Transfer film, method for manufacturing a laminate

Abstract

The present invention provides a method for manufacturing a transfer film and a laminate, and the transfer film has a photosensitive composition layer capable of forming a pattern with excellent scratch resistance and excellent edge shape. The transfer film has a temporary support and a photosensitive composition layer, and the photosensitive composition layer contains a photoinitiator, an alkali-soluble resin, and a polymerizable compound. The photoinitiator contains a first photoinitiator and a second photoinitiator. The molar extinction coefficient ε1 of the first photoinitiator at a wavelength of 365 nm is 500 L / mol·cm or more, and the ratio of the molar extinction coefficient ε2 of the second photoinitiator at a wavelength of 365 nm to the molar extinction coefficient ε3 of the second photoinitiator at a wavelength of 313 nm is 0.200 or less.

Description

Technical Field

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

[0002] Since the number of processes for obtaining a pattern with a specified shape is small, a method is widely used in which a photosensitive composition layer provided on an arbitrary substrate is exposed through a mask including a desired pattern using a transfer film and then developed.

[0003] For example, a transfer film having a photosensitive composition layer may be used to form a protective layer for protecting sensor electrodes and lead wirings in a touch panel. More specifically, Patent Document 1 discloses a thin film (transfer film) having a photosensitive resin layer (photosensitive composition layer) containing an alkali-soluble binder polymer, a photopolymerizable compound, and a photoinitiator.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2019-175226 Summary of the Invention

[0007] Technical Problem to be Solved by the Invention

[0008] On the other hand, in recent years, further improvement in the shape of a pattern formed from a photosensitive composition layer has been demanded. Specifically, it is required that no unevenness is generated in the edge portion of the formed pattern, and when the pattern on the substrate is visually recognized from the normal direction of the substrate, the edge portion is linear. Hereinafter, in the present specification, the case where the edge portion of the pattern has no unevenness and is linear as described above is referred to as excellent edge shape.

[0009] In addition, excellent scratch resistance is also required in the pattern formed from the photosensitive composition layer.

[0010] As a result of forming a pattern using a transfer film having the photosensitive composition layer described in Patent Document 1, the present inventors found that it is impossible to achieve both the edge shape and scratch resistance of the formed pattern, and further improvement is required.

[0011] Therefore, an object of the present invention is to provide a transfer film having a photosensitive composition layer capable of forming a pattern with excellent scratch resistance and excellent edge shape.

[0012] Another object of the present invention is to provide a method for manufacturing a laminate using the above transfer film.

[0013] Means for Solving the Technical Problem

[0014] As a result of the inventors' in - depth research on the above - mentioned problems, it has been found that the above - mentioned problems can be solved by the following structure.

[0015] A transfer film having a temporary support and a photosensitive composition layer,

[0016] The photosensitive composition layer contains a photoinitiator, an alkali - soluble resin, and a polymerizable compound.

[0017] The photoinitiator contains a first photoinitiator and a second photoinitiator,

[0018] The molar extinction coefficient ε1 of the first photoinitiator at a wavelength of 365 nm is 500 L / mol·cm or more.

[0019] The ratio of the molar extinction coefficient ε2 of the second photoinitiator at a wavelength of 365 nm to the molar extinction coefficient ε3 of the second photoinitiator at a wavelength of 313 nm is 0.200 or less.

[0020] (2) The transfer film according to (1), wherein,

[0021] The ratio of the molar extinction coefficient ε2 of the second photoinitiator at a wavelength of 365 nm to the molar extinction coefficient ε3 of the second photoinitiator at a wavelength of 313 nm is 0.100 or less.

[0022] (3) The transfer film according to (1) or (2), wherein,

[0023] The maximum absorption wavelength of the second photoinitiator is 320 nm or less.

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

[0025] The maximum absorption wavelength of the second photoinitiator is 300 nm or less.

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

[0027] The second photoinitiator contains at least one selected from the group consisting of aminobenzoate - based photoinitiators, alkylbenzophenone - based photoinitiators, and acylphosphine oxide - based photoinitiators.

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

[0029] The second photoinitiator contains an aminobenzoate - based photoinitiator.

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

[0031] The first photopolymerization initiator contains at least one selected from the group consisting of oxime ester-based photopolymerization initiators and alkyl phenyl ketone-based photopolymerization initiators.

[0032] (8) The transfer film according to any one of (1) to (7), wherein

[0033] The ratio of the molar extinction coefficient ε2 of the second photopolymerization initiator at a wavelength of 365 nm to the molar extinction coefficient ε1 of the first photopolymerization initiator at a wavelength of 365 nm is 0.50 or less.

[0034] (9) The transfer film according to any one of (1) to (8), wherein

[0035] The photosensitive composition layer is used to form an electrode protective film.

[0036] (10) The transfer film according to any one of (1) to (9), further comprising a refractive index adjustment layer,

[0037] The refractive index adjustment layer is disposed in contact with the photosensitive composition layer,

[0038] The refractive index of the refractive index adjustment layer is 1.60 or more.

[0039] (11) A method for manufacturing a laminate, comprising:

[0040] A laminating step of laminating a transfer film on a substrate having a conductive layer with the photosensitive composition layer side of the transfer film according to any one of (1) to (10) facing the substrate to obtain a substrate with a photosensitive composition layer;

[0041] An exposure step of pattern-exposing the photosensitive composition layer using light having a wavelength of 365 nm as a main wavelength;

[0042] A developing step of developing the exposed photosensitive composition layer to form a pattern; and

[0043] A post-exposure step of irradiating the pattern with light that sensitizes the second photopolymerization initiator,

[0044] The method for manufacturing a laminate further has a peeling step of peeling a 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.

[0045] (12) The method for manufacturing a laminate according to (11), wherein

[0046] The substrate having a conductive layer is a substrate having a sensor electrode portion for a touch panel and a lead wiring portion electrically connected to the sensor electrode for a touch panel.

[0047] Advantages of the Invention

[0048] According to the present invention, it is possible to provide a transfer film having a photosensitive composition layer capable of forming a pattern excellent in scratch resistance and edge shape.

[0049] Moreover, according to the present invention, it is also possible to provide a method for manufacturing a laminate using the above transfer film. Detailed Description of the Invention

[0050] Hereinafter, the present invention will be described in detail.

[0051] In addition, in this specification, a 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.

[0052] Moreover, in the numerical ranges described step by step in this specification, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the upper limit value or the lower limit value of the numerical range described in other steps. And, in the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the value shown in the examples.

[0053] Moreover, the term "process" in this specification includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired purpose of the process can be achieved.

[0054] 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.

[0055] Moreover, the average transmittance of visible light is a value measured using a spectrophotometer. For example, it can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0056] In this specification, unless otherwise specified, the content ratio of each structural unit of the polymer is a molar ratio.

[0057] Moreover, regarding the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention, unless otherwise specified, they are molecular weights converted using a gel permeation chromatography (GPC) analysis apparatus with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by TOSOH CORPORATION), detected by THF (tetrahydrofuran) and a differential refractometer, and using polystyrene as a standard substance.

[0058] In the present invention, unless otherwise specified, the molecular weight of the compound having a molecular weight distribution is the weight average molecular weight (Mw).

[0059] Also, in this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0060] In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth)acryloxy" is a concept that includes both acryloxy and methacryloxy.

[0061] As described later, as a characteristic point of the transfer film of the present invention, it can be cited that it includes a first photopolymerization initiator and a second photopolymerization initiator in which the photosensitive composition layer satisfies specified characteristics.

[0062] As a result of the inventors' research on the problems of the prior art, it has been found that in the prior art using only one type of photopolymerization initiator, increasing the exposure amount to improve the scratch resistance of the formed pattern results in deterioration of the edge shape, and reducing the exposure amount to improve the edge shape results in deterioration of the scratch resistance.

[0063] In contrast, in the present invention, it has been found that the desired effect can be obtained by using two types of photopolymerization initiators, namely a first photopolymerization initiator and a second photopolymerization initiator. The first photopolymerization initiator easily absorbs light when performing pattern exposure using light having a main wavelength of 365 nm and sufficiently causes the polymerization reaction of the polymerizable compound. The second photopolymerization initiator is hardly photosensitive during pattern exposure, easily absorbs light during post-exposure, and sufficiently causes the polymerization reaction of the polymerizable compound.

[0064] The transfer film of the present invention has at least a temporary support and a photosensitive composition layer.

[0065] Hereinafter, each component constituting the transfer film will be described in detail.

[0066] <Temporary support>

[0067] The transfer film has a temporary support. The temporary support is a component that supports the photosensitive composition layer and the like described later, and is finally removed by a peeling treatment.

[0068] The temporary support is preferably a thin film, more preferably a resin thin film. As the temporary support, a thin film having flexibility and not undergoing significant deformation, shrinkage, or expansion under pressure or under pressure and heating can be used.

[0069] Examples of such a thin film include polyethylene terephthalate films (e.g., biaxially stretched polyethylene terephthalate films), cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films.

[0070] Among these, as the temporary support, a biaxially oriented polyethylene terephthalate film is preferred.

[0071] Moreover, the film used as the temporary support preferably has no deformations such as wrinkles and no scratches or the like.

[0072] From the viewpoint of enabling pattern exposure via the temporary support, it is preferred that the temporary support has high transparency, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more.

[0073] From the viewpoints of pattern formability when performing pattern exposure via the temporary support and the transparency of the temporary support, it is preferred that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and further preferably 0.1% or less.

[0074] From the viewpoints of pattern formability when performing pattern exposure via the temporary support and the transparency of the temporary support, it is preferred that the number of fine particles, foreign substances, and defects contained in the temporary support is small. The number of fine particles, foreign substances, and defects having a diameter of 1 μm or more is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, further preferably 3 pieces / 10 mm 2 or less, and particularly preferably 0 pieces / 10 mm 2 .

[0075] The thickness of the temporary support is not particularly limited, but it is preferably 5 to 200 μm, more preferably 10 to 150 μm, and further preferably 10 to 50 μm from the viewpoints of ease of operation and versatility.

[0076] From the viewpoint of imparting processability, a layer having fine particles (lubricant layer) can be provided on the surface of the temporary support. The lubricant layer can be provided on one side of the temporary support or on both sides. The diameter of the particles contained in the lubricant layer can be set to 0.05 to 0.8 μm. Moreover, the film thickness of the lubricant layer can be set to 0.05 to 1.0 μm.

[0077] In order to improve the adhesion between the temporary support and the photosensitive composition layer described later, the side in contact with the photosensitive composition layer of the temporary support can be surface-modified by UV irradiation, corona discharge, plasma, or the like.

[0078] When performing surface modification by UV irradiation, the exposure amount is preferably 10 mJ / cm 2 to 2000 mJ / cm 2 , more preferably 50 to 1000 mJ / cm 2 .

[0079] As a light source for UV irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, a light-emitting diode (LED), etc. that emit light in the wavelength band of 150 to 450 nm can be cited. As long as the light irradiation amount is within this range, the lamp output and illuminance are not particularly limited.

[0080] As a temporary support, for example, a biaxially stretched polyethylene terephthalate film with a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a film thickness of 9 μm can be cited.

[0081] As a preferred mode of the temporary support, for example, it is described in paragraphs

[0017] to

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

[0019] to

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

[0041] to

[0057] of WO2012 / 081680A1, and paragraphs

[0029] to

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

[0082] <Photosensitive composition layer>

[0083] The transfer film has a photosensitive composition layer. A pattern can be formed on the object to be transferred by exposing and developing after transferring the photosensitive composition layer to the object to be transferred.

[0084] The photosensitive composition layer contains a photoinitiator, an alkali-soluble resin, and a polymerizable compound.

[0085] When the photosensitive composition layer is irradiated with light, polymerization proceeds and the exposed part is cured. That is, the photosensitive composition layer is a layer that is cured by photo-sensitization, and is a so-called negative photosensitive composition layer (curing type photosensitive composition layer).

[0086] Hereinafter, the components contained in the photosensitive composition layer will be described in detail.

[0087] [Photoinitiator]

[0088] The photosensitive composition layer contains a first photoinitiator and a second photoinitiator.

[0089] A photoinitiator is a substance that receives actinic rays such as ultraviolet rays and visible light to initiate the polymerization of a polymerizable compound.

[0090] In the present invention, the values of the molar extinction coefficient and the maximum absorption wavelength are calculated from the absorption spectrum obtained in the following manner.

[0091] Specifically, first, an acetonitrile solution of a photopolymerization initiator with a concentration of 0.001% by mass is prepared, and the absorbance of the obtained solution is measured (measurement range: 200 to 500 nm) using a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and the molar extinction coefficient and the maximum absorption wavelength are calculated from the obtained absorption spectrum.

[0092] (First photopolymerization initiator)

[0093] The first photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator having a molar extinction coefficient ε1 of 500 L / mol·cm or more at a wavelength of 365 nm. Among them, from the viewpoint of at least one of the effects of obtaining a more excellent scratch resistance of the formed pattern and a more excellent edge shape of the formed pattern (hereinafter, also simply referred to as "the viewpoint of more excellent effects of the present invention"), the molar extinction coefficient ε1 is preferably 1000 L / mol·cm or more, more preferably 1200 L / mol·cm or more. The upper limit is not particularly limited, but it is often 30000 L / mol·cm or less, and more often 20000 L / mol·cm or less.

[0094] The maximum absorption wavelength of the first photopolymerization initiator is not particularly limited, but is preferably 300 nm or more, more preferably 320 nm or more. The upper limit is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 400 nm or less. In addition, when there are multiple maximum absorption wavelengths of the first photopolymerization initiator, the maximum absorption wavelength on the longest wavelength side is adopted.

[0095] Examples of the first photopolymerization initiator include a photopolymerization initiator containing an oxime ester structure (hereinafter, also referred to as "oxime ester-based photopolymerization initiator"), a photopolymerization initiator containing an α-aminoalkyl phenyl ketone structure or an α-hydroxyalkyl phenyl ketone structure (hereinafter, also referred to as "alkyl phenyl ketone-based photopolymerization initiator"), a photopolymerization initiator containing an acylphosphine oxide structure (hereinafter, also referred to as "acylphosphine oxide-based photopolymerization initiator"), a photopolymerization initiator containing an alkyl p-aminobenzoate structure (hereinafter, also referred to as "p-aminobenzoate-based photopolymerization initiator"), and a photopolymerization initiator containing an N-phenylglycine structure (hereinafter, also referred to as "N-phenylglycine-based photopolymerization initiator").

[0096] In addition, examples of the p-aminobenzoate-based photopolymerization initiator include 2-ethylhexyl 4-(dimethylamino)benzoate and ethyl 4-(dimethylamino)benzoate.

[0097] The first photoinitiator preferably contains at least one selected from the group consisting of oxime ester-based photoinitiators and alkyl phenyl ketone-based photoinitiators.

[0098] The content of the first photoinitiator is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.2 to 5% by mass with respect to the total mass of the photosensitive composition layer.

[0099] (Second photoinitiator)

[0100] The second photoinitiator is not particularly limited as long as it is a compound different from the above-mentioned first photoinitiator, and the ratio of the molar extinction coefficient ε2 at a wavelength of 365 nm to the molar extinction coefficient ε3 at a wavelength of 313 nm of the second photoinitiator (molar extinction coefficient ε2 at a wavelength of 365 nm of the second photoinitiator / molar extinction coefficient ε3 at a wavelength of 313 nm of the second photoinitiator) is a photoinitiator of 0.200 or less.

[0101] Among them, from the viewpoint of more excellent effects of the present invention, the above ratio is preferably 0.100 or less, and more preferably 0.050 or less. The lower limit is not particularly limited, but 0 can be cited.

[0102] The molar extinction coefficient ε2 of the second photoinitiator at a wavelength of 365 nm is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 1500 L / mol·cm or less, more preferably 500 L / mol·cm or less, and still more preferably 200 L / mol·cm or less. The lower limit is not particularly limited, but in many cases it is 0 L / mol·cm or more, and more in many cases it is 10 L / mol·cm or more.

[0103] The molar extinction coefficient ε3 of the second photoinitiator at a wavelength of 313 nm is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 2000 L / mol·cm or more, more preferably 5000 L / mol·cm or more, and still more preferably 10000 L / mol·cm or more. The upper limit is not particularly limited, but in many cases it is 200000 L / mol·cm or less, more in many cases it is 30000 L / mol·cm or less, and still more in many cases it is 25000 L / mol·cm or less.

[0104] The maximum absorption wavelength of the second photopolymerization initiator is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 320 nm or less, more preferably 300 nm or less. The lower limit is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 200 nm or more. In addition, when there are a plurality of maximum absorption wavelengths of the second photopolymerization initiator, the maximum absorption wavelength on the longest wavelength side is adopted.

[0105] Examples of the second photopolymerization initiator include the same compounds as those exemplified for the first photopolymerization initiator described above.

[0106] Among them, from the viewpoint of more excellent effects of the present invention, the second photopolymerization initiator preferably contains at least one selected from the group consisting of aminobenzoate-based photopolymerization initiators, alkylbenzophenone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators, and more preferably contains aminobenzoate-based photopolymerization initiators.

[0107] The content of the second photopolymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.2 to 5% by mass based on the total mass of the photosensitive composition layer.

[0108] Moreover, as the first photopolymerization initiator and the second photopolymerization initiator, for example, the photopolymerization initiators described in paragraphs

[0031] to

[0042] of Japanese Patent Application Laid-Open No. 2011-095716 and paragraphs

[0064] to

[0081] of Japanese Patent Application Laid-Open No. 2015-014783 can be used.

[0109] Examples of commercially available products of the first photopolymerization initiator and the second photopolymerization initiator include 1-[4-(phenylthio)]phenyl-1,2-octanedione-2-(O-benzoyl oxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl]][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetoxime) [trade name: IRGACURE® OXE-03, manufactured by BASF], 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl-4-methyl-1-pentanone-1-(O-acetoxime) [trade name: IRGACURE® OXE-04, manufactured by BASF], 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: IRGACURE® 379EG, manufactured by BASF], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: IRGACURE® 907, manufactured by BASF], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: IRGACURE® 127, manufactured by BASF], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 [trade name: IRGACURE® 369, manufactured by BASF], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [trade name: IRGACURE® 1173, manufactured by BASF], 1-hydroxycyclohexyl phenyl ketone [trade name: IRGACURE® 184, manufactured by BASF], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: IRGACURE® 651, manufactured by BASF], oxime ester compound [trade name: Lunar® 6, manufactured by DKSH Japan K.K.], ethyl 4-(dimethylamino)benzoate [trade name: DAROCUR EDB, manufactured by BASF], 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylacetophenone [trade name: IRGACURE® 2959, manufactured by BASF], and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide [trade name: IRGACURE® 819, manufactured by BASF].

[0110] The ratio of the molar extinction coefficient ε2 of the second photoinitiator at a wavelength of 365 nm to the molar extinction coefficient ε1 of the first photoinitiator at a wavelength of 365 nm is not particularly limited. However, from the viewpoint of more excellent effects of the present invention, it is preferably 0.500 or less, more preferably 0.200 or less. The lower limit is not particularly limited, but it is often 0.01 or more.

[0111] In addition, from the viewpoint of more excellent effects of the present invention, it is preferred that the absorbance of the second photoinitiator at a wavelength of 313 nm is greater than the absorbance of the first photoinitiator at a wavelength of 313 nm.

[0112] The photosensitive composition layer only needs to contain at least two photoinitiators among the first photoinitiator and the second photoinitiator, and may contain three or more photoinitiators.

[0113] The total content of the photoinitiator is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, based on the total mass of the photosensitive composition layer. Moreover, the upper limit of the content of the photoinitiator is preferably 10% by mass or less, more preferably 5.0% by mass or less, based on the total mass of the photosensitive composition layer.

[0114] The total content of the above-mentioned photoinitiator refers to the total content of all photoinitiators including the first photoinitiator and the second photoinitiator.

[0115] The content of the second photoinitiator is preferably 1.2 times or more, more preferably 1.5 times or more, relative to the content of the first photoinitiator. The upper limit is not particularly limited, but it is often 5 times or less.

[0116] [Alkali-soluble resin]

[0117] The photosensitive composition layer contains an alkali-soluble resin.

[0118] The photosensitive composition layer contains an alkali-soluble resin, thereby improving the solubility of the photosensitive composition layer (unexposed portion) in the developer.

[0119] As the alkali-soluble resin, an alkali-soluble acrylic resin is preferred.

[0120] Hereinafter, the alkali-soluble acrylic resin will be described in detail.

[0121] In the present invention, "alkali-soluble" means that the dissolution rate obtained by the following method is 0.01 μm / second or more.

[0122] A propylene glycol monomethyl ether acetate solution with a concentration of 25% by mass of the target compound (e.g., a resin) was coated on a glass substrate, and then heated in an oven at 100 °C for 3 minutes to form a coating film (thickness 2.0 μm) of the above-mentioned target compound. The dissolution rate (μm / sec) of the above-mentioned coating film was determined by immersing the above-mentioned coating film in a 1% by mass aqueous solution of sodium carbonate (liquid temperature 30 °C).

[0123] In addition, when the target compound is insoluble in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent having a boiling point of less than 200 °C other than propylene glycol monomethyl ether acetate (e.g., tetrahydrofuran, toluene, or ethanol).

[0124] As the alkali-soluble acrylic resin, there is no limitation as long as it is an alkali-soluble acrylic resin as described above. Here, the “(meth)acrylic resin” means a resin containing at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylate.

[0125] The total proportion of the structural unit derived from (meth)acrylic acid and the structural unit derived from (meth)acrylate in the alkali-soluble acrylic resin is preferably 30 mol% or more, more preferably 50 mol% or more.

[0126] In the present invention, when the content of the “structural unit” is specified in terms of mole fraction (mole ratio), unless otherwise specified, the meaning of the above-mentioned “structural unit” is the same as the meaning of “monomer unit”. And, in the present invention, when the resin or polymer has two or more specific structural units, unless otherwise specified, the content of the above-mentioned specific structural unit represents the total content of the two or more specific structural units.

[0127] From the viewpoint of developability, the alkali-soluble acrylic resin preferably has a carboxyl group. As a method for introducing a carboxyl group into the alkali-soluble acrylic resin, for example, a method of synthesizing an alkali-soluble acrylic resin using a monomer having a carboxyl group can be cited. By the above method, a monomer having a carboxyl group is introduced into the alkali-soluble acrylic resin as a structural unit having a carboxyl group. As a monomer having a carboxyl group, for example, acrylic acid and methacrylic acid can be cited.

[0128] The alkali-soluble acrylic resin may have one carboxyl group or two or more carboxyl groups. And, the structural unit having a carboxyl group in the alkali-soluble acrylic resin may be a single type or two or more types.

[0129] The content of the structural unit having a carboxyl group relative to the total amount of the alkali-soluble acrylic resin is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 30 mol%.

[0130] The content of the structural unit having a carboxyl group is preferably 3 to 40% by mass, more preferably 3 to 30% by mass, and still more preferably 5 to 20% by mass, relative to the total amount of the alkali-soluble acrylic resin, as a mass ratio.

[0131] Examples of the (meth)acrylic acid compound used for forming the acrylic resin include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylic acid amide, and (meth)acrylonitrile.

[0132] Examples of the (meth)acrylic acid ester include alkyl (meth)acrylate, 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, and alkyl (meth)acrylate is preferred.

[0133] Examples of the (meth)acrylic acid amide include acrylamide such as diacetone acrylamide.

[0134] The alkyl group of the alkyl (meth)acrylate may be linear or branched. As specific examples, for example, there can be cited 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.

[0135] As the (meth)acrylic acid 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.

[0136] The acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic acid compound.

[0137] From the viewpoints of moisture permeability and strength after curing, the alkali-soluble acrylic resin preferably has a structural unit containing an aromatic ring. As the structural unit having an aromatic ring, a structural unit derived from a styrene compound is preferred.

[0138] Examples of the monomer for forming the structural unit having an aromatic ring include the monomer for forming the structural unit derived from a styrene compound and benzyl (meth)acrylate.

[0139] As monomers for forming structural units derived from the above styrene compounds, for example, styrene, p-methylstyrene, α-methylstyrene, α,p-dimethylstyrene, p-ethylstyrene, p-tert-butylstyrene, tert-butoxystyrene, and 1,1-distyrene can be cited. Styrene or α-methylstyrene is preferred, and styrene is more preferred.

[0140] The structural units having an aromatic ring in the alkali-soluble acrylic resin can be a single type or two or more types.

[0141] When the alkali-soluble acrylic resin has a structural unit containing an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and still more preferably 15 to 70 mol% with respect to the total amount of the alkali-soluble acrylic resin.

[0142] From the viewpoints of viscosity and strength after curing, the alkali-soluble acrylic resin preferably contains a structural unit having an alicyclic skeleton. As the alicyclic skeleton, monocyclic and polycyclic rings can be cited.

[0143] As the alicyclic rings in the alicyclic skeleton, for example, dicyclopentane ring, cyclohexane ring, isophorone ring, and tricyclodecane ring can be cited. Among them, as the alicyclic ring in the alicyclic skeleton, the tricyclodecane ring is preferred.

[0144] As monomers for forming a structural unit having an alicyclic skeleton, for example, dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate can be cited.

[0145] The structural units having an alicyclic skeleton in the alkali-soluble acrylic resin can be a single type or two or more types.

[0146] When the alkali-soluble acrylic resin has a structural unit containing an alicyclic skeleton, the content of the structural unit having an alicyclic skeleton is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and still more preferably 10 to 60 mol% with respect to the total amount of the alkali-soluble acrylic resin.

[0147] From the viewpoints of viscosity and strength after curing, the alkali-soluble acrylic resin preferably has a reactive group.

[0148] As the reactive group, a radically polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. And when the alkali-soluble acrylic resin has an ethylenically unsaturated group, the alkali-soluble acrylic resin preferably has a structural unit having an ethylenically unsaturated group on the side chain.

[0149] In the present invention, the "main chain" refers to the relatively longest connecting chain in the molecule of the high molecular compound constituting the resin, and the "side chain" refers to the atomic group branched from the main chain.

[0150] As the ethylenically unsaturated group, a (meth)acryloyl group or a (meth)acryloyloxy group is preferred, and a (meth)acryloyloxy group is more preferred.

[0151] The structural unit having an ethylenically unsaturated group in the alkali-soluble acrylic resin may be a single kind or two or more kinds.

[0152] When the alkali-soluble acrylic resin has a structural unit containing an ethylenically unsaturated group, the content of the structural unit having an ethylenically unsaturated group is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol% based on the total amount of the alkali-soluble acrylic resin.

[0153] As an example of the structural unit having a reactive group, the structural units shown below can be cited, but are not limited thereto.

[0154] [Chemical formula 1]

[0155]

[0156] As a means for introducing a reactive group into the alkali-soluble acrylic resin, methods of reacting an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a hydroxymethyl compound, a carboxylic anhydride, etc. with a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, etc. can be cited.

[0157] As a preferred example of the means for introducing a reactive group into the alkali-soluble acrylic resin, a method of synthesizing an alkali-soluble acrylic resin having a carboxyl group by a polymerization reaction and then reacting a part of the carboxyl group of the alkali-soluble acrylic resin with glycidyl (meth)acrylate by a polymer reaction to introduce a (meth)acryloyloxy group into the alkali-soluble acrylic resin can be cited. By the above method, an alkali-soluble acrylic resin having a (meth)acryloyloxy group on the side chain can be obtained.

[0158] 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 for the above polymerization reaction, an azo-based initiator is preferred, and more preferably, for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. Further, 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.

[0159] The weight-average molecular weight (Mw) of the alkali-soluble acrylic resin is preferably 10,000 or more, more preferably 10,000 to 100,000, still more preferably 15,000 to 70,000, and most preferably 15,000 to 30,000.

[0160] From the viewpoint of developability, the acid value of the alkali-soluble acrylic resin is preferably 50 mgKOH / g or more, more preferably 60 mgKOH / g or more, still more preferably 70 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more. In the present invention, the acid value of the alkali-soluble acrylic resin is a value measured by the method described in JIS K0070:1992.

[0161] From the viewpoint of suppressing dissolution in the developer, the upper limit of the acid value of the alkali-soluble acrylic resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

[0162] Specific examples of the alkali-soluble acrylic resin are shown below. In addition, the content ratio (molar ratio) of each structural unit in the following alkali-soluble acrylic resin can be appropriately set according to the purpose.

[0163] [Chemical formula 2]

[0164]

[0165] [Chemical formula 3]

[0166]

[0167] [Chemical formula 4]

[0168]

[0169] [Chemical formula 5]

[0170]

[0171] In the above chemical formulas, a is preferably 20 wt% to 60 wt%, b is preferably 10 wt% to 50 wt%, c is preferably 5.0 wt% to 25 wt%, and d is preferably 10 wt% to 50 wt%.

[0172] [Chemical formula 6]

[0173]

[0174] In the above chemical formulas, a is preferably 30 wt% to 65 wt%, b is preferably 1.0 wt% to 20 wt%, c is preferably 5.0 wt% to 25 wt%, and d is preferably 10 wt% to 50 wt%.

[0175] The photosensitive composition layer may contain a single alkali-soluble resin or two or more alkali-soluble resins.

[0176] From the viewpoints of pattern formability and reliability, the content of the residual monomer of each structural unit of the alkali-soluble resin is preferably 2,000 mass ppm or less, more preferably 1,000 mass ppm or less, and still more preferably 500 mass ppm or less, relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, and is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.

[0177] From the viewpoints of pattern formability and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 1,000 mass ppm or less, more preferably 200 mass ppm or less, and still more preferably 100 mass ppm or less, relative to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, and is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

[0178] From the viewpoint of developability, the content of the alkali-soluble resin is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and still more preferably 25 to 70 mass%, relative to the total mass of the photosensitive composition layer.

[0179] [Polymerizable compound]

[0180] The photosensitive composition layer contains a polymerizable compound.

[0181] The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group, and a radical polymerizable group is preferred.

[0182] The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as "ethylenically unsaturated compound").

[0183] As the ethylenically unsaturated group, (meth)acryloyloxy is preferred.

[0184] The ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having two or more functional groups. Herein, the "ethylenically unsaturated compound having two or more functional groups" refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0185] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0186] As an ethylenically unsaturated compound, for example, from the viewpoint of the strength of the cured film, a difunctional ethylenically unsaturated compound (preferably a difunctional (meth)acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound) are preferably contained.

[0187] Examples of the difunctional ethylenically unsaturated compound include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

[0188] Examples of commercially available difunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate [trade name: NK ESTER A-DCP, Shin Nakamura Chemical Co., Ltd.], tricyclodecane dimethanol dimethacrylate [trade name: NK ESTER DCP, Shin Nakamura Chemical Co., Ltd.], 1,9-nonanediol diacrylate [trade name: NK ESTER A-NOD-N, Shin Nakamura Chemical Co., Ltd.], 1,10-decanediol diacrylate [trade name: NK ESTER A-DOD-N, Shin Nakamura Chemical Co., Ltd.], and 1,6-hexanediol diacrylate [trade name: NK ESTER A-HD-N, Shin Nakamura Chemical Co., Ltd.].

[0189] Examples of the trifunctional or higher ethylenically unsaturated compound include 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.

[0190] 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.

[0191] Regarding the trifunctional or higher ethylenically unsaturated compound, there is no particular limitation on the upper limit of the number of functional groups, and for example, it can be set to 20 functional groups or less, or can also be set to 15 functional groups or less.

[0192] As commercially available products of ethylenically unsaturated compounds having three or more functional groups, examples include dipentaerythritol hexaacrylate [trade name: A-DPH, SHIN-NAKAMURA CHEMICAL CO,LTD.].

[0193] The ethylenically unsaturated compound more preferably contains 1,9-nonanediol di(meth)acrylate or 1,10-decanediol di(meth)acrylate and dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate.

[0194] As the ethylenically unsaturated compound, examples also include caprolactone-modified compounds of (meth)acrylate compounds [KAYARAD (registered trademark) DPCA-20 of Nippon Kayaku Co.,Ltd., A-9300-1CL of Shin Nakamura Chemical Co.,Ltd., etc.], alkylene oxide-modified compounds of (meth)acrylate compounds [KAYARAD (registered trademark) RP-1040 of Nippon Kayaku Co.,Ltd., ATM-35E, A-9300 of Shin Nakamura Chemical Co.,Ltd., EBECRYL (registered trademark) 135 of DAICEL-ALLNEX LTD., etc.], ethoxylated glycerol triacrylate [NK ESTER A-GLY-9E of ShinNakamura Chemical Co.,Ltd., etc.].

[0195] As the ethylenically unsaturated compound, urethane (meth)acrylate compounds can also be cited. As the urethane (meth)acrylate compound, a urethane (meth)acrylate compound having three or more functional groups is preferred. As the urethane (meth)acrylate compound having three or more functional groups, examples include 8UX-015A [Taisei FineChemical Co.,Ltd.], NK ESTER UA-32P [Shin Nakamura Chemical Co.,Ltd.] and NK ESTERUA-1100H [Shin Nakamura Chemical Co.,Ltd.].

[0196] From the viewpoint of improving developability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group.

[0197] As the acid group, examples include a phosphoric acid group, a sulfonic acid group and a carboxyl group. Among the above, as the acid group, a carboxyl group is preferred.

[0198] As the ethylenically unsaturated compound having an acid group, 3-4 functional ethylenically unsaturated compounds having an acid group [compounds obtained by introducing a carboxyl group into the pentaerythritol tri- and tetraacrylate (PETA) skeleton (acid value: 80-120 mgKOH / g)] and 5-6 functional ethylenically unsaturated compounds having an acid group [compounds obtained by introducing a carboxyl group into the dipentaerythritol penta- and hexaacrylate (DPHA) skeleton (acid value: 25-70 mgKOH / g)] can be mentioned. The ethylenically unsaturated compound having 3 or more functional groups having an acid group can be used simultaneously with the ethylenically unsaturated compound having 2 functional groups having an acid group as needed.

[0199] As the ethylenically unsaturated compound having an acid group, at least one compound selected from the group consisting of ethylenically unsaturated compounds having 2 or more functional groups having a carboxyl group and their carboxylic anhydrides is preferably used. When the ethylenically unsaturated compound having an acid group is at least one compound selected from the group consisting of ethylenically unsaturated compounds having 2 or more functional groups having a carboxyl group and their carboxylic anhydrides, the developability and film strength are further improved.

[0200] Examples of the ethylenically unsaturated compound having 2 or more functional groups having a carboxyl group include ARONIX (registered trademark) TO-2349 [TOAGOSEI CO., LTD.], ARONIX (registered trademark) M-520 [TOAGOSEI CO., LTD.], and ARONIX (registered trademark) M-510 [TOAGOSEI CO., LTD.].

[0201] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of Japanese Patent Application Laid-Open No. 2004-239942 can be preferably used, and the content described in this publication is incorporated herein by reference.

[0202] The molecular weight of the ethylenically unsaturated 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.

[0203] In the ethylenically unsaturated compound, the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0204] The photosensitive composition layer may contain a single ethylenically unsaturated compound or may contain two or more ethylenically unsaturated compounds.

[0205] The content of the ethylenically unsaturated compound is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to the total mass of the photosensitive composition layer.

[0206] When the photosensitive composition layer contains an ethylenically unsaturated compound having two or more functional groups, a monofunctional ethylenically unsaturated compound may also be contained.

[0207] When the photosensitive composition layer contains an ethylenically unsaturated compound having two or more functional groups, the ethylenically unsaturated compound having two or more functional groups is preferably the main component among the ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0208] When the photosensitive composition layer contains an ethylenically unsaturated compound having two or more functional groups, the content of the ethylenically unsaturated compound having two or more functional groups is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, relative to the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.

[0209] When the photosensitive composition layer contains an ethylenically unsaturated compound having an acid group (preferably an ethylenically unsaturated compound having two or more carboxyl groups or its carboxylic anhydride), the content of the ethylenically unsaturated compound having an acid group is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, still more preferably 1 to 10% by mass, relative to the total mass of the photosensitive composition layer.

[0210] [Polymer containing a structural unit having a carboxylic anhydride structure]

[0211] The photosensitive composition layer may also contain, as an adhesive, a polymer containing a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as "polymer B"). By containing polymer B in the photosensitive composition layer, the developability and the strength after curing can be improved.

[0212] The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, and a cyclic carboxylic anhydride structure is preferred.

[0213] As the ring of the cyclic carboxylic anhydride structure, a 5- to 7-membered ring is preferred, a 5-membered ring or a 6-membered ring is more preferred, and a 5-membered ring is still more preferred.

[0214] The structural unit having a carboxylic anhydride structure preferably contains, in the main chain, a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 or a monovalent group obtained by removing one hydrogen atom from the compound represented by the following formula P-1 and bonded directly or via a divalent linking group.

[0215] [Chemical formula 7]

[0216]

[0217] In formula P-1, R A1a represents a substituent, and n 1a R groups A1a may be the same or different, and 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.

[0218] As the substituent represented by R A1a alkyl groups can be exemplified, for example.

[0219] As Z 1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further preferably an alkylene group having 2 carbon atoms.

[0220] 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.

[0221] When n 1a represents an integer of 2 or more, multiple R A1a groups may be the same or different. Also, multiple R A1a groups may bond to each other to form a ring, but preferably do not bond to each other to form a ring.

[0222] As the 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.

[0223] The structural unit having a carboxylic anhydride structure in polymer B can be a single type or two or more types.

[0224] The content of the structural unit having a carboxylic anhydride structure relative to the total amount of polymer B is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 35 mol%.

[0225] The photosensitive composition layer may contain a single type of polymer B or two or more types of polymer B.

[0226] When the photosensitive composition layer contains Polymer B, from the viewpoints of developability and strength after curing, the content of Polymer B is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 20% by mass, and particularly preferably 1 to 20% by mass with respect to the total mass of the photosensitive composition layer.

[0227] [Heterocyclic compound]

[0228] The photosensitive composition layer preferably contains a heterocyclic compound.

[0229] The heterocycle of the heterocyclic compound may be either a monocyclic or polycyclic heterocycle.

[0230] Examples of the heteroatom of 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 the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

[0231] 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, and a pyrimidine compound.

[0232] Among the above, as the heterocyclic compound, at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound, and a benzoxazole compound is preferred, and at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, and a benzoxazole compound is more preferred.

[0233] Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

[0234] [Chemical formula 8]

[0235]

[0236] [Chemical formula 9]

[0237]

[0238] Examples of the tetrazole compound include the following compounds.

[0239] [Chemical formula 10]

[0240]

[0241] [Chemical Formula 11]

[0242]

[0243] As thiazole compounds, the following compounds can be exemplified.

[0244] [Chemical Formula 12]

[0245]

[0246] As triazine compounds, the following compounds can be exemplified.

[0247] [Chemical Formula 13]

[0248]

[0249] As rhodanine compounds, the following compounds can be exemplified.

[0250] [Chemical Formula 14]

[0251]

[0252] As thiazole compounds, the following compounds can be exemplified.

[0253] [Chemical Formula 15]

[0254]

[0255] As benzothiazole compounds, the following compounds can be exemplified.

[0256] [Chemical Formula 16]

[0257]

[0258] As benzimidazole compounds, the following compounds can be exemplified.

[0259] [Chemical Formula 17]

[0260]

[0261] [Chemical Formula 18]

[0262]

[0263] As benzoxazole compounds, the following compounds can be exemplified.

[0264] [Chemical Formula 19]

[0265]

[0266] The photosensitive composition layer may contain a single heterocyclic compound or two or more heterocyclic compounds.

[0267] When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20% by mass, more preferably 0.01 to 5% by mass, based on the total mass of the photosensitive composition layer.

[0268] [Aliphatic thiol compound]

[0269] The photosensitive composition layer preferably contains an aliphatic thiol compound.

[0270] By including an aliphatic thiol compound in the photosensitive composition layer, an ene-thiol reaction occurs between the aliphatic thiol compound and a radically polymerizable compound having an ethylenically unsaturated group, thereby suppressing the curing shrinkage of the formed film and relieving stress.

[0271] 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.

[0272] In the above, as the aliphatic thiol compound, from the viewpoint of the adhesion of the formed pattern (especially the adhesion after exposure), a polyfunctional aliphatic thiol compound is preferred.

[0273] In the present invention, 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.

[0274] As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of preferably 100 or more is preferred. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and further preferably 150 to 1,000.

[0275] As the number of functional groups of the polyfunctional aliphatic thiol compound, 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 further preferably 2 to 6 functional groups.

[0276] As polyfunctional aliphatic thiol compounds, for example, 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)diethanethiol, meso-2,3-dimercaptosuccinic acid, and bis(mercaptoethyl) ether can be mentioned.

[0277] Among the above, as the polyfunctional aliphatic thiol compound, at least one compound selected from the group consisting of 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 preferably selected.

[0278] As the monofunctional aliphatic thiol compound, for example, 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 can be mentioned.

[0279] The photosensitive composition layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds.

[0280] 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 relative to the total mass of the photosensitive composition layer.

[0281] [Blocked isocyanate compound]

[0282] The photosensitive composition layer preferably contains a blocked isocyanate compound. The blocked isocyanate compound helps to improve the strength of the formed pattern.

[0283] Since the blocked isocyanate compound reacts with hydroxyl groups and carboxyl groups, for example, when at least one of an adhesive polymer and a radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, there is a tendency for the hydrophilicity of the formed film to decrease and the function as a protective film to be enhanced. In addition, the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent."

[0284] The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160 °C, more preferably 110 to 150 °C.

[0285] In the present invention, 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 measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter. As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably cited. However, the differential scanning calorimeter is not limited to the above differential scanning calorimeter.

[0286] As the blocking agent having a dissociation temperature of 100 to 160 °C, 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, for example, from the viewpoint of storage stability, oxime compounds are preferred.

[0287] From the viewpoints of improving the brittleness of the film and increasing the adhesion to the transfer body, etc., it is preferred to have an isocyanurate structure. The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate.

[0288] Among the blocked isocyanate compounds having an isocyanurate structure, from the viewpoints that it is easier to set the dissociation temperature within a preferred range compared to compounds without an oxime structure and it is easier to reduce development residues, compounds having an oxime structure using an oxime compound as a blocking agent are preferred.

[0289] From the viewpoint of the strength of the formed pattern, the blocked isocyanate compound preferably has a polymerizable group, and more preferably has a radically polymerizable group.

[0290] As the polymerizable group, examples thereof include ethylenically unsaturated groups such as (meth)acryloyloxy group, (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 viewpoints of the planar shape of the surface in the obtained pattern, the development rate and the reactivity, an ethylenically unsaturated group is preferred, and (meth)acryloyloxy group is more preferred.

[0291] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available products of the blocked isocyanate compound include 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, manufactured by Asahi Kasei Chemicals Corporation].

[0292] The photosensitive composition layer may contain a single kind of blocked isocyanate compound or may contain two or more kinds of blocked isocyanate compounds.

[0293] When the photosensitive composition layer contains a blocked isocyanate compound, the content of the blocked isocyanate compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

[0294] [Surfactant]

[0295] The photosensitive composition layer may contain a surfactant.

[0296] Examples of the surfactant include those described in paragraphs

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Patent Application Laid-Open No. 2009-237362.

[0297] As the surfactant, a nonionic surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferred.

[0298] Examples of commercially available fluorosurfactants include: MEGAFAC 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-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation);

[0299] Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited);

[0300] Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc.);

[0301] PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.);

[0302] Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by Neos Corporation), etc.

[0303] Furthermore, fluorosurfactants can also preferably be acrylic compounds that contain a molecular structure having a functional group containing a fluorine atom and in which a part of the functional group containing a fluorine atom is cleaved and fluorine atoms volatilize upon heating. Examples of these fluorosurfactants include the MAGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016)), such as MAGAFACE DS-21.

[0304] Further, as the fluorosurfactant, a polymer of a fluoroatom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is preferably used.

[0305] Block polymers can also be used as the fluorosurfactant. Fluoropolymers are also preferably used as the fluorosurfactant, and the fluoropolymers contain: repeating units derived from (meth)acrylate compounds having fluorine atoms; and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group).

[0306] Fluoropolymers having a group containing an ethylenically unsaturated bond in the side chain can also be used as the fluorosurfactant. Examples thereof include MEGAFAC RS-101, RS-102, RS-718K, RS-72-K (the above are manufactured by DIC Corporation).

[0307] Further, as the fluorosurfactant, from the viewpoint of improving environmental adaptability, a surfactant as a substitute material for compounds having a linear perfluoroalkyl group with 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) is preferably used.

[0308] Examples of the silicone surfactant include a linear polymer including a siloxane bond, and a modified silicone polymer having an organic group introduced into the side chain or the terminal.

[0309] Examples of commercially available products of the silicone surfactant include: DOWSIL 8032ADDITIVE, ToraySilicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray SiliconeSH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are manufactured by Dow Toray Co., Ltd.);

[0310] 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 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.);

[0311] F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.);

[0312] BYK307, BYK323, BYK330 (manufactured by BYK Co., LTD), etc.

[0313] Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc.

[0314] Examples of commercially available nonionic surfactants include: PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation);

[0315] TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation);

[0316] SOLSPERSE 20000 (manufactured by Lubrizol Japan Ltd.);

[0317] NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation);

[0318] Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.);

[0319] OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical co., ltd.), etc.

[0320] The surfactant can be used alone or two or more kinds can be used simultaneously.

[0321] 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.

[0322] [Hydrogen-donating compound]

[0323] The photosensitive composition layer preferably contains a hydrogen-donating compound. 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 caused by oxygen.

[0324] Examples of the hydrogen-donating compound include amines, such as the 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 Publication No. 51-082102, Japanese Unexamined Patent Publication No. 52-134692, Japanese Unexamined Patent Publication No. 59-138205, Japanese Unexamined Patent Publication No. 60-084305, Japanese Unexamined Patent Publication No. 62-018537, Japanese Unexamined Patent Publication No. 64-033104, and Research Disclosure No. 33825.

[0325] Examples of the hydrogen-donating compound include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0326] In addition, examples of the hydrogen-donating compound include amino acid compounds (such as N-phenylglycine), 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 Publication No. 6-308727.

[0327] The photosensitive composition layer may contain a single hydrogen-donating compound or two or more hydrogen-donating compounds.

[0328] When the photosensitive composition layer contains a hydrogen-donating compound, from the viewpoint of increasing the curing rate by the balance between the polymerization growth rate and chain transfer, the content of the hydrogen-donating compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and still more preferably 0.05 to 3% by mass, based on the total mass of the photosensitive composition layer.

[0329] [Other components]

[0330] The photosensitive composition layer may also contain components other than the above components (hereinafter, also referred to as "other components"). As other components, for example, particles (e.g., metal oxide particles), sensitizers, and colorants can be cited. Further, as other components, for example, heat polymerization inhibitors described in paragraph

[0018] of Japanese Patent No. 4502784 and other additives described in paragraphs

[0058] to

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

[0331] The photosensitive composition layer may contain particles for the purpose of adjusting the refractive index, light transmittance, etc. As the particles, for example, metal oxide particles can be cited.

[0332] The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0333] As the average primary particle diameter of the particles, for example, from the viewpoint of the transparency of the pattern, it is preferably 1 to 200 nm, more preferably 3 to 80 nm. The average primary particle diameter of the particles is calculated by measuring the particle diameters 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 diameter.

[0334] The photosensitive composition layer may contain a single type of particle or two or more types of particles. Further, when the photosensitive composition layer contains particles, it may contain only one type of particle having different metal types, sizes, etc., or two or more types.

[0335] The photosensitive composition layer preferably does not contain particles, or the content of the particles is more than 0% by mass and 35% by mass or less based on the total mass of the photosensitive composition layer, more preferably does not contain particles, or the content of the particles is more than 0% by mass and 10% by mass or less based on the total mass of the photosensitive composition layer, further preferably does not contain particles, or the content of the particles is more than 0% by mass and 5% by mass or less based on the total mass of the photosensitive composition layer, particularly preferably does not contain particles, or the content of the particles is more than 0% by mass and 1% by mass or less based on the total mass of the photosensitive composition layer, and most preferably does not contain particles.

[0336] The photosensitive composition layer may contain a small amount of colorants (e.g., pigments and dyes). For example, from the viewpoint of transparency, it preferably substantially does not contain colorants.

[0337] When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive composition layer.

[0338] [Impurities, etc.]

[0339] The photosensitive composition layer may contain a specified amount of impurities.

[0340] Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, and thus the following contents are preferably set.

[0341] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and still more preferably 2 ppm or less on a mass basis. The content of impurities in the photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.

[0342] As a method for setting the impurities within the above range, the following methods can be cited: selecting those with less impurity content as raw materials for the photosensitive composition layer, preventing the mixing of impurities during the formation of the photosensitive composition layer, and removing them by washing. By this method, the amount of impurities can be set within the above range.

[0343] Impurities can be quantified, for example, by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0344] The contents 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 are preferably low. The content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and still more preferably 4 ppm or less on a mass basis. The lower limit can be 10 ppb or more on a mass basis, and can also be 100 ppb or more. The contents of these compounds can be suppressed by the same method as the metal impurities above. And they can be quantified by known measurement methods.

[0345] From the viewpoints of improving reliability and stackability, the water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0346] [Thickness of the photosensitive composition layer]

[0347] The thickness of the photosensitive composition layer is not particularly limited, and is preferably 10.0 μm or less, more preferably 8.0 μm or less.

[0348] There is no limit to the lower limit of the thickness of the photosensitive composition layer. The smaller the thickness of the photosensitive composition layer, the more the bending resistance can be improved. From the viewpoint of manufacturing suitability, the lower limit of the thickness of the photosensitive composition layer is preferably 0.05 μm or more. From the viewpoint of improving the protection of the transparent resin layer, the lower limit of the thickness of the photosensitive composition layer is preferably 0.5 μm or more, more preferably 1.1 μm or more.

[0349] 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).

[0350] [Refractive index of the photosensitive composition layer]

[0351] The refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

[0352] [Color of the photosensitive composition layer]

[0353] The photosensitive composition layer is preferably achromatic. In the L * a * b * colorimetric system, 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.

[0354] [Moisture permeability of the photosensitive composition layer]

[0355] From the viewpoint of rust prevention, the moisture permeability of the pattern obtained by curing the photosensitive composition layer (cured film of the photosensitive composition layer) at a film thickness of 40 μm is preferably 500 g / m 2 / 24 h or less, more preferably 300 g / m 2 / 24 h or less, and further preferably 100 g / m 2 / 24 h or less.

[0356] In addition, regarding the moisture permeability, a cured film obtained by exposing the photosensitive composition layer with i-rays at an exposure amount of 300 mJ / cm 2 and then performing post-baking at 145 °C for 30 minutes to cure the photosensitive composition layer is used for measurement.

[0357] <Other layers>

[0358] The transfer film may include other layers in addition to the above-mentioned temporary support and photosensitive composition layer.

[0359] [Protective film]

[0360] The transfer film may have a protective film on the surface on the side opposite to the temporary support for protecting the photosensitive composition layer.

[0361] The protective film is preferably a resin film, and a resin film having heat resistance and solvent resistance can be used. For example, polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films can be cited. Further, a resin film made of the same material as the above-mentioned temporary support can be used as the protective film.

[0362] The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. From the viewpoint of excellent mechanical strength, the thickness of the protective film is preferably 1 μm or more, and from the viewpoint of relatively low cost, it is preferably 100 μm or less.

[0363] Further, in the protective film, the number of fisheyes having a diameter of 80 μm or more contained in the protective film is preferably 5 pieces / m 2 or less.

[0364] In addition, "fisheye" means that when the material is heated and melted and a film is manufactured by methods such as kneading, extrusion, biaxial stretching, and casting methods, foreign matters, undissolved matters, and oxidation deteriorated matters of the material are incorporated into the film.

[0365] The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 pieces / mm 2 or less, more preferably 10 pieces / mm 2 or less, still more preferably 5 pieces / mm 2 or less.

[0366] Thereby, it is possible to suppress defects caused by unevenness due to particles contained in the protective film being transferred to the photosensitive composition layer or the like.

[0367] From the viewpoint of imparting winding property, the arithmetic mean roughness Ra of the surface on the side of the protective film opposite to the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

[0368] From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface on the photosensitive composition layer side of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

[0369] [Refractive Index Adjustment Layer]

[0370] The transfer film may have a refractive index adjustment layer. The position of the refractive index adjustment layer is not particularly limited, and it is preferably disposed in contact with the photosensitive composition layer. Among them, the transfer film preferably has a temporary support, a photosensitive composition layer, and a refractive index adjustment layer in this order.

[0371] In addition, when the transfer film further has the above-mentioned protective film, it preferably has a temporary support, a photosensitive composition layer, a refractive index adjustment layer, and a protective film in this order.

[0372] As the refractive index adjustment layer, a known refractive index adjustment layer can be used. As the material contained in the refractive index adjustment layer, for example, and particles can be cited.

[0373] As the binder, for example, the alkali-soluble resin described in the above item "Photosensitive Composition Layer" can be cited.

[0374] As the particles, for example, zirconia particles (ZrO 2 particles), niobium oxide particles (Nb 2 O 5 particles), titanium oxide particles (TiO 2 particles), and silica particles (SiO 2 particles) can be cited.

[0375] Moreover, the refractive index adjustment layer preferably contains a metal antioxidant. By containing a metal antioxidant in the refractive index adjustment layer, the oxidation of the metal in contact with the refractive index adjustment layer can be suppressed.

[0376] As the metal antioxidant, a compound having an aromatic ring containing a nitrogen atom in the molecule is preferably used. As the metal antioxidant, for example, imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole can be cited.

[0377] The refractive index of the refractive index adjustment layer is preferably 1.60 or more, more preferably 1.63 or more.

[0378] The upper limit of the refractive index of the refractive index adjustment layer is preferably 2.10 or less, more preferably 1.85 or less.

[0379] 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.

[0380] The thickness of the refractive index adjustment layer is preferably 20 nm or more, more preferably 50 nm or more.

[0381] The thickness of the refractive index adjustment layer is calculated as the average value of any five points measured by cross-sectional observation based on a scanning electron microscope (SEM).

[0382] <Method for manufacturing transfer film>

[0383] The method for manufacturing the transfer film of the present invention is not particularly limited, and known methods can be used.

[0384] Among them, from the viewpoint of excellent productivity, a method of coating a photosensitive composition on a temporary support and performing a drying treatment as needed to form a photosensitive composition layer is preferred.

[0385] Hereinafter, the above method will be described in detail.

[0386] The photosensitive composition preferably contains components constituting the above photosensitive composition layer (for example, polymerizable compounds, alkali-soluble resins, photoinitiators, etc.) and a solvent.

[0387] As the solvent, an organic solvent is preferred. As the organic solvent, for example, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol can be cited. As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferred.

[0388] Furthermore, as the solvent, an organic solvent (high-boiling solvent) having a boiling point of 180 to 250 °C can also be used as needed.

[0389] The photosensitive composition may contain a single solvent or two or more solvents.

[0390] When the photosensitive composition contains a solvent, the total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and further preferably 5 to 30% by mass with respect to the total mass of the photosensitive composition.

[0391] When the photosensitive composition contains a solvent, for example, from the viewpoint of coatability, the viscosity of the photosensitive composition at 25 °C is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and further preferably 3 to 30 mPa·s. The viscosity is measured using a viscometer. As the viscometer, for example, a viscometer (trade name: VISCOMETER TV-22) manufactured by TOKI SANGYO CO., LTD. can be suitably used. However, the viscometer is not limited to the above viscometer.

[0392] When the photosensitive composition contains a solvent, from the viewpoint of coatability, for example, the surface tension of the photosensitive composition at 25°C is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and further preferably 15 to 40 mN / m. The surface tension is measured using a surface tensiometer. As the surface tensiometer, for example, a surface tensiometer manufactured by Kyowa InterfaceScience Co., Ltd. (trade name: Automatic Surface Tensiometer CBVP-Z) can be suitably used. However, the surface tensiometer is not limited to the above surface tensiometer.

[0393] As a 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 mentioned.

[0394] As a drying method, for example, natural drying, heat drying, and reduced-pressure drying can be mentioned. The above methods can be used alone or in combination.

[0395] In the present invention, "drying" means removing at least a part of the solvent contained in the composition.

[0396] When the transfer film has a refractive index adjusting layer on the photosensitive composition layer, for example, a composition for forming a refractive index adjusting layer is coated on the photosensitive composition layer, and then it can be dried as needed to form a refractive index adjusting layer.

[0397] Moreover, when the transfer film has a protective film, the transfer film is manufactured by laminating the protective film on the photosensitive composition layer.

[0398] The method of laminating the protective film on the photosensitive composition layer is not particularly limited, and known methods can be mentioned.

[0399] 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 mentioned.

[0400] The laminator includes an arbitrary heatable roll such as a rubber roll, and preferably can perform pressurization and heating.

[0401] <Method for manufacturing a laminate>

[0402] By using the above transfer film, the photosensitive composition layer can be transferred to the object to be transferred.

[0403] The object to be transferred is not particularly limited, but a substrate having a conductive layer is preferred.

[0404] As a method for manufacturing a laminate, it preferably has: a lamination step of laminating a transfer film on the substrate having a conductive layer with the photosensitive composition layer side of the transfer film facing the substrate, thereby obtaining a substrate with a photosensitive composition layer; an exposure step of pattern-exposing the photosensitive composition layer using light having a main wavelength of 365 nm; a development step of developing the exposed photosensitive composition layer to form a pattern; and a post-exposure step of irradiating the pattern with light that sensitizes the second photoinitiator. In addition, a method for manufacturing a laminate having a peeling step of peeling a temporary support from the substrate with a photosensitive composition layer between the lamination step and the exposure step or between the exposure step and the development step.

[0405] In the laminate obtained in the above order, a pattern is disposed on the substrate having a conductive layer.

[0406] Hereinafter, the order of each step of the laminate will be described in detail.

[0407] [Lamination step]

[0408] The lamination step is a step of laminating a transfer film on the substrate having a conductive layer with the photosensitive composition layer side of the transfer film facing the substrate, thereby obtaining a substrate with a photosensitive composition layer. That is, the photosensitive composition layer is faced toward the substrate side rather than the support in the transfer film, and the transfer film and the substrate are laminated. By this lamination, a photosensitive composition layer and a temporary support are disposed on the substrate having a conductive layer.

[0409] In the above lamination, it is preferable that the conductive layer and the surface of the photosensitive composition layer are pressure-bonded to contact each other. In such a case, the pattern obtained after exposure and development can preferably be used as an etch resist when etching the conductive layer.

[0410] As the method for the above pressure bonding, 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 the substrate having a conductive layer and perform pressing and heating by a roller or the like.

[0411] Known laminators such as a vacuum laminator and an automatic cutting laminator can be used for lamination.

[0412] The substrate having a conductive layer has a conductive layer on the substrate and can form any layer 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.

[0413] As the substrate, for example, a resin substrate, a glass substrate, and a semiconductor substrate can be cited.

[0414] As a preferred embodiment of the substrate, for example, it is described in paragraph 0140 of International Publication No. 2018 / 155193, and this content is incorporated into this specification.

[0415] As the conductive layer, from the viewpoints of conductivity and fine line formability, at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer is preferably selected.

[0416] Moreover, on the substrate, only one layer of the conductive layer may be disposed, or two or more layers may be disposed. When two or more layers of the conductive layer are disposed, it is preferable that the conductive layers have different materials.

[0417] 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 this specification.

[0418] From the viewpoint of applying the obtained laminate to a touch panel, it is preferable that the conductive layer has a sensor electrode portion for a touch panel and a lead wiring portion that is electrically connected to the sensor electrode for a touch panel. That is, the substrate having the conductive layer preferably has a sensor electrode portion for a touch panel and a lead wiring portion that is electrically connected to the sensor electrode for a touch panel.

[0419] 〔Exposure step〕

[0420] The exposure step is a step of performing pattern exposure on the photosensitive composition layer using light having a main wavelength of 365 nm. By performing this step, the first photoinitiator having high photosensitivity at a wavelength of 365 nm is sensitized, and the polymerizable compound is polymerized.

[0421] In addition, herein, "pattern exposure" means exposure in a form of being exposed in a pattern shape, that is, in a form having an exposed portion and a non-exposed portion.

[0422] The detailed configuration and specific dimensions of the pattern in the pattern exposure are not particularly limited. In addition, the pattern formed by the subsequent development step preferably includes a fine line having a width of 20 μm or less, more preferably includes a fine line having a width of 10 μm or less.

[0423] As the light source for the pattern exposure, as long as it can at least irradiate light having a main wavelength of 365 nm (exposure light), it can be appropriately selected and used.

[0424] In addition, the main wavelength is the wavelength having the highest intensity in the exposure light.

[0425] 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.

[0426] The exposure amount is preferably 5 to 200 mJ / cm2 , more preferably 10 to 100 mJ / cm 2 .

[0427] As a preferred mode of the light source, exposure amount, and exposure method for exposure, for example, paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193 are described, and these contents are incorporated into this specification.

[0428] In addition, when the exposure step is performed before the peeling step described later, the exposure is performed in a state where the temporary support remains on the photosensitive composition layer.

[0429] When exposing from the temporary support side, a part of the light for exposure (especially the light on the short wavelength side) is easily absorbed by the temporary support. As a result, the light on the long wavelength side in the light emitted from the light source easily reaches the photosensitive composition.

[0430] That is, by performing the peeling step between the exposure step and the development step described later, it is easy to achieve exposure conditions in which the second photoinitiator is difficult to be sensitized and the first photoinitiator is easily sensitized.

[0431] [Peeling step]

[0432] The peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the development step described later.

[0433] The peeling method is not particularly limited, and an apparatus similar to that described in paragraphs

[0161] to

[0162] of JP-A-2010-072589 can be used.

[0434] [Development step]

[0435] The development step is a step of developing the exposed photosensitive composition layer to form a pattern.

[0436] The development of the above-mentioned photosensitive composition layer can be carried out using a developer.

[0437] As the developer, an alkaline aqueous solution is preferred. Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0438] As the development method, for example, spin immersion development, spray development, rotary development, and dip development can be mentioned.

[0439] As the developer preferably used in the present invention, for example, the developer described in paragraph

[0194] of International Publication No. 2015 / 093271 can be cited. As the developing method preferably used, for example, the developing method described in paragraph

[0195] of International Publication No. 2015 / 093271 can be cited.

[0440] [Post-exposure process]

[0441] The post-exposure process is a process of irradiating the pattern obtained through the above-described developing process with light that sensitizes the second photoinitiator. By implementing this process, the remaining second photoinitiator that is difficult to be sensitized in the exposure process is sensitized, and the polymerizable compound is further polymerized to form a pattern with excellent scratch resistance.

[0442] As the light source for exposure, as long as it can irradiate light (exposure light) that can sensitize the second photoinitiator, it can be appropriately selected and used.

[0443] Among them, it is preferable to irradiate light (exposure light) containing the maximum absorption wavelength of the above-described second photoinitiator.

[0444] The light irradiated in this process preferably contains light of 313 nm.

[0445] 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.

[0446] The exposure amount is not particularly limited, but it is preferably greater than the exposure amount in the above-described exposure process. Specifically, it is preferably 100 to 600 mJ / cm 2 , and more preferably 300 to 500 mJ / cm 2 .

[0447] The pattern (cured film of the photosensitive composition layer) formed through the above steps is preferably colorless. Specifically, in the L * a * b * colorimetric system, the a * value of the pattern is preferably -1.0 to 1.0, and the b * value of the pattern is preferably -1.0 to 1.0.

[0448] [Other processes]

[0449] The manufacturing method of the laminate of the present invention may include any other processes (other processes) in addition to the above.

[0450] When the transfer film has a protective film, it is preferable to have a peeling step of peeling the protective film from the transfer film before the above-mentioned laminating step. In this case, it is preferable to perform the laminating step so that the exposed surface side (photosensitive composition layer side) exposed in the peeling step is laminated on the substrate having the above-mentioned conductive layer.

[0451] The method for peeling the protective film is not particularly limited, and a known method can be adopted. For example, the film peeling mechanism described in paragraphs

[0161] to

[0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

[0452] Moreover, the method for manufacturing the laminate of the present invention may have a step of heating the obtained pattern (post-baking step).

[0453] The heating temperature in the post-baking step is not particularly limited, but it is preferably 110 to 180°C.

[0454] The method for manufacturing the above-mentioned laminate may have an etching step of etching the conductive layer in the region where the pattern is not disposed in the obtained laminate.

[0455] In the above-mentioned etching step, the pattern formed from the photosensitive composition layer through the above-mentioned developing step is used as an etching resist, and the etching treatment of the conductive layer is performed.

[0456] As the method for the etching treatment, the methods described in paragraphs

[0209] to

[0210] of Japanese Patent Application Laid-Open No. 2017-120435, paragraphs

[0048] to

[0054] of Japanese Patent Application Laid-Open No. 2010-152155, etc., methods based on known dry etching such as plasma etching, etc., and known methods can be applied.

[0457] The method for manufacturing the above-mentioned laminate may have a removing step of removing the pattern.

[0458] The removing step can be performed as needed, but it is preferably performed after the etching step.

[0459] The method for removing the pattern is not particularly limited, but a method of removing by chemical treatment can be cited, and it is preferable to use a removing solution.

[0460] As the method for removing the pattern, it is preferable to immerse the laminate having the pattern in a removing solution stirred at 30 to 80°C, more preferably at 50 to 80°C, for 1 to 30 minutes.

[0461] As the removal liquid, for example, a removal liquid in which an inorganic base component such as sodium hydroxide or potassium hydroxide or an organic base component such as a primary amine compound, a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt compound is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof can be cited.

[0462] Moreover, the removal liquid can be used for removal by a spraying method, a shower method, a spin-dip method, or the like.

[0463] Moreover, the method for manufacturing the laminate can have a step of reducing the visible light reflectance described in paragraph

[0172] of International Publication No. 2019 / 022089.

[0464] Moreover, the method for manufacturing the laminate can have a step of forming a new conductive layer on the insulating film described in paragraph

[0172] of International Publication No. 2019 / 022089.

[0465] The laminate manufactured by the method for manufacturing the laminate of the present invention can be applied to various devices. As a device including the above laminate, for example, an input device or the like can be cited, preferably a touch panel, more preferably a capacitive touch panel. Moreover, the above input device can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device.

[0466] When the laminate is applied to a touch panel, a pattern formed of the photosensitive composition layer is preferably used as a protective film for the touch panel electrode. That is, the photosensitive composition layer contained in the transfer film is preferably used for forming an electrode protective film (particularly, a touch panel electrode protective film).

[0467] Examples

[0468] Hereinafter, examples are given to further specifically illustrate the present invention. The materials, amounts used, ratios, processing details, processing order, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0469] In addition, in the following examples, the weight average molecular weight of the resin was the weight average molecular weight determined by polystyrene conversion based on gel permeation chromatography (GPC). Moreover, the acid value used was the theoretical acid value.

[0470] <Preparation of Photosensitive Composition>

[0471] Photosensitive compositions A-1 to A-32 and A'-1 to A'-3 were respectively prepared to have the compositions shown in Tables 1 to 5 below. In addition, the numerical values in the respective component columns in Tables 1 to 5 represent parts by mass.

[0472] [Table 1]

[0473]

[0474] [Table 2]

[0475]

[0476] [Table 3]

[0477]

[0478] [Table 4]

[0479]

[0480] [Table 5]

[0481]

[0482] [Table 6]

[0483]

[0484] [Table 7]

[0485]

[0486] [Chemical formula 20]

[0487] Compound B

[0488]

[0489] Compound C

[0490]

[0491] (Preparation of a 36.3 mass% solution of the solid component of alkali-soluble resin P-1)

[0492] A 36.3 mass% solution of the solid component of polymer P-1 having the following structure was used (solvent: propylene glycol monomethyl ether acetate). In P-1, the numerical values at the lower right of each structural unit represent the content ratio (mol%) of each structural unit.

[0493] A 36.3 mass% solution of the solid component of P-1 was prepared through the polymerization process and addition process shown below.

[0494] - Polymerization process -

[0495] Propylene glycol monomethyl ether acetate (manufactured by SANWA KAGAKU SANGYO co.,ltd., trade name PGM-Ac) (60 g) and propylene glycol monomethyl ether (manufactured by SANWA KAGAKU SANGYO co.,ltd., trade name PGM) (240 g) were introduced into a 2000 mL flask. The obtained liquid was heated to 90 °C while stirring at a stirring speed of 250 rpm (round per minute; the same applies hereinafter).

[0496] For the preparation of the dropping solution (1), 107.1 g of methacrylic acid (manufactured by MITSUBISHI RAYON CO.,LTD., trade name acrylic ester M), 5.46 g of methyl methacrylate (manufactured by Mitsubishi Gas Chemical Company,Inc., trade name MMA), and 231.42 g of cyclohexyl methacrylate (manufactured by Mitsubishi Gas Chemical Company,Inc., trade name CHMA) were mixed and diluted with PGM-Ac (60 g) to obtain the dropping solution (1).

[0497] For the preparation of the dropping solution (2), 9.637 g of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries,Ltd., trade name V-601) was dissolved in PGM-Ac (136.56 g) to obtain the dropping solution (2).

[0498] The dropping solution (1) and the dropping solution (2) were simultaneously dropped into the above-mentioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90 °C) over 3 hours.

[0499] Next, the container of the dropping solution (1) was washed with PGM-Ac (12 g), and the washing solution was dropped into the above-mentioned 2000 mL flask. Next, the container of the dropping solution (2) was washed with PGM-Ac (6 g), and the washing solution was dropped into the above-mentioned 2000 mL flask. During these droppings, the reaction solution in the above-mentioned 2000 mL flask was maintained at 90 °C and stirred at a stirring speed of 250 rpm. In addition, as a post-reaction, it was stirred at 90 °C for 1 hour.

[0500] V-601 (2.401 g) was added to the reaction solution after the post-reaction as the initiator for the first additional addition. In addition, the container of V-601 was washed with PGM-Ac (6 g), and the washing solution was introduced into the reaction solution. Then, it was stirred at 90 °C for 1 hour.

[0501] Next, V-601 (2.401 g) was added to the reaction solution as the initiator for the second additional addition. In addition, the container of V-601 was washed with PGM-Ac (6 g), and the washing solution was introduced into the reaction solution. Then, it was stirred at 90 °C for 1 hour.

[0502] Next, V-601 (2.401 g) was added to the reaction solution as the initiator for the third additional addition. In addition, the container of V-601 was washed with PGM-Ac (6 g), and the washing solution was introduced into the reaction solution. Then, it was stirred at 90 °C for 3 hours.

[0503] -Addition step-

[0504] After stirring at 90 °C for 3 hours, PGM-Ac (178.66 g) was introduced into the reaction solution. Next, tetraethylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) (1.8 g) and hydroquinone monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) (0.8 g) were added to the reaction solution. In addition, each container was washed with PGM-Ac (6 g), and the washing solution was introduced into the reaction solution. Then, the temperature of the reaction solution was raised to 100 °C.

[0505] Next, glycidyl methacrylate (manufactured by NOF CORPORATION, trade name Brenmar G) (76.03 g) was added dropwise to the reaction solution over 1 hour. The container of Brenmar G was washed with PGM-Ac (6 g), and the washing solution was introduced into the reaction solution. Then, as an addition reaction, it was stirred at 100 °C for 6 hours.

[0506] Next, the reaction solution was cooled and filtered using a mesh filter (100 mesh) for dust removal to obtain a solution (1158 g) of polymer D (solid content concentration: 36.3 mass%). The weight-average molecular weight of the obtained polymer P-1 was 27,000, the number-average molecular weight was 15,000, and the acid value was 95 mg KOH / g.

[0507] P-1 (hereinafter, the molar ratio of the repeating units in the formula is 51.5:2:26.5:20 in order from the leftmost repeating unit).

[0508] [Chemical formula 21]

[0509]

[0510] In the synthesis of P-1, a 36.3 mass% solution of the solid component of P-2 (solvent: propylene glycol monomethyl ether acetate) was prepared by changing the types and amounts of the monomers of the dropping solution (1). The obtained polymer P-2 had a weight-average molecular weight of 17,000, a number-average molecular weight of 6,200, and an acid value of 95 mg KOH / g.

[0511] P-2 (hereinafter, the molar ratio of the repeating units in the formula is 41:15.2:23.9:19.9 in order from the repeating unit on the left side).

[0512] [Chemical formula 22]

[0513]

[0514] (Preparation of a 36.2 mass% solution of the solid component of the alkali-soluble resin P-5)

[0515] 113.5 g of propylene glycol monomethyl ether was charged into a flask and heated to 90 °C under a nitrogen stream. A solution obtained by dissolving 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid in 30 g of propylene glycol monomethyl ether and a solution obtained by dissolving 27.6 g of the polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 57.7 g of propylene glycol monomethyl ether were simultaneously dropped into this solution over 3 hours. After the dropping was completed, 2.5 g of V-601 was added 3 times at intervals of 1 hour. Then, it was allowed to react for another 3 hours. Then, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. Under an air stream, the reaction solution was heated to 100 °C, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added. 71.9 g of glycidyl methacrylate (Brenmar G manufactured by NOF CORPORATION) was dropped into it over 20 minutes. It was reacted at 100 °C for 7 hours to obtain a solution of resin P-5. The solid component concentration of the obtained solution was 36.2%. The weight-average molecular weight in terms of standard polystyrene in GPC was 18,000, the dispersity was 2.3, and the acid value of the polymer was 124 mg KOH / g. The residual monomer amount measured by gas chromatography was less than 0.1 mass% with respect to the polymer solid component for any monomer.

[0516] P-5 (hereinafter, the molar ratio of the repeating units in the formula is 55.1:26.5:1.6:16.9 in order from the repeating unit on the left side).

[0517] [Chemical formula 23]

[0518]

[0519] In the synthesis of P-5, a 36.2 mass% solution of the solid component of P-6 (solvent: propylene glycol monomethyl ether acetate) was prepared by changing the types and amounts of monomers. The weight-average molecular weight of the obtained polymer P-6 was 18,000, the dispersity was 2.3, and the acid value was 114 mg KOH / g.

[0520] P-6 (hereinafter, the molar ratio of the repeating units in the formula is 55.1:24.6:1.6:17.0:1.7 in order from the repeating unit on the left.)

[0521] [Chemical formula 24]

[0522]

[0523] <Preparation of the composition for forming the refractive index adjustment layer>

[0524] Next, compositions B to B-4 for forming the refractive index adjustment layer were prepared using the compositions described in Table 8 below. The values in Table 6 represent "parts by mass".

[0525] [Table 8]

[0526]

[0527] The polymer A in Table 8 was synthesized as follows.

[0528] 1-Methoxypropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0 g) was introduced into a 1 L three-necked flask, and while stirring, the temperature was raised to 70 °C under a nitrogen stream. On the other hand, a dropping solution was prepared by dissolving allyl methacrylate (45.6 g) (manufactured by FFWK) and methacrylic acid (14.4 g) (manufactured by FFWK) in 1-methoxypropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0 g), and further dissolving V-65 (manufactured by FFWK) in 3.94 g, and the dropping solution was dropped into the flask over 2.5 hours. The reaction was carried out while maintaining the stirring state for 2 hours.

[0529] Then, the temperature was returned to room temperature, and it was dropped into ion-exchanged water (2.7 L) under a stirring state, and reprecipitation was carried out to obtain a suspension. The suspension was introduced through a Nutsche funnel with filter paper for filtration, and the filtrate was further washed with ion-exchanged water to obtain a wet powder. Drying was carried out by blowing air at 45 °C until a constant weight was confirmed, and A was obtained as a powder with a yield of 70%.

[0530] The ratio of methacrylic acid / allyl methacrylate of the obtained polymer A was 76 / 24 mass%. The weight-average molecular weight Mw was 38,000.

[0531] <Example 1>

[0532] On a temporary support of a polyethylene terephthalate film with a thickness of 16 μm (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)), using a slit-shaped nozzle, the coating amount of the photosensitive composition A-1 was adjusted so that the thickness of the dried photosensitive composition layer became 8 μm, and the photosensitive composition A-1 was coated. Then, the obtained temporary support was placed in a drying zone at 100 °C to volatilize the solvent, thereby forming a photosensitive composition layer. Then, a protective film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) was pressed onto the photosensitive composition layer to produce the transfer film X1 shown in Table 8.

[0533] <Examples 2 to 32 and Comparative Examples 1 to 4>

[0534] Instead of the photosensitive composition A-1, the photosensitive compositions A-2 to A-32 and A'-1 to A'-4 were used, and except for this, the transfer films X2 to 32 and C1 to 4 were obtained in the same order as in Example 1.

[0535] <Examples 33 to 52>

[0536] Instead of the photosensitive composition A-1, the photosensitive compositions A-33 to A-52 were used, and the coating amount was adjusted so that the thickness of the dried photosensitive composition layer became 5.0 μm. Except for this, the transfer films X33 to X52 were obtained in the same order as in Example 1.

[0537] <Manufacture of the laminate>

[0538] A cycloolefin resin film with a film thickness of 38 μm and a refractive index of 1.53 was subjected to corona discharge treatment for 3 seconds under the conditions of an electrode length of 240 mm and a working electrode gap of 1.5 mm using a high-frequency oscillator with an output voltage of 100% and an output of 250 W and a wire electrode with a diameter of 1.2 mm, and surface modification was carried out to obtain a transparent substrate.

[0539] Next, the following Material-C shown in Table 9 was coated on the corona discharge-treated surface of the transparent substrate using a slit-shaped nozzle, and then ultraviolet rays were irradiated (cumulative light amount: 300 mJ / cm 2 )), and drying was carried out at about 110 °C to form a transparent film with a refractive index of 1.60 and a film thickness of 80 nm.

[0540] [Table 9]

[0541]

[0542] [Chemical Formula 25]

[0543]

[0544] A film with a transparent film formed on a transparent substrate is introduced into a vacuum chamber, and an ITO target (indium:tin = 95:5 (molar ratio)) with a content of 10% by mass is used. An ITO thin film with a thickness of 40 nm and a refractive index of 1.82 is formed on the transparent film by DC magnetron sputtering (conditions: temperature of the transparent substrate is 150 °C, argon pressure is 0.13 Pa, oxygen pressure is 0.01 Pa). The surface resistance of the ITO thin film is 80 Ω / □ (Ω per square). 2 Then, the ITO thin film is etched and patterned by a known chemical etching method to obtain a conductive substrate having a transparent film and a transparent electrode portion on the transparent substrate.

[0545] Next, the protective film of the transfer film 1 obtained above is peeled off, and the surface of the exposed photosensitive composition layer is brought into contact with the formation surface of the transparent electrode portion of the conductive substrate, and they are laminated (bonded) in such a way that the photosensitive composition layer covers the transparent electrode portion, thereby forming a laminate having a photosensitive composition layer and a temporary support on the conductive substrate.

[0546] In addition, the above lamination was performed using a vacuum laminator manufactured by MCK Co., Ltd. under the conditions of a temperature of 40 °C for the transparent substrate, a temperature of 100 °C for the rubber roller, a line pressure of 3 N / cm, and a transfer speed of 2 m / min.

[0547] Then, using a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) including an ultra-high pressure mercury lamp, the exposure mask (quartz exposure mask including a pattern for forming an outer coating) surface is brought into close contact with the temporary support, and pattern exposure is performed through the temporary support with an exposure amount of 60 mJ / cm

[0548] (i-ray). 2 (i-ray) for pattern exposure.

[0549] In addition, in the exposure light during irradiation, the light with a wavelength of 365 nm is the main wavelength.

[0550] Then, after peeling off the temporary support from the laminate, the exposed photosensitive composition layer is developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate at a temperature of 32 °C. Then, the residue is removed by spraying ultrapure water from an ultra-high pressure cleaning nozzle onto the developed laminate. Next, air is blown onto the surface of the laminate to remove moisture.

[0551] Next, using an exposure machine (manufactured by Ushio Inc.) including a high-pressure mercury lamp, the obtained pattern was exposed (post-exposure) with an exposure dose of 400 mJ / cm 2 (i-ray).

[0552] Then, a post-baking treatment was performed at 145 °C for 30 minutes, and a laminate LX1 having a transparent film, a transparent electrode portion, and a pattern (a cured film of the photosensitive composition layer) in this order was formed on the transparent substrate.

[0553] Instead of the transfer film X1, transfer films X2 to 52 and C1 to C4 were used respectively, and laminates LX2 to 52 and LC1 to 4 were formed in the above order.

[0554] <Edge shape evaluation (pattern linearity)>

[0555] As an exposure mask, an exposure mask with a line / space of 50 μm / 50 μm was used to perform the exposure treatment. Except for this, evaluation samples were produced in the same order as the above <Method for manufacturing laminate>.

[0556] The edge portion of the pattern in the produced evaluation sample was observed visually and with an optical microscope (20 times magnification). Based on the following evaluation criteria, the shape of the edge portion (pattern linearity) was evaluated.

[0557] <<Evaluation criteria>>

[0558] A: Even when observed with an optical microscope, there are no irregularities on the edge of the pattern.

[0559] B: Some irregularities are observed on the edge of the pattern by observation with an optical microscope.

[0560] C: Although it cannot be known visually, by observation with an optical microscope, irregularities can be clearly observed on the edge of the pattern.

[0561] D: Irregularities can be clearly observed on the edge of the pattern visually.

[0562] <Scratch resistance evaluation (surface scratch evaluation)>

[0563] In the order of the above <Method for manufacturing laminate>, evaluation samples were produced up to post-exposure. Then, the surface of the pattern was wiped with gauze, and the surface of the pattern was observed visually and with a microscope (5 times magnification).

[0564] <<Evaluation criteria>>

[0565] A: No scratches were seen on the entire surface of the pattern either visually or by observation with an optical microscope.

[0566] B: There are no visible scratches, but they can be seen under an optical microscope.

[0567] C: There are parts where scratches can be faintly seen by the naked eye.

[0568] D: The scratches can be clearly seen by the naked eye.

[0569] In Tables 10 to 12, the symbols in the "Type" column of the "First Photoinitiator" column and the "Type" column of the "Second Photoinitiator" column represent the following respectively.

[0570] "OXE02": 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxime) (OXE-02, manufactured by BASF)

[0571] "OXE01": 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyloxime) (OXE01, manufactured by BASF)

[0572] "OXE03": [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl]][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetoxime) (OXE03, manufactured by BASF)

[0573] "Irgacure379EG": 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one (Irgacure379EG, manufactured by BASF)

[0574] "DAROCUR EDB": Ethyl 4-(dimethylamino)benzoate (DAROCUR EDB, manufactured by BASF)

[0575] "Irgacure2959": 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylacetophenone (Irgacure2959, manufactured by BASF)

[0576] "Irgacure307": 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (Irgacure307, manufactured by BASF)

[0577] "Irgacure819": Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0578] "IrgacureTPO": 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide

[0579] In Tables 10 to 12, “ε1” represents the molar extinction coefficient of the first photoinitiator at a wavelength of 365 nm, “ε2” represents the molar extinction coefficient of the second photoinitiator at a wavelength of 365 nm, and “ε3” represents the molar extinction coefficient of the second photoinitiator at a wavelength of 313 nm.

[0580] [Table 10]

[0581]

[0582] [Table 11]

[0583]

[0584] [Table 12]

[0585]

[0586] As shown in Tables 10 to 12, it was confirmed that by using the transfer film of the present invention, the desired effects can be obtained.

[0587] <Examples 101 to 152>

[0588] In the production of the transfer film of Example 1, on the photosensitive composition layer, a slit-shaped nozzle was used to adjust the coating amount of the composition B for forming the refractive index adjustment layer so that the thickness of the dried refractive index adjustment layer became 70 nm, and the composition B for forming the refractive index adjustment layer was coated. Then, the obtained coating film was dried at a drying temperature of 80° C. to form a refractive index adjustment layer on the photosensitive composition layer.

[0589] In addition, the refractive index of the refractive index adjustment layer was 1.68.

[0590] Next, a protective film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) was pressure-bonded to the surface of the refractive index adjustment layer to produce a transfer film Y1.

[0591] In the production of the transfer films of Examples 2 to 52, the same procedure as above was carried out to produce transfer films Y2 to Y52 corresponding to Examples 101 to 152 and including a refractive index adjustment layer.

[0592] Using these transfer films Y1 to Y52 respectively, the same evaluations as <Edge shape evaluation (pattern linearity)> and <Scratch resistance evaluation (surface scratch evaluation)> were carried out, and the same results as those of the transfer films of Examples 1 to 52 corresponding to the method not including the refractive index adjustment layer of each transfer film were obtained. That is, for example, the same evaluation results were obtained for the transfer film X1 of Example 1 and the transfer film Y1 having a refractive index adjustment layer on the transfer film X1.

[0593] Further, in the production of the transfer film of Y34, the composition B for forming the refractive index adjustment layer was changed to B-2 to B-4, and except for this, the same procedure as above was carried out to produce transfer films Y34-2 to Y34-4. Using these transfer films Y34-2 to Y34-4 respectively, the same evaluations as <Edge shape evaluation (pattern linearity)> and <Scratch resistance evaluation (surface scratch evaluation)> were carried out, and the same results as those of the transfer film of Example 34 corresponding to the mode not including the refractive index adjustment layer of each transfer film were obtained.

[0594] In Example 1, the coating amount was adjusted, and the thicknesses of the photosensitive resin layers were adjusted to 1.0 μm, 2.0 μm, and 4.0 μm respectively. Except for this, transfer films with different photosensitive resin layer thicknesses were produced in the same manner as in Example 1, and the same evaluations as <Edge shape evaluation (pattern linearity)> and <Scratch resistance evaluation (surface scratch evaluation)> were carried out, and the same evaluation results as those of Example 1 were obtained in all cases.

[0595] In Example 34, the coating amount was adjusted, and the thicknesses of the photosensitive resin layers were adjusted to 1.0 μm, 2.0 μm, 4.0 μm, and 8.0 μm respectively. Except for this, transfer films with different photosensitive resin layer thicknesses were produced in the same manner as in Example 1, and the same evaluations as <Edge shape evaluation (pattern linearity)> and <Scratch resistance evaluation (surface scratch evaluation)> were carried out, and the same evaluation results as those of Example 34 were obtained in all cases.

[0596] In the transfer film Y34, the thicknesses of the refractive index adjustment layer were adjusted to 40 nm, 100 nm, and 150 nm respectively. Except for this, transfer films with different refractive index adjustment layer thicknesses were produced in the same manner as Y34, and the same evaluations as <Edge shape evaluation (pattern linearity)> and <Scratch resistance evaluation (surface scratch evaluation)> were carried out, and the same evaluation results as those of Y34 were obtained in all cases.

Claims

1. A transfer film having a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer contains a photoinitiator, an alkali-soluble acrylic resin, and a polymerizable compound having an ethylenically unsaturated group, wherein a total proportion of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate in the alkali-soluble acrylic resin is 30 mol% or more, wherein a weight-average molecular weight Mw of the alkali-soluble acrylic resin is from 10,000 to 100,000, wherein the photoinitiator contains a first photoinitiator and a second photoinitiator which is a compound different from the first photoinitiator, wherein the first photoinitiator contains at least one selected from the group consisting of oxime ester-based photoinitiators, alkyl phenyl ketone-based photoinitiators, and acylphosphine oxide-based photoinitiators, wherein the second photoinitiator contains an aminobenzoate-based photoinitiator, wherein a molar extinction coefficient ε1 of the first photoinitiator at a wavelength of 365 nm is 500 L / mol·cm or more, wherein a ratio of a molar extinction coefficient ε2 of the second photoinitiator at a wavelength of 365 nm to a molar extinction coefficient ε3 of the second photoinitiator at a wavelength of 313 nm is 0.200 or less, wherein the molar extinction coefficient ε2 is 0 L / mol·cm or more and 1500 L / mol·cm or less, wherein the molar extinction coefficient ε3 is 2000 L / mol·cm or more and 200000 L / mol·cm or less.

2. The transfer film according to claim 1, wherein a ratio of a molar extinction coefficient ε2 of the second photoinitiator at a wavelength of 365 nm to a molar extinction coefficient ε3 of the second photoinitiator at a wavelength of 313 nm is 0.100 or less.

3. The transfer film according to claim 1 or 2, wherein a maximum absorption wavelength of the second photoinitiator is 320 nm or less.

4. The transfer film according to claim 1 or 2, wherein a maximum absorption wavelength of the second photoinitiator is 300 nm or less.

5. The transfer film according to claim 1 or 2, wherein the first photoinitiator contains at least one selected from the group consisting of oxime ester-based photoinitiators and alkyl phenyl ketone-based photoinitiators.

6. The transfer film according to claim 1 or 2, wherein a ratio of a molar extinction coefficient ε2 of the second photoinitiator at a wavelength of 365 nm to a molar extinction coefficient ε1 of the first photoinitiator at a wavelength of 365 nm is 0.50 or less.

7. The transfer film according to claim 1 or 2, wherein the photosensitive composition layer is used to form an electrode protective film.

8. The transfer film according to claim 1 or 2, further comprising a refractive index adjustment layer, wherein the refractive index adjustment layer is disposed in contact with the photosensitive composition layer, wherein a refractive index of the refractive index adjustment layer is 1.60 or more.

9. A method for manufacturing a laminate, comprising: Laminating step: The transfer film is laminated on the substrate such that the photosensitive composition layer side of the transfer film according to any one of claims 1 to 8 faces the substrate having a conductive layer, to obtain a substrate with a photosensitive composition layer; Exposure step: The photosensitive composition layer is pattern-exposed using light having a main wavelength of 365 nm; Development step: The exposed photosensitive composition layer is developed to form a pattern; and Post-exposure step: The pattern is irradiated with light that sensitizes the second photoinitiator, The method for manufacturing the laminate further has a peeling step of peeling the temporary support from the substrate with the photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the development step.

10. The method for manufacturing a laminate according to claim 9, wherein the substrate having a conductive layer is a substrate having a sensor electrode portion for a touch panel and a lead wiring portion electrically connected to the sensor electrode for the touch panel.

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