation above); TETRONIC 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF Corporation above); SOLSPERSE 20000 (manufactured by The Lubrizol Corporation above); NCW-101, NCW-1001, and NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation above); PIONIN D-6112, D-6112-W, and D-6315 (manufactured by TAKEMOTO OIL&FAT Co., Ltd. above); OLFINE E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd. above).

[0664] The surfactant may be used alone or two or more kinds thereof may be used simultaneously.

[0665] When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 1.0% by mass, and still more preferably 0.10 to 0.80% by mass, based on the total mass of the photosensitive composition layer.

[0666] [Phosphate ester compound]

[0667] The photosensitive composition layer may contain a phosphate ester compound.

[0668] As a phosphate compound, as long as at least one or more of the three hydrogens in phosphoric acid (O=P(OH)3) are substituted with organic groups, there is no particular limitation. Examples include the Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP) manufactured by Uni-Chemical Co., Ltd., the KAYAMER series (KAYAMER PM-21, KAYAMER PM-2) manufactured by Nippon Kayaku Co., Ltd., and the LIGHT ESTER series (LIGHT ESTER P-2M (trade name)) manufactured by KYOEISHA CHEMICAL Co., LTD.

[0669] The phosphate compound may be used alone or two or more thereof may be used simultaneously.

[0670] The content of the phosphate compound is not particularly limited, and is preferably 0.05 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, and still more preferably 0.2 to 1.0% by mass, based on the total mass of the photosensitive composition layer.

[0671] When the photosensitive composition layer contains a phosphate compound, the content of the phosphate compound is not particularly limited. From the viewpoint of further improving the adhesion to the transfer target, it is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass in total of the binder polymer and the polymerizable compound. Moreover, the upper limit of the above content is not particularly limited, and is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more.

[0672] [Polymerization inhibitor]

[0673] The photosensitive composition layer may contain a polymerization inhibitor.

[0674] A polymerization inhibitor refers to a compound having a function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, known compounds used as polymerization inhibitors can be used.

[0675] As polymerization inhibitors, for example, there may be mentioned phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; hindered phenol compounds such as bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinyl bis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, and pentaerythritol tetra-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitroso-cyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and tert-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate.

[0676] Among them, as the polymerization inhibitor, at least one selected from phenothiazine compounds, nitroso compounds or their salts, and hindered phenol compounds is preferably used, and more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][vinyl bis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), and aluminum salt of N-nitrosophenylhydroxylamine.

[0677] The polymerization inhibitor can be used alone or two or more kinds can be used simultaneously.

[0678] When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 5.00% by mass, still more preferably 0.01 to 3.00% by mass, and particularly preferably 0.01 to 1.00% by mass based on the total mass of the photosensitive composition layer.

[0679] [Hydrogen-donating compound]

[0680] The photosensitive composition layer may contain a hydrogen-donating compound.

[0681] The hydrogen-donating compound has the effects of further improving the sensitivity of the photoinitiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound by oxygen.

[0682] As the hydrogen-donating compound, for example, amines and amino acid compounds may be mentioned.

[0683] As amines, for example, compounds described in "Journal of Polymer Society", Vol. 10, p. 3173 (1972) by M.R. Sander et al., Japanese Patent Publication No. 44-020189, Japanese Unexamined Patent Application Publication No. 51-082102, Japanese Unexamined Patent Application Publication No. 52-134692, Japanese Unexamined Patent Application Publication No. 59-138205, Japanese Unexamined Patent Application Publication No. 60-084305, Japanese Unexamined Patent Application Publication No. 62-018537, Japanese Unexamined Patent Application Publication No. 64-033104, and Research Disclosure No. 33825, etc. can be cited. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline can be cited.

[0684] Among them, from the aspect of more excellent effects of the present invention, as amines, at least one selected from 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is preferred.

[0685] As amino acid compounds, for example, N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine can be cited.

[0686] Among them, from the aspect of more excellent effects of the present invention, as amino acid compounds, N-phenylglycine is preferred.

[0687] In addition, as hydrogen-donating compounds, for example, organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithiane) described in Japanese Unexamined Patent Application Publication No. 6-308727 can also be cited.

[0688] The hydrogen-donating compounds can be used alone or two or more of them can be used simultaneously.

[0689] When the photosensitive composition layer contains a hydrogen-donating compound, from the aspect of improving the curing rate by balancing the polymerization growth rate and chain transfer, the content of the hydrogen-donating compound is preferably 0.01 to 10.00% by mass, more preferably 0.03 to 8.00% by mass, and further preferably 0.05 to 5.00% by mass based on the total mass of the photosensitive composition layer.

[0690] [Pigment]

[0691] The photosensitive composition layer can be a colored resin layer containing a pigment.

[0692] In recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the peripheral portion of the back surface of a transparent glass substrate or the like is sometimes installed on a liquid crystal display window to protect the liquid crystal display window. A colored resin layer can be used to form such a light-shielding layer.

[0693] As the pigment, it can be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and colored pigments other than black and white. Among them, when forming a black-based pattern, as the pigment, a black pigment is preferably selected.

[0694] As the black pigment, as long as it is within the range that does not impair the effects of the present invention, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected. Among them, from the viewpoint of optical density, as the black pigment, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite can be preferably selected, and carbon black is particularly preferred. As carbon black, from the viewpoint of surface resistance, carbon black having at least a part of its surface coated with resin is preferred.

[0695] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm in terms of number average particle size.

[0696] Here, the particle size refers to the diameter of a circle when the area of the pigment particle is obtained from a photograph image of the pigment particle taken by an electron microscope and a circle having the same area as the area of the pigment particle is assumed, and the number average particle size is an average value obtained by calculating the above particle size for any 100 particles and averaging the 100 obtained particle sizes.

[0697] As pigments other than black pigments, regarding white pigments, the white pigments described in paragraphs

[0015] and

[0114] of Japanese Patent Laid-Open No. 2005-007765 can be used. Specifically, among white pigments, as inorganic pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferred, titanium oxide or zinc oxide is more preferred, and titanium oxide is further preferred. As inorganic pigments, rutile-type or anatase-type titanium oxide is further preferred, and rutile-type titanium oxide is particularly preferred.

[0698] And, the surface of titanium oxide can be subjected to silica treatment, alumina treatment, titanium dioxide treatment, zirconia treatment, or organic treatment, or two or more kinds of treatments can be carried out. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance, light fading resistance, etc. are improved.

[0699] From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, as the surface treatment of the surface of titanium oxide, at least one of alumina treatment and zirconia treatment is preferred, and both alumina treatment and zirconia treatment are particularly preferred.

[0700] Further, when the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, the photosensitive composition layer preferably further contains a colored pigment other than a black pigment and a white pigment. When a colored pigment is contained, the particle diameter of the colored pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the aspect of more excellent dispersibility. The lower limit is not particularly limited, and preferably 0.001 μm or more.

[0701] Examples of the colored pigment include Victoria Pure Blue B0 (Pigment Index: Color Index (hereinafter C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), MONOLITE Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), HOSTABERM Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), FASTEL Pink B SUPRA (C.I. Pigment Red 81), Phthalocyanine Fast Blue (C.I. Pigment Blue 15), MONOLITE FAST Black B (C.I. Pigment Black 1), and carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, and C.I. Pigment Violet 23. Among them, C.I. Pigment Red 177 is preferred.

[0702] When the photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, further preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass, relative to the total mass of the photosensitive composition layer.

[0703] When the photosensitive composition layer contains a pigment other than a black pigment (a white pigment and a colored pigment), the content of the pigment other than the black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and further preferably 3 to 15% by mass, relative to the black pigment.

[0704] In addition, when the photosensitive composition layer contains a black pigment and the photosensitive composition layer is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion liquid.

[0705] The dispersion can be prepared by the following method: adding a mixture obtained by premixing a black pigment and a pigment dispersant to an organic solvent (or carrier) and dispersing it with a disperser. The pigment dispersant can be selected according to the pigment and the solvent. For example, commercially available dispersants can be used. In addition, the carrier refers to the part that serves as the medium for dispersing the pigment in the pigment dispersion liquid. The carrier is in a liquid state and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0706] There is no particular limitation on the disperser. For example, known dispersers such as kneaders, roll mills, grinders, super mills, dissolvers, homogenizers, and sand mills can be cited. Moreover, mechanical grinding can be carried out to perform fine pulverization by frictional force. Regarding the disperser and fine pulverization, reference can be made to the descriptions in "Encyclopedia of Pigments" (written by Kunizo Asakura, first edition, Asakura Shoten, 2000, pages 438 and 310).

[0707] [Residual monomers]

[0708] The photosensitive composition layer sometimes contains residual monomers of each structural unit of the above-mentioned binder polymer.

[0709] From the viewpoints of pattern formability and reliability, the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and further preferably 500 mass ppm or less, relative to the total mass of the binder polymer. There is no particular limitation on the lower limit, and it is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, relative to the total mass of the binder polymer.

[0710] From the viewpoints of pattern formability and reliability, the residual monomer of each structural unit of the binder polymer is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and further preferably 100 mass ppm or less, relative to the total mass of the photosensitive composition layer. There is no particular limitation on the lower limit, and it is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, relative to the total mass of the photosensitive composition layer.

[0711] The amount of the residual monomer of the monomer during the synthesis of the binder polymer by a polymer reaction is also preferably within the above range. For example, when synthesizing a binder polymer by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.

[0712] The amount of the residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[0713] [Other components]

[0714] The photosensitive composition layer may contain components other than the above components (hereinafter, also referred to as "other components"). As the other components, for example, sensitizers, dyes, antioxidants, particles (for example, metal oxide particles) can be cited. And, as the other components, other additives described in paragraphs

[0058] to

[0071] of Japanese Patent Laid-Open No. 2000-310706 can also be cited.

[0715] -Sensitizer-

[0716] There is no particular limitation on the sensitizer, and known sensitizers, dyes and pigments can be used. As the sensitizer, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1, 2, 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds can be cited.

[0717] -Particles-

[0718] As the particles, metal oxide particles are preferred.

[0719] The metals in the metal oxide particles also include metalloids such as B, Si, Ge, As, Sb and Te.

[0720] For example, from the viewpoint of the transparency of the cured film, the average primary particle size of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0721] The average primary particle size of the particles is calculated by measuring the particle sizes of any 200 particles using an electron microscope and taking the arithmetic mean of the measurement results. In addition, when the shape of the particles is not spherical, the longest side is taken as the particle size.

[0722] When the photosensitive composition layer contains particles, it may contain only one kind of particles with different metal types and sizes, or may contain two or more kinds.

[0723] When the photosensitive composition layer does not contain particles, or when the photosensitive composition layer contains particles, preferably the content of the particles is more than 0% by mass and 35% by mass or less relative to the total mass of the photosensitive composition layer; more preferably, it does not contain particles, or the content of the particles is more than 0% by mass and 10% by mass or less relative to the total mass of the photosensitive composition layer; further preferably, it does not contain particles, or the content of the particles is more than 0% by mass and 5% by mass or less relative to the total mass of the photosensitive composition layer; further preferably, it does not contain particles, or the content of the particles is more than 0% by mass and 1% by mass or less relative to the total mass of the photosensitive composition layer; particularly preferably, it does not contain particles.

[0724] - Dye -

[0725] The photosensitive composition layer may contain a dye.

[0726] There is no particular limitation on the dye, and known dyes can be used. For example, colorless compounds can be cited.

[0727] - Antioxidant -

[0728] As antioxidants, for example, 3 - pyrazolones such as 1 - phenyl - 3 - pyrazolone (also known as: phenidone), 1 - phenyl - 4,4 - dimethyl - 3 - pyrazolone, and 1 - phenyl - 4 - methyl - 4 - hydroxymethyl - 3 - pyrazolone can be cited; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chloro - hydroquinone; p - methylaminophenol, p - aminophenol, p - hydroxyphenylglycine, and p - phenylenediamine.

[0729] Among them, from the aspect of more excellent effects of the present invention, as the antioxidant, 3 - pyrazolones are preferred, and 1 - phenyl - 3 - pyrazolone is more preferred.

[0730] When the photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.01% by mass or more with respect to the total mass of the photosensitive composition layer. There is no particular limitation on the upper limit, and it is preferably 1% by mass or less with respect to the total mass of the photosensitive composition layer.

[0731] [Impurities]

[0732] The photosensitive composition layer may contain impurities.

[0733] As impurities, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions can be cited.

[0734] Among them, since halide ions, sodium ions, and potassium ions are easily mixed as impurities, the following contents are preferably set.

[0735] The content of impurities in the photosensitive composition layer is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less with respect to the total mass of the photosensitive composition layer. There is no particular limitation on the lower limit, and it is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more with respect to the total mass of the photosensitive composition layer.

[0736] As a method for setting the impurities within the above range, there may be mentioned a method of selecting a raw material with a small content of impurities as the raw material contained in the photosensitive composition layer; a method of preventing impurities from being mixed in when forming the photosensitive composition layer; and a method of cleaning and removing. By such methods, the amount of impurities can be made within the above range.

[0737] For example, impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0738] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably small. With respect to the total mass of the photosensitive composition layer, it is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and still more preferably 4 mass ppm or less. The lower limit is not particularly limited, and with respect to the total mass of the photosensitive composition layer, it is preferably 10 mass ppb or more, more preferably 100 mass ppb or more. The content of these compounds can be suppressed by the same method as the impurities of the above metals. Also, they can be quantified by known measurement methods.

[0739] From the viewpoints of improving reliability and laminability, the content of water in the photosensitive composition layer is preferably 0.01 to 1.0 mass% with respect to the total mass of the photosensitive composition layer, and more preferably 0.05 to 0.5 mass%.

[0740] [Refractive Index Adjusting Layer]

[0741] The transfer film may have a refractive index adjusting layer disposed on the photosensitive composition layer.

[0742] The transfer film preferably has a temporary support, a photosensitive composition layer, and a refractive index adjusting layer in this order.

[0743] In addition, when the transfer film further has a protective film described later, it preferably has a temporary support, a photosensitive composition layer, a refractive index adjusting layer, and the protective film described later in this order.

[0744] As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. As the material contained in the refractive index adjusting layer, for example, there may be mentioned an adhesive and particles.

[0745] As the adhesive, for example, there may be mentioned an adhesive polymer contained in the photosensitive composition layer and a polymer having a structural unit with a carboxylic anhydride structure.

[0746] As particles, for example, zirconia particles (ZrO2 particles), niobium oxide particles (Nb2O5 particles), titanium oxide particles (TiO2 particles), and silica particles (SiO2 particles) can be cited.

[0747] The refractive index adjustment layer preferably contains a metal oxidation inhibitor.

[0748] By including a metal oxidation inhibitor in the refractive index adjustment layer, oxidation of the metal in contact with the refractive index adjustment layer can be suppressed.

[0749] As the metal oxidation inhibitor, for example, a compound having an aromatic ring containing a nitrogen atom in the molecule is preferred. As the metal oxidation inhibitor, for example, imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole can be cited.

[0750] The refractive index of the refractive index adjustment layer is preferably 1.60 or more, more preferably 1.63 or more. There is no particular limitation on the upper limit, and it is preferably 2.10 or less, more preferably 1.85 or less.

[0751] The thickness of the refractive index adjustment layer is preferably 500 nm or less, more preferably 110 nm or less, and further preferably 100 nm or less. There is no particular limitation on the lower limit, and it is preferably 20 nm or more, more preferably 50 nm or more.

[0752] The thickness of the refractive index adjustment layer is calculated as the average value of any five places measured by cross-sectional observation based on a scanning electron microscope (SEM).

[0753] [Other Layers]

[0754] The transfer film may have other layers in addition to the above-mentioned temporary support, photosensitive composition layer, and refractive index adjustment and protective film layer.

[0755] As other layers, for example, a thermoplastic resin layer, an intermediate layer, and an antistatic layer can be cited.

[0756] (Thermoplastic Resin Layer)

[0757] Generally, the thermoplastic resin layer is disposed between the temporary support and the photosensitive composition layer. Since the transfer film has a thermoplastic resin layer, the followability to the substrate in the process of bonding the transfer film to the substrate is improved, and the mixing of air bubbles between the substrate and the transfer film can be suppressed. As a result, the adhesion between the layer adjacent to the thermoplastic resin layer (for example, the temporary support) can be ensured.

[0758] The thermoplastic resin layer contains a resin. The above-mentioned resin contains a thermoplastic resin as a part or all thereof. That is, in one aspect, the resin of the thermoplastic resin layer is preferably also a thermoplastic resin.

[0759] As the thermoplastic resin, an alkali-soluble resin is preferred.

[0760] Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0761] As the alkali-soluble resin, an acrylic resin is preferred from the viewpoints of developability and adhesion to an adjacent layer.

[0762] Herein, the acrylic resin refers to a resin having at least one structural unit selected from a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylate, and a structural unit derived from (meth)acrylamide.

[0763] As for the acrylic resin, the total content of the structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylate, and the structural unit derived from (meth)acrylamide is preferably 50% by mass or more relative to the total mass of the acrylic resin.

[0764] Among them, the total content of the structural unit derived from (meth)acrylic acid and the structural unit derived from (meth)acrylate is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, relative to the total mass of the acrylic resin.

[0765] Moreover, the alkali-soluble resin is preferably a polymer having an acid group.

[0766] Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxyl group is preferred.

[0767] From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and further preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more.

[0768] The upper limit of the acid value of the alkali-soluble resin is not particularly limited, and is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0769] There is no particular limitation on the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and it can be appropriately selected from known resins.

[0770] For example, an acrylic resin containing a carboxyl group, i.e., an alkali-soluble resin, having an acid value of 60 mgKOH / g or more in the polymer described in paragraph

[0025] of Japanese Patent Laid-Open No. 2011-095716, an acrylic resin containing a carboxyl group having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs

[0033] to

[0052] of Japanese Patent Laid-Open No. 2010-237589, and an acrylic resin containing a carboxyl group having an acid value of 60 mgKOH / g or more in the binder polymer described in paragraphs

[0053] to

[0068] of Japanese Patent Laid-Open No. 2016-224162 can be cited.

[0771] The copolymerization ratio of the structural unit having a carboxyl group in the above-mentioned acrylic resin containing a carboxyl group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 12 to 30% by mass, relative to the total mass of the acrylic resin.

[0772] As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred from the viewpoints of developability and adhesion to an adjacent layer.

[0773] The alkali-soluble resin may have a reactive group. As the reactive group, any group capable of addition polymerization can be used, and examples thereof include an ethylenically unsaturated group; a polycondensable group such as a hydroxyl group and a carboxyl group; an addition polymerization reactive group such as an epoxy group and a (blocked) isocyanate group.

[0774] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and further preferably 20,000 to 50,000.

[0775] The alkali-soluble resin may be used alone or in combination of two or more.

[0776] From the viewpoints of developability and adhesion to an adjacent layer, the content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, further preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer.

[0777] (Intermediate layer)

[0778] In the transfer film 10, the intermediate layer 5 is present between the thermoplastic resin layer 3 and the photosensitive composition layer 7, and it is possible to suppress the mixing of components that may occur during the coating formation and storage after the coating formation of the thermoplastic resin layer 3 and the photosensitive composition layer 7.

[0779] As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used.

[0780] Further, as the intermediate layer, an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese Patent Laid-Open No. 5-072724 can also be used. When the intermediate layer is an oxygen barrier layer, the sensitivity during exposure is improved, the time load on the exposure machine is reduced, and the productivity is increased, so it is preferred.

[0781] The oxygen barrier layer that can be used as the intermediate layer may be appropriately selected from known layers described in the above-mentioned gazette and the like. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1% by mass aqueous solution of sodium carbonate at 22°C) is preferred.

[0782] Hereinafter, each component that the water-soluble resin layer (intermediate layer) may contain will be described.

[0783] The water-soluble resin layer (intermediate layer) contains a resin.

[0784] The above resin contains a water-soluble resin as part or all of it.

[0785] Examples of the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

[0786] Further, as the water-soluble resin, a copolymer of (meth)acrylic acid / vinyl compound or the like can also be used. As the copolymer of (meth)acrylic acid / vinyl compound, a copolymer of (meth)acrylic acid / (meth)allyl acrylate is preferred, and a copolymer of methacrylic acid / methacrylic acid allyl ester is more preferred.

[0787] When the water-soluble resin is a copolymer of (meth)acrylic acid / vinyl compound, as the composition ratio (mol%), for example, it is preferably 90 / 10 to 20 / 80, and more preferably 80 / 20 to 30 / 70.

[0788] As the lower limit value of the weight-average molecular weight of the water-soluble resin, it is preferably 5,000 or more, more preferably 7,000 or more, and further preferably 10,000 or more. And as the upper limit value, it is preferably 200,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less.

[0789] The dispersity (Mw / Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

[0790] In addition, from the aspect of further improving the ability to suppress interlayer mixing of the water-soluble resin layer (intermediate layer), the resin in the water-soluble resin layer (intermediate layer) is preferably a resin different from the resin contained in the layer disposed on one side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other side. For example, when polymer A is contained in the photosensitive composition layer 17 and a thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer 13, the resin of the water-soluble resin layer (intermediate layer) 15 is preferably a resin different from polymer A and the thermoplastic resin (alkali-soluble resin).

[0791] From the aspect of further improving oxygen barrier properties and the ability to suppress interlayer mixing, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0792] The water-soluble resin can be used alone as one kind, or two or more kinds can be used.

[0793] The content of the water-soluble resin is not particularly limited. From the aspect of further improving oxygen barrier properties and the ability to suppress interlayer mixing, it is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the water-soluble resin layer (intermediate layer). In addition, as its upper limit value, there is no particular limitation, and it is preferably 99.9% by mass or less, and further preferably 99.8% by mass or less.

[0794] The layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, and is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. If the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the ability to suppress interlayer mixing is excellent and the oxygen barrier properties will not be reduced. Moreover, it is also possible to further suppress an increase in the removal time of the water-soluble resin layer (intermediate layer) during development.

[0795] (Antistatic layer)

[0796] By having an antistatic layer on the transfer film, it is possible to suppress the generation of static electricity when peeling off a film or the like disposed on the antistatic layer, and it is also possible to suppress the generation of static electricity caused by friction with equipment or other films, etc. Therefore, for example, it is possible to suppress the occurrence of defects in electronic devices.

[0797] The antistatic layer is preferably disposed between the temporary support and the photosensitive composition layer.

[0798] The antistatic layer is a layer having antistatic properties and contains at least an antistatic agent. There is no particular limitation on the antistatic agent, and known antistatic agents can be applied.

[0799] [Manufacturing method of the temporary support]

[0800] The manufacturing method of the temporary support is not particularly limited, and known methods can be cited.

[0801] The manufacturing method of the temporary support can be a manufacturing method including an extrusion molding process and a coating process, or a manufacturing method including a co-extrusion molding process. Moreover, it is preferable to have a biaxial stretching process in addition to the above processes.

[0802] As the extrusion molding method, for example, a method of extruding a raw material resin using an extruder to mold the raw material resin into a desired shape can be cited.

[0803] As the co-extrusion forming process, for example, a method of extruding a plurality of raw material resins using an extruder to mold the raw material resins into a shape having a multilayer structure can be cited.

[0804] As the biaxial stretching process, it can be a simultaneous biaxial stretching in which longitudinal stretching and transverse stretching are performed simultaneously, or a successive biaxial stretching in which longitudinal stretching and transverse stretching are performed in two or more stages. As the mode of successive biaxial stretching, for example, modes of [the order of longitudinal stretching and transverse stretching], [the order of longitudinal stretching, transverse stretching, and longitudinal stretching], [the order of longitudinal stretching, longitudinal stretching, and transverse stretching], and [the order of transverse stretching and longitudinal stretching] can be cited. Among them, it is preferable to perform longitudinal stretching and transverse stretching in sequence.

[0805] Next, an example of the manufacturing method of the temporary support according to this specification will be specifically described.

[0806] The manufacturing method of the temporary support preferably includes: a process of forming an unstretched temporary support body by melt-extruding polyester (hereinafter, also referred to as "extrusion molding process"), a coating process, a process of stretching the above temporary support body in the length direction (hereinafter, also referred to as "longitudinal stretching process"), and a process of stretching the temporary support body stretched in the length direction in the width direction (hereinafter, also referred to as "transverse stretching process"). Moreover, the manufacturing method of the temporary support preferably further includes: a process of forming an unstretched temporary support by simultaneously melt-extruding the raw material resins of the first layer, the second layer, and the temporary support body (hereinafter, also referred to as "co-extrusion molding process"), a process of stretching the above temporary support in the length direction (hereinafter, also referred to as "longitudinal stretching process"), and a process of stretching the temporary support stretched in the length direction in the width direction (hereinafter, also referred to as "transverse stretching process").

[0807] <Extrusion molding process>

[0808] In the extrusion molding process, an unstretched temporary support body is formed by melt-extruding a raw material resin (for example, polyester).

[0809] As a melt extrusion method, for example, a method using an extruder can be cited. For example, an extruder equipped with one or two or more screws is used to heat the raw material resin (e.g., polyester) to a temperature above the melting point, and then the screw is rotated to perform melt kneading while performing melt extrusion. Polyester is melted in the extruder to become a melt through heating and kneading by the screw.

[0810] The melt is extruded from an extrusion die (hereinafter, also referred to as a "die".) through a gear pump, a filter, etc. (JIS B8650:2006, a, extrusion molding machine, No. 134). The melt can be extruded into a single layer or into multiple layers.

[0811] At the time of melt extrusion, from the viewpoint of suppressing thermal decomposition (e.g., hydrolysis of polyester) in the extruder, it is preferable to perform nitrogen replacement in the extruder. And from the aspect of being able to suppress the kneading temperature to a lower level, the extruder is preferably a twin-screw extruder.

[0812] The melt extruded from the extrusion die is cooled and formed into a film shape. For example, the melt is brought into contact with a casting roll, and the melt is cooled and solidified on the casting roll, thereby forming the melt into a film shape. In the cooling of the melt, it is preferable to further blow air (preferably cold air) to the melt.

[0813] The temperature of the casting roll is preferably more than -10°C and 30°C or less, more preferably -7 to +20°C, and further preferably -5 to +10°C with respect to the glass transition temperature (Tg) of polyester.

[0814] When using a casting roll in the extrusion molding process, it is preferable to improve the adhesion between the casting roll and the melt. As a method for improving the adhesion, for example, an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, and a contact roll method can be cited.

[0815] The temporarily supported body main body cooled using a casting roll or the like is peeled off from the cooling member such as a casting roll using a peeling member such as a peeling roll.

[0816] <Coating process>

[0817] The coating process is a process for forming the first layer or the second layer.

[0818] There is no particular limitation on the coating process, and known methods can be cited.

[0819] There is no particular limitation on the coating process, and known methods can be cited. For example, a reverse roll coating method, a gravure coating method, a kiss coating method, a die coating method, a roller brush method, a spraying method, an air knife coating method, a wire bar coating method, a tube blade coating method, an impregnation coating method, and a curtain coating method can be cited. And these methods can be used alone or in combination.

[0820] In the coating step, it is preferable to dissolve the components contained in the first layer or the second layer in a solvent to prepare a coating liquid for forming the first layer or the second layer and use it. Examples of the solvent include water and organic solvents.

[0821] The coating step can be provided before or after any step in the manufacturing process of the temporary support. Specifically, it can be provided after the extrusion molding step or after the biaxial stretching step. And it can be carried out once or multiple times.

[0822] Among them, it is preferably provided after the biaxial stretching step, and more preferably, after coating the coating liquid for forming the first layer or the second layer on the temporary support body stretched in the length direction, lateral stretching is carried out.

[0823] <Coextrusion molding step>

[0824] As the coextrusion molding step, there is no particular limitation, and known methods can be cited. As the coextrusion molding step, for example, the method described in Japanese Unexamined Patent Application Publication No. 2019-65271 can be cited, and these contents are incorporated into this specification.

[0825] <Biaxial stretching step>

[0826] The biaxial stretching step is not particularly limited, and known methods can be cited.

[0827] As the biaxial stretching step, it preferably has a longitudinal stretching step and a lateral stretching step.

[0828] [Longitudinal stretching step]

[0829] In the longitudinal stretching step, it is preferable to stretch the above-mentioned unstretched film (for example, the unstretched temporary support and the unstretched temporary support body) in the length direction (hereinafter, also referred to as "longitudinal stretching").

[0830] In the longitudinal stretching step, it is preferable to preheat the unstretched film (for example, the unstretched temporary support and the unstretched temporary support body) before longitudinal stretching. By preheating the unstretched film, it is possible to easily perform longitudinal stretching on the above-mentioned film.

[0831] The preheating temperature is preferably -10 to +60°C, more preferably 0 to +50°C, relative to the Tg of the unstretched film (for example, the unstretched temporary support and the unstretched temporary support body). Specifically, the preheating temperature is preferably 60 to 100°C, more preferably 65 to 80°C.

[0832] Longitudinal stretching can be carried out, for example, by applying tension between two or more pairs of pinch rolls arranged in the conveying direction while conveying an unstretched film (e.g., an unstretched temporary support and an unstretched temporary support body) in the longitudinal direction. For example, when one pair of pinch rolls A is arranged on the upstream side in the conveying direction and one pair of pinch rolls B is arranged on the downstream side in the conveying direction, when conveying an unstretched polyester film, the rotational speed of pinch roll B is set higher than that of pinch roll A, whereby the unstretched film (e.g., an unstretched temporary support and an unstretched temporary support body) is stretched in the longitudinal direction.

[0833] The draw ratio in the longitudinal stretching process is preferably less than the draw ratio in the subsequent transverse stretching process described below. The draw ratio in the longitudinal stretching process is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.0 times, and further preferably 2.8 to 4.0 times.

[0834] The heating temperature in the longitudinal stretching process is preferably -20 to +50 °C, more preferably -10 to +40 °C, and further preferably 0 to +30 °C with respect to the Tg of the unstretched film (e.g., an unstretched temporary support and an unstretched temporary support body). Specifically, the heating temperature in the longitudinal stretching process is preferably 70 to 120 °C, more preferably 80 to 110 °C, and further preferably 85 to 100 °C.

[0835] As a method for heating the unstretched film (e.g., an unstretched temporary support and an unstretched temporary support body), a method of heating a roll such as a pinch roll in contact with the unstretched film can be cited. As a method for heating the roll, for example, a method of providing a heater or a pipe through which a hot solvent can flow inside the roll can be cited. In addition to the above, for example, a method of blowing warm air onto the unstretched film (e.g., an unstretched temporary support and an unstretched temporary support body), a method of bringing it into contact with a heat source such as a heater, and a method of heating the unstretched film (e.g., an unstretched temporary support and an unstretched temporary support body) by passing it near a heat source can be cited.

[0836] The stretching speed in the longitudinal stretching process is preferably 800 to 1500% / second, more preferably 1000 to 1400% / second, and further preferably 1200 to 1400% / second. Herein, the "stretching speed" refers to a value obtained by dividing the length Δd stretched in 1 second from the length d0 before stretching by the length d0 before stretching and expressing it as a percentage.

[0837] [Transverse Stretching Process]

[0838] In the transverse stretching step, the film stretched in the above-mentioned length direction (for example, the temporarily supported body stretched in the length direction and the main body of the temporarily supported body stretched in the length direction) is stretched in the width direction (hereinafter, also referred to as "transverse stretching").

[0839] In the transverse stretching step, it is preferable to preheat the film stretched in the length direction (for example, the temporarily supported body stretched in the length direction and the main body of the temporarily supported body stretched in the length direction) before transverse stretching. By preheating the above-mentioned film, it is possible to easily perform transverse stretching on the above-mentioned film.

[0840] The preheating temperature is preferably -10 to +60°C, more preferably 0 to +50°C, relative to the Tg of the unstretched film (for example, the unstretched temporarily supported body and the unstretched main body of the temporarily supported body). Specifically, the preheating temperature is preferably 80 to 120°C, more preferably 90 to 110°C.

[0841] The stretching ratio in the transverse stretching step is preferably greater than the stretching ratio in the above-mentioned longitudinal stretching step. The stretching ratio in the transverse stretching step is preferably 3.0 to 6.0 times, more preferably 3.5 to 5.0 times, and further preferably 3.5 to 4.5 times.

[0842] The area ratio represented by the product of the stretching ratio in the longitudinal stretching step and the stretching ratio in the transverse stretching step is preferably 12.8 to 15.5 times, more preferably 13.5 to 15.2 times, and further preferably 14.0 to 15.0 times. If the area ratio is 12.8 times or more, the molecular orientation in the film width direction becomes good. And if the area ratio is 15.5 times or less, it is easy to maintain the state where the molecular orientation is not easily relaxed during the heat treatment.

[0843] The heating temperature in the transverse stretching step is preferably -10 to +80°C, more preferably 0 to +70°C, and further preferably 0 to +60°C, relative to the Tg of the unstretched film (for example, the unstretched temporarily supported body and the unstretched main body of the temporarily supported body). Specifically, the heating temperature in the transverse stretching step is preferably 100 to 140°C, more preferably 110 to 135°C, and further preferably 115 to 130°C.

[0844] The stretching speed in the transverse stretching step is preferably 10 to 100% / second, more preferably 10 to 70% / second, and further preferably 20 to 60% / second.

[0845] <Heat treatment step>

[0846] A method for manufacturing a temporary support preferably includes a step of heat-treating the film stretched in the width direction (e.g., a temporarily stretched support in the width direction and a main body of a temporarily stretched support in the width direction) (hereinafter, also referred to as the "heat treatment step"). As the heat treatment step, for example, a heat setting step and a heat relaxation step can be cited. The heat treatment step preferably includes at least one of a heat setting step and a heat relaxation step, and more preferably includes both a heat setting step and a heat relaxation step.

[0847] (Heat setting step)

[0848] In the heat setting step, heat setting is performed by heating the film stretched in the width direction (e.g., a temporarily stretched support in the width direction and a main body of a temporarily stretched support in the width direction). Since the raw material resin can be crystallized by heat setting, shrinkage of the film can be suppressed.

[0849] The heating temperature in the heat setting step is preferably 190 to 240 °C, more preferably 200 to 240 °C, and further preferably 210 to 230 °C.

[0850] In the heat setting step, the deviation of the film surface in the film width direction reaching the highest temperature is preferably 0.5 to 10.0 °C, more preferably 0.5 to 7.0 °C, further preferably 0.5 to 5.0 °C, and particularly preferably 0.5 to 4.0 °C. By adjusting the deviation of the film surface in the film width direction reaching the highest temperature within the above range, the deviation of the degree of crystallinity in the width direction can be suppressed.

[0851] As a heating method, for example, a method of blowing hot air onto the film and a method of radiatively heating the film can be cited. As a device used in the radiative heating method, for example, an infrared heater can be cited.

[0852] The heating time in the heat setting step is preferably 5 to 50 seconds, more preferably 5 to 30 seconds, and further preferably 5 to 10 seconds.

[0853] (Heat relaxation step)

[0854] In the heat relaxation step, heat relaxation is performed by heating the film stretched in the width direction (e.g., a temporarily stretched support in the width direction and a main body of a temporarily stretched support in the width direction). Through heat relaxation, the residual strain of the film (e.g., a temporarily stretched support in the width direction and a main body of a temporarily stretched support in the width direction) can be relaxed.

[0855] The heating temperature in the heat relaxation step is preferably a temperature 5 °C or more lower than the heating temperature in the heat setting step, more preferably 15 °C or more lower, further preferably 25 °C or more lower, and particularly preferably 30 °C or more lower.

[0856] The lower limit of the heating temperature in the heat relaxation step is preferably 100 °C or higher, more preferably 110 °C or higher, and still more preferably 120 °C or higher.

[0857] As the heating method, for example, a method of blowing hot air onto the film and a method of radiating heat to the film can be cited. As the device used in the radiation heating method, for example, an infrared heater can be cited.

[0858] <Cooling step>

[0859] The method for manufacturing the temporary support preferably includes a step of cooling the above-mentioned heat-treated film (for example, the heat-treated temporary support and the heat-treated temporary support body) (hereinafter, also referred to as the "cooling step").

[0860] As the cooling method, for example, a method of blowing air (preferably cold air) onto the film and a method of bringing the film into contact with a temperature-adjustable member (for example, a temperature-adjusting roll) can be cited.

[0861] The average cooling rate in the cooling step is preferably 500 to 4000 °C / minute, more preferably 1000 to 3500 °C / minute, and still more preferably 1500 to 3000 °C / minute. By adjusting the average cooling rate within the above range, the surface temperature of the film in the cooling step can be made uniform, and thus the non-uniformity of the expansion coefficient in the width direction can be reduced. The average cooling rate is obtained using a non-contact thermometer (for example, a radiation thermometer). For example, based on the distance Z between the point where the surface temperature of the film (for example, the temporary support and the temporary support body) reaches 150 °C and the point where the film surface temperature reaches 70 °C and the conveyance speed S of the film, the cooling time (Z / S) from 150 °C to 70 °C is obtained. Then, by calculating (150 - 70) / (Z / S), the average cooling rate is obtained.

[0862] 〔Method for manufacturing transfer film〕

[0863] The method for manufacturing the transfer film of the present invention is not particularly limited, and a known method can be used.

[0864] Among them, from the aspect of excellent productivity, the following method is preferred: a photosensitive composition is coated on the temporary support, and a drying treatment is performed as needed to form a photosensitive composition layer.

[0865] Hereinafter, the above method will be described in detail.

[0866] As the coating method of the photosensitive composition, for example, a printing method, a spraying method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (i.e., a slit coating method) can be cited.

[0867] As drying methods, for example, natural drying, heat drying, and reduced-pressure drying can be cited. These methods can be used alone or in combination of multiple ones.

[0868] In this specification, "drying" means removing at least a part of the solvent contained in the photosensitive composition.

[0869] When the transfer film has a refractive index adjusting layer on the photosensitive composition layer, for example, the refractive index adjusting layer can be formed by coating a composition for forming a refractive index adjusting layer on the photosensitive composition layer and then drying as needed.

[0870] Moreover, a transfer film can be manufactured by laminating a protective film on the photosensitive composition layer.

[0871] The method of laminating the protective film on the photosensitive composition layer is not particularly limited, and known methods can be cited.

[0872] As a device for laminating the protective film on the photosensitive composition layer, known laminators such as a vacuum laminator and an automatic cutting laminator can be cited.

[0873] The laminator preferably includes any heatable roller such as a rubber roller and can perform pressurization and heating.

[0874] 〔Method for manufacturing a laminate〕

[0875] By using the above transfer film, the photosensitive composition layer can be transferred to the object to be transferred.

[0876] Among them, the method for manufacturing a laminate preferably includes:

[0877] A laminating step of obtaining a substrate with a photosensitive composition layer having a conductive portion, a photosensitive composition layer, and a temporary support in this order by peeling the protective film from the transfer film and bringing the surface on the side opposite to the temporary support into contact with and laminating it on a substrate having a conductive portion;

[0878] An exposure step of performing pattern exposure on the photosensitive composition layer; and

[0879] A developing step of forming a pattern by developing the exposed photosensitive composition layer;

[0880] The method for manufacturing a laminate further includes:

[0881] A peeling step of peeling the temporary support from the substrate with a photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the developing step.

[0882] Hereinafter, the order of the above steps will be described in detail.

[0883] <Laminating step>

[0884] The laminating step is a step of obtaining a substrate with a photosensitive composition layer, which sequentially has a conductive layer, a photosensitive composition layer, and a temporary support, by peeling the protective film from the transfer film and bringing the surface on the side opposite to the temporary support of the transfer film into contact with and laminating it on a substrate having a conductive portion.

[0885] As a method for peeling the protective film from the transfer film, there is no particular limitation, and a known method can be used.

[0886] When the transfer film has a refractive index adjusting layer, the surface on the side opposite to the temporary support of the transfer film is preferably the refractive index adjusting layer, and when the transfer film does not have a refractive index adjusting layer, it is preferably the photosensitive composition layer. That is, in the laminating step, it is preferable to perform lamination by bringing the refractive index adjusting layer of the transfer film into contact with the object to be transferred, or by bringing the photosensitive composition layer of the transfer film into contact with the object to be transferred.

[0887] The photosensitive composition layer exposed on the temporary support of the transfer film is brought into contact with and laminated on the conductive layer. By this lamination, the photosensitive composition layer and the temporary support are disposed on the conductive layer.

[0888] In the above lamination, crimping is performed in such a manner that the surface of the conductive layer comes into contact with the surface of the photosensitive composition layer.

[0889] As the above crimping method, there is no particular limitation, and known transfer methods and lamination methods can be used. Among them, it is preferable to overlap the surface of the photosensitive composition layer on a substrate having a difference in conductive portion and perform it by pressurization and heating based on a roller or the like.

[0890] Known laminators such as a vacuum laminator and an automatic cutting laminator can be used for lamination.

[0891] The substrate having a conductive layer has a conductive layer on the substrate, and any layer can be formed as needed. That is, the substrate having a conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

[0892] Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

[0893] As a preferred mode of the substrate, for example, it is described in paragraph

[0140] of International Publication No. 2018 / 155193, and this content is incorporated into the present specification.

[0894] As the conductive layer, from the viewpoints of conductivity and fine line formability, it is preferably at least one layer selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer.

[0895] Moreover, only one layer of conductive layer can be disposed on the substrate, or two or more layers can be disposed. When two or more layers of conductive layers are disposed, it is preferable to have conductive layers of different materials.

[0896] As a preferred embodiment of the conductive layer, for example, it is described in paragraph

[0141] of International Publication No. 2018 / 155193, and this content is incorporated into the present specification.

[0897] As the substrate having the conductive layer, a substrate having at least one of a transparent electrode and a detour wiring is preferred. The substrate as described above can be preferably used as a substrate for a touch panel.

[0898] The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal fine wire such as a metal mesh and silver nanowires.

[0899] As the metal fine wire, fine wires of silver, copper, etc. can be mentioned. Among them, silver conductive materials such as a silver mesh and silver nanowires are preferred.

[0900] As the material of the detour wiring, a metal is preferred.

[0901] As the metal which is the material of the detour wiring, gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements can be mentioned. Among them, as the material of the detour wiring, copper, molybdenum, aluminum, or titanium is preferred, and copper is more preferred.

[0902] The electrode protection film for a touch panel formed using the photosensitive composition layer in the transfer film of the present invention is preferably provided for the purpose of protecting electrodes etc. (that is, at least one of the electrode for a touch panel and the wiring for a touch panel), and is provided so as to directly cover the electrodes etc. or cover them with other layers interposed therebetween.

[0903] <Exposure process>

[0904] The exposure process is a process of pattern-exposing the photosensitive composition layer.

[0905] In addition, herein, "pattern exposure" means exposure in a pattern-like manner, that is, exposure in a manner where there are exposed portions and non-exposed portions.

[0906] The detailed configuration and specific dimensions of the pattern in the pattern exposure are not particularly limited. In addition, the pattern formed by the development process described later preferably includes a fine line having a width of 500 μm or less, and more preferably includes a fine line having a width of 100 μm or less.

[0907] As the light source for the pattern exposure, as long as it is a light source that can at least irradiate a wavelength region of light that can cure the photosensitive composition layer (for example, a wavelength of 365 nm or 405 nm), it can be appropriately selected. Among them, the main wavelength of the exposure light for the pattern exposure is preferably a wavelength of 365 nm. In addition, the main wavelength means the wavelength with the highest intensity.

[0908] As the light source, for example, various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps can be cited.

[0909] The exposure dose is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 200 mJ / cm 2 .

[0910] As the preferred modes of the light source, exposure dose, and exposure method used in the exposure, for example, paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193 are described, and these contents are incorporated into this specification.

[0911] <Peeling step>

[0912] The peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the lamination step and the exposure step or between the exposure step and the development step described later.

[0913] The peeling method is not particularly limited, and a mechanism similar to the film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

[0914] <Development step>

[0915] The development step is a step of developing the exposed photosensitive composition layer to form a pattern.

[0916] The development of the above-mentioned photosensitive composition layer can be carried out using a developer.

[0917] As the developer, an alkaline aqueous solution is preferred. As the alkaline compound that can be contained in the alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) can be cited.

[0918] As the development method, for example, spin immersion development, spray development, rotary development, and dip development can be cited.

[0919] In this specification, as the developer preferably used, for example, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271 can be cited.

[0920] As the development method that can be preferably used, for example, the development method described in paragraph

[0195] of International Publication No. 2015 / 093271 can be cited.

[0921] <Post-exposure step and post-baking step>

[0922] The manufacturing method of the above laminate may include a step of exposing the pattern obtained through the above development step (post-exposure step) and / or a step of heating (post-baking step).

[0923] When both the post-exposure step and the post-baking step are included, it is preferable to perform the post-baking after the post-exposure.

[0924] 〔Manufacturing method of circuit wiring〕

[0925] The transfer film can also be used in the manufacturing method of circuit wiring.

[0926] As the manufacturing method of circuit wiring, there is no particular limitation, and known manufacturing methods can be cited.

[0927] Among them, as the manufacturing method of circuit wiring, it is preferable that the manufacturing method of the laminate includes:

[0928] Laminating step: By peeling off the protective film from the transfer film, the photosensitive composition layer on the temporary support is laminated on the substrate having a conductive layer to obtain a substrate with a photosensitive composition layer having a conductive layer, a photosensitive composition layer, and a temporary support in this order.

[0929] Exposure step: Pattern exposure is performed on the photosensitive composition layer.

[0930] Development step: A pattern is formed by developing the exposed photosensitive composition layer; and

[0931] Etching step: The conductive layer in the area where no pattern is disposed is etched.

[0932] The manufacturing method of circuit wiring further includes:

[0933] Peeling step: The temporary support is peeled off from the substrate with a photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the development step.

[0934] In the manufacturing method of circuit wiring, the meanings of the laminating step, the exposure step, the development step, and the peeling step are the same as those of the respective steps in the above <Manufacturing method of laminate>, and the preferred ranges are also the same.

[0935] <Etching step>

[0936] The etching step is a step of etching the conductive layer in the area where the pattern obtained in the development step is not disposed (etching step).

[0937] That is, in the etching step, the pattern formed by the photosensitive composition layer is used as a resist to perform the etching treatment of the conductive layer.

[0938] As the etching process, a known method can be applied. For example, the methods described in paragraphs

[0209] to

[0210] of Japanese Patent Laid-Open No. 2017-120435, the methods described in paragraphs

[0048] to

[0054] of Japanese Patent Laid-Open No. 2010-152155, a wet etching method of immersing in an etching solution, and a dry etching method based on plasma etching can be cited.

[0939] For the etching solution used in wet etching, an acidic or alkaline etching solution can be appropriately selected according to the object to be etched.

[0940] As the acidic etching solution, for example, an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate can be cited. The acidic component can be a component composed of a combination of multiple acidic components.

[0941] As the alkaline etching solution, for example, an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), and a mixed aqueous solution of an alkaline component and a salt (such as potassium permanganate) can be cited. The alkaline component can be a component composed of a combination of multiple alkaline components.

[0942] <Removal process>

[0943] The method for manufacturing a circuit wiring can include a process of removing a residual pattern (removal process).

[0944] The removal process is not particularly limited and can be performed before or after each process. It is preferably performed after the etching process.

[0945] As the method for removing the residual pattern, there is no particular limitation. For example, a method of removing by chemical treatment can be cited, and a method of removing using a removal solution is preferably used.

[0946] As the method of removing using a removal solution, a method of immersing the transfer body having a residual pattern in the stirring removal solution for 1 to 30 minutes can be cited.

[0947] As the liquid temperature of the removal solution, 30 to 80°C is preferred, and 50 to 80°C is more preferred.

[0948] As the removal solution, for example, a removal solution in which an inorganic base component or an organic base component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof can be cited. As the inorganic base component, for example, sodium hydroxide and potassium hydroxide can be cited. As the organic base component, primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds can be cited.

[0949] Moreover, a stripping liquid can be used and removed by known methods such as spraying, showering, spin immersion, etc.

[0950] 〔Other processes〕

[0951] The method for manufacturing a laminate and the method for manufacturing a circuit wiring may include any process (other processes) other than the above processes.

[0952] As other processes, for example, a process for reducing the visible light reflectance described in paragraph

[0172] of International Publication No. 2019 / 022089 and a process for forming a new conductive layer on an insulating film described in paragraph

[0172] of International Publication No. 2019 / 022089 can be cited, but are not limited to these processes.

[0953] <Process for reducing visible light reflectance>

[0954] The method for manufacturing a laminate and the method for manufacturing a circuit wiring may include the following process: performing a process for reducing the visible light reflectance of a part or all of a plurality of conductive layers included in the transfer body.

[0955] As the process for reducing the visible light reflectance, for example, an oxidation process can be cited. When the transfer body has a copper-containing conductive layer, the copper is oxidized to form copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectance of the conductive layer.

[0956] Regarding the process for reducing the visible light reflectance, the descriptions in paragraphs

[0017] to

[0025] of Japanese Patent Application Laid-Open No. 2014-150118, and paragraphs

[0041] to

[0042] ,

[0048] , and

[0058] of Japanese Patent Application Laid-Open No. 2013-206315 can be cited, and these are incorporated into this specification.

[0957] <Process for forming an insulating film, process for forming a new conductive layer on the surface of the insulating film>

[0958] The method for manufacturing a circuit wiring preferably further includes a process for forming an insulating film on the surface of the circuit wiring and a process for forming a new conductive layer on the surface of the insulating film.

[0959] Through the above processes, a first electrode pattern and an insulating second electrode pattern can be formed.

[0960] As the process for forming an insulating film, there is no particular limitation, and known methods for forming a permanent film can be cited. Moreover, a photosensitive material having insulating properties can be used to form an insulating film having a desired pattern by photolithography.

[0961] The process of forming a new conductive layer on the insulating film is not particularly limited. For example, a photosensitive composition having conductivity can be used to form a new conductive layer with a desired pattern by lithography.

[0962] The method for manufacturing circuit wiring preferably also uses a substrate having a plurality of conductive layers on each of the two surface sides of the substrate, and circuits are formed on the conductive layers disposed on the two surface sides of the substrate successively or simultaneously. With such a structure, it is possible to form circuit wiring for a touch panel as follows: a first conductive pattern is formed on one surface of the substrate, and a second conductive pattern is formed on the other surface of the substrate. Also preferably, the circuit wiring for the touch panel having such a structure is formed from both sides of the substrate by roll-to-roll.

[0963] 〔Use〕

[0964] The laminate and circuit wiring manufactured by the laminate manufacturing method and the circuit wiring manufacturing method can be applied to various devices. As a device having the laminate or circuit wiring manufactured by the above manufacturing method, for example, a display device, a printed wiring board, a semiconductor package, and an input device can be cited. Preferably, it is a touch panel, and more preferably a capacitive touch panel. Also, the above input device can be applied to display devices such as an organic EL display device and a liquid crystal display device.

[0965] 〔Manufacturing method of electronic device〕

[0966] The transfer film can also be used in the manufacturing method of an electronic device.

[0967] As the manufacturing method of the above electronic device, a manufacturing method of an electronic device preferably using the above transfer film is used.

[0968] Among them, the manufacturing method of the electronic device preferably includes the above laminate manufacturing method.

[0969] As the above electronic device, for example, an input device etc. can be cited, and preferably it is a touch panel. Also, the above input device can be applied to display devices such as an organic electroluminescent display device and a liquid crystal display device.

[0970] As a manufacturing method of a touch panel, for example, it also preferably includes a process of forming wiring for a touch panel by etching a conductive layer in a region where no resin pattern is disposed in a laminate in which a transfer body (for example, a substrate, a conductive layer (a conductive layer possessed by the substrate)) and a pattern manufactured using the above transfer film are successively laminated, and more preferably a method using a pattern manufactured by a manufacturing method including the above lamination process, the above exposure process, and the above development process.

[0971] Regarding the embodiments such as the specific manners of each process and the order of performing each process in the method for manufacturing a touch panel including a process of forming wiring for a touch panel, as described in the above <Method for Manufacturing Circuit Wiring>, the preferred manners are the same.

[0972] Moreover, the method for manufacturing a touch panel including a process of forming wiring for a touch panel may include any other processes (other processes) than the above.

[0973] As a method for forming wiring for a touch panel, for example, the method described in International Publication No. 2016 / 190405 can also be cited. Figure 1 The method described therein.

[0974] By the above method for manufacturing a touch panel, a touch panel having at least wiring for a touch panel can be manufactured. The touch panel preferably has a transparent substrate, electrodes, an insulating layer, or a protective layer.

[0975] As a detection method in a touch panel, for example, well-known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method can be cited, and the capacitive method is preferred.

[0976] As a touch panel, for example, an in-cell type (for example, the touch panel described in FIGS. 5 to 8 of Japanese Patent Application Laid-Open No. 2012-517051), an on-cell type (for example, the touch panel described in FIG. 19 of Japanese Patent Application Laid-Open No. 2013-168125, and the touch panel described in Figure 1 and FIG. 5 of Japanese Patent Application Laid-Open No. 2012-089102), an OGS (One Glass Solution) type, a TOL (Touch-on-Lens) type (for example, the touch panel described in Figure 2 Japanese Patent Application Laid-Open No. 2013-054727), various out-cell types (for example, GG, G1·G2, GFF, GF2, GF1, and G hall, etc.), and other structures (for example, the touch panel described in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871).

[0977] As a touch panel, for example, the touch panel described in paragraph

[0229] of Japanese Patent Application Laid-Open No. 2017-120345 can be cited.

[0978] In the method for manufacturing an electronic device using a transfer film, it is also preferred (especially when the transfer film includes a negative photosensitive composition layer) that the manufactured electronic device includes a resin pattern as a cured film.

[0979] The cured film of such a resin pattern can be used as a protective film (permanent film) that covers part or all of electrodes and the like of an electronic device (such as a touch panel). By disposing the cured film of the above resin pattern on the electrodes and the like as a protective film (permanent film), it is possible to prevent defects such as corrosion of metals, an increase in resistance between the electrodes and the driving circuit, and short circuits.

[0980] Examples

[0981] Hereinafter, examples will be given to specifically illustrate the present invention. The materials, amounts used, ratios, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of this specification. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are based on mass.

[0982] In the following examples, the weight average molecular weight (Mw) is the weight average molecular weight determined by conversion to polystyrene based on gel permeation chromatography (GPC).

[0983] [Temporary support Z-1]

[0984] The temporary support Z-1 of Example 1 was produced in the following order.

[0985] Particles A of polyethylene terephthalate produced using a titanium compound (citric acid chelated titanium complex, VERTEC AC-420, manufactured by Johnson Matthey) described in Japanese Patent No. 5575671 as a polymerization catalyst were obtained.

[0986] 90 parts by mass of the above particles A and 10 parts by mass of a 10% aqueous slurry of organic particles obtained by crosslinking polystyrene resin particles with an average particle diameter of 500 nm with divinylbenzene (crosslinked polystyrene resin particles produced by the following method) were supplied to a twin-screw kneading extruder, and the exhaust hole was maintained at a vacuum degree of 1 kPa or less to remove moisture, thereby obtaining a masterbatch A containing 1% by mass of crosslinked polystyrene resin particles (organic particles).

[0987] [Manufacture of crosslinked polystyrene resin particles]

[0988] After adding potassium persulfate (3.2 parts by mass) and sodium lauryl sulfate (0.15 parts by mass) to deionized water (1500 parts by mass) and uniformly dissolving them, a mixed solution of styrene (92 parts by mass) and divinylbenzene (8 parts by mass) was added. A polymerization reaction was carried out at 70 °C for 24 hours while stirring in a nitrogen atmosphere, thereby obtaining crosslinked polystyrene resin particles.

[0989] Particle A (90 parts by mass) and a 10% aqueous slurry of alumina particles with an average particle diameter of 30 nm (alumina sol, manufactured by Nissan Chemical Corporation) (10 parts by mass) were supplied to a twin-screw kneading extruder, and the exhaust port was maintained at a vacuum of 1 kPa or less to remove moisture, thereby obtaining masterbatch B containing 1% by mass of alumina particles.

[0990] Furthermore, particle A (70 parts by mass), masterbatch A (10 parts by mass), and masterbatch B (20 parts by mass) were mixed to obtain mixture X.

[0991] After drying particle A and mixture X to a moisture content of 50 ppm or less, they were put into an extruder so that the intermediate layer was particle A, melted at 290°C, and joined and laminated through a layer joining block, thereby producing an unstretched temporary support having a three-layer structure in the order of X layer (layer composed of mixture X) / A layer (layer composed of particle A) / X layer (layer composed of mixture X). In addition, by means of the electrostatic printing method, the extruded melt was closely adhered to one X layer side of the cooling roll.

[0992] The obtained unstretched temporary support was subjected to sequential biaxial stretching by the following method.

[0993] First, the unstretched temporary support was passed between two pairs of pinch rolls having different circumferential speeds, thereby performing stretching in the longitudinal direction (transport direction). In addition, longitudinal stretching was performed under the conditions of a preheating temperature of 75°C, a stretching temperature of 95°C, a stretching ratio of 3.4 times, and a stretching speed of 1300% / second.

[0994] Next, using a tenter, the longitudinally stretched temporary support was transversely stretched. In addition, longitudinal stretching was performed under the conditions of a preheating temperature of 100°C, a stretching temperature of 120°C, a stretching ratio of 4.2 times, and a stretching speed of 50% / second to obtain temporary support Z-1. In addition, the thickness of each layer of temporary support Z-1 was X layer / A layer / X layer = 1 μm / 14 μm / 1 μm.

[0995] The components were changed according to Tables 2 to 3, and except for this, the temporary supports of each example and each comparative example were produced in the same order as the above-mentioned temporary support Z-1.

[0996] 〔Transfer film〕

[0997] The transfer film of Example 1 was produced in the following order.

[0998] First, the components contained in each transfer film will be described in detail.

[0999] <Adhesive polymer A>

[1000] PGMEA (55.8 parts by mass) and toluene (55.8 parts by mass) were mixed to prepare the first liquid. Further, a mixed liquid of methacrylic acid (12 parts by mass), methyl methacrylate (58 parts by mass) and ethyl acrylate (30 parts by mass), AIBN (azobisisobutyronitrile) (1.0 part by mass), PGMEA (6.2 parts by mass) and toluene (6.2 parts by mass) were mixed and stirred at room temperature for 1 hour to prepare the second liquid.

[1001] The above first liquid was added to a flask, and the temperature was raised to 80 °C under a nitrogen atmosphere. Subsequently, while stirring the obtained mixed liquid and maintaining the liquid temperature at 80 °C, the above second liquid was further added to the flask over 4 hours using a dropping pump. After the addition was completed, the obtained mixed liquid was stirred and the liquid temperature was maintained at 80 °C, and the reaction was further continued for 6 hours to obtain a solution containing the binder polymer A. The weight-average molecular weight of the obtained binder polymer A was 65,000. The composition ratio (mass ratio) derived from each monomer was methacrylic acid / methyl methacrylate / ethyl acrylate = 12 / 58 / 30.

[1002] <Binder Polymer B>

[1003] PGMEA (116.5 parts by mass) was added to a three-necked flask, and the temperature was raised to 90 °C under a nitrogen atmosphere. While maintaining the liquid temperature in the three-necked flask at 90 °C ± 2 °C, a mixed liquid of styrene (52.0 parts by mass), methyl methacrylate (24.0 parts by mass), methacrylic acid (24.0 parts by mass), V-601 (2,2'-azobis(isobutyric acid)dimethyl ester, manufactured by Fujifilm Corporation) (4.0 parts by mass) and PGMEA (116.5 parts by mass) was added dropwise to the three-necked flask over 2 hours. After the addition was completed, the liquid temperature was maintained at 90 °C ± 2 °C while stirring the mixed liquid for 2 hours to obtain a solution containing the binder polymer B (solid content concentration: 30.0 mass%). In addition, the acid value of the binder polymer B was 159 mgKOH / g, the weight-average molecular weight was 60,000, and the glass transition temperature was 126 °C. The composition ratio (mass ratio) derived from each monomer was styrene / methacrylic acid / methyl methacrylate = 52 / 24 / 24.

[1004] <Binder Polymer C>

[1005] Propylene glycol monomethyl ether (82.4 g) was added to a flask and heated to 90 °C under a nitrogen stream. Meanwhile, a solution in which styrene (38.4 g), dicyclopentanyl methacrylate (30.1 g), and methacrylic acid (34.0 g) were dissolved in propylene glycol monomethyl ether (20 g) and a solution in which a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) (5.4 g) was dissolved in propylene glycol monomethyl ether acetate (43.6 g) were added dropwise to the liquid over 3 hours. After the addition dropwise was completed, V-601 (0.75 g) was added 3 times at 1-hour intervals. Thereafter, the reaction was further continued for 3 hours. Then, it was diluted with propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). Under an air stream, the reaction solution was heated to 100 °C, and tetraethylammonium bromide (0.53 g) and p-methoxyphenol (0.26 g) were added. Glycidyl methacrylate (BLEMMER GH manufactured by NOF CORPORATION) (25.5 g) was added dropwise thereto over 20 minutes. The reaction was carried out at 100 °C for 7 hours to obtain a solution of polymer P-1. The solid content concentration of the obtained solution was 36.5 mass%. The weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersity was 2.4, and the acid value of the polymer was 94.5 mgKOH / g. Among all the monomers, the residual monomer amount measured by gas chromatography was less than 0.1 mass% relative to the polymer solid content.

[1006] Hereinafter, the structure of the binder polymer C (the repeating units in the formula are in molar ratio) is shown.

[1007] [Chemical formula 27]

[1008]

[1009] <Photosensitive composition>

[1010] The photosensitive compositions Y-1 to Y-5 were adjusted.

[1011] (Photosensitive composition Y-1)

[1012] · Tricyclodecane dimethanol diacrylate (polymerizable compound, A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 19.31 parts by mass

[1013] · Carboxylic acid-containing monomer (polymerizable compound, ARONIX T02349, manufactured by TOAGOSEI CO., LTD.): 3.21 parts by mass

[1014] · Carbamate - acrylic monomer (polymerizable compound, ACRIT 8UX - 015A, manufactured by Taisei Fine Chemical Co., Ltd.): 9.65 parts by mass

[1015] · The following binder polymer P - 1 (acid value 95 mgKOH / g, Mw = 27,000, solid content concentration 36.3% by mass): 53.64 parts by mass in terms of solid content

[1016] [Chemical formula 28]

[1017]

[1018] · Duranate WT32 - B75P (thermally cross - linkable compound, manufactured by Asahi Kasei Corporation): 12.50 parts by mass

[1019] · Irgacure OXE - 02 (photoinitiator, manufactured by BASF): 0.37 parts by mass

[1020] · Omnirad 907 (photoinitiator, manufactured by IGM Resins B.V.): 0.74 parts by mass

[1021] · N - phenylglycine (hydrogen - donating compound, manufactured by JUNSEI CHEMICAL CO., LTD.): 0.10 parts by mass

[1022] · Benzimidazole (heterocyclic compound, manufactured by Tokyo Chemical Industry Co., Ltd.): 0.30 parts by mass

[1023] · MEGAFACE F551 (surfactant, manufactured by DIC Corporation): 0.16 parts by mass

[1024] · Mixed solvent of 1 - methoxy - 2 - propyl acetate (PGMEA) and methyl ethyl ketone (MEK) (PGMEA∶MEK = 4∶6): an amount such that the solid content concentration of the photosensitive composition Y - 1 becomes 29%

[1025] (Photosensitive composition Y - 2)

[1026] · Binder polymer A: 63.00 parts by mass in terms of solid content

[1027] · Pentaerythritol triacrylate (ethylenically unsaturated compound, “A - TMM - 3LM - N” manufactured by SHIN - NAKAMURA CHEMICAL Co., Ltd.): 37.00 parts by mass

[1028] · Bis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide (polymerization initiator, “Omnirad 819” manufactured by IGM Resins B.V.): 10.00 parts by mass

[1029] · Polyether-modified silicone (surfactant (leveling agent), “8032 ADDITIVE” manufactured by Dow Corning Toray Co., Ltd.): 0.06 parts by mass

[1030] · MEK: An amount such that the solid content concentration of photosensitive composition Y-2 becomes 30%

[1031] (Photosensitive composition Y-3)

[1032] · Binder polymer B (solid content concentration 30.0 mass%): 53.27 parts by mass

[1033] · NK ESTER BPE-500 (polymerizable compound, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 22.5 parts by mass

[1034] · NK ESTER BPE-200 (polymerizable compound, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 10.0 parts by mass

[1035] · NK ESTER A-TMPT (polymerizable compound, trimethylolpropane triacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 10 parts by mass

[1036] · B-CIM (polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Hampford): 3.00 parts by mass

[1037] · SB-PI 701 (sensitizer, 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd.): 0.30 parts by mass

[1038] · Dye N-1 (colorless crystal violet, manufactured by Tokyo Chemical Industry Co., Ltd., developed by free radicals): 0.60 parts by mass

[1039] · Pigment N-2 (Brilliant Green, manufactured by Tokyo Chemical Industry Co., Ltd.): 0.02 parts by mass

[1040] · A mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole (hydrogen-donating compound, mass ratio 1:1): 0.10 parts by mass

[1041] · Irganox 245 (antioxidant, vinyl bis(oxyethylene) bis(3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate), manufactured by BASF): 0.20 parts by mass

[1042] · Aluminum N-nitrosophenylhydroxylamine salt (polymerization inhibitor): 0.01 parts by mass

[1043] · Methyl ethyl ketone (manufactured by SANKYO CHEMICAL CO., LTD.): The amount that makes the solid component concentration of photosensitive composition Y-3 30%

[1044] · PGMEA (manufactured by SHOWA DENKO K.K): 50.00 parts by mass

[1045] · Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.): 10.00 parts by mass

[1046] (Photosensitive composition Y-4)

[1047] · Binder polymer C: 52.67 parts by mass (solid component amount)

[1048] · A-NOD-N (1,9-nonanediol diacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 2.73 parts by mass

[1049] · A-DCP (tricyclodecane dimethanol diacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 17.90 parts by mass

[1050] · ARONIX TO-2349 (polyfunctional ethylenically unsaturated compound having a carboxyl group, manufactured by TOAGOSEI CO., LTD.): 2.98 parts by mass

[1051] · DPHA: Dipentaerythritol hexaacrylate (manufactured by Toshin Yushi Co., Ltd.): 7.99 parts by mass

[1052] · 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime) (D-1, Irgacure OXE-02, manufactured by BASF): 0.36 parts

[1053] · 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (D-2, Irgacure 907, manufactured by BASF): 0.73 parts

[1054] · Duranate WT32-B75P (E-3, blocked isocyanate compound, manufactured by Asahi Kasei Corporation): 12.50 parts by mass

[1055] · Isonicotinamide: 0.52 parts by mass

[1056] · Benzimidazole: 0.13 parts by mass

[1057] · N-Phenylglycine (manufactured by JUNSEI CHEMICAL CO., LTD.): 0.10 parts by mass

[1058] · Copolymer of styrene / maleic anhydride = 4:1 (molar ratio) (anhydride value 1.94 mmol / g, weight average molecular weight 10,500) (SMA EF-40, manufactured by Cray Valley): 1.20 parts by mass.

[1059] · BYK-330 (manufactured by BYK-Chemie GmbH): 0.10 parts by mass

[1060] · PGMEA: 70 parts by mass

[1061] · MEK: 30 parts by mass

[1062] (Photosensitive composition Y-5)

[1063] · Binder polymer C: 40 parts by mass (solid content amount)

[1064] · Copolymer of benzyl methacrylate / methacrylic acid = 80 / 20 (mass ratio) (weight average molecular weight 30,000): 12.67 parts by mass (solid content amount)

[1065] · A-NOD-N (1,9-Nonanediol diacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 2.73 parts

[1066] · KAYARAD R-604 (manufactured by Nippon Kayaku Co., Ltd.): 10 parts

[1067] · A-DCP (tricyclodecane dimethanol diacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 7.90 parts by mass

[1068] · A-TMMT (pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.): 2.98 parts by mass

[1069] · DPHA: dipentaerythritol hexaacrylate (manufactured by Toshin Yushi Co., Ltd.): 8 parts by mass

[1070] · (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (trade name: APi-307, manufactured by Shenzhen UV-ChemTech Ltd.): 2.1 parts by mass

[1071] · Naphthalenethiol: 0.10 parts by mass

[1072] · BYK-330 (manufactured by BYK-Chemie GmbH): 0.10 parts by mass

[1073] · PGMEA: 50 parts by mass

[1074] · MEK: 30 parts by mass

[1075] (Photosensitive compositions A to C)

[1076] The following photosensitive compositions A to C were prepared. In Table 1 below, the numerical values of each component represent the content (parts by mass) of each component, and the amount of the binder polymer represents the amount of the binder polymer solution (solid content concentration: 36.3 mass%).

[1077] In addition, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline contained in the photosensitive composition B was synthesized by the method according to the following scheme.

[1078] [Chemical formula 29]

[1079]

[1080] Anisaldehyde (20.4 g), acetone (4.4 g), sodium hydroxide (15.0 g) and distilled water (120 mL) were dissolved in ethanol (150 mL), and the mixture was stirred at room temperature for 3 hours. The obtained solution was filtered, rinsed with distilled water (500 mL), and then the filtrate was dried by blowing air at room temperature to obtain a pale yellow solid (18.7 g).

[1081] The obtained pale yellow solid (9.0 g) and phenylhydrazine (3.3 g) were dissolved in acetic acid (100 mL), stirred at room temperature for 3 hours, and then cooled in ice. The obtained solution was filtered, rinsed successively with acetic acid (200 mL), distilled water (200 mL), and methanol (200 mL), and the filtrate was dried by air blowing at room temperature to obtain 4.7 g (yield 40%) of 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline as a pale yellow solid.

[1082] [Table 1]

[1083]

[1084] [Examples 1 to 14, 16 to 28, 30 and Comparative Examples 1 to 5]

[1085] Using a slit nozzle, the thickness after drying was adjusted to 8.8 μm, and the photosensitive composition Y-1 was coated on the temporary support Z-1 obtained above. After drying at 100 °C for 2 minutes, it was further dried at 120 °C for 1 minute.

[1086] Thereafter, a polyethylene terephthalate film with a thickness of 16 μm (16KS40, manufactured by TORAY INDUSTRIES, INC.) as a protective film was laminated on the photosensitive composition layer to obtain the transfer film of Example 1.

[1087] By changing the components and the thickness of each layer according to Tables 2 to 3, and in the same order as in Example 1, the transfer films of Examples 2 to 14, 16 to 28, 30 and Comparative Examples 1 to 5 were obtained.

[1088] [Example 15]

[1089] For the transfer film of Example 1 obtained above, the thickness after drying was adjusted to 73 nm, and then the following refractive index adjustment layer-forming composition X-1 was coated on the photosensitive composition layer and dried at 80 °C for 1 minute. Thereafter, it was further dried at 110 °C for 1 minute to form a refractive index adjustment layer directly disposed on the photosensitive composition layer, and the transfer film of Example 15 was obtained.

[1090] [Example 29]

[1091] For the transfer film of Example 28 obtained above, the thickness after drying was adjusted to 73 nm, and then the following refractive index adjustment layer-forming composition X-1 was coated on the photosensitive composition layer and dried at 80 °C for 1 minute. Thereafter, it was further dried at 110 °C for 1 minute to form a refractive index adjustment layer directly disposed on the photosensitive composition layer, and the transfer film of Example 29 was obtained.

[1092] (Composition for forming refractive index adjusting layer)

[1093] The composition for forming a refractive index adjusting layer was prepared using the following respective components.

[1094] In addition, the composition for forming a refractive index adjusting layer is the following aqueous resin composition: prepared using a resin having an acid group and an aqueous ammonia solution, and the resin having an acid group is neutralized in the aqueous ammonia solution and contains an ammonium salt of the resin having an acid group.

[1095] · Metal oxide particles (ZrO2 particles, NanoUse OZ-S30M, solid component concentration 30.5% by mass, methanol 69.5% by mass, refractive index 2.2, average particle size about 12 nm, manufactured by NIssan Chemical Corporation): 80.()0 parts by mass in terms of solid components

[1096] · Adhesive polymer having an acid group (acrylic resin, ZB-015M, manufactured by FUJIFILM Wako PureChemical Corporation, copolymer resin of methacrylic acid / allyl methacrylate (composition ratio (molar ratio) = 20 / 80), weight average molecular weight 25,000, solid component concentration 5.00%, aqueous ammonia solution): 14.78 parts by mass in terms of solid components

[1097] · Adhesive polymer having an acid group (acrylic resin, ARUFON UC3920, manufactured by TOAGOSEI CO., LTD.): 0.53 part by mass

[1098] · Olefinically unsaturated compound (polyfunctional olefinically unsaturated compound having a carboxyl group, ARONIX TO-2349, manufactured by TOAGOSEI CO., LTD.): 2.00 parts by mass

[1099] · Surfactant (fluorine-based surfactant, MEGAFACE F-444, manufactured by DIC Corporation): 0.68 part by mass

[1100] · BT-LX (manufactured by JOHOKU CHEMICAL CO., LTD.): 2.00 parts by mass

[1101] · Mixed solvent of methanol and distilled water (methanol:distilled water = 7:3 (mass ratio)): an amount such that the solid component concentration of the composition for forming a refractive index adjusting layer becomes 1.66% by mass

[1102] 〔Evaluation〕

[1103] <Pattern formability>

[1104] On a cyclic olefin polymer (COP) film with a thickness of 100 μm, a copper layer with a thickness of 200 nm was formed by sputtering, and thus 4 COP film substrates with copper layers were fabricated. Under the lamination conditions of a crimping roll temperature of 100 °C, a line pressure of 0.6 MPa, and a line speed of 4.0 m / min, after laminating each transfer film on the obtained COP film substrate with a copper layer, it was left standing for 3 hours.

[1105] After that, without peeling off the temporary support, through a mask for forming a line and space pattern with a line width of 100 μm (duty ratio = 1:1), the photosensitive composition layer of the transfer film was exposed. As the exposure light source, an ultra-high pressure mercury lamp was used. The exposure amount was adjusted within the range where the line width of the resin pattern formed by development became 100 μm.

[1106] The temporary support was peeled off from the surface of the exposed photosensitive composition layer, and the photosensitive composition layer was developed. Specifically, using a 1.0 mass% aqueous sodium carbonate solution at 33 °C, spray development was carried out for 45 seconds, and a laminate with a resin pattern was obtained.

[1107] The line widths at 20 arbitrary positions of the obtained resin pattern were measured. For the measured 20 line width values, the standard deviation σ and the average value α were calculated. The dispersion β was further calculated by the following formula, and the pattern formability was evaluated according to the following evaluation criteria. In the following evaluation criteria, the pattern formability of A is the best, and that of E is the worst. It is preferably any one of A, B, and C, more preferably A or B, and further preferably A.

[1108] Dispersion β (%) = 100 × (standard deviation o / average value α)

[1109] (Evaluation criteria)

[1110] A: Dispersion β is less than 3%

[1111] B: Dispersion β is 3% or more and less than 5%

[1112] C: Dispersion β is 5% or more and less than 8%

[1113] D: Dispersion β is 8% or more and less than 10%

[1114] E: Dispersion β is 10% or more

[1115] <Peelability>

[1116] (Peelability between the photosensitive composition layer and the temporary support)

[1117] After peeling off the protective film from each of the above-obtained transfer films, the photosensitive composition was laminated layer by layer on a copper plate. The lamination conditions were a lamination roll temperature of 100°C, a line pressure of 3 N / cm, and a conveyance speed of 4 m / minute. After that, after peeling off the temporary support upward vertically at a speed of 0.01 m / minute, the photosensitive composition layer remaining on the copper plate was visually confirmed and evaluated according to the following evaluation criteria. In addition, among the following evaluation criteria, A has the best peelability and E has the worst peelability. Any one of A, B, and C is preferred, more preferably A or B, and further preferably A.

[1118] The residual area (%) of the photosensitive composition layer on the copper plate = 100 × (the area of the photosensitive composition layer remaining on the copper plate after peeling / the area of the photosensitive composition layer on the copper plate before peeling)

[1119] (Evaluation criteria)

[1120] A: The residual area of the photosensitive composition layer on the copper plate is 100%

[1121] B: The residual area of the photosensitive composition layer on the copper plate is 99% or more and less than 100%

[1122] C: The residual area of the photosensitive composition layer on the copper plate is 95% or more and less than 99%

[1123] D: The residual area of the photosensitive composition layer on the copper plate is 90% or more and less than 95%

[1124] E: The residual area of the photosensitive composition layer on the copper plate is less than 90%

[1125] (Peelability between the photosensitive composition layer and the protective film)

[1126] After peeling off the protective film upward vertically at a speed of 0.01 m / minute, the photosensitive composition layer remaining on the temporary support was visually confirmed and evaluated according to the following evaluation criteria. In addition, among the following evaluation criteria, A has the best peelability and E has the worst peelability. Any one of A, B, and C is preferred, more preferably A or B, and further preferably A.

[1127] The residual area (%) of the photosensitive composition layer on the temporary support = 10() × (the area of the photosensitive composition layer remaining on the temporary support after peeling / the area of the photosensitive composition layer on the temporary support before peeling)

[1128] (Evaluation criteria)

[1129] A: The residual area of the photosensitive composition layer on the temporary support is 100%

[1130] B: The remaining area of the photosensitive composition layer on the temporary support is 99% or more and less than 100%.

[1131] C: The remaining area of the photosensitive composition layer on the temporary support is 95% or more and less than 99%.

[1132] D: The remaining area of the photosensitive composition layer on the temporary support is 90% or more and less than 95%.

[1133] E: The remaining area of the photosensitive composition layer on the temporary support is less than 90%.

[1134] <Evaluation of kurtosis Rku>

[1135] Using New View 6000 manufactured by Zygo Corporation, the kurtosis Rku of the surface of the first layer of the temporary support that comes into contact with the photosensitive composition layer was evaluated by a method in accordance with ISO 4287:1997.

[1136] In the table, each description represents the following.

[1137] The column of "photosensitive composition layer / temporary support" shows the peelability between the photosensitive composition layer and the temporary support.

[1138] The column of "photosensitive composition layer / protective film" shows the peelability between the photosensitive composition layer and the protective film.

[1139]

[1140]

[1141] Based on the results in the table, it was confirmed that when using the transfer film of the present invention, the desired effects can be obtained.

[1142] Based on the comparison between Examples 1 and 8 to 10 and Examples 7 and 11, it was confirmed that when the average particle diameter of the first organic particles is 350 to 800 nm, the effects of the present invention are more excellent.

[1143] Furthermore, based on the same comparison, it was confirmed that when the kurtosis Rku of the surface of the first layer is 2.5 to 10, the effects of the present invention are more excellent.

[1144] Based on the comparison between Example 1 and the like and Examples 12 and 13, it was confirmed that when the average particle diameter of the first inorganic particles and the average particle diameter of the second inorganic particles are 10 to 50 nm, the effects of the present invention are more excellent.

[1145] Based on the comparison between Example 1 and the like and Examples 14 and 21, it was confirmed that when the first inorganic particles and the second inorganic particles contain alumina, the effects of the present invention are more excellent.

[1146] It was confirmed by comparing Example 1 etc. with Example 21 that when the components contained in the first layer and the second layer and the thicknesses of the first layer and the second layer are the same, the effects of the present invention are more excellent.

[1147] It was confirmed by comparing Example 1 etc. with Examples 7, 11 to 14 and 21 that when the kurtosis Rku of the surface of the first layer is 3.0 to 5.0 and the first inorganic particles and the second inorganic particles contain alumina, the effects of the present invention are more excellent.

[1148] Symbol Explanation

[1149] 1, 11 - Temporary support, 2, 12 - Composition layer, 3, 17 - Photosensitive composition layer, 5 - Refractive index adjustment layer, 7, 19 - Protective film, 10, 20 - Transfer film, 13 - Thermoplastic resin layer, 15 - Intermediate layer.

Claims

1. A transfer film which successively has a temporary support, a photosensitive composition layer disposed on the temporary support, and a protective film. The temporary support has a temporary support main body, a first layer disposed on one surface of the temporary support main body, and a second layer disposed on the other surface of the temporary support main body. Among the first layer and the second layer, the first layer is disposed on the photosensitive composition layer side. The first layer contains first organic particles having an average particle diameter of 100 nm to 1000 nm and first inorganic particles having an average particle diameter of 70 nm or less, and the kurtosis Rku of the surface of the first layer in contact with the photosensitive composition layer is 2.0 to 100. The second layer contains second inorganic particles having an average particle diameter of 70 nm or less and second organic particles having an average particle diameter of 100 - 1000 nm. The content of the first organic particles in the first layer is 0.01 to 10.0% by mass relative to the total mass of the first layer, and the content of the first inorganic particles in the first layer is 0.01 to 10.0% by mass relative to the total mass of the first layer. The content of the second organic particles in the second layer is 0.01 to 10.0% by mass relative to the total mass of the second layer, and the content of the second inorganic particles in the second layer is 0.01 to 10.0% by mass relative to the total mass of the second layer. The temporary support is in direct contact with the photosensitive composition layer. The kurtosis Rku is the average value of the measured values obtained by measuring 10 randomly selected portions in the surface of the first layer in contact with the photosensitive composition layer using New View 6000 manufactured by Zygo Corporation, excluding the minimum value and the maximum value.

2. The transfer film according to claim 1, wherein, The first organic particles contain polystyrene resin particles.

3. The transfer film according to claim 1 or 2, wherein The average particle diameter of the first organic particles is 350 nm to 800 nm.

4. The transfer film according to claim 1 or 2, wherein, At least one of the first inorganic particles and the second inorganic particles contains at least one selected from silicon atoms and aluminum atoms.

5. The transfer film according to claim 1 or 2, wherein At least one of the first inorganic particles and the second inorganic particles contains alumina.

6. The transfer film according to claim 1 or 2, wherein The average particle diameter of the first inorganic particles and the average particle diameter of the second inorganic particles are 10 nm to 50 nm.

7. The transfer film according to claim 1 or 2, wherein, The thickness of the temporary support main body is 6.0 μm to 30.0 μm. The thickness of the first layer and the second layer is 0.8 μm to 3.0 μm.

8. The transfer film according to claim 1 or 2, wherein The average particle diameter of the first organic particles is 350 nm to 800 nm, the first inorganic particles contain alumina, and the average particle diameter of the first inorganic particles is 10 nm to 50 nm.

9. The transfer film according to claim 1 or 2, wherein The second layer contains second organic particles having an average particle diameter of 350 nm to 800 nm, the second inorganic particles contain alumina, and the average particle diameter of the second inorganic particles is 10 nm to 50 nm.

10. The transfer film according to claim 1 or 2, wherein, The kurtosis Rku of the surface of the first layer is 2.5 to 10.

11. The transfer film according to claim 1 or 2, wherein, The kurtosis Rku of the surface of the first layer is 3.0 to 5.

0. The first inorganic particles and the second inorganic particles contain alumina.

12. The transfer film according to claim 1 or 2, wherein The photosensitive composition layer contains a binder polymer, a polymerizable compound, and a polymerization initiator.

13. The transfer film according to claim 1 or 2, wherein, There is also a refractive index adjustment layer between the photosensitive composition layer and the protective film.

14. The transfer film according to claim 1 or 2, wherein, The photosensitive composition layer is used to form an electrode protective film for a touch panel.

15. The transfer film according to claim 1 or 2, wherein The mass ratio of the content of the first inorganic particles to the content of the first organic particles is 1.0 or more and 10.0 or less.

16. A method for manufacturing a laminate, comprising: A laminating step of peeling the protective film from the transfer film according to any one of claims 1 to 15 and laminating the surface on the side opposite to the temporary support on a substrate having a conductive layer, to obtain a substrate with a photosensitive composition layer having, in sequence, the conductive layer, the photosensitive composition layer, and the temporary support, An exposure step of performing pattern exposure on the photosensitive composition layer; And A developing step of developing the exposed photosensitive composition layer to form a pattern; The method for manufacturing the laminate further includes: A peeling step of peeling the temporary support from the substrate with the photosensitive composition layer between the exposure step and the developing step.

17. A method for manufacturing a circuit wiring, comprising: A laminating step of peeling the protective film from the transfer film according to any one of claims 1 to 15 and laminating the surface on the side opposite to the temporary support on a substrate having a conductive layer, to obtain a substrate with a photosensitive composition layer having, in sequence, the conductive layer, the photosensitive composition layer, and the temporary support, An exposure step of performing pattern exposure on the photosensitive composition layer; A developing step of developing the exposed photosensitive composition layer to form a pattern; An etching step of etching the conductive layer in a region where the pattern is not disposed; And A peeling step of further peeling the temporary support from the substrate with the photosensitive composition layer between the exposure step and the developing step.

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