JP7416969B2 - Transfer film, laminate manufacturing method, circuit wiring manufacturing method - Google Patents

Description

The present invention relates to a transfer film, a method for manufacturing a laminate, and a method for manufacturing circuit wiring.

Since the number of steps required to obtain a predetermined pattern is small, a photosensitive composition layer is placed on a transfer target such as a substrate using a transfer film, and a mask is applied to the photosensitive composition layer. A method in which the film is exposed to light and then developed is widely used.

For example, Patent Document 1 discloses an ultrafine polyester film for photoresist that includes predetermined particles on the surface of a laminated polyester film opposite to the resist layer side.

Japanese Patent Application Publication No. 2006-327158

In recent years, when using a transfer film, it is required to have excellent patterning properties. Specifically, it is required that the pattern obtained by exposing and developing the photosensitive composition layer of the transfer film has small variations in line width. Hereinafter, in this specification, a small variation in line width of a pattern is also referred to as having excellent patterning properties.

It is also required that the transfer film has excellent releasability. Specifically, first, when using the transfer film, the protective film is peeled off. It is required that the photosensitive composition layer hardly remains on the surface of the protective film when the protective film is peeled off. Further, after the photosensitive composition layer of the transfer film is bonded to the object to be transferred, the temporary support is peeled off. It is also required that the photosensitive composition layer hardly remains on the surface of the temporary support when the temporary support is peeled off. In other words, it is required that the photosensitive composition layer hardly remains on the surface of the temporary support and the surface of the protective film when the protective film is peeled off and when the temporary support is peeled off. . Hereinafter, in this specification, the term "excellent releasability" means that the photosensitive composition layer hardly remains on the surface of the temporary support and the protective film and can be peeled off when the photosensitive composition layer is peeled off.

The present inventor studied the characteristics of a conventional transfer film having a temporary support such as that disclosed in Patent Document 1, and found that the patterning property and peelability of the transfer film cannot be achieved at the same time.

Therefore, an object of the present invention is to provide a transfer film that has excellent patterning properties and excellent peelability.
Another object of the present invention is to provide a method for manufacturing a laminate and a method for manufacturing circuit wiring using a transfer film.

As a result of intensive study on the above-mentioned problem, the present inventors found that the above-mentioned problem can be solved by the following configuration.

[1] A transfer film comprising a temporary support, a photosensitive composition layer disposed on the temporary support, and a protective film in this order,
The temporary support has a temporary support body, a first layer disposed on one surface of the temporary support body, and a second layer disposed on the other surface of the temporary support body,
Of the first layer and the second layer, the first layer is arranged on the photosensitive composition layer side,
The first layer includes first organic particles with an average particle diameter of 100 to 1000 nm and first inorganic particles with an average particle diameter of 70 nm or less, and the kurtosis Rku of the surface in contact with the photosensitive composition layer of the first layer is 2. .0 to 100,
A transfer film in which the second layer contains second inorganic particles having an average particle diameter of 70 nm or less, or does not contain inorganic particles.
[2] The transfer film according to [1], wherein the first organic particles include polystyrene resin particles.
[3] The transfer film according to [1] or [2], wherein the first organic particles have an average particle diameter of 350 to 800 nm.
[4] The method according to any one of [1] to [3], wherein at least one of the first inorganic particles and the second inorganic particles contains at least one selected from the group consisting of silicon atoms and aluminum atoms. transfer film.
[5] The transfer film according to any one of [1] to [4], wherein at least one of the first inorganic particles and the second inorganic particles contains aluminum oxide.
[6] The transfer film according to any one of [1] to [5], wherein the first inorganic particles have an average particle diameter and the second inorganic particles have an average particle diameter of 10 to 50 nm.
[7] The thickness of the temporary support body is 6.0 to 30.0 μm,
The transfer film according to any one of [1] to [6], wherein the first layer and the second layer have a thickness of 0.8 to 3.0 μm.
[8] The average particle diameter of the first organic particles is 350 to 800 nm,
the first inorganic particles contain aluminum oxide,
The transfer film according to any one of [1] to [7], wherein the first inorganic particles have an average particle diameter of 10 to 50 nm.
[9] The second layer contains second organic particles with an average particle diameter of 350 to 800 nm,
the second inorganic particles contain aluminum oxide,
The transfer film according to any one of [1] to [8], wherein the second inorganic particles have an average particle diameter of 10 to 50 nm.
[10] The transfer film according to any one of [1] to [9], wherein the first layer has a surface kurtosis Rku of 2.5 to 10.
[11] Any one of [1] to [10], wherein the kurtosis Rku of the surface of the first layer is 3.0 to 5.0, and the first inorganic particles and the second inorganic particles contain aluminum oxide. Transfer film described in .
[12] The transfer film according to any one of [1] to [11], wherein the photosensitive composition layer contains a binder polymer, a polymerizable compound, and a polymerization initiator.
[13] The transfer film according to any one of [1] to [12], further comprising a refractive index adjusting layer between the photosensitive composition layer and the protective film.
[14] The transfer film according to any one of [1] to [13], wherein the photosensitive composition layer is used for forming an electrode protective film for a touch panel.
[15] Peel off the protective film from the transfer film according to any one of [1] to [14], and bond the surface opposite to the temporary support to a substrate having a conductive layer. , a bonding step of obtaining a photosensitive composition layer-attached substrate having a photosensitive composition layer and a temporary support in this order;
an exposure step of exposing the photosensitive composition layer to pattern light;
A developing step of developing the exposed photosensitive composition layer to form a pattern,
A method for producing a laminate, further comprising a peeling step of peeling off the temporary support from the photosensitive composition layer-coated substrate between the bonding step and the exposure step or between the exposure step and the development step. .
[16] Peel the protective film from the transfer film according to any one of [1] to [14], and bond the surface opposite to the temporary support to a substrate having a conductive layer. , a bonding step of obtaining a photosensitive composition layer-attached substrate having a photosensitive composition layer and a temporary support in this order;
an exposure step of exposing the photosensitive composition layer to pattern light;
a developing step of developing the exposed photosensitive composition layer to form a pattern;
an etching process of etching the conductive layer in a region where the pattern is not arranged;
Furthermore, a method for manufacturing circuit wiring, comprising a peeling step of peeling off the temporary support from the photosensitive composition layer-coated substrate between the bonding step and the exposure step or between the exposure step and the development step. .

According to the present invention, a transfer film having excellent patterning properties and excellent peeling properties can be provided. Moreover, according to the present invention, it is also possible to provide a method for manufacturing a laminate and a method for manufacturing circuit wiring using a transfer film.

It is a schematic diagram showing an example of composition of a transfer film of a 1st embodiment. It is a schematic diagram showing an example of composition of a transfer film of a 2nd embodiment.

The present invention will be explained in detail below.
In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In this specification, in numerical ranges described in stages, the upper limit or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. . In the numerical ranges described in this specification, the upper limit value or lower limit value described in a certain numerical range may be replaced with the value shown in the Examples.

In this specification, the term "process" is used not only to refer to an independent process, but also to include it in the term even if the process cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. .

As used herein, "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.
In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed as follows: Three TSK gel Super HZM-N (manufactured by Tosoh Corporation) columns are connected in series, and THF is used as an eluent. (Tetrahydrofuran), using a differential refractometer as a detector and polystyrene as a standard substance, and is a value converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer.
In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.
In this specification, unless otherwise specified, the ratio of constituent units of a polymer is a mass ratio.

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

In this specification, "(meth)acrylic" is a concept that includes both acrylic and methacryl, "(meth)acrylate" is a concept that includes both acrylate and methacrylate, and "(meth)acryloxy "Group" is a concept that includes both an acryloxy group and a methacryloxy group.

As used herein, "organic group" means a group containing at least one carbon atom.

In this specification, the type of substituent, the position of the substituent, and the number of substituents in the case of "may have a substituent" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of the substituent include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituent group T, for example.
(Substituent T)
Examples of the substituent T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy and p-tolyloxy groups; Aryloxy groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; Acetyl group, benzoyl group, isobutyryl group , acryloyl group, methacryloyl group, and methoxalyl group; alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl group; cyclo Alkyl group; aryl group; heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; nitro group; ether group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; Examples include monoalkylamino groups; dialkylamino groups; arylamino groups; and combinations thereof.

[Transfer film]
The transfer film includes a temporary support, a photosensitive composition layer disposed on the temporary support, and a protective film in this order. The temporary support has a temporary support body, a first layer disposed on one surface of the temporary support body, and a second layer disposed on the other surface of the temporary support body, Of the first layer and the second layer, the first layer is disposed on the photosensitive composition layer side. That is, the transfer film has the second layer, the temporary support body, the first layer, the photosensitive composition layer, and the protective film in this order.

A characteristic feature of the transfer film of the present invention is that the temporary support of the transfer film has a first layer and a second layer, as described below.
As mentioned above, the present inventors investigated conventional transfer films and found that patterning properties and peelability were not compatible at the same time.
In contrast, in the present invention, the desired effect was obtained when the temporary support had a first layer and a second layer. Regarding the mechanism, the present inventors speculate as follows.
By controlling the first inorganic particles that may be included in each layer to have a predetermined average particle diameter, scattering of light during exposure is suppressed, uniform exposure is achieved, and variations in line width of the resin pattern are reduced. In addition, by including organic particles having a predetermined particle size in the first layer, the kurtosis Rku is adjusted to a predetermined range, and the curtosis Rku is adjusted to a predetermined range, and the photosensitive composition It is presumed that the desired releasability between the layer and the protective film could be imparted.
Hereinafter, in this specification, the effect of the present invention is also referred to as superior if at least one of the effects of superior patterning properties of the transfer film and superior releasability of the transfer film is obtained.

An example of the embodiment of the transfer film of the present invention is shown below, but the present invention is not limited thereto.
(1) “Temporary support/photosensitive composition layer/refractive index adjustment layer/protective film”
(2) “Temporary support/photosensitive composition layer/protective film”
(3) “Temporary support/intermediate layer/photosensitive composition layer/protective film”
(4) “Temporary support/thermoplastic resin layer/intermediate layer/photosensitive composition layer/protective film”
In each of the above configurations, the photosensitive composition layer is preferably a negative photosensitive composition layer. Moreover, it is also preferable that the photosensitive composition layer is a colored resin layer.
The transfer film of the present invention may be used as a transfer film for a wiring protection film or as a transfer film for an etching resist, as described later.
In the case of a transfer film for a wiring protection film, the structure of the transfer film is preferably one of the above-mentioned structures (1) to (2). Further, in the case of a transfer film for an etching resist, the structure of the transfer film is preferably one of the above-mentioned structures (2) to (4).
Specifically, examples include a first embodiment and a second embodiment, which will be described later.

An example of an embodiment of the transfer film of the first embodiment will be described below.
The transfer film 10 shown in FIG. 1 includes a temporary support 1, a composition layer 2 including a photosensitive composition layer 3 and a refractive index adjustment layer 5, and a protective film 7 in this order.
Further, although the transfer film 10 shown in FIG. 1 has the refractive index adjusting layer 5 disposed therein, the refractive index adjusting layer 5 may not be disposed.

An example of an embodiment of the transfer film of the second embodiment will be described below.
The transfer film 20 shown in FIG. 2 includes, in this order, a temporary support 11, a composition layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive composition layer 17, and a protective film 19. .
Moreover, although the transfer film 20 shown in FIG. 2 has a form in which the thermoplastic resin layer 13 and the intermediate layer 15 are arranged, the thermoplastic resin layer 13 and the intermediate layer 15 may not be arranged.
In the transfer film of the second embodiment, the temporary support 11 and the protective film 17 may be the same as the temporary support 1 and the protective film 9 of the first embodiment described above.
Each structure of the transfer film will be described in detail below.

<Temporary support>
The transfer film has a temporary support.
The temporary support has a temporary support main body, a first layer described below, and a second layer described below.
The temporary support is a member that supports the photosensitive composition layer, and is finally removed by a peeling process.
Each member constituting the temporary support will be described in detail below.

[Temporary support body]
The temporary support has a temporary support body.
The temporary support body is a member disposed between the first layer and the second layer.
Examples of the temporary support body include a glass substrate and a film, with a resin film being preferred. Further, as the temporary support body, a film that does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat and has flexibility is preferable.

Examples of the resin film include polyester films such as polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films.
Among these, as the temporary support body, a polyester film is preferred, a biaxially stretched polyester film is more preferred, and a biaxially stretched PET film is even more preferred. Further, it is also preferable that the temporary support body is free from deformation such as wrinkles and scratches.

As the temporary support body, a biaxially stretched polyester film is preferable.
Biaxial stretching means performing biaxial stretching treatment and having molecular orientation in two axial directions.
Molecular orientation is measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Scientific Instruments). The angle formed by the two axes is preferably 90°±5°, more preferably 90°±3°, and even more preferably 90°±1°.
The biaxially stretched polyester film preferably has molecular orientation in the longitudinal direction and the width direction.
The width direction means a direction perpendicular to the longitudinal direction. If the width direction is unknown, the direction with the strongest orientation measured using a microwave transmission molecular orientation meter (for example, MOA-6004, manufactured by Oji Scientific Instruments) is determined as the width direction. shall be. Further, orthogonal is not limited to strictly orthogonal, but includes substantially orthogonal. Substantially orthogonal means that they intersect at 90°±5°, preferably at 90°±3°, and more preferably at 90°±1°.

A biaxially oriented polyester film is a biaxially oriented polyester film containing polyester as the main polymer component. The main polymer component means a polymer having the largest content ratio (mass%) among all the polymers contained in the film, and polyester means a polymer having an ester bond in the main chain.

Examples of the polyester include known polyesters.
Examples of polyester include polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN). Among these, PET is preferred as the polyester.

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

The biaxially stretched polyester film may contain only one type of polyester, or may contain two or more types of polyester.
The content of polyester is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and 98% by mass or more, based on the total mass of the polymer in the biaxially stretched polyester film. Particularly preferred. The upper limit is not particularly limited, and is preferably 100% by mass or less based on the total mass of the polymer in the biaxially stretched polyester film.
The content of polyester is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more, based on the total mass of the biaxially stretched polyester film. The upper limit is not particularly limited, and is preferably 100% by mass or less based on the total mass of the biaxially stretched polyester film.
When the biaxially stretched polyester film contains PET, the content of PET is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and 98 to 100% by mass, based on the total mass of polyester in the biaxially stretched polyester film. It is more preferably 100% by weight, and particularly preferably 100% by weight.

The method for producing polyester is not particularly limited and includes known methods.
As a method for producing polyester, for example, polyester can be produced by polycondensing at least one dicarboxylic acid compound and at least one diol compound in the presence of a catalyst.
Examples of dicarboxylic acid compounds include aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and aromatic dicarboxylic acid compounds.
Examples of the diol compound include aliphatic diol compounds, alicyclic diol compounds, and aromatic diol compounds.
Examples of the catalyst include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, germanium compounds, and phosphorus compounds.
In the production of polyester, a known end-capping agent can be used as necessary. Examples of the terminal capping agent include oxazoline compounds, carbodiimide compounds, and epoxy compounds.

As a method for synthesizing polyester, known synthesis methods can be applied, such as the methods described in paragraphs [0033] to [0070] of Japanese Patent No. 5575671, the contents of which are herein incorporated by reference. be incorporated into.

The smaller the haze of the temporary support body, the better.
Specifically, the haze of the temporary support is preferably less than 0.5%, more preferably 0.4% or less. The lower limit is not particularly limited, and is preferably 0% or more.
Note that haze can be measured using a haze meter in accordance with JIS K 7105:1981, and the haze described in this specification can be measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). This is the value.

In the temporary support body, the b ^* value in the L ^* a ^* b ^* color system is preferably 0 to 1, more preferably 0 to 0.8, even more preferably 0 to 0.6, and 0 to 0. 4 is particularly preferred. When the b ^* value in the L ^* a ^* b ^* color system is 0 to 1, the yellowness of the film can be reduced, and the hue of the film can be made close to colorless. As a result, it can be preferably applied, for example, to applications that require high visibility (eg, display devices).
The b ^* value in the L ^* a ^* b ^* color system of the temporary support body is measured by a transmission method using a spectrophotometer (for example, SE-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

The thickness of the temporary support body is preferably 1.0 to 100.0 μm, more preferably 6.0 to 30.0 μm, from the viewpoint of handling suitability (particularly handling suitability when laminating films). More preferably, the thickness is from 0 to 30.0 μm. When the thickness of the temporary support body is 10.0 μm or more, good strength can be obtained and handling in the processing step is easy, and when it is 50.0 μm or less, a better haze value can be obtained.

It is preferable that the dimensional change rate of the temporary support main body is within the following range because it is possible to suppress the occurrence of distortion and wrinkles due to heat shrinkage in the DFR processing step. The above-mentioned dimensional change rate can be adjusted by appropriately adjusting conditions such as relaxation and heat treatment in the film forming conditions by a known method. The dimensional change rate at 150°C is preferably less than 3% in the longitudinal direction and less than 2.5% in the width direction, and 0.5% or more and less than 2% in the longitudinal direction and 1% or more and 2% in the width direction. Less than is more preferable. Moreover, the dimensional change rate in the longitudinal direction and the width direction at 100° C. is preferably less than 1%, more preferably less than 0.8%. When the dimensional change rate is within the above range, the flatness when applying the photosensitive composition tends to be better.

In the temporary support body, the strength when the longitudinal film is stretched by 5% (hereinafter also referred to as "F-5") is preferably 70 MPa or more and less than 150 MPa. If F-5 in the longitudinal direction is less than 70 MPa, the machining characteristics may deteriorate due to the occurrence of scratches due to insufficient strength. On the other hand, if F-5 in the longitudinal direction is 150 MPa or more, it may be difficult to achieve both F-5 in the width direction. F-5 in the longitudinal direction is more preferably 80 MPa or more and less than 140 MPa, and even more preferably 90 MPa or more and less than 130 MPa.
Further, F-5 in the width direction is preferably 80 MPa or more and less than 160 MPa.
When F-5 in the width direction is within the above range, deterioration in processing characteristics due to occurrence of scratches due to insufficient strength is suppressed, and it is also compatible with F-5 in the longitudinal direction. More preferably 90 MPa or more and less than 150 MPa, still more preferably 100 MPa or more and less than 140 MPa.

The breaking strength in the longitudinal direction of the temporary support body is preferably 200 MPa or more and less than 360 MPa, more preferably 220 MPa or more and less than 340 MPa. Moreover, the breaking strength in the width direction is preferably 260 MPa or more and less than 420 MPa, more preferably 280 MPa or more and less than 400 MPa.
F-5 and breaking strength can be achieved by appropriately adjusting the stretching temperature and stretching ratio in the longitudinal and transverse directions.

[First layer]
The temporary support has a first layer disposed on the side of the photosensitive composition layer.
The first layer includes first organic particles with an average particle diameter of 100 to 1000 nm and first inorganic particles with an average particle diameter of 70 nm or less, and the kurtosis Rku of the surface in contact with the photosensitive composition layer of the first layer is 2. ~100.

(Kurtosis Rku)
The kurtosis Rku (hereinafter also simply referred to as "kurtosis Rku") of the surface in contact with the photosensitive composition layer of the first layer is preferably 2.5 to 80, more preferably 2.5 to 10, and 2.5 to 80. 6.0 is more preferable, and 3.0 to 5.0 is particularly preferable.
Kurtosis Rku was measured using a New View 6000 manufactured by Zygo Co., Ltd. at 10 randomly selected locations on the surface in contact with the photosensitive composition layer of the first layer (the surface opposite to the temporary support body). Measure and use the average value of the obtained measured values, excluding the minimum and maximum values.

Examples of the method for adjusting kurtosis Rku include a method for adjusting the type and content of the first organic particles and first inorganic particles, which will be described later.

(First organic particle)
The average particle diameter of the first organic particles is 100 to 1000 nm, and from the standpoint of achieving better effects of the present invention, it is preferably 350 to 800 nm, more preferably 350 to 700 nm, and even more preferably 400 to 600 nm.
The average particle diameter of the first organic particles is determined by calculating the arithmetic average of the particle diameters of 50 first organic particles randomly selected from a transmission electron microscope (TEM) image. Specifically, after cutting out a cross section of the temporary support, the cross section of the temporary support is observed using a TEM, and 50 particles are randomly selected from the TEM image. Energy dispersive X-ray spectroscopy (EDX) is performed on the selected particles, and from the EDX results, particles that do not contain inorganic elements are classified as organic particles, and particles that contain inorganic elements are classified as inorganic particles. The particles can be determined by arithmetic averaging the particle diameters of each particle. In addition, when each particle is not spherical, the average particle diameter of each particle is determined by determining the cross-sectional area of the organic particle or inorganic particle obtained from the cross-sectional TEM image of the temporary support, and replacing it with a circle with the same area as the cross-sectional area. The diameter at that time is taken as the average particle diameter of each particle. Note that the average particle diameter means a value obtained by arithmetic average of the diameters in a cross-sectional TEM image.

As the first organic particles, resin particles are preferred.
Examples of the resin particles include polystyrene resin particles, acrylic resin particles, polyester resin particles, silicone organic particles, and styrene-acrylic organic particles, with polystyrene resin particles being preferred.
Moreover, it is preferable that the first organic particles have a crosslinked structure.

The first layer may contain only one type of first organic particles, or may contain two or more types of first organic particles.
The content of the first organic particles is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, and more preferably 0.1 to 1.0% by mass, based on the total mass of the first layer. 0% by weight is more preferable, and 0.1 to 0.3% by weight is particularly preferable.

(First inorganic particle)
The average particle diameter of the first inorganic particles is 70 nm or less, preferably 65 nm or less, and more preferably 50 nm or less, since the effects of the present invention are more excellent. The lower limit is not particularly limited, and is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 8 nm or more, and particularly preferably 10 nm or more.
The average particle diameter of the first inorganic particles can be measured using the method for measuring the average particle diameter of organic particles described above.

The first inorganic particles preferably contain at least one selected from the group consisting of silicon atoms and aluminum atoms, and more preferably contain aluminum atoms.
Examples of the first inorganic particles include silicon dioxide particles (silica particles), titania particles (titanium oxide particles), calcium carbonate, barium sulfate, and aluminum oxide particles (alumina particles). Among these, as the inorganic particles, aluminum oxide particles or silicon dioxide particles are preferable, and aluminum oxide particles are more preferable in terms of haze and durability.

The silicon dioxide particles are not particularly limited, and include known silica particles.
Examples of silicon dioxide particles include fumed silica particles and colloidal silica particles.
Fumed silica particles can be obtained, for example, by reacting a compound containing a silicon atom with oxygen and hydrogen in a gas phase. Examples of the silicon compound used as a raw material include silicon halide (eg, silicon chloride).
Colloidal silica particles can be synthesized, for example, by a sol-gel method in which raw material compounds are hydrolyzed and condensed. Examples of raw material compounds for colloidal silica include alkoxy silicon (eg, tetraethoxysilane) and halogenated silane compounds (eg, diphenyldichlorosilane).
The silicon dioxide particles may be in the form of primary particles or aggregates of primary particles (agglomerated silica particles).

The first layer may contain only one type of first inorganic particles, or may contain two or more types of first inorganic particles.
The content of the first inorganic particles is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, and more preferably 0.1 to 1.0% by mass, based on the total mass of the first layer. 0% by weight is more preferable, and 0.2 to 0.5% by weight is particularly preferable.

In the first layer, the content of the first inorganic particles is preferably greater than the content of the first organic particles. Specifically, the mass ratio of the content of the first inorganic particles to the content of the first organic particles (content of the first inorganic particles/content of the first organic particles) is preferably 1.0 or more, and 2. .0 or more is more preferable. The upper limit is not particularly limited, and is preferably 10.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less.

(other ingredients)
The first layer may contain other components in addition to the components described above.
Other components include, for example, resins, surfactants, crosslinking agents, and film forming aids, with resins being preferred.
The first layer may contain only one kind of other components, or may contain two or more kinds of other components.

-resin-
Resin means a polymer having a weight average molecular weight of 3000 or more.
The weight average molecular weight of the resin can be measured using gel permeation chromatography (GPC).
Examples of the resin include an olefin resin, a resin constituting the temporary support body described above, and a binder polymer contained in the photosensitive composition layer described later. Preferably, polyester resin is more preferable, and PET resin is even more preferable.
Examples of the olefin resin include known olefin resins. Examples of the olefin resin include polyethylene and polypropylene.

In terms of the durability of the first layer and the dispersibility of particles, the resin content is preferably 50% by mass or more, more preferably 80% by mass or more, and 90% by mass or more based on the total mass of the first layer. is even more preferable. The upper limit is not particularly limited, and is preferably 99.99% by mass or less, more preferably 99.9% by mass or less.

-Surfactant-
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with anionic surfactants and nonionic surfactants being preferred.
Examples of the anionic surfactant include Rapizol (registered trademark) A-90 (manufactured by NOF Corporation), Sundead BL (manufactured by Sanyo Chemical Industries, Ltd.), and Nikkor SCS (manufactured by Nikko Chemicals).
Examples of nonionic surfactants include NAROACTY (registered trademark) CL95 (manufactured by Sanyo Chemical Industries, Ltd.).
Examples of the surfactant include, in addition to the above, surfactants described in the Surfactant Physical Properties and Performance Handbook (Technical Information Association).

The content of the surfactant is preferably 10% by mass or less, more preferably 0.001 to 10% by mass, and even more preferably 0.01 to 3% by mass, based on the total mass of the first layer.

-Crosslinking agent-
Examples of the crosslinking agent include known crosslinking agents such as carbodiimide compounds, oxazoline compounds, epoxy compounds, melamine compounds, and isocyanate compounds.
Examples of the crosslinking agent include Carbodilite (registered trademark) V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.), Epocross (registered trademark) WS-700 (manufactured by Nippon Shokubai Co., Ltd.), and Denacol (registered trademark) EX614B (manufactured by Nagase ChemteX Co., Ltd.). (manufactured by Asahi Kasei Chemicals) and Duranate (registered trademark) WM44 (manufactured by Asahi Kasei Chemicals).

The content of the crosslinking agent is preferably 1 to 50% by weight, more preferably 2 to 20% by weight, based on the total weight of the first layer.

The thickness of the first layer is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. The upper limit is not particularly limited, and is preferably 10.0 μm or less, more preferably 5.0 μm or less, even more preferably 3.0 μm or less, particularly preferably 2.0 μm or less, and most preferably 1.0 μm or less.

[Second layer]
The second layer is a layer containing second inorganic particles having an average particle diameter of 70 nm or less, or a layer containing no inorganic particles. In other words, the second layer either contains the second inorganic particles or does not contain any inorganic particles regardless of the average particle diameter. Among these, it is preferable that the second layer contains second inorganic particles.
When the second layer contains second inorganic particles having an average particle diameter of 70 nm or less, the average particle diameter of the second inorganic particles contained in the second layer is preferably 65 nm or less, and 50 nm or less, since the effect of the present invention is more excellent. The following are more preferred. The lower limit is not particularly limited, and is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 8 nm or more, and particularly preferably 10 nm or more.
The average particle diameter of the second inorganic particles can be measured using the method for measuring the average particle diameter of the first organic particles described above.

The second inorganic particles preferably contain at least one selected from the group consisting of silicon atoms and aluminum atoms, and more preferably contain aluminum atoms.
Examples of the second inorganic particles include silicon dioxide particles (silica particles), titania particles (titanium oxide particles), calcium carbonate, barium sulfate, and aluminum oxide particles (alumina particles). Among these, as the inorganic particles, aluminum oxide particles or silicon dioxide particles are preferable, and aluminum oxide particles are more preferable in terms of haze and durability.
The aspect of the silicon dioxide particles is as described above.

The second layer may contain only one type of second inorganic particles, or may contain two or more types of second inorganic particles.
The content of the second inorganic particles is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, and more preferably 0.1 to 1.0% by mass, based on the total mass of the second layer. 0% by weight is more preferable, and 0.2 to 0.5% by weight is particularly preferable.

When the second layer does not contain inorganic particles, the second layer does not contain inorganic particles regardless of the average particle size.

The second layer may contain second organic particles having an average particle diameter of 100 to 1000 nm.
The definition of the second organic particles is the same as the first organic particles included in the first layer described above, and the preferred embodiments are also the same.

The second layer may contain only one type of second organic particles, or may contain two or more types of second organic particles.
The content of the second organic particles is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 1.0% by mass, and more preferably 0.1 to 1.0% by mass, based on the total mass of the second layer. 0% by weight is more preferable, and 0.1 to 0.3% by weight is particularly preferable.

(other ingredients)
The second layer may contain other components in addition to the components described above.
The other components have the same meaning as the other components included in the first layer described above, and the preferred embodiments are also the same.

The thickness of the second layer is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. The upper limit is not particularly limited, and is preferably 10.0 μm or less, more preferably 5.0 μm or less, even more preferably 3.0 μm or less, particularly preferably 2.0 μm or less, and most preferably 1.0 μm or less.

The aspect of the first layer and the aspect of the second layer may be the same layer or different layers. Among these, the same layer is preferable since the effect of the present invention is more excellent. In addition, the same layer means a layer in which the components contained in the layer and the thickness of the layer are the same.
The first organic particles contained in the first layer and the second organic particles contained in the second layer may be the same organic particles or different organic particles. Among them, the same organic particles are preferable since the effects of the present invention are more excellent.
Moreover, the content of the first organic particles contained in the first layer and the content of the second organic particles contained in the second layer may be the same content or different content. Among these, the same content is preferable since the effect of the present invention is more excellent.
The first inorganic particles contained in the first layer and the second inorganic particles contained in the second layer may be the same inorganic particles or different inorganic particles. Among them, the same inorganic particles are preferable since the effects of the present invention are more excellent.
Further, the content of the first inorganic particles included in the first layer and the content of the second inorganic particles included in the second layer may be the same content or different content. Among these, the same content is preferable since the effect of the present invention is more excellent.
The thickness of the first layer and the thickness of the second layer may be the same or different. Among these, the same thickness is preferable in that the effects of the present invention are more excellent.

[Physical properties of temporary support]
It is preferable that the temporary support has light transmittance.
When exposing the photosensitive composition layer, the photosensitive composition layer can be exposed through a temporary support. In this specification, having light transmittance means that the transmittance of light at the wavelength used for pattern exposure is 50% or more.
The transmittance of light with a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more, from the viewpoint of pattern exposure through the temporary support. The upper limit is not particularly limited, and is preferably 100% or less.
Transmittance refers to the intensity of the emitted light that passes through the layer to be measured relative to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer to be measured (thickness direction). means the ratio of the intensities of For example, the transmittance can be measured using MCPD Series manufactured by Otsuka Electronics.

The smaller the haze of the temporary support, the better.
Specifically, the haze of the temporary support is preferably less than 0.5%, more preferably 0.4% or less. The lower limit is not particularly limited, and is preferably 0% or more. When the haze of the temporary support is within the above range, scattering of light when the photosensitive composition layer supported by the temporary support is exposed in the exposure process is effectively suppressed, and the resin pattern after the development process is It is possible to form a resin pattern with good wall surface condition by suppressing distortion and omission of the resin.
Note that haze can be measured using a haze meter in accordance with JIS K 7105:1981, and the haze described in this specification can be measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). This is the value.

The thickness of the temporary support can be determined depending on, for example, the strength, light transmittance, and material of the temporary support, and the flexibility required for bonding the transfer film and the substrate.
The thickness of the temporary support is not particularly limited, but is often 200.0 μm or less, and in terms of the effects of the present invention being more excellent, it is preferably 100.0 μm or less, more preferably 40.0 μm or less, and 35.0 μm or less. is even more preferable. The lower limit is not particularly limited, and is preferably 1.0 μm or more, more preferably 5.0 μm or more, and even more preferably 10.0 μm or more.
The thickness of the temporary support can be calculated as the average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP 2014-085643, paragraphs [0019] to [0026] of JP 2016-027363, and WO 2012/081680A1. The descriptions in paragraphs [0041] to [0057] and paragraphs [0029] to [0040] of WO2018/179370A1 publication can be cited, and the contents of these publications are incorporated into the present specification.

<Protective film>
The transfer film has a protective film.
By having a protective film, the surface of a layer (for example, a photosensitive composition layer) that is in contact with the protective film can be protected.

Examples of the protective film include resin films and paper, and resin films are preferred from the viewpoints of strength and flexibility.
Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, as the resin film, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable, and a polyethylene terephthalate film is more preferable.

The thickness of the protective film is preferably 5 to 100 μm, more preferably 10 to 50 μm, and even more preferably 10 to 20 μm.

The arithmetic mean roughness Ra of the side of the protective film on which the photosensitive composition layer is arranged is preferably 0.3 μm or less, more preferably 0.1 μm or less, and 0.05 μm or less, from the viewpoint of better resolution. is even more preferable. When the arithmetic mean roughness of the surface of the protective film on which the photosensitive composition layer is disposed is within the above range, the uniformity of the thickness of the photosensitive composition layer and the formed resin pattern is improved. The lower limit of the arithmetic mean roughness Ra is not particularly limited, and is preferably 0.001 μm or more. The arithmetic mean roughness Ra of the surface of the protective film on which the photosensitive composition layer is arranged is the surface roughness Ra of the surface in contact with the photosensitive composition layer of the first layer (the surface opposite to the temporary support body). Measurements were taken at 10 randomly selected locations using New View 6000 manufactured by Zygo, and the average value obtained by excluding the minimum and maximum values was used as the average value.

<Photosensitive composition layer>
The transfer film has a photosensitive composition layer placed on a temporary support.
The photosensitive composition layer preferably contains a binder polymer, a polymerizable compound, and a polymerization initiator, which will be described later.
After transferring the photosensitive composition layer onto the transfer target, a pattern can be formed on the transfer target by performing exposure and development.
The photosensitive composition layer may be a positive photosensitive composition layer or a negative photosensitive composition layer. The positive-working photosensitive composition layer is a photosensitive composition layer in which the solubility of exposed areas in a developing solution is improved by exposure. A negative photosensitive composition layer is a photosensitive composition layer whose exposed areas have reduced solubility in a developer upon exposure.
Among these, it is preferable to use a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to a protective film.

From the viewpoint of coating properties, the thickness of the photosensitive composition layer is preferably 20.0 μm or less, more preferably 15.0 μm or less, and even more preferably 10.0 μm or less. The above lower limit is not particularly limited, and is preferably 0.05 μm or more, more preferably 3.0 μm or more, even more preferably 4.0 μm or more, and particularly preferably 5.0 μm or more.
The thickness of the photosensitive composition layer is calculated as the average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

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

The photosensitive composition layer is preferably achromatic. The a ^* value of the photosensitive composition layer is preferably from -1.0 to 1.0, and the b ^* value of the photosensitive composition layer is preferably from -1.0 to 1.0.
The hue of the photosensitive composition layer can be measured using a color difference meter (CR-221, manufactured by Minolta).

Each material constituting the photosensitive composition layer will be explained below.

[Binder polymer]
The photosensitive composition layer may include a binder polymer.
Examples of binder polymers include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, and the reaction between epoxy resins and (meth)acrylic acid. Examples include the obtained epoxy acrylate resin and the acid-modified epoxy acrylate resin obtained by reacting the epoxy acrylate resin with an acid anhydride.

One of the preferred embodiments of the binder polymer is (meth)acrylic resin, which has excellent alkali developability and film-forming properties.
In addition, in this specification, a (meth)acrylic resin means resin which has a structural unit derived from a (meth)acrylic compound. The content of the structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, based on all the structural units of the (meth)acrylic resin.
The (meth)acrylic resin may be composed only of structural units derived from a (meth)acrylic compound, or may have structural units derived from a polymerizable monomer other than the (meth)acrylic compound. . That is, the upper limit of the content of the structural units derived from the (meth)acrylic compound is preferably 100% by mass or less based on all the structural units of the (meth)acrylic resin.

Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile.
Examples of (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, ) Acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, ( Preferred are meth)acrylic acid alkyl esters.
Examples of (meth)acrylamide include acrylamide such as diacetone acrylamide.

The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include 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 (meth)acrylic acid Examples include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl.
As the (meth)acrylic ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.

The (meth)acrylic resin may have structural units other than the structural units derived from the (meth)acrylic compound.
The polymerizable monomer forming the above-mentioned structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that can be copolymerized with a (meth)acrylic compound, such as styrene, vinyltoluene, and α-methyl Styrene compounds that may have a substituent at the α-position or aromatic ring such as styrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, Examples include maleic acid monoesters such as monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid.
These polymerizable monomers may be used alone or in combination of two or more.

Moreover, it is preferable that the (meth)acrylic resin has a structural unit having an acid group in order to improve the alkali developability. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
Among these, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

The content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is determined based on the total mass of the (meth)acrylic resin in terms of excellent developability. It is preferably 10% by mass or more. Further, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, more preferably 40% by mass or less.

Moreover, it is more preferable that the (meth)acrylic resin has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester.
The content of structural units derived from (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 1 to 90% by mass, and 1 to 80% by mass based on the total structural units of the (meth)acrylic resin. It is more preferably 5 to 60% by mass.

As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferable. More preferred is a resin composed only of structural units derived from (meth)acrylic acid alkyl ester.
Moreover, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

Furthermore, in order to achieve better effects of the present invention, the (meth)acrylic resin may contain at least one type selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters. Preferably, it has both a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester.
The total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl ester in the (meth)acrylic resin is determined based on the total content of the structural units derived from the (meth)acrylic resin, since the effect of the present invention is more excellent. The content is preferably 40% by mass or more, more preferably 60% by mass or more. The upper limit is not particularly limited, and is preferably 100% by mass or less, more preferably 80% by mass or less.

In addition, the (meth)acrylic resin contains at least one type selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester, and acrylic acid. It is also preferable to have at least one kind selected from the group consisting of structural units derived from and structural units derived from acrylic acid alkyl esters.
In view of the superior effects of the present invention, the total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters should be The mass ratio is preferably 60/40 to 80/20 with respect to the total content of.

The (meth)acrylic resin preferably has an ester group at the end, since the photosensitive composition layer after transfer has excellent developability.
Note that the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at the end can be synthesized by using a polymerization initiator that generates a radical having an ester group.

Further, another preferred embodiment of the binder polymer is an acrylic soluble resin.
In the present disclosure, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22° C. is 0.1 g or more.
The binder polymer is preferably a binder polymer having an acid value of 60 mgKOH/g or more, for example, from the viewpoint of developability.
In addition, the binder polymer is, for example, a resin having a carboxyl group with an acid value of 60 mgKOH/g or more (so-called carboxyl group-containing resin) because it is easily thermally crosslinked with a crosslinking component by heating and forms a strong film. More preferably, it is a (meth)acrylic resin having a carboxy group having an acid value of 60 mgKOH/g or more (so-called carboxy group-containing (meth)acrylic resin).
When the binder polymer is a resin having a carboxyl group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to thermally crosslink. Moreover, when the carboxyl group of a resin having a carboxyl group is anhydrous and made hydrophobic, the resistance to wet heat can be improved.

The carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the above acid value condition, and can be appropriately selected from known (meth)acrylic resins.
For example, among the polymers described in paragraph [0025] of JP-A-2011-095716, carboxy group-containing acrylic resins with an acid value of 60 mgKOH/g or more, paragraphs [0033] to [0052] of JP-A-2010-237589 Among the polymers described in , carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more can be preferably used.

Other preferred embodiments of the binder polymer include styrene-acrylic copolymers.
In the present disclosure, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and includes a structural unit derived from the styrene compound, The total content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer. The lower limit is not particularly limited, but is preferably 100% by mass or less.
Further, the content of the structural units derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5 to 80% by mass, based on all the structural units of the copolymer.
Further, the content of the structural units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20 to 95% by mass, based on all the structural units of the copolymer. is even more preferable.

The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, in order to improve the effects of the present invention.
Monomers forming structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid). , styrene dimer, styrene trimer, etc.). Among these, monomers having an aralkyl group or styrene are preferred.
Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferred.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride; Examples include vinylbenzyl alcohol. Among them, benzyl (meth)acrylate is preferred.
Moreover, it is more preferable that the binder polymer has a structural unit represented by the following formula (S) (a structural unit derived from styrene) in order to obtain more excellent effects of the present invention.

When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is 5 to 90% by weight based on all the structural units of the binder polymer, since the effect of the present invention is more excellent. %, more preferably 10 to 70% by weight, even more preferably 20 to 60% by weight.
In addition, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, and 10 to 60 mol%, based on the total structural units of the binder polymer, in order to obtain better effects of the present invention. is more preferable, and even more preferably 20 to 60 mol%.
Further, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol%, based on the total structural units of the binder polymer, from the viewpoint of achieving better effects of the present invention, and 10 to 70 mol%. It is more preferably 60 mol%, and even more preferably 20 to 60 mol%.
In addition, in this disclosure, when the content of a "constituent unit" is defined by a molar ratio, the above-mentioned "constituent unit" is synonymous with a "monomer unit." Furthermore, in the present disclosure, the above-mentioned "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

It is preferable that the binder polymer has a monocyclic aliphatic hydrocarbon ring structure or a polycyclic aliphatic hydrocarbon ring structure in order to obtain better effects of the present invention. That is, the binder polymer preferably has a structural unit having a monocyclic or polycyclic aliphatic hydrocarbon ring structure. Among these, the binder polymer preferably has a polycyclic aliphatic hydrocarbon ring structure, and even more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

Examples of the rings constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
Among these, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable in terms of the effects of the present invention being more excellent, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 ^2,6 ]decane) is preferable. ring) is more preferred.
Monomers forming the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
In addition, the binder polymer preferably has a structural unit represented by the following formula (Cy), from the viewpoint of more excellent effects of the present invention, and a structural unit represented by the above formula (S), and a structural unit represented by the following formula (Cy). It is more preferable to have a structural unit represented by (Cy).

In formula (Cy), R ^M represents a hydrogen atom or a methyl group, and R ^Cy represents a monovalent group having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) may be a monocyclic aliphatic hydrocarbon ring structure or a polycyclic aliphatic hydrocarbon ring structure.

R ^M in formula (Cy) is preferably a methyl group.
R ^Cy in formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, and an aliphatic group having 6 to 16 carbon atoms, from the viewpoint that the effects of the present invention are more excellent. A monovalent group having a hydrocarbon ring structure is more preferable, and a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms is even more preferable.
In addition, as the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy), monocyclic aliphatic hydrocarbons such as a cyclopentane ring structure, a cyclohexane ring structure, or an isoborone ring structure are preferable, since the effects of the present invention are more excellent. It is preferably a hydrocarbon ring structure, a polycyclic aliphatic hydrocarbon ring structure such as a tetrahydrodicyclopentadiene ring structure, or a norbornane ring structure, and a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure. More preferably, it is a tetrahydrodicyclopentadiene ring structure.
Further, the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) is preferably a polycyclic aliphatic hydrocarbon ring, from the viewpoint of achieving better effects of the present invention, and two or more aliphatic hydrocarbon rings. It is more preferable to have a ring structure in which the rings are condensed, and even more preferable to be a ring in which 2 to 4 aliphatic hydrocarbon rings are condensed.
Furthermore, R ^Cy in formula (Cy) is a combination of the oxygen atom of -C(=O)O- in formula (Cy) and an aliphatic hydrocarbon ring structure (monocyclic or polycyclic is preferably a group directly bonded to (may be), that is, an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group; It is even more preferable that there be.

The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types of structural units.
When the binder polymer has a constituent unit having an aliphatic hydrocarbon ring structure, the content of the constituent unit having an aliphatic hydrocarbon ring structure is determined based on the total constituent units of the binder polymer in order to improve the effect of the present invention. The amount is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and even more preferably 20 to 70% by weight.
In addition, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, and 10 to 70 mol% based on the total structural units of the binder polymer, in order to obtain better effects of the present invention. 60 mol% is more preferable, and 20 to 60 mol% is even more preferable.
Furthermore, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol%, based on the total structural units of the binder polymer, from the viewpoint of achieving better effects of the present invention. It is more preferably 60 mol%, and even more preferably 20 to 60 mol%.

When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural units having an aromatic ring structure and aliphatic hydrocarbon ring structure is In order to obtain better effects of the invention, the amount is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 75% by mass, based on the total structural units of the binder polymer.
In addition, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the binder polymer is 10 It is preferably 80 to 80 mol%, more preferably 20 to 70 mol%, even more preferably 30 to 60 mol%.
Furthermore, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the binder polymer is determined from the viewpoint that the effect of the present invention is more excellent, It is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, even more preferably 30 to 60 mol%.
In addition, the molar amount nS of the structural unit represented by the above formula (S) in the binder polymer and the molar amount nCy of the structural unit represented by the above formula (Cy) are determined by the following formula from the viewpoint that the effect of the present invention is more excellent. It is preferable that the relationship shown in (SCy) is satisfied, it is more preferable that the following formula (SCy-1) is satisfied, and it is even more preferable that the following formula (SCy-2) is satisfied.
0.20≦nS/(nS+nCy)≦0.80 Formula (SCy)
0.30≦nS/(nS+nCy)≦0.75 Formula (SCy-1)
0.40≦nS/(nS+nCy)≦0.70 Formula (SCy-2)

It is preferable that the binder polymer has a structural unit having an acid group, since the effects of the present invention are more excellent.
Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with a carboxy group being preferred.
As the above-mentioned structural unit having an acid group, the following structural units derived from (meth)acrylic acid are preferable, and structural units derived from methacrylic acid are more preferable.

The binder polymer may have only one type of structural unit having an acid group, or may have two or more types of structural units having an acid group.
When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is 5 to 50% by mass based on the total structural units of the binder polymer, since the effect of the present invention is more excellent. It is preferably 5 to 40% by weight, more preferably 10 to 30% by weight.
In addition, the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, and 10 to 50 mol%, based on the total structural units of the binder polymer, in order to obtain better effects of the present invention. More preferably, 15 to 40 mol% is even more preferable.
Further, the content of the (meth)acrylic acid-derived structural units in the binder polymer is preferably 5 to 70 mol%, and 10 to 50 mol%, based on the total structural units of the binder polymer, in order to obtain better effects of the present invention. It is more preferably mol%, and even more preferably 15 to 40 mol%.

The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, in order to obtain more excellent effects of the present invention.
As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. Moreover, when the binder polymer has an ethylenically unsaturated group, it is preferable that the binder polymer has a structural unit having an ethylenically unsaturated group in a side chain.
In the present disclosure, the "main chain" refers to the relatively longest bond chain in the molecules of the polymer compound constituting the resin, and the "side chain" refers to an atomic group branching from the main chain. .
As the ethylenically unsaturated group, a (meth)acrylic group is preferable, and a (meth)acryloxy group is more preferable.
Examples of the structural unit having a reactive group include, but are not limited to, those shown below.

The binder polymer may have one type of structural unit having a reactive group, or may have two or more types of structural units.
When the binder polymer has a constitutional unit having a reactive group, the content of the constitutional unit having a reactive group is 5 to 70% by mass based on all the constitutional units of the binder polymer, since the effect of the present invention is more excellent. %, more preferably 10 to 50% by weight, even more preferably 20 to 40% by weight.
In addition, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, and 10 to 60 mol%, based on the total structural units of the binder polymer, in order to obtain better effects of the present invention. is more preferable, and even more preferably 20 to 50 mol%.

As a means of introducing reactive groups into the binder polymer, epoxy compounds, blocked isocyanates, etc. are added to functional groups such as hydroxy groups, carboxy groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups. Examples include a method of reacting compounds such as a compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.
A preferred example of a means for introducing a reactive group into a binder polymer is to synthesize a polymer having a carboxyl group by a polymerization reaction, and then add glycidyl (meth)acrylate to some of the carboxyl groups of the obtained polymer by a polymer reaction. An example of this method is to introduce a (meth)acryloxy group into a polymer by reacting the following. By this means, a binder polymer having a (meth)acryloxy group in the side chain can be obtained.
The above polymerization reaction is preferably carried out at a temperature of 70 to 100°C, more preferably 80 to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. is more preferable. The above polymer reaction is preferably carried out at a temperature of 80 to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

As the binder polymer, the following polymers are preferable because the effects of the present invention are more excellent. Note that the content ratios (a to d) of each structural unit, weight average molecular weight Mw, etc. shown below can be changed as appropriate depending on the purpose.
The content ratio a of each structural unit shown below is preferably 20 to 60% by mass with respect to all the structural units of the binder polymer below. b is preferably 10 to 50% by mass based on all the structural units of the binder polymer below. c is preferably 5.0 to 25% by mass based on the total structural units of the binder polymer below. d is preferably 10 to 50% by mass based on all the structural units of the binder polymer below.

The content ratio a of each structural unit shown below is preferably 20 to 60% by mass with respect to all the structural units of the binder polymer below. b is preferably 10 to 50% by mass based on all the structural units of the binder polymer below. c is preferably 5.0 to 25% by mass based on the total structural units of the binder polymer below. d is preferably 10 to 50% by mass based on all the structural units of the binder polymer below.

The content ratio a of each structural unit shown below is preferably 30 to 65% by mass with respect to all the structural units of the binder polymer below. b is preferably 1.0 to 20% by mass based on all the structural units of the binder polymer below. c is preferably 5.0 to 25% by mass based on the total structural units of the binder polymer below. d is preferably 10 to 50% by mass based on all the structural units of the binder polymer below.

The content ratio a of each structural unit shown below is preferably 1.0 to 20% by mass with respect to all the structural units of the binder polymer below. b is preferably 20 to 60% by mass based on the total structural units of the binder polymer below. c is preferably 5.0 to 25% by mass based on the total structural units of the binder polymer below. d is preferably 10 to 50% by mass based on all the structural units of the binder polymer below.

Further, the binder polymer may include a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X").
The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.
The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

The structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group in the main chain obtained by removing two hydrogen atoms from the compound represented by the following formula P-1, or a structural unit having the following formula P-1. It is preferable to use a structural unit in which a monovalent group obtained by removing one hydrogen atom from the represented compound is bonded to the main chain directly or via a divalent linking group.

In formula P-1, R ^A1a represents a substituent, n ^1a R ^A1a 's may be the same or different, and Z ^1a is -C(=O)-O-C(=O)- represents a divalent group forming a ring containing n ^1a represents an integer of 0 or more.

Examples of the substituent represented by R ^A1a include an alkyl group.
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 even more preferably an alkylene group having 2 carbon atoms.
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 even more preferably 0.
When n ^1a represents an integer of 2 or more, multiple R ^A1a 's may be the same or different. Further, a plurality of R ^A1a may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, and a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is more preferable. Structural units derived from acid anhydrides are more preferred, structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and structural units derived from maleic anhydride are most preferred.

Specific examples of structural units having a carboxylic anhydride structure are listed below, but the structural units having a carboxylic anhydride structure are not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group, or a CF ₃ group, and Me represents a methyl group.

The number of structural units having a carboxylic acid anhydride structure in the polymer X may be one type alone, or two or more types may be used.

The total content of the structural units having a carboxylic acid anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 35 mol%, based on the total structural units of the polymer X. preferable.

The photosensitive composition layer may contain only one type of polymer X, or may contain two or more types of polymer X.
When the photosensitive composition layer contains polymer X, the effect of the present invention is more excellent, so the content of polymer It is preferably 0.20 to 20.00% by weight, even more preferably 0.20 to 5.00% by weight, and particularly preferably 0.50 to 1.50% by weight.

The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and still more preferably 10,000 or more, in terms of the effect of the present invention being more excellent. ~30,000 is particularly preferred.
The degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the binder polymer is preferably 1.0 to 3.0, more preferably 2.0 to 3.0, from the viewpoint of reducing development residue.

The acid value of the binder polymer is preferably 10 to 200 mgKOH/g, more preferably 60 to 200 mgKOH/g, even more preferably 60 to 150 mgKOH/g, and particularly preferably 60 to 110 mgKOH/g.
The acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992.

Polymer A is also preferred as the binder polymer.
When the binder polymer is Polymer A, the photosensitive composition layer is preferably a negative photosensitive composition layer.
Preferably, polymer A is an alkali-soluble resin.
The acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and 190 mgKOH/g from the viewpoint of better resolution by suppressing swelling of the photosensitive composition layer by the developer. More preferably less than g.
The lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, even more preferably 150 mgKOH/g or more, and 170 mgKOH/g or more. Particularly preferred.

Note that the acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. The acid value can be calculated, for example, from the average content of acid groups in the compound.
The acid value of the polymer A may be adjusted depending on the type of structural units constituting the polymer A and the content of the structural units containing acid groups.

The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferred from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, and even more preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, the properties of the developed aggregate and the properties of the unexposed film such as edge fusing property and cut chip property when formed into a negative photosensitive resin laminate are controlled. preferred. The weight average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fusing property refers to the degree to which the photosensitive composition layer easily protrudes from the end surface of the roll when it is wound up into a roll as a negative photosensitive resin laminate. The cut chip property refers to the degree to which chips easily fly when an unexposed film is cut with a cutter. If this chip adheres to the upper surface of the negative photosensitive resin laminate, it will be transferred to a mask during a subsequent exposure process, etc., resulting in defective products. The degree of dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0. .

In the photosensitive composition layer, from the viewpoint of suppressing thickening of line width and deterioration of resolution when the focal position shifts during exposure, polymer A contains a structural unit based on a monomer having an aromatic hydrocarbon group. It is preferable to include. Note that such aromatic hydrocarbon groups include, for example, substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A. Although the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 85% by mass or less, based on the total mass of the polymer A. In addition, when multiple types of polymers A are included, it is preferable that the average value of the content of structural units based on monomers having aromatic hydrocarbon groups falls within the above range.

Monomers having an aromatic hydrocarbon group include, for example, monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoate). acids, styrene dimers, styrene trimers, etc.). Among these, monomers having an aralkyl group or styrene are preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in Polymer A is styrene, the content of the styrene-based structural unit is 20 to 70% by mass based on the total mass of Polymer A. is preferable, 25 to 65% by weight is more preferable, even more preferably 30 to 60% by weight, and particularly preferably 30 to 55% by weight.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferred.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride; Examples include vinylbenzyl alcohol. Among these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the structural unit based on benzyl (meth)acrylate is based on the total mass of polymer A. On the other hand, it is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, even more preferably 70 to 90% by weight, and particularly preferably 75 to 90% by weight.

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

It is preferable that the polymer A containing no structural unit based on a monomer having an aromatic hydrocarbon group is obtained by polymerizing at least one of the first monomers described below, and the first monomer It is more preferable to obtain the monomer by copolymerizing at least one of the monomers and at least one of the second monomers described below.

The first monomer is a monomer having a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.
The content of the structural unit based on the first monomer in polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 10 to 30% by mass, based on the total mass of polymer A. % is more preferable.
It is preferable that the content be 5% by mass or more from the viewpoint of achieving good developability and controlling edge fusing properties. It is preferable that the content be 50% by mass or less from the viewpoint of high resolution and groove shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. (meth)acrylates such as , tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; acetic acid Esters of vinyl alcohol such as vinyl; examples include (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred.
The content of the structural unit based on the second monomer in polymer A is preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and 20 to 45% by mass, based on the total mass of polymer A. % is more preferable.

When polymer A contains a structural unit based on a monomer having an aralkyl group and/or a structural unit based on a styrene monomer, it suppresses thickening of line width and deterioration of resolution when the focal position shifts during exposure. It is preferable from the viewpoint of For example, a copolymer containing a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, a structural unit based on benzyl methacrylate, and a structural unit based on styrene. Copolymers containing structural units based on the above are preferred.
In one embodiment, Polymer A contains 25 to 55% by mass of structural units based on a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of structural units based on a first monomer, and 20 to 35% by mass of structural units based on a monomer having an aromatic hydrocarbon group. A polymer containing 15 to 45% by mass of structural units based on monomers is preferable. In another embodiment, the polymer contains 70 to 90% by mass of structural units based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of structural units based on the first monomer. is preferred.

Polymer A may have a branched structure and/or alicyclic structure in its side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or alicyclic structure can be introduced into the side chain of the polymer A. .
Specific examples of monomers containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, and t-(meth)acrylate. -butyl, i-amyl (meth)acrylate, t-amyl (meth)acrylate, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate is preferred, and i-propyl methacrylate or t-butyl methacrylate is more preferred.
Specific examples of the monomer containing a group having an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Also included are (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-2-adamantyl; 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-(meth)acrylate Ethyl-1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2 -Methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-menthanoindene-5-(meth)acrylate yl, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-(meth)acrylate 2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl, (meth)acrylic acid Examples include (nor)bornyl acid, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth)acrylic acid -2-adamantyl, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, More preferred are isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.

One type of polymer A may be used alone, or two or more types may be used.
When using two or more types, use a mixture of two types of polymer A containing structural units based on monomers having aromatic hydrocarbon groups, or use polymers based on monomers having aromatic hydrocarbon groups. It is preferable to use a mixture of a polymer A containing a structural unit and a polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, and 70% by mass or more based on the total mass of polymer A. It is more preferably 80% by mass or more, even more preferably 90% by mass or more. The upper limit is not particularly limited, and is preferably 100% by mass or less.

Polymer A is synthesized by adding a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution of the monomer or plural monomers mentioned above diluted with a solvent such as acetone, methyl ethyl ketone, and isopropanol. It is preferable to add an appropriate amount of and heat and stir. In some cases, synthesis may be carried out while dropping a portion of the mixture into the reaction solution. After the reaction is completed, a solvent may be further added to adjust the concentration to a desired level. As a synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

The glass transition temperature Tg of polymer A is preferably 30 to 135°C. By using Polymer A having a Tg of 135° C. or less, it is possible to suppress thickening of line width and deterioration of resolution when the focal position during exposure is shifted. From this viewpoint, the Tg of the polymer A is more preferably 130°C or less, even more preferably 120°C or less, and particularly preferably 110°C or less. Further, it is preferable to use Polymer A having a Tg of 30° C. or higher from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

The photosensitive composition layer may also contain other resins as the polymer A than those mentioned above.
Other resins include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, Examples include benzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The photosensitive composition layer may contain only one type of binder polymer, or may contain two or more types of binder polymer.
The content of the binder polymer is preferably 10.00 to 90.00% by mass, and 30.00 to 80.00% by mass, based on the total mass of the photosensitive composition layer, in order to obtain better effects of the present invention. is more preferred, 40.00 to 70.00% by mass is even more preferred, and 45.00 to 60.00% by mass is particularly preferred.

[Polymerization initiator]
The photosensitive composition layer may contain a polymerization initiator.
The polymerization initiator is not particularly limited, and any known polymerization initiator can be used. As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator is preferable.
The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.
As the polymerization initiator, for example, a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as "oxime type photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter referred to as "α-amino photoinitiator"), ), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an “α-hydroxyalkylphenone polymerization initiator”), and a photopolymerization initiator having an acylphosphine oxide structure. Photopolymerization initiator (hereinafter also referred to as "acylphosphine oxide photopolymerization initiator"), photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine photopolymerization initiator") can be mentioned.

In addition, from the viewpoint of photosensitivity, visibility of exposed and non-exposed areas, and resolution, the photosensitive composition layer contains 2,4,5-triarylimidazole dimer and a photoradical polymerization initiator. It is preferable to include at least one selected from the group consisting of derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
Examples of derivatives of 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. (methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2- (p-methoxyphenyl)-4,5-diphenylimidazole dimer.

The polymerization initiator is selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photoinitiators, α-hydroxyalkylphenone-based polymerization initiators, and N-phenylglycine-based photoinitiators. Preferably, it contains at least one kind selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator. is more preferable, and it is even more preferable that at least one selected from the group consisting of an oxime photopolymerization initiator and an α-aminoalkylphenone photopolymerization initiator is included.

Examples of the polymerization initiator include, for example, the polymerization initiators described in paragraphs [0031] to [0042] of JP-A No. 2011-95716 and paragraphs [0064] to [0081] of JP-A No. 2015-014783. Can be mentioned.

As a polymerization initiator, for example, 1-[4-(phenylthio)]phenyl-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation] [Product name: IRGACURE (registered trademark) OXE-02, BASF ], 8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazoyl][2-(2,2,3,3-tetrafluoro propoxy)phenyl]methanone-(O-acetyloxime) [Product name: IRGACURE (registered trademark) OXE-03, manufactured by BASF], 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio] Phenyl]-4-methyl-1-pentanone-1-(O-acetyloxime) [Product name: IRGACURE (registered trademark) OXE-04, manufactured by BASF], oxime ester compound [Product name: Lunar (registered trademark) )6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O -acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloximino)hexanoyl)-9-ethyl-9H- Carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 2-(dimethylamino)-2 -[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Product name: Omnirad (registered trademark) 379EG, IGM Resins B. V. 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad (registered trademark) 907, IGM Resins B. V. 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one [Product name: Omnirad (registered trademark) 127] , IGM Resins B. V. Co., Ltd.], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 [trade name: Omnirad (registered trademark) 369, IGM Resins B. V. manufactured by IGM Resins B. Co., Ltd.], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [trade name: Omnirad (registered trademark) 1173, IGM Resins B. V. manufactured by IGM Resins B. Co., Ltd.], 1-hydroxycyclohexylphenyl ketone [trade name: Omnirad (registered trademark) 184, IGM Resins B. V. manufactured by IGM Resins B. Co., Ltd.], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: Omnirad651, IGM Resins B. V. 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (trade name: APi-307) , Shenzhen UV-ChemTech Ltd.).

A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving actinic rays. The cationic photopolymerization initiator is preferably a compound that is sensitive to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is not limited. In addition, even for photocationic polymerization initiators that are not directly sensitive to actinic rays with a wavelength of 300 nm or more, if they are compounds that are sensitive to actinic rays with a wavelength of 300 nm or more and generate acid when used in combination with a sensitizer, they can be used as sensitizers. It can be preferably used in combination with
As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is preferable. Particularly preferred are photocationic polymerization initiators that are generated. Although the lower limit of pKa is not particularly determined, it is preferably -10.0 or more, for example.

Examples of the cationic photopolymerization initiator include ionic cationic photopolymerization initiators and nonionic cationic photopolymerization initiators.
Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP 2014-085643A may be used.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, compounds described in paragraphs 0083 to 0088 of JP-A No. 2011-221494 may be used. Furthermore, as the oxime sulfonate compound, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.

The photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

The polymerization initiators may be used alone or in combination of two or more.
The content of the polymerization initiator in the photosensitive composition layer is not particularly limited, but 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. The upper limit is not particularly limited, and is preferably 10.00% by mass or less, more preferably 5.00% by mass or less, based on the total mass of the photosensitive composition layer.

[Polymerizable compound]
The photosensitive composition layer may contain a polymerizable compound.
A polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, with the radically polymerizable group being preferred.

The polymerizable compound preferably includes a radically polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as an "ethylenic unsaturated compound").
As the ethylenically unsaturated group, a (meth)acryloxy group is preferable.
In this specification, the ethylenically unsaturated compound is a compound other than the above binder polymer, and preferably has a molecular weight of less than 5,000.

As the polymerizable compound, a compound represented by the following formula (M) (also simply referred to as "compound M") is preferable.
Q ² -R ^1a -Q ¹ formula (M)
In formula (M), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

Q ¹ and Q ² in formula ⁽ M ⁾ are preferably the same group from the viewpoint of ease of synthesis.
Further, Q ¹ and Q ² in formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
R ^1a in formula (M) is an alkylene group, an alkyleneoxyalkylene group (-L ¹ -O-L ¹ -), or a polyalkyleneoxyalkylene group (-(L ¹ -O) _p -L ¹ -) is preferable, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is still more preferable, and an alkylene group having 6 to 20 carbon atoms is preferable. 18 linear alkylene groups are particularly preferred.
The above-mentioned hydrocarbon group only needs to have a chain structure at least in part, and the part other than the above-mentioned chain structure is not particularly limited. For example, it is branched, cyclic, or has 1 to 1 carbon atoms. It may be a linear alkylene group, an arylene group, an ether bond, or a combination thereof as shown in 5. An alkylene group, or a group combining two or more alkylene groups and one or more arylene groups Preferably, an alkylene group is more preferable, and a linear alkylene group is even more preferable.
Note that L ¹ above each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer of 2 to 10.

In addition, the number of atoms in the shortest linking chain connecting Q ¹ and Q ² in compound M is preferably 3 to 50, more preferably 4 to 40, from the viewpoint of achieving better effects of the present invention. More preferably 6 to 20, particularly preferably 8 to 12.
In the present disclosure, "the number of atoms in the shortest connecting chain connecting Q ¹ and Q ² " refers to the shortest number of atoms connecting the atom in R ¹ connecting to Q ¹ to the atom in R ¹ connecting to Q ² . is the number of atoms.

Examples of the compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 , 7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, hydrogenated bisphenol Di(meth)acrylate of A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol/propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture.
Among them, Compound M is 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate because the effect of the present invention is more excellent. It is preferably at least one compound selected from the group consisting of meth)acrylate, and neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, More preferably, it is at least one compound selected from the group consisting of (meth)acrylate and 1,10-decanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate and More preferably, it is at least one compound selected from the group consisting of 1,10-decanediol di(meth)acrylate.

Further, as the polymerizable compound, an ethylenically unsaturated compound having two or more functionalities is preferable.
As used herein, the term "bifunctional or more ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferable.
As the ethylenically unsaturated compound, (meth)acrylate compounds are preferred.

The bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
Examples of bifunctional ethylenically unsaturated compounds other than the compound M include tricyclodecane dimethanol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate.

Commercially available bifunctional ethylenically unsaturated compounds include, for example, tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), Methacrylate (trade name: NK Ester DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin Nakamura Chemical Co., Ltd.), and Examples include 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

The trifunctional or higher-functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
Examples of trifunctional or more ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples include ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

Here, "(tri/tetra/penta/hexa)(meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. , "(tri/tetra)(meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

Examples of the polymerizable compound include caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ), alkylene oxide modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) R-604 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and Daicel Allnex) EBECRYL (registered trademark) 135, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated glycerin triacrylates (NK Ester A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

Examples of the polymerizable compound include urethane (meth)acrylate compounds [preferably trifunctional or higher functional urethane (meth)acrylate compounds].
Examples of trifunctional or higher functional urethane (meth)acrylate compounds include Acryt 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), NK Ester UA-32P (manufactured by Shin Nakamura Chemical Co., Ltd.), and NK Ester UA-1100H (manufactured by Shin Nakamura Chemical Co., Ltd.). (manufactured by the company).
Furthermore, examples of urethane (meth)acrylates include trifunctional or higher functional urethane (meth)acrylates. The lower limit of the number of functional groups is more preferably 6 functional groups or more, and even more preferably 8 functional groups or more. Note that the upper limit of the number of functional groups is preferably 20 functional groups or less. Examples of trifunctional or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Co., Ltd.). ), UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600 (product name) manufactured by Kyoeisha Chemical Co., Ltd., as well as UA-306H, UA-306T, UA-306I, UA-510H , and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable compound, an ethylenically unsaturated compound having an acid group is preferred.
Examples of the acid group include a phosphoric acid group, a sulfo group, and a carboxy group.
Among these, a carboxy group is preferred as the acid group.
Examples of ethylenically unsaturated compounds having an acid group include tri- to tetrafunctional ethylenically unsaturated compounds having an acid group [pentaerythritol tri- and tetraacrylate (PETA) with a carboxy group introduced into the skeleton (acid value: 80~ 120mgKOH/g)] and a penta- to hexa-functional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) with a carboxy group introduced into the skeleton [acid value: 25-70mgKOH/g)] ].
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxy group and their carboxylic acid anhydrides.
When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxy group and their carboxylic acid anhydrides, developability and film strength are improved. It increases more.
The bifunctional or more ethylenically unsaturated compound having a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
Examples of the bifunctional or more ethylenically unsaturated compound having a carboxyl group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.). ), Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

As the ethylenically unsaturated compound having an acid group, the polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of JP-A No. 2004-239942 are preferable, and the contents described in this publication are similar to those described in this publication. Incorporated into the specification.

Examples of polymerizable compounds include compounds obtained by reacting polyhydric alcohols with α,β-unsaturated carboxylic acids, compounds obtained by reacting glycidyl group-containing compounds with α,β-unsaturated carboxylic acids, and urethane. Urethane monomers such as (meth)acrylate compounds having bonds, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl Also included are phthalic acid compounds such as -o-phthalate and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters.
These may be used alone or in combination of two or more.

Examples of compounds obtained by reacting polyhydric alcohols with α,β-unsaturated carboxylic acids include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis Bisphenol A-based (meth)acrylate compounds such as (4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane , polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, and polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups. , and polyethylene polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate having 2 to 14 propylene oxide groups. , trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane) ) Tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be mentioned.
Among these, the above compound is preferably an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure, such as tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, or trimethylolpropane tri(meth)acrylate. ) acrylate or di(trimethylolpropane)tetraacrylate is more preferred.

Among these, as the polymerizable compound (particularly the ethylenically unsaturated compound), those containing an ester bond are also preferable in terms of the excellent developability of the photosensitive composition layer after transfer.
The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in its molecule, but since the effects of the present invention are excellent, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred. Saturated compounds are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.
From the viewpoint of imparting reliability, the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms, and an ethylenically unsaturated compound having the above-mentioned tetramethylolmethane structure or trimethylolpropane structure. It is preferable to include the following.
Examples of ethylenically unsaturated compounds having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol. Examples include di(meth)acrylate.

Examples of the polymerizable compound include polymerizable compounds having an aliphatic hydrocarbon ring structure (preferably bifunctional ethylenically unsaturated compounds).
The above-mentioned polymerizable compound is a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure). Preferably, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed is more preferable, and tricyclodecane dimethanol di(meth)acrylate is even more preferable.
The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure, since the effects of the present invention are more excellent.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, particularly preferably 300 to 2,200.
Among the polymerizable compounds contained in the photosensitive composition layer, the content ratio of polymerizable compounds with a molecular weight of 300 or less is 30% by mass with respect to the content of all polymerizable compounds contained in the photosensitive composition layer. % or less, more preferably 25% by mass or less, even more preferably 20% by mass or less.
The lower limit of the content of the polymerizable compound having a molecular weight of 300 or less is not particularly limited, but is preferably 1.0% by mass or more.

The photosensitive composition layer preferably contains a bifunctional or more functional ethylenically unsaturated compound, more preferably contains a trifunctional or more functional ethylenically unsaturated compound, and contains a trifunctional or tetrafunctional ethylenically unsaturated compound. It is more preferable to include.

It is also preferable that the photosensitive composition layer contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring.

The photosensitive composition layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, such as 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid modified product of dipentaerythritol pentaacrylate. It is more preferable to include.

The photosensitive composition layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described below, and the compound represented by formula (M), It is more preferable to include an ethylenically unsaturated compound having an acid group and a blocked isocyanate compound described below.

The photosensitive composition layer contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound). ) acrylate compound).

From the viewpoint of rust prevention, the photosensitive composition layer preferably contains Compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure.

The photosensitive composition layer preferably contains Compound M and an ethylenically unsaturated compound having an acid group from the viewpoint of adhesion, development residue suppression, and rust prevention. It is more preferable to include a bifunctional ethylenically unsaturated compound having a ring structure and an ethylenically unsaturated compound having an acid group, and compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional It is more preferable to include the above ethylenically unsaturated compounds and an ethylenically unsaturated compound having an acid group, compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or more ethylenically functional compound It is particularly preferable to include an unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound.

The photosensitive composition layer should contain 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group in terms of adhesion, development residue suppression, and rust prevention. is preferred, and more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, 1,9-nonanediol diacrylate, It is more preferable to include tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate (A-DPH), and an ethylenically unsaturated compound having a carboxylic acid group; It is particularly preferable to include candimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

The photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
The content of the ethylenically unsaturated compound having two or more functionalities in the ethylenically unsaturated compound is 60 to 100% by mass based on the total content of all ethylenically unsaturated compounds contained in the photosensitive composition layer. It is preferably 80 to 100% by mass, more preferably 90 to 100% by mass.

(Polymerizable compound B1)
It is also preferable that the photosensitive composition layer contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. Polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the polymerizable compounds B mentioned above.

In the photosensitive composition layer, the mass ratio of the content of polymerizable compound B1 to the total mass of polymerizable compounds is preferably 40% by mass or more, and more preferably 50% by mass or more, from the viewpoint of better resolution. It is preferably 55% by mass or more, more preferably 60% by mass or more. The upper limit is not particularly limited, but from the viewpoint of releasability, it is preferably 100% by mass or less, more preferably 99% by mass or less, even more preferably 95% by mass or less, particularly preferably 90% by mass or less, and most preferably 85% by mass or less. preferable.

Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, naphthalene ring, and anthracene ring; aromatic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; Examples include heterocycles and fused rings thereof, with aromatic hydrocarbon rings being preferred and benzene rings being more preferred. Note that the aromatic ring may have a substituent.
Polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive composition layer caused by the developer.
Examples of bisphenol structures include bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and bisphenol A structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). F structure and bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), and bisphenol A structure is preferred.

Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.
Both ends of the bisphenol structure and the two polymerizable groups may be bonded directly or via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.
Polymerizable compound B1 having a bisphenol structure is described in paragraphs [0072] to [0080] of JP-A-2016-224162, and the content described in this publication is incorporated herein.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.
As the 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane, for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd. ), EO-modified bisphenol A dimethacrylate (FA-321M, Hitachi Chemical Co., Ltd.), ethoxylated bisphenol A dimethacrylate (BPE-80N, Shin-Nakamura Chemical Co., Ltd.), nonylphenoxy polyethylene glycol acrylate (FA-318AS, Hitachi Chemical Co., Ltd.), Kasei Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin Nakamura Chemical Co., Ltd.) ), 2,2-bis(4-(methacryloxydecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl) Propane (BPE-1300, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and ethoxylation (10) Bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) is mentioned.

As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferable.

In general formula B1, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents _{C2H4 .} B represents _{C3H6 .} n1 and n3 are each independently an integer of 1 to 39, and n1+n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30. The arrangement of the constituent units of -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side.
In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

One kind of polymerizable compound B1 may be used alone, or two or more kinds thereof may be used.
From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin oozes out from the edge of the transfer member), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

The polymerizable compounds (especially ethylenically unsaturated compounds) may be used alone or in combination of two or more.
The content of the polymerizable compound (especially ethylenically unsaturated compound) in the photosensitive composition layer is preferably 1.00 to 70.00% by mass, and 10.00% by mass based on the total mass of the photosensitive composition layer. It is more preferably from 15.0 to 50.0% by weight, and particularly preferably from 20.0 to 40.0% by weight.

[Heterocyclic compound]
The photosensitive composition layer may contain a heterocyclic compound.
The heterocycle possessed by the heterocyclic compound may be either a monocyclic or polycyclic heterocycle.
Examples of the heteroatom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a nitrogen atom.

Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, pyrimidine compounds, and pyridine compounds. Can be mentioned.
Among these, the heterocyclic compound is selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyridine compounds. Preferably, at least one compound is selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds. More preferred.

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

Examples of the tetrazole compound include the following compounds.

Examples of thiadiazole compounds include the following compounds.

Examples of triazine compounds include the following compounds.

Examples of rhodanine compounds include the following compounds.

Examples of thiazole compounds include the following compounds.

Examples of benzothiazole compounds include the following compounds.

Examples of benzimidazole compounds include the following compounds.

Examples of benzoxazole compounds include the following compounds.

Examples of the pyridine compound include (iso)nicotinic acid and (iso)nicotinamide.

The photosensitive composition layer may contain one type of individual heterocyclic compound, or may contain two or more types of heterocyclic compounds.
When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.00% by mass, and 0.10 to 10% by mass, based on the total mass of the photosensitive composition layer. 0.00% by mass is more preferred, 0.10 to 5.00% by mass is even more preferred, and 0.10 to 1.00% by mass is particularly preferred.

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

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 functionalities) is preferable, and the adhesion of the formed pattern (especially, exposure From the viewpoint of later adhesion), polyfunctional aliphatic thiol compounds are more preferred.

As used herein, the term "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

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

The number of functional groups in the polyfunctional aliphatic thiol compound is preferably 2 to 10 functional, more preferably 2 to 8 functional, and even more preferably 2 to 6 functional, from the viewpoint of adhesion of the formed pattern.

Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(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 tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate) pionate), dipentaerythritol hexakis (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1, Examples include 3-propanedithiol, 1,6-hexamethylene dithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.
Among them, polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris( At least one compound selected from the group consisting of (3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.

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

The photosensitive composition layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of aliphatic thiol compounds.

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, based on the total mass of the photosensitive composition layer. , more preferably 5 to 30% by weight, particularly preferably 8 to 20% by weight.

[Thermal crosslinkable compound]
The photosensitive composition layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film.
In addition, in this specification, the thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.
Further, the thermally crosslinkable compound is a compound different from the components (binder polymer, polymerization initiator, polymerizable compound, etc.) contained in the photosensitive composition layer described above.
Examples of thermally crosslinkable compounds include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds.
Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film.
Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, The hydrophilicity of the formed film tends to decrease, and its function as a protective film tends to be strengthened.
Note that 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."

(1st block isocyanate compound)
The blocked isocyanate compound preferably contains a blocked isocyanate compound (hereinafter also referred to as "first block isocyanate compound") having a blocked isocyanate equivalent (hereinafter also referred to as "NCO value") of 4.5 mmol/g or more. This provides better bending resistance and also suppresses corrosion of the conductive layer.

The NCO value of the first block isocyanate compound is 4.5 mmol/g or more, more preferably 5.0 mmol/g or more, and even more preferably 5.3 mmol/g or more, from the standpoint of achieving better effects of the present invention.
The upper limit of the NCO value of the first block isocyanate compound is preferably 6.0 mmol/g or less, more preferably less than 5.8 mmol/g, and still more preferably 5.7 mmol/g or less, in order to achieve better effects of the present invention. preferable.
The NCO value of the blocked isocyanate compound in the present invention means the number of millimoles of blocked isocyanate groups contained per 1 g of the blocked isocyanate compound, and can be calculated from the following formula.
Formula: NCO value of blocked isocyanate compound = 1000 x (number of blocked isocyanate groups contained in molecule) / (molecular weight of blocked isocyanate compound)

The dissociation temperature of the first block isocyanate compound is preferably 100 to 160°C, more preferably 110 to 150°C.

As used herein, the term "dissociation temperature of the blocked isocyanate compound" refers to the endothermic peak associated with the deprotection reaction of the blocked isocyanate compound when measured by DSC (differential scanning calorimetry) analysis using a differential scanning calorimeter. means temperature. The differential scanning calorimeter is not particularly limited, and for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used.

Examples of the blocking agent having a dissociation temperature of 100 to 160°C include active methylene compounds [(diester malonate (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)), etc. ], and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime). Among the above, as a blocking agent having a dissociation temperature of 100 to 160°C, oxime compounds are preferred from the viewpoint of storage stability.

It is preferable that the first block isocyanate compound has a ring structure, since the effects of the present invention are more excellent. Examples of the ring structure include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocycle. From the viewpoint of achieving better effects of the present invention, aliphatic hydrocarbon rings and aromatic hydrocarbon rings are preferable, and aliphatic hydrocarbon rings are preferable. Group hydrocarbon rings are more preferred.
Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, with a cyclohexane ring being preferred.
Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, with a benzene ring being preferred.
A specific example of the heterocycle is an isocyanurate ring.
When the first block isocyanate compound has a ring structure, the number of rings is preferably 1 to 2, more preferably 1, from the viewpoint of achieving better effects of the present invention. In addition, when the first block isocyanate compound includes a condensed ring, the number of rings constituting the condensed ring is counted, and for example, the number of rings in a naphthalene ring is counted as two.

The number of block isocyanate groups possessed by the first block isocyanate compound is preferably 2 to 5, more preferably 2 to 3, from the viewpoint of superior strength of the formed pattern and superior effect of the present invention. is even more preferable.

The first block isocyanate compound is preferably a block isocyanate compound represented by formula Q, since the effects of the present invention are more excellent.
B ¹ -A ¹ -L ¹ -A ² -B ² Formula Q

In formula Q, B ¹ and B ² each independently represent a blocked isocyanate group.
The blocked isocyanate group is not particularly limited, but from the viewpoint of achieving better effects of the present invention, a group in which the isocyanate group is blocked with an oxime compound is preferable, and a group in which the isocyanate group is blocked with methyl ethyl ketoxime (specifically, A group represented by *-NH-C(=O)-O-N=C(CH ₃ )-C ₂ H _5. * represents the bonding position with A ¹ or A ² ) is more preferable.
B ¹ and B ² are preferably groups having the same structure.

In formula Q, A ¹ and A ² each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.
The alkylene group may be linear, branched, or cyclic, and is preferably linear.
The number of carbon atoms in the alkylene group is 1 to 10, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 in terms of the effects of the present invention.
It is preferable that A ¹ and A ² are groups having the same structure.

In formula Q, L ¹ represents a divalent linking group.
Specific examples of the divalent linking group include divalent hydrocarbon groups.
Specific examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by connecting two or more of these groups.
The divalent saturated hydrocarbon group may be linear, branched, or cyclic, and is preferably cyclic because the effects of the present invention are more excellent. The number of carbon atoms in the divalent saturated hydrocarbon group is preferably from 4 to 15, more preferably from 5 to 10, and even more preferably from 5 to 8, from the standpoint of achieving better effects of the present invention.
The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and includes, for example, a phenylene group. The divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group).
Among these, examples of divalent linking groups include linear, branched, or cyclic divalent saturated hydrocarbon groups having 5 to 10 carbon atoms, and cyclic saturated hydrocarbon groups having 5 to 10 carbon atoms. A group in which 1 to 3 linear alkylene groups are connected, a divalent aromatic hydrocarbon group that may have a substituent, or a divalent aromatic hydrocarbon group and a carbon number of 1 to 3 A group in which 3 linear alkylene groups are connected is preferable, a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, or a phenylene group which may have a substituent is more preferable, and a cycloalkylene group is preferable. A hexylene group or a phenylene group which may have a substituent is more preferred, and a cyclohexylene group is particularly preferred.

The blocked isocyanate compound represented by formula Q is preferably a blocked isocyanate compound represented by formula QA, since the effects of the present invention are more excellent.
B ^1a -A ^1a -L ^1a -A ^2a -B ^2a formula QA

In formula QA, B ^1a and B ^2a each independently represent a blocked isocyanate group. Preferred embodiments of B ^1a and B ^2a are the same as B ¹ and B ² in formula Q.

In formula QA, A ^1a and A ^2a each independently represent a divalent linking group. Preferred embodiments of the divalent linking group in A ^1a and A ^2a are the same as in A ^1a and A ^2a in formula Q.

In formula QA, L ^1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.
The number of carbon atoms in the cyclic divalent saturated hydrocarbon group in L ^1a is preferably 5 to 10, more preferably 5 to 8, even more preferably 5 to 6, and particularly preferably 6.
Preferred embodiments of the divalent aromatic hydrocarbon group in L ^1a are the same as L ¹ in formula QA.
Among these, L ^1a is preferably a cyclic divalent saturated hydrocarbon group, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, and more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms. A hydrocarbon group is more preferred, a cyclic divalent saturated hydrocarbon group having 5 to 6 carbon atoms is particularly preferred, and a cyclohexylene group is most preferred.

Specific examples of the first block isocyanate compound are shown below, but the first block isocyanate compound is not limited thereto.

The photosensitive composition layer may contain only one kind of first block isocyanate compound, or may contain two or more kinds of first block isocyanate compounds.

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

The first block isocyanate compound is obtained, for example, by reacting the isocyanate group of a compound having an isocyanate group (for example, a compound in which B ¹ and B ² in the above formula Q are isocyanate groups) and the above blocking agent.

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

The NCO value of the second block isocyanate compound is less than 4.5 mmol/g, preferably 2.0 to 4.5 mmol/g, and more preferably 2.5 to 4.0 mmol/g.

The dissociation temperature of the second block isocyanate compound is preferably 100 to 160°C, more preferably 110 to 150°C.
Specific examples of the blocking agent having a dissociation temperature of 100 to 160°C are as described above.

The second block isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving the brittleness of the film or improving the adhesion to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into isocyanurate and protecting it.

As a blocked isocyanate compound having an isocyanurate structure, an oxime structure using an oxime compound as a blocking agent is used because it is easier to set the dissociation temperature to a preferable range than a compound without an oxime structure, and it is also easier to reduce development residue. Compounds having the following are preferred.

The second block isocyanate compound may have a polymerizable group from the viewpoint of the strength of the pattern formed. As the polymerizable group, a radically polymerizable group is preferable.
Examples of the polymerizable group include groups having an ethylenically unsaturated group such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, and an epoxy group such as a glycidyl group. Among the above, as the polymerizable group, an ethylenically unsaturated group is preferable, and a (meth)acryloxy group is more preferable, from the viewpoint of the surface condition of the resulting pattern, development rate, and reactivity.

Specific examples of the second block isocyanate compound are shown below, but the second block isocyanate compound is not limited thereto.

As the second block isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karen's (registered trademark) AOI-BM, Karen's (registered trademark) MOI-BM, Karen's (registered trademark) AOI-BP, Karen's (registered trademark) MOI-BP [and above] , manufactured by Showa Denko Co., Ltd.], and the block-type Duranate series (for example, Duranate (registered trademark) TPA-B80E, WT32-B75P, manufactured by Asahi Kasei Chemicals).

The photosensitive composition layer may contain one type of second block isocyanate compound, or may contain two or more types of second block isocyanate compounds.

When the photosensitive composition layer contains the second block isocyanate compound, the content of the second block isocyanate compound is determined from the following points:1. The amount is preferably 00 to 25.00% by weight, more preferably 1.00 to 20.0% by weight, and even more preferably 10.00 to 15.00% by weight.

When the photosensitive composition layer contains a first block isocyanate compound and a second block isocyanate compound, the mass ratio of the content of the first block isocyanate compound to the content of the second block isocyanate compound (first block isocyanate compound/second block isocyanate compound) 2-block isocyanate compound) is preferably 0.10 to 9.00, more preferably 0.18 to 2.35, and even more preferably 0.18 to 1.00, from the viewpoint of bending resistance and reducing moisture permeability.

Thermal crosslinkable compounds may be used alone or in combination of two or more.
When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1.00 to 50.00% by mass, and 10.00% by mass based on the total mass of the photosensitive composition layer. It is more preferably from 10.00 to 20.00% by weight, and even more preferably from 10.00 to 20.00% by weight.

[Surfactant]
The photosensitive composition layer may contain a surfactant.
Examples of the surfactant include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of Japanese Patent Application Publication No. 2009-237362. Incorporated herein.
Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants, with fluorine-based surfactants or silicone-based surfactants being preferred, and fluorine-based surfactants being preferred. More preferred.

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, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (manufactured by DIC); Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC -1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC); PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA); Ftergent 710FM, Examples include 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, and 681 (all manufactured by NEOS).
In addition, fluorine-based surfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing a fluorine atom is severed and the fluorine atom volatizes. It can be used suitably. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC (Kagaku Kogyo Daily, February 22, 2016, Nikkei Sangyo Shimbun, February 23, 2016, for example, Megafac DS-21). It will be done.

Moreover, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant.

A block polymer can also be used as the fluorosurfactant. The fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.

As the fluorine-containing surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC).
From the perspective of improving environmental suitability, fluorosurfactants are derived from alternative materials for compounds with perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Preferably, it is a surfactant that

Examples of silicone surfactants include linear polymers comprising siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals.
Commercially available silicone surfactants include DOWSIL 8032 ADDITIVE, Tore Silicone DC3PA, Tore Silicone SH7PA, Tore Silicone DC11PA, Tore Silicone SH21PA, Tore Silicone SH28PA, Tore Silicone SH29PA, Tore Silicone SH30PA, and Tore Silicone SH. 8400 (more than (Manufactured by Toray Dow Corning); X-22-4952, X-22-4272, 643, X-22-6191, 109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (manufactured by Shin-Etsu Silicone); F-4440, TSF-4300, TSF- 4445, and TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials); BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347 , BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (manufactured by BYK Chemie).

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.); polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, Examples include oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
Commercially available nonionic surfactants include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF); Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF); Solsperse 20000 (manufactured by Japan Lubrizol); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries); Pionin D-6112, Examples include D-6112-W and D-6315 (all manufactured by Takemoto Yushi Co., Ltd.), Olfine E1010, Surfynol 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).

The surfactants may be used alone or in combination of two or more.
When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, and 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. 0.0% by weight is more preferable, and 0.10 to 0.80% by weight is even more preferable.

[Phosphate ester compound]
The photosensitive composition layer may contain a phosphoric acid ester compound.
The phosphoric acid ester compound is not particularly limited as long as at least one of the three hydrogens in phosphoric acid (O=P(OH) ₃ ) is substituted with an organic group, and Phosmer manufactured by Unichemical Co., Ltd. series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP), KAYAMER series manufactured by Nippon Kayaku Co., Ltd. (KAYAMER PM-21, KAYAMER PM-2), and KYOEISHA CHEMICAL CO., LTD. One example is the Light Ester series (Light Ester P-2M (trade name)) manufactured by Co., Ltd.

The phosphoric acid ester compounds may be used alone or in combination of two or more.
The content of the phosphoric acid ester compound is not particularly limited, but is preferably 0.05 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, based on the total mass of the photosensitive composition layer. More preferably 0.2 to 1.0% by mass.
When the photosensitive composition layer contains a phosphoric ester compound, the content of the phosphoric ester compound is not particularly limited, but from the viewpoint of further improving the adhesion to the transfer target, the total amount of the binder polymer and the polymerizable compound is 100 mass. It is preferably 10 parts by mass or less, more preferably 3 parts by mass or less. Further, the upper limit of the content is not particularly limited, but is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more.

[Polymerization inhibitor]
The photosensitive composition layer may contain a polymerization inhibitor.
A polymerization inhibitor means a compound that has the function of delaying or inhibiting a polymerization reaction. As the polymerization inhibitor, for example, known compounds used as polymerization inhibitors can be used.

Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5- methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4- hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3 , 5-di-t-butylanilino)-1,3,5-triazine, and hindered phenol compounds such as pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 4 - Nitroso compounds or salts thereof such as nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone , and quinone compounds such as 4-benzoquinone; 4-methoxyphenol, 4-methoxy-1-naphthol, and phenolic compounds such as t-butylcatechol; copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and metal salt compounds such as manganese diphenyldithiocarbamate.
Among these, the polymerization inhibitor is preferably at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound. 4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di- t-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt are more preferred.

The polymerization inhibitors may be used alone or in combination of two or more.
When the photosensitive composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 10.0% by mass, and 0.01 to 5% by mass based on the total mass of the photosensitive composition layer. 0.00% by mass is more preferred, 0.01 to 3.00% by mass is even more preferred, and 0.01 to 1.00% by mass is particularly preferred.

[Hydrogen-donating compound]
The photosensitive composition layer may contain a hydrogen donating compound.
The hydrogen-donating compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.

Examples of hydrogen-donating compounds include amines and amino acid compounds.

Examples of amines include M. R. "Journal of Polymer Society" Vol. 10, p. 3173 (1972) by Sander et al. Examples include compounds described in JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure 33825. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl Dimethylaniline and p-methylthiodimethylaniline are mentioned.
Among them, the amines are at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane, in that the effects of the present invention are more excellent. is preferred.

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
Among these, N-phenylglycine is preferred as the amino acid compound since it provides better effects of the present invention.

Examples of hydrogen-donating compounds include organometallic compounds (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and JP-A-6 Also included are sulfur compounds (such as trithiane) described in JP-A-308727.

The hydrogen-donating compounds may be used alone or in combination of two or more.
When the photosensitive composition layer contains a hydrogen donating compound, the content of the hydrogen donating compound is determined based on the total mass of the photosensitive composition layer from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. On the other hand, it is preferably 0.01 to 10.00% by mass, more preferably 0.03 to 8.00% by mass, and even more preferably 0.05 to 5.00% by mass.

[Pigment]
The photosensitive composition layer may be a colored resin layer containing a pigment.
In order to protect the liquid crystal display window of recent electronic devices, a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc., is sometimes attached to the liquid crystal display window of recent electronic devices. be. A colored resin layer can be used to form such a light blocking layer.
The pigment may be appropriately selected depending on the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among these, when forming a black pattern, a black pigment is preferably selected as the pigment.

As the black pigment, any known black pigment (such as an organic pigment or an inorganic pigment) can be appropriately selected as long as it does not impair the effects of the present invention. Among them, from the viewpoint of optical density, suitable examples of the black pigment include carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, with carbon black being particularly preferred. From the viewpoint of surface resistance, carbon black whose surface is at least partially coated with resin is preferable as carbon black.

From the viewpoint of dispersion stability, the number average particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm.
Here, the particle size refers to the diameter of a circle when the area of the pigment particle is determined from a photographic image of the pigment particle taken with an electron microscope and the area is the same as the area of the pigment particle, and the number average particle size is the average value obtained by determining the above particle size for 100 arbitrary particles and averaging the 100 determined particle sizes.

As a pigment other than the black pigment, the white pigment described in paragraphs [0015] and [0114] of JP-A No. 2005-007765 can be used. Specifically, among white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable as inorganic pigments, and titanium oxide or zinc oxide is more preferable. Preferably, titanium oxide is more preferable. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
Further, the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment, or two or more treatments may be performed. This suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, and the like.
From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and both alumina treatment and zirconia treatment are particularly preferred.

Moreover, when the photosensitive composition layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive composition layer further contains a chromatic pigment other than the black pigment and the white pigment. When a chromatic pigment is included, the particle size of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, in terms of better dispersibility. Although the lower limit is not particularly limited, it is preferably 0.001 μm or more.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter referred to as C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), and Monolight. - Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Splatter (C.I. Pigment・Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C. I. Pigment Red 122, C. I. Pigment Red 149, C. I. Pigment Red 168, C. I. Pigment Red 177, C. I. Pigment Red 180, C. I. Pigment Red 192, C. I. Pigment Red 215, C. I. Pigment Green 7, C. I. Pigment Blue 15:1, C. I. Pigment Blue 15:4, C. I. Pigment Blue 22, C. I. Pigment Blue 60, C. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 is mentioned. Among them, C. I. Pigment Red 177 is preferred.

When the photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3% by mass and not more than 40% by mass, and more than 3% by mass and not more than 35% by mass, based on the total mass of the photosensitive composition layer. More preferably, more than 5% by mass and 35% by mass or less, particularly preferably 10 to 35% by mass.

When the photosensitive composition layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of pigments other than black pigments is preferably 30% by mass or less, and 1 to 20% by mass based on the black pigment. It is more preferably % by mass, and even more preferably 3-15% by mass.

Note that when the photosensitive composition layer contains a black pigment and is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is used as a photosensitive composition in the form of a pigment dispersion. Preferably, it is introduced into the resin composition.
The dispersion liquid may be prepared by adding a mixture obtained by premixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture using a dispersion machine. The pigment dispersant may be selected depending on the pigment and the solvent, and for example, commercially available dispersants can be used. Note that the vehicle refers to the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion, and is liquid, and includes a binder component that holds the black pigment in a dispersed state and a solvent component that dissolves and dilutes the binder component. (organic solvent).

The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, roll mill, attritor, super mill, dissolver, homomixer, and sand mill. Furthermore, it may be finely pulverized by mechanical grinding using frictional force. Regarding the dispersing machine and fine pulverization, reference can be made to the description in "Encyclopedia of Pigments" (written by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pages 438 and 310).

[Residual monomer]
The photosensitive composition layer may contain residual monomers of each structural unit of the binder polymer described above.
From the viewpoint of patterning properties and reliability, the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less based on the total mass of the binder polymer. More preferred. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, based on the total mass of the binder polymer.
The residual monomer of each structural unit of the binder polymer is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, based on the total mass of the photosensitive composition layer, from the viewpoint of patterning properties and reliability. , more preferably 100 mass ppm or less. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, based on the total mass of the photosensitive composition layer.

It is also preferable that the amount of residual monomers when synthesizing the binder polymer by polymer reaction is within the above range. For example, when a binder polymer is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.
The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

[Other ingredients]
The photosensitive composition layer may contain components other than those described above (hereinafter also referred to as "other components"). Examples of other components include sensitizers, dyes, antioxidants, and particles (eg, metal oxide particles). Further, other components include other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706.

-Sensitizer-
The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

-particle-
As the particles, metal oxide particles are preferred.
Metals in the metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
The average primary particle diameter of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of transparency of the cured film.
The average primary particle diameter of the particles is calculated by measuring the particle diameter of 200 arbitrary particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particle is not spherical, the longest side is taken as the particle diameter.

When the photosensitive composition layer contains particles, it may contain only one type of particles having different metal types and sizes, or may contain two or more types of particles.
The photosensitive composition layer does not contain particles, or if the photosensitive composition layer contains particles, the content of particles is more than 0% by mass based on the total mass of the photosensitive composition layer. The content of particles is preferably 35% by mass or less and does not contain particles, or the content of particles is more preferably more than 0% by mass and 10% by mass or less based on the total mass of the photosensitive composition layer, and does not contain particles. , or the content of particles is more preferably more than 0% by mass and 5% by mass or less based on the total mass of the photosensitive composition layer, and the content of particles is not included or the content of particles is more than 5% by mass based on the total mass of the photosensitive composition layer. It is more preferably more than 0% by mass and 1% by mass or less based on the total mass of the material layer, and it is particularly preferred that it does not contain particles.

-Pigment-
The photosensitive composition layer may contain a dye.
The dye is not particularly limited, and any known dye can be used, such as a leuco compound.

-Antioxidant-
Examples of antioxidants include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. It will be done.
Among these, 3-pyrazolidones are preferable as the antioxidant, and 1-phenyl-3-pyrazolidone is more preferable, since the effects of the present invention are more excellent.

When the photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total mass of the photosensitive composition layer. It is preferably 0.01% by mass or more, and more preferably 0.01% by mass or more. Although the upper limit is not particularly limited, it is preferably 1% by mass or less based on the total mass of the photosensitive composition layer.

[impurities]
The photosensitive composition layer may contain impurities.
Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof.
Among these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to have the following content.

The content of impurities in the photosensitive composition layer is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably 2 mass ppm or less, based on the total mass of the photosensitive composition layer. The lower limit is not particularly limited, and is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, based on the total mass of the photosensitive composition layer.

Methods for keeping impurities within the above range include selecting raw materials with a low content of impurities to be included in the photosensitive composition layer, preventing contamination of impurities during formation of the photosensitive composition layer, and cleaning. For example, it can be removed by By such a method, the amount of impurities can be kept within the above range.

Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is as follows: Preferably less. The content of these compounds is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and even more preferably 4 mass ppm or less, based on the total mass of the photosensitive composition layer. The lower limit is not particularly limited, and is preferably 10 mass ppb or more, more preferably 100 mass ppb or more, based on the total mass of the photosensitive composition layer. The content of these compounds can be suppressed in the same manner as for the metal impurities described above. Moreover, it can be quantified by a known measuring method.

The content of water in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, and 0.05% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of improving reliability and lamination properties. ~0.5% by mass is more preferred.

[Refractive index adjustment layer]
The transfer film may have a refractive index adjustment layer disposed on the photosensitive composition layer.
It is preferable that the transfer film has a temporary support, a photosensitive composition layer, and a refractive index adjustment layer in this order.
In addition, when a transfer film further has the protective film mentioned later, it is preferable to have a temporary support body, a photosensitive composition layer, a refractive index adjustment layer, and the protective film mentioned later in this order.

A known refractive index adjusting layer can be used as the refractive index adjusting layer. Examples of materials included in the refractive index adjusting layer include binders and particles.

Examples of the binder include a binder polymer contained in the photosensitive composition layer and a polymer containing a structural unit having a carboxylic acid anhydride structure.

Examples of the particles include zirconium oxide particles (ZrO ₂ particles), niobium oxide particles (Nb ₂ O ₅ particles), titanium oxide particles (TiO ₂ particles), and silicon dioxide particles (SiO ₂ particles).

The refractive index adjusting layer preferably contains a metal oxidation inhibitor.
When the refractive index adjustment layer contains a metal oxidation inhibitor, oxidation of the metal in contact with the refractive index adjustment layer can be suppressed.
As the metal oxidation inhibitor, for example, a compound having an aromatic ring containing a nitrogen atom in the molecule is preferable. Examples of metal oxidation inhibitors include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole.

The refractive index of the refractive index adjusting layer is preferably 1.60 or more, more preferably 1.63 or more. The upper limit is not particularly limited, and is preferably 2.10 or less, more preferably 1.85 or less.

The thickness of the refractive index adjusting layer is preferably 500 nm or less, more preferably 110 nm or less, and even more preferably 100 nm or less. The lower limit is not particularly limited, and is preferably 20 nm or more, more preferably 50 nm or more.
The thickness of the refractive index adjusting layer is calculated as the average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM).

[Other layers]
The transfer film may have other layers in addition to the above-mentioned temporary support, photosensitive composition layer, refractive index adjustment layer, and protective film.
Examples of other layers include a thermoplastic resin layer, an intermediate layer, and an antistatic layer.

(Thermoplastic resin layer)
The thermoplastic resin layer is usually placed between the temporary support and the photosensitive composition layer. By including the thermoplastic resin layer in the transfer film, followability to the substrate in the step of bonding the transfer film and the substrate is improved, and it is possible to suppress the inclusion of air bubbles between the substrate and the transfer film. As a result, adhesion between the thermoplastic resin layer and the layer adjacent to it (eg, temporary support) can be ensured.

The thermoplastic resin layer contains resin. The resin includes a thermoplastic resin as part or all of the resin. That is, in one embodiment, it is also preferable that the resin in the thermoplastic resin layer is a thermoplastic resin.

The thermoplastic resin is preferably an alkali-soluble resin.
Examples of alkali-soluble resins include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin. , polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

As the alkali-soluble resin, acrylic resin is preferable from the viewpoint of developability and adhesion with adjacent layers.
Here, the acrylic resin is at least one selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic esters, and structural units derived from (meth)acrylic acid amide. It means a resin having one type of structural unit.
As an acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic esters, and structural units derived from (meth)acrylic acid amide is It is preferable that the amount is 50% by mass or more based on the mass.
Among them, the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid ester is preferably 30 to 100% by mass, and 50 to 100% by mass, based on the total mass of the acrylic resin. 100% by mass is more preferred.

Moreover, it is preferable that the alkali-soluble resin is a polymer having an acid group.
Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with a carboxy group being preferred.
From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and even more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more.
The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, even more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins.
For example, among the polymers described in paragraph [0025] of JP-A No. 2011-095716, an alkali-soluble resin that is a carboxy group-containing acrylic resin with an acid value of 60 mgKOH/g or more, paragraph [0033] of JP-A No. 2010-237589 Carboxy group-containing acrylic resins with an acid value of 60 mgKOH/g or more among the polymers described in ~[0052], and acids among the binder polymers described in paragraphs [0053] to [0068] of JP2016-224162A Examples include carboxy group-containing acrylic resins having a value of 60 mgKOH/g or more.
The copolymerization ratio of structural units having a carboxyl group in the above carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass based on the total mass of the acrylic resin. is even more preferable.
As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoint of developability and adhesion with an adjacent layer.

The alkali-soluble resin may have a reactive group. The reactive group may be any group that is capable of addition polymerization, and includes ethylenically unsaturated groups; polycondensable groups such as hydroxy groups and carboxy groups; and polyaddition reactive groups such as epoxy groups and (block) isocyanate groups. Can be mentioned.

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

One type of alkali-soluble resin may be used alone, or two or more types may be used.
The content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion with adjacent layers. More preferably 40 to 80% by weight, particularly preferably 50 to 75% by weight.

(middle class)
In the transfer film 10, the intermediate layer 5 exists between the thermoplastic resin layer 3 and the photosensitive composition layer 7, so that the intermediate layer 5 can be used during the coating formation and coating of the thermoplastic resin layer 3 and the photosensitive composition layer 7. Mixing of components that may occur during storage after formation can be suppressed.
As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used.
Further, as the intermediate layer, an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in JP-A-5-072724, can also be used. It is preferable that the intermediate layer is an oxygen barrier layer because sensitivity during exposure is improved, time load on the exposure machine is reduced, and productivity is improved.
The oxygen barrier layer used as the intermediate layer may be appropriately selected from the known layers described in the above-mentioned publications. Among these, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred.

Each component that the water-soluble resin layer (intermediate layer) may contain will be described below.

The water-soluble resin layer (intermediate layer) contains resin.
The above resin includes a water-soluble resin as part or all of it.
Examples of resins that can be used as water-soluble resins include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Examples include resins such as coalescence.
Further, as the water-soluble resin, a copolymer of (meth)acrylic acid/vinyl compound, etc. can also be used. As the (meth)acrylic acid/vinyl compound copolymer, a (meth)acrylic acid/allyl (meth)acrylate copolymer is preferred, and a methacrylic acid/allyl methacrylate copolymer is more preferred.
When the water-soluble resin is a copolymer of (meth)acrylic acid/vinyl compound, each composition ratio (mol%) is preferably 90/10 to 20/80, and 80/20 to 30/70, for example. More preferred.

The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Further, the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
The degree of dispersion (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

In addition, in order to further improve the interlayer mixing suppression ability of the water-soluble resin layer (intermediate layer), the resin in the water-soluble resin layer (intermediate layer) is placed on one side of the water-soluble resin layer (intermediate layer). It is preferable that the resin contained in the layer disposed on the other surface is different from the resin contained in the layer disposed on the other surface side. For example, when the photosensitive composition layer 17 contains polymer A and the thermoplastic resin layer 13 contains a thermoplastic resin (alkali-soluble resin), the resin of the water-soluble resin layer (intermediate layer) 15 is It is preferable that the resin is different from the polymer A and the thermoplastic resin (alkali-soluble resin).

The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of further improving oxygen barrier properties and interlayer mixing suppression ability.

One type of water-soluble resin may be used alone, or two or more types may be used.
The content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more based on the total mass of the water-soluble resin layer (intermediate layer) in order to further improve oxygen barrier properties and ability to suppress interlayer mixing. , more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more. The upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.

The layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property is not reduced and the ability to suppress interlayer mixing is excellent. Furthermore, an increase in the time required to remove the water-soluble resin layer (intermediate layer) during development can also be suppressed.

(Antistatic layer)
Since the transfer film has an antistatic layer, it is possible to suppress the generation of static electricity when peeling off the film placed on the antistatic layer, and also suppress the generation of static electricity due to rubbing with equipment or other films, etc. Therefore, for example, it is possible to suppress the occurrence of malfunctions in electronic equipment.
The antistatic layer is preferably disposed between the temporary support and the photosensitive composition layer.

The antistatic layer is a layer having antistatic properties and contains at least an antistatic agent. The antistatic agent is not particularly limited, and any known antistatic agent can be used.

[Method for manufacturing temporary support]
The method for producing the temporary support is not particularly limited, and includes known methods.
The method for manufacturing the temporary support may be a manufacturing method that includes an extrusion molding step and a coating step, or a manufacturing method that includes a coextrusion molding step. Moreover, in addition to the above steps, it is preferable to further include a biaxial stretching step.
Examples of the extrusion molding method include a method of molding the raw resin into a desired shape by extruding the raw resin using an extruder.
Examples of the coextrusion forming step include a method of extruding a plurality of raw resins using an extruder to mold the raw resins into a shape having a multilayer structure.

The biaxial stretching step may be simultaneous biaxial stretching in which longitudinal stretching and transverse stretching are performed simultaneously, or sequential biaxial stretching in which longitudinal stretching and transverse stretching are divided into two stages or two or more stages. You can. Examples of the sequential biaxial stretching include [order of longitudinal stretching and transverse stretching], [order of longitudinal stretching, transverse stretching and longitudinal stretching], [order of longitudinal stretching, longitudinal stretching and transverse stretching], and [order of longitudinal stretching, longitudinal stretching and transverse stretching]. horizontal stretching and longitudinal stretching]. Among these, it is preferable to carry out the longitudinal stretching and the transverse stretching in this order.

Next, an example of a method for manufacturing a temporary support according to the present specification will be specifically described.
The method for producing a temporary support includes a process of forming an unstretched temporary support body by melt-extruding polyester (hereinafter also referred to as an "extrusion molding process"), a coating process, and a longitudinal process of the temporary support body. (hereinafter also referred to as "longitudinal stretching step"); and a step of stretching the temporary support body stretched in the longitudinal direction in the width direction (hereinafter also referred to as "lateral stretching step"). It is preferable to have. In addition, the method for manufacturing the temporary support includes a step (hereinafter referred to as "co-extrusion molding") of forming an unstretched temporary support by simultaneously melting and extruding the raw material resins of the first layer, the second layer, and the main body of the temporary support. ), a step of stretching the temporary support in the longitudinal direction (hereinafter also referred to as "longitudinal stretching step"), and a step of stretching the temporary support stretched in the longitudinal direction in the width direction ( It is also preferable to have a step (hereinafter also referred to as a "lateral stretching step").

<Extrusion molding process>
In the extrusion molding process, a raw material resin (for example, polyester) is melt-extruded to form an unstretched temporary support body.

Examples of the melt extrusion method include a method using an extruder. For example, melt extrusion uses an extruder equipped with one or more screws to heat a raw material resin (for example, polyester) to a temperature above its melting point, and then rotates the screws to melt and knead the material. It will be done. The polyester is heated and kneaded using a screw to melt it in an extruder and become a melt.

The melt is extruded from an extrusion die (hereinafter also referred to as "die") through a gear pump, a filter, etc. (JIS B8650:2006, a, extrusion molding machine, number 134). The melt may be extruded in a single layer or in multiple layers.

In melt extrusion, from the viewpoint of suppressing thermal decomposition (for example, hydrolysis of polyester) within the extruder, it is preferable to replace the inside of the extruder with nitrogen. Further, the extruder is preferably a twin-screw extruder because the kneading temperature can be kept low.

The melt extruded from the extrusion die is cooled and shaped into a film. For example, the melt can be formed into a film by bringing the melt into contact with a casting roll and cooling and solidifying the melt on the casting roll. In cooling the molten material, it is further preferable to apply wind (preferably cold air) to the molten material.

The temperature of the casting roll is preferably higher than -10°C and lower than +30°C, more preferably -7 to +20°C, and even more preferably -5+10°C, relative to the glass transition temperature (Tg) of the polyester.

When using a casting roll in the extrusion molding process, it is preferable to increase the adhesion between the casting roll and the melt. Examples of methods for increasing adhesion include an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, and a touch roll method.

The temporary support body cooled using a casting roll or the like is peeled off from the cooling member such as a casting roll using a peeling member such as a peeling roll.

<Coating process>
The coating process is a process of forming the first layer or the second layer.
The coating process is not particularly limited, and known methods may be used.

The coating process is not particularly limited, and known methods may be used. Examples include reverse roll coating method, gravure coating method, kiss coating method, die coater method, roll brushing method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, impregnation coating method, and curtain coating method. It will be done. Further, these methods may be used alone or in combination.
In the coating step, it is preferable to dissolve the components contained in the first layer or the second layer in a solvent to prepare and use a coating liquid for forming the first layer or the second layer. Examples of the solvent include water and organic solvents.

The coating step may be provided before or after any step in the manufacturing process of the temporary support. Specifically, it may be provided after the extrusion molding process or after the biaxial stretching process. Moreover, it may be performed once or multiple times.
Among these, it is preferable to provide it after the biaxial stretching step, and it is more preferable to apply the coating liquid for forming the first layer or the second layer on the temporary support main body stretched in the longitudinal direction, and then stretch it laterally.

<Coextrusion molding process>
The coextrusion molding process is not particularly limited, and known methods may be used. Examples of the coextrusion molding process include the method described in JP-A-2019-65271, the contents of which are incorporated herein.

<Biaxial stretching process>
The biaxial stretching step is not particularly limited, and known methods may be used.
The biaxial stretching process preferably includes a longitudinal stretching process and a lateral stretching process.

[Longitudinal stretching process]
In the longitudinal stretching step, it is preferable to stretch the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body) in the longitudinal direction (hereinafter also referred to as "longitudinal stretching").

In the longitudinal stretching step, it is preferable to preheat the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body) before the longitudinal stretching. By preheating the unstretched film, the film can be easily longitudinally stretched.

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

Longitudinal stretching can be carried out, for example, by applying tension between two or more pairs of nip rolls installed in the transport direction while transporting the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body) in the longitudinal direction. It can be carried out. For example, if a pair of nip rolls A is installed on the upstream side of the transport direction and a pair of nip rolls B is installed on the downstream side of the transport direction, the rotation speed of nip roll B is set to By making it faster than the speed, the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body) is stretched in the longitudinal direction.

The stretching ratio in the longitudinal stretching step is preferably smaller than the stretching ratio in the laterally described horizontal stretching step. The stretching ratio in the longitudinal stretching step is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.0 times, and even more preferably 2.8 to 4.0 times. preferable.

The heating temperature in the longitudinal stretching step is preferably -20 to +50°C, and preferably -10 to +40°C with respect to the Tg of the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body). The temperature is more preferably 0 to +30°C, and even more preferably 0 to +30°C. Specifically, the heating temperature in the longitudinal stretching step is preferably 70 to 120°C, more preferably 80 to 110°C, and even more preferably 85 to 100°C.

The method of heating the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body) includes a nip roll that contacts the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body), etc. One example is a method of heating a roll. Examples of methods for heating the roll include a method of providing a heater or piping through which a hot solvent can flow inside the roll. In addition to the above, for example, a method of applying hot air to the unstretched film (for example, the unstretched temporary support and the unstretched temporary support main body), a method of bringing the film into contact with a heat source such as a heater, and a method of causing the unstretched film to pass near the heat source. For example, a method of heating an unstretched film (for example, an unstretched temporary support and an unstretched temporary support main body) may be mentioned.

The stretching speed in the longitudinal stretching step is preferably 800 to 1500%/sec, more preferably 1000 to 1400%/sec, and even more preferably 1200 to 1400%/sec. Here, the "stretching speed" is a value obtained by dividing the length Δd stretched in 1 second from the length d ₀ before stretching by the length d ₀ before stretching, expressed as a percentage.

[Lateral stretching process]
In the lateral stretching step, the film stretched in the longitudinal direction (for example, the temporary support stretched in the longitudinal direction and the temporary support main body stretched in the longitudinal direction) is stretched in the width direction (hereinafter also referred to as "lateral stretching"). say.) do.

In the transverse stretching step, it is preferable to preheat the film stretched in the longitudinal direction (for example, the temporary support stretched in the longitudinal direction and the temporary support main body stretched in the longitudinal direction) before the transverse stretching. By preheating the film, the film can be easily laterally stretched.

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

The stretching ratio in the transverse stretching step is preferably larger than the stretching ratio in the longitudinal stretching step. The stretching ratio in the transverse stretching step is preferably 3.0 to 6.0 times, more preferably 3.5 to 5.0 times, and even more preferably 3.5 to 4.5 times. preferable.

The area magnification represented by the product of the stretching magnification in the longitudinal stretching step and the stretching magnification in the lateral stretching step is preferably 12.8 to 15.5 times, and preferably 13.5 to 15.2 times. is more preferable, and even more preferably 14.0 to 15.0 times. When the area magnification is 12.8 times or more, the molecular orientation in the film width direction becomes good. Further, when the area magnification is 15.5 times or less, it is easy to maintain a state in which the molecular orientation is difficult to relax when subjected to heat treatment.

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

The stretching speed in the transverse stretching step is preferably 10 to 100%/sec, more preferably 10 to 70%/sec, and even more preferably 20 to 60%/sec.

<Heat treatment process>
The method for producing the temporary support includes a step (hereinafter referred to as "heating") of heating the film stretched in the width direction (for example, the temporary support stretched in the width direction and the temporary support main body stretched in the width direction). It is preferable to have a treatment step). Examples of the heat treatment process include a heat setting process and a heat relaxation process. The heat treatment step preferably includes at least one of a heat setting step and a heat relaxation step, and more preferably a heat setting step and a heat relaxation step.

(Heat fixation process)
In the heat-setting step, the film stretched in the width direction (for example, the temporary support stretched in the width direction and the temporary support main body stretched in the width direction) is heat-set by heating. Since the raw resin can be crystallized by heat setting, shrinkage of the film can be suppressed.

The heating temperature in the heat setting step is preferably 190 to 240°C, more preferably 200 to 240°C, even more preferably 210 to 230°C.

In the heat setting step, the variation in the maximum film surface temperature in the film width direction is preferably 0.5 to 10.0°C, more preferably 0.5 to 7.0°C, and 0.5 to 7.0°C. The temperature is more preferably 5.0°C to 5.0°C, and particularly preferably 0.5 to 4.0°C. By adjusting the variation in the maximum film surface temperature in the film width direction within the above range, variation in crystallinity in the width direction can be suppressed.

Examples of the heating method include a method of applying hot air to the film and a method of heating the film by radiation. Examples of devices used in the radiant heating method include infrared heaters.

The heating time in the heat fixing step is preferably 5 to 50 seconds, more preferably 5 to 30 seconds, and even more preferably 5 to 10 seconds.

(Thermal relaxation process)
In the thermal relaxation step, the film stretched in the width direction (for example, the temporary support body stretched in the width direction and the temporary support body stretched in the width direction) is thermally relaxed by heating. Residual strain in the film (for example, the temporary support stretched in the width direction and the temporary support main body stretched in the width direction) can be alleviated by thermal relaxation.

The heating temperature in the thermal relaxation step is preferably 5° C. or more lower than the heating temperature in the heat setting step, more preferably 15° C. or more lower, still more preferably 25° C. or more lower. , it is particularly preferable that the temperature is lower by 30°C or more.

The lower limit of the heating temperature in the thermal relaxation step is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher.

Examples of the heating method include a method of applying hot air to the film and a method of heating the film by radiation. Examples of devices used in the radiant heating method include infrared heaters.

<Cooling process>
The method for producing a temporary support includes a step (hereinafter also referred to as "cooling step") of cooling the heat-treated film (for example, the heat-treated temporary support and the heat-treated temporary support body). It is preferable.

Examples of the cooling method include a method in which the film is exposed to wind (preferably cold air), and a method in which the film is brought into contact with a temperature-adjustable member (for example, a temperature control roll).

The average cooling rate in the cooling step is preferably 500 to 4000°C/min, more preferably 1000 to 3500°C/min, and even more preferably 1500 to 3000°C/min. By adjusting the average cooling rate within the above range, the film surface temperature during the cooling process can be made uniform, so that the unevenness in the expansion coefficient in the width direction can be reduced. The average cooling rate is determined using a non-contact thermometer (eg, a radiation thermometer). For example, from the distance Z between the point where the surface temperature of the film (for example, the temporary support and the main body of the temporary support) is 150°C and the point where the film surface temperature is 70°C, and the transport speed S of the film, 150°C Find the cooling time (Z/S) from to 70°C. Next, the average cooling rate is determined by calculating (150-70)/(Z/S).

[Manufacturing method of transfer film]
The method for producing the transfer film of the present invention is not particularly limited, and any known method can be used.
Among these, preferred is a method in which a photosensitive composition layer is formed by applying a photosensitive composition onto a temporary support and subjecting it to a drying treatment if necessary, from the viewpoint of excellent productivity.
The above method will be explained in detail below.

Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (ie, slit coating).

Examples of the drying method include natural drying, heat drying, and reduced pressure drying. The above methods can be applied alone or in combination.
As used herein, "drying" means removing at least a portion of the solvent contained in the photosensitive composition.

When the transfer film has a refractive index adjusting layer on the photosensitive composition layer, for example, the composition for forming a refractive index adjusting layer is applied on the photosensitive composition layer and dried as necessary to adjust the refractive index. A rate adjustment layer can be formed.

Moreover, a transfer film can be manufactured by laminating a protective film to a photosensitive composition layer.
The method of bonding the protective film to the photosensitive composition layer is not particularly limited, and known methods may be used.
As a device for bonding the protective film to the photosensitive composition layer, known laminators such as a vacuum laminator and an auto-cut laminator can be used.
The laminator is preferably equipped with any heatable roller such as a rubber roller, and is capable of applying pressure and heating.

[Method for manufacturing laminate]
By using the above-mentioned transfer film, the photosensitive composition layer can be transferred to the object to be transferred.
In particular, the protective film is peeled off from the transfer film, the surface opposite to the temporary support is brought into contact with a substrate having a conductive part, and the conductive part, the photosensitive composition layer, and the temporary support are bonded together. a laminating step of obtaining a substrate with a photosensitive composition layer having the following in this order;
an exposure step of exposing the photosensitive composition layer to pattern light;
a developing step of developing the exposed photosensitive composition layer to form a pattern,
A method for producing a laminate, further comprising a peeling step of peeling off the temporary support from the photosensitive composition layer-coated substrate between the bonding step and the exposure step or between the exposure step and the development step. is preferred.
Hereinafter, the procedure of the above steps will be explained in detail.

<Lamination process>
In the bonding step, the protective film is peeled off from the transfer film, and the surface of the transfer film opposite to the temporary support is bonded by contacting with a substrate having a conductive part, thereby forming a conductive layer, a photosensitive composition layer, and a step of obtaining a photosensitive composition layer-coated substrate having temporary supports in this order.

The method for peeling the protective film from the transfer film is not particularly limited, and any known method can be used.
The surface of the transfer film opposite to the temporary support is preferably a refractive index adjustment layer when the transfer film has a refractive index adjustment layer, and a photosensitive surface when the transfer film does not have a refractive index adjustment layer. The layer is preferably a sexual composition layer. In other words, in the bonding step, the refractive index adjustment layer of the transfer film may be brought into contact with the object to be transferred, or the photosensitive composition layer of the transfer film may be bonded by contact with the object to be transferred. preferable.
The exposed photosensitive composition layer on the temporary support of the transfer film is brought into contact with the conductive layer and bonded together. By this lamination, the photosensitive composition layer and the temporary support are placed on the conductive layer.
In the above-mentioned bonding, the above-mentioned conductive layer and the surface of the above-mentioned photosensitive composition layer are pressure-bonded so that they are in contact with each other.
There are no particular limitations on the method of pressure bonding, and known transfer methods and lamination methods can be used. Among these, it is preferable to stack the surface of the photosensitive composition layer on a substrate having a conductive part, and press and heat it with a roll or the like.
For bonding, known laminators such as a vacuum laminator and an auto-cut laminator can be used.

A substrate having a conductive layer has a conductive layer on the substrate, and an arbitrary layer may be formed as necessary. 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.

Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
A preferred embodiment of the substrate is described, for example, in paragraph [0140] of International Publication No. 2018/155193, the contents of which are incorporated herein.

The conductive layer is 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, in terms of conductivity and fine line formation. It is preferable to have one.
Furthermore, only one conductive layer, or two or more conductive layers may be disposed on the substrate. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials.
A preferred embodiment of the conductive layer is described, for example, in paragraph [0141] of International Publication No. 2018/155193, the content of which is incorporated herein.

As the substrate having a conductive layer, a substrate having at least one of a transparent electrode and a lead wiring is preferable. The above substrate can be suitably used as a touch panel substrate.
The transparent electrode can suitably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a metal thin wire such as silver nanowire.
Examples of the thin metal wire include thin wires made of silver, copper, and the like. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

Metal is preferable as the material for the lead-out wiring.
Examples of the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys made of two or more of these metal elements. Among these, the material for the routing wiring is preferably copper, molybdenum, aluminum, or titanium, and more preferably copper.

The electrode protective film for a touch panel formed using the photosensitive composition layer in the transfer film of the present invention protects the electrode, etc. (that is, at least one of the electrode for the touch panel and the wiring for the touch panel). It is preferable to provide it directly or so as to cover it with another layer.

<Exposure process>
The exposure step is a step of exposing the photosensitive composition layer to light in a pattern.
Note that the term "pattern exposure" as used herein refers to exposure in a pattern, that is, an exposure in which exposed areas and non-exposed areas exist.
The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited. Note that the pattern formed by the development process described below preferably includes a thin line with a width of 500 μm or less, and more preferably includes a thin line with a width of 100 μm or less.

The light source for pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range that can at least cure the photosensitive composition layer (for example, a wavelength of 365 nm or 405 nm). Among these, the main wavelength of the exposure light for pattern exposure is preferably 365 nm. Note that the dominant wavelength is the wavelength with the highest intensity.

Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
The exposure amount is preferably 5 to 200 mJ/cm ² , more preferably 10 to 200 mJ/cm ² .

Preferred aspects of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs [0146] to [0147] of International Publication No. 2018/155193, the contents of which are incorporated herein. .

<Peeling process>
The peeling process is a process of peeling off the temporary support from the photosensitive composition layer-coated substrate between the bonding process and the exposure process, or between the exposure process and the development process described below.
The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.

<Developing process>
The developing step is a step of developing the exposed photosensitive composition layer to form a pattern.
The photosensitive composition layer can be developed using a developer.
As the developer, an alkaline aqueous solution is preferred. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxy. and choline (2-hydroxyethyltrimethylammonium hydroxide).

Examples of development methods include paddle development, shower development, spin development, and dip development.

In the present specification, examples of the developer suitably used include the developer described in paragraph [0194] of International Publication No. 2015/093271. The development method described in paragraph [0195] of No. 2015/093271 can be mentioned.

<Post-exposure process and post-bake process>
The method for manufacturing the laminate may include a step of exposing the pattern obtained by the developing step (post-exposure step) and/or a step of heating (post-bake step).
When both a post-exposure step and a post-bake step are included, it is preferable to perform the post-bake after the post-exposure.

[Circuit wiring manufacturing method]
The transfer film can also be used in a method of manufacturing circuit wiring.
The method for manufacturing the circuit wiring is not particularly limited, and includes known manufacturing methods.
Among them, as a manufacturing method of circuit wiring,
The protective film is peeled off from the transfer film, and the photosensitive composition layer on the temporary support is bonded to the substrate having the conductive layer. a bonding step for obtaining a substrate with a sexual composition layer;
an exposure step of exposing the photosensitive composition layer to pattern light;
a developing step of developing the exposed photosensitive composition layer to form a pattern;
an etching process of etching the conductive layer in a region where the pattern is not arranged;
A method for producing a laminate, further comprising a peeling step of peeling off the temporary support from the photosensitive composition layer-coated substrate between the bonding step and the exposure step or between the exposure step and the development step. is preferred.

In the method for manufacturing circuit wiring, the bonding step, the exposure step, the development step, and the peeling step are synonymous with each step of the above-mentioned <method for manufacturing a laminate>, and the preferred ranges are also the same.

<Etching process>
The etching process is a process (etching process) of etching the conductive layer in the area where the pattern obtained in the development process is not arranged.
That is, the etching process involves etching the conductive layer using a pattern formed from the photosensitive composition layer as an etching resist.

As the etching process, known methods can be applied, such as the method described in paragraphs [0209] to [0210] of JP2017-120435A, and paragraphs [0048] to [0054] of JP2010-152155A. ], a wet etching method using immersion in an etching solution, and a dry etching method using plasma etching.

As the etching liquid used for wet etching, an acidic or alkaline etching liquid may be appropriately selected depending on the object to be etched.
Examples of the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an aqueous solution containing an acidic component and ferric chloride or fluoride. Mention may be made of mixed aqueous solutions with salts selected from ammonium and potassium permanganate. The acidic component may be a combination of multiple acidic components.
Examples of the alkaline etching solution include an aqueous solution of an alkali component alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), and alkaline components. and a salt (potassium permanganate, etc.). The alkaline component may be a combination of a plurality of alkaline components.

<Removal process>
The method for manufacturing circuit wiring may include a step of removing the remaining pattern (removal step).
The removal step is particularly limited and may be performed before or after each step, and is preferably performed after the etching step.
The method for removing the remaining pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it using a removal liquid is preferable.
An example of a method for removing using a removal liquid is a method of immersing a transfer target having a remaining pattern in a stirring removal liquid for 1 to 30 minutes.
The temperature of the removal liquid is preferably 30 to 80°C, more preferably 50 to 80°C.

Examples of the removal liquid include a removal liquid in which an inorganic alkali component or an organic alkali component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.
Alternatively, it may be removed by a known method such as a spray method, a shower method, or a paddle method using a removal solution.

[Other processes]
The method for manufacturing a laminate and the method for manufacturing circuit wiring may include any steps (other steps) other than the steps described above.
Other steps include, for example, the step of reducing visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089, and the step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089, and Another step is to form a new conductive layer. However, the steps are not limited to these steps.

<Step of reducing visible light reflectance>
The method of manufacturing a laminate and the method of manufacturing a circuit wiring may include a process of reducing the visible light reflectance of some or all of the plurality of conductive layers included in the transfer target.
Examples of the treatment for reducing visible light reflectance include oxidation treatment. When the transfer target has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer.
Regarding the process of reducing visible light reflectance, see paragraphs [0017] to [0025] of JP-A No. 2014-150118, and paragraphs [0041]-[0042] and [0048] of JP-A No. 2013-206315. ] and paragraph [0058], the contents of which are incorporated herein.

<Process of forming an insulating film, process of forming a new conductive layer on the surface of the insulating film>
It is also preferable that the method for manufacturing the circuit wiring includes the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film.
Through the above steps, a first electrode pattern and an insulated second electrode pattern can be formed.
The step of forming the insulating film is not particularly limited, and includes known methods for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer with a desired pattern may be formed by photolithography using a photosensitive composition having conductivity. .

In the method for manufacturing circuit wiring, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the substrate, and to form circuits sequentially or simultaneously on the conductive layers arranged on both surfaces of the substrate. With such a configuration, it is possible to form circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the surface of the other substrate. Moreover, it is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.

[Application]
The laminate and circuit wiring manufactured by the laminate manufacturing method and the circuit wiring manufacturing method can be applied to various devices. Examples of the device including a laminate or circuit wiring manufactured by the above manufacturing method include a display device, a printed wiring board, a semiconductor package, and an input device, and a touch panel is preferable, and a capacitive touch panel is more preferable. . Furthermore, the input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[Manufacturing method of electronic device]
Transfer films may also be used in methods of manufacturing electronic devices.
As the method for manufacturing the electronic device, the method for manufacturing the electronic device using the above-described transfer film is preferable.
Among these, it is preferable that the method for manufacturing an electronic device includes the method for manufacturing a laminate described above.
Examples of the electronic device include an input device, and preferably a touch panel. Furthermore, the input device can be applied to display devices such as organic electroluminescent display devices and liquid crystal display devices.

As a method for manufacturing a touch panel, for example, a laminate in which a transfer target (for example, a substrate, a conductive layer (a conductive layer included in the substrate)) and a pattern manufactured using the above transfer film are laminated in this order is used. A method including a step of forming touch panel wiring by etching the conductive layer in an area where the resin pattern is not arranged is also preferable, and the method includes the step of forming touch panel wiring by etching the conductive layer in the region where the resin pattern is not arranged, and the method includes the step of forming the wiring for the touch panel, and the above-mentioned bonding step, the above-mentioned exposure step, and the above-mentioned development step are More preferred is a method using a pattern manufactured by a manufacturing method including.

The specific aspects of each step in the touch panel manufacturing method including the step of forming touch panel wiring, and the order in which each step is performed are as explained in <Circuit wiring manufacturing method> above. The preferred embodiments are also the same.
Further, the method for manufacturing a touch panel including the step of forming touch panel wiring may include any steps (other steps) other than those described above.
Examples of the method for forming touch panel wiring include the method described in FIG. 1 of International Publication No. 2016/190405.

By the above touch panel manufacturing method, a touch panel having at least touch panel wiring is manufactured. It is preferable that the touch panel has a transparent substrate, an electrode, and an insulating layer or a protective layer.
Examples of the detection method in the touch panel include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method, with the capacitance method being preferred.

Examples of touch panels include in-cell type (for example, those shown in FIGS. 5 to 8 of Japanese Patent Publication No. 2012-517051), on-cell type (for example, those shown in FIG. 19 of Japanese Patent Application Laid-open No. 2013-168125), and , those shown in FIGS. 1 and 5 of JP-A No. 2012-089102), OGS (One Glass Solution) type, and TOL (Touch-on-Lens) type (for example, those shown in FIG. 2 of JP-A No. 2013-054727) ), various outsell types (for example, GG, G1/G2, GFF, GF2, GF1, and G1F, etc.), and other configurations (for example, those described in FIG. 6 of JP-A No. 2013-164871) ).
Examples of the touch panel include those described in paragraph [0229] of JP-A No. 2017-120345.

In the method for manufacturing an electronic device using a transfer film, it is also preferable that the electronic device to be manufactured includes a resin pattern as a cured film (especially when the transfer film includes a negative photosensitive composition layer).
A cured film of such a resin pattern can be used as a protective film (permanent film) that covers part or all of the electrodes, etc. of an electronic device (touch panel, etc.). By placing a cured film of the above resin pattern on the electrode etc. as a protective film (permanent film), it is possible to prevent problems such as metal corrosion, increase in electrical resistance between the electrode and drive circuit, and disconnection. be.

The present invention will be specifically described below with reference to Examples. The materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of this specification. Therefore, the scope of the present invention is not limited to the specific examples shown below. Note that unless otherwise specified, "parts" and "%" are based on mass.
In the following examples, the weight average molecular weight (Mw) is the weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC).

[Temporary support Z-1]
Temporary support Z-1 of Example 1 was produced according to the following procedure.

Polyethylene terephthalate pellets A were obtained using a titanium compound (citric acid chelate titanium complex, VERTEC AC-420, manufactured by Johnson Matthey) as a polymerization catalyst described in Japanese Patent No. 5,575,671.

90 parts by mass of the above pellets A and 10 parts by mass of a 10% by mass water slurry of organic particles (crosslinked polystyrene resin particles manufactured as described below) obtained by crosslinking polystyrene resin particles with an average particle diameter of 500 nm with divinylbenzene are mixed on a twin screw. A masterbatch A containing 1% by mass of crosslinked polystyrene resin particles (organic particles) was obtained by supplying the mixture to an extruder and removing moisture by maintaining the vent hole at a reduced pressure of 1 kPa or less.

[Manufacture of crosslinked polystyrene resin particles]
After adding potassium persulfate (3.2 parts by mass) and sodium lauryl sulfate (0.15 parts by mass) to demineralized water (1500 parts by mass) and dissolving them uniformly, styrene (92 parts by mass) and divinylbenzene were added. (8 parts by mass) was added. A polymerization reaction was carried out at 70° C. for 24 hours with stirring under a nitrogen gas atmosphere to obtain crosslinked polystyrene resin particles.

Pellet A (90 parts by mass) and a 10% by mass water slurry of alumina particles with an average particle diameter of 30 nm (alumina sol, manufactured by Nissan Chemical Co., Ltd.) (10 parts by mass) were supplied to a twin-screw kneading extruder, and the vent hole A masterbatch B containing 1% by mass of alumina particles was obtained by maintaining the pressure at a reduced pressure of 1 kPa or less and removing moisture.

Further, a mixture X was obtained by mixing pellets A (70 parts by mass), masterbatch A (10 parts by mass), and masterbatch B (20 parts by mass).
After drying pellets A and mixture An unstretched temporary support having a three-layer structure in the order of layer A (layer consisting of pellets A)/layer A (layer consisting of pellet A)/layer X (layer consisting of mixture X) was prepared. In addition, the extruded molten body (melt) was brought into close contact with one X layer side on a cooling roll using an electrostatic application method.
The obtained unstretched temporary support was sequentially subjected to biaxial stretching by the following method.
First, an unstretched temporary support was passed between two pairs of nip rolls having different circumferential speeds to be stretched in the longitudinal direction (conveying direction). The longitudinal stretching was carried out at a preheating temperature of 75° C., a stretching temperature of 95° C., a stretching ratio of 3.4 times, and a stretching speed of 1300%/sec.
Next, the obtained temporary support stretched in the longitudinal direction was stretched in the transverse direction using a tenter. The longitudinal stretching was carried out at a preheating temperature of 100° C., a stretching temperature of 120° C., a stretching ratio of 4.2 times, and a stretching speed of 50%/sec to obtain a temporary support Z-1. The thickness of each layer of the temporary support Z-1 was: X layer/A layer/X layer=1 μm/14 μm/1 μm.
According to Tables 2 and 3, temporary supports for each Example and each Comparative Example were produced in the same manner as for the above-mentioned Temporary Support Z-1, except that each component was changed.

[Transfer film]
The transfer film of Example 1 was produced according to the following procedure.
First, the components contained in each transfer film will be explained in detail.

<Binder polymer A>
PGMEA (55.8 parts by mass) and toluene (55.8 parts by mass) were mixed to prepare a first liquid. In addition, a mixed solution of methacrylic acid (12 parts by mass), methyl methacrylate (58 parts by mass), and ethyl acrylate (30 parts by mass), and AIBN (azobisisobutyronitrile) (1.0 parts by mass) , PGMEA (6.2 parts by mass), and toluene (6.2 parts by mass) were mixed and stirred at room temperature for 1 hour to prepare a second liquid.
The first liquid was placed in a flask, and the temperature was raised to 80° C. under a nitrogen atmosphere. Next, the second liquid was further added to the flask over 4 hours using a dropping pump while stirring the obtained mixed liquid and maintaining the liquid temperature at 80°C. After the addition was completed, the temperature of the resulting mixed solution was maintained at 80° C. while stirring, and the reaction was further carried out for 6 hours to obtain a solution containing binder polymer A. The weight average molecular weight of the obtained binder polymer A was 65,000. The composition ratio (mass ratio) derived from each monomer was methacrylic acid/methyl methacrylate/ethyl acrylate = 12/58/30.

<Binder polymer B>
PGMEA (116.5 parts by mass) was placed in a three-necked flask, and the temperature was raised to 90° C. under a nitrogen atmosphere. While maintaining the liquid temperature in the three-neck flask at 90°C ± 2°C, styrene (52.0 parts by mass), methyl methacrylate (24.0 parts by mass), methacrylic acid (24.0 parts by mass), V -601 (2,2'-azobis(isobutyric acid) dimethyl, manufactured by Fujifilm Corporation (4.0 parts by mass) and PGMEA (116.5 parts by mass) were poured into a three-necked flask over 2 hours. After dropping, the mixture was stirred for 2 hours while maintaining the liquid temperature at 90°C ± 2°C to obtain a solution containing binder polymer B (solid content concentration: 30.0% by mass). The acid value of binder polymer B was 159 mgKOH/g, the weight average molecular weight was 60,000, and the glass transition temperature was 126°C.The composition ratio (mass ratio) derived from each monomer was styrene/methacrylic acid/methacrylic acid. Methyl = 52/24/24.

<Binder polymer C>
Propylene glycol monomethyl ether (82.4 g) was charged into a flask and heated to 90° C. under a nitrogen stream. A solution of styrene (38.4 g), dicyclopentanyl methacrylate (30.1 g), and methacrylic acid (34.0 g) dissolved in propylene glycol monomethyl ether (20 g) was added to this liquid, and a polymerization initiator V-601 was added. (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) (5.4 g) in propylene glycol monomethyl ether acetate (43.6 g) was simultaneously added dropwise over 3 hours. After the dropwise addition was completed, V-601 (0.75 g) was added three times at 1 hour intervals. Thereafter, the reaction was continued for an additional 3 hours. Thereafter, the mixture was diluted with propylene glycol monomethyl ether acetate (58.4 g) and propylene glycol monomethyl ether (11.7 g). The reaction solution was heated to 100° C. under a stream of air, and tetraethylammonium bromide (0.53 g) and p-methoxyphenol (0.26 g) were added. Glycidyl methacrylate (Blemmer GH manufactured by NOF Corporation) (25.5 g) was added dropwise to this over 20 minutes. This was reacted at 100° C. for 7 hours to obtain a solution of polymer P-1. The solid content concentration of the obtained solution was 36.5% by mass. The weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the degree of dispersion was 2.4, and the acid value of the polymer was 94.5 mgKOH/g. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass based on the solid content of the polymer in all monomers.
The structure of binder polymer C (the repeating unit in the formula is a molar ratio) is shown below.

<Photosensitive composition>
Photosensitive compositions Y-1 to Y-5 were prepared.

(Photosensitive composition Y-1)
・Tricyclodecane dimethanol diacrylate (polymerizable compound, A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 19.31 parts by mass ・Carboxylic acid-containing monomer (polymerizable compound, Aronix TO2349, manufactured by Toagosei Co., Ltd.): 3 .21 parts by mass Urethane-acrylic monomer (polymerizable compound, Acryt 8UX-015A, manufactured by Taisei Fine Chemical Co., Ltd.): 9.65 parts by mass The following binder polymer P-1 (acid value 95 mgKOH/g, Mw = 27,000, Solid content concentration: 36.3% by mass): 53.64 parts by mass in terms of solid content

・Duranate WT32-B75P (thermal crosslinkable compound, manufactured by Asahi Kasei Chemicals): 12.50 parts by mass ・Irgacure OXE-02 (photopolymerization initiator, manufactured by BASF): 0.37 parts by mass ・Omnirad 907 (photopolymerization initiator) agent, manufactured by IGM Resins B.V.): 0.74 parts by mass ・N-phenylglycine (hydrogen donating compound, manufactured by Junsei Kagaku Co., Ltd.): 0.10 parts by mass ・Benzimidazole (heterocyclic compound, manufactured by Tokyo Kasei Kogyo Co., Ltd.) ): 0.30 parts by mass ・Megafac F551 (surfactant, manufactured by DIC Corporation): 0.16 parts by mass ・Mixed solvent of 1-methoxy-2-propyl acetate (PGMEA) and methyl ethyl ketone (MEK) ( PGMEA:MEK=4:6): Amount that makes the solid content concentration of photosensitive composition Y-1 29%

(Photosensitive composition Y-2)
・Binder polymer A: 63.00 parts by mass in terms of solid content ・Pentaerythritol triacrylate (ethylenic unsaturated compound, “A-TMM-3LM-N” manufactured by Shin Nakamura Chemical Co., Ltd.): 37.00 parts by mass ・Bis( 2,4,6-trimethylbenzoyl) phenylphosphine oxide (polymerization initiator, "Omnirad 819" manufactured by IGM Resins B.V.): 10.00 parts by mass, polyether-modified silicone (surfactant (leveling agent)) , "8032 ADDITIVE" manufactured by Dow Corning Toray): 0.06 parts by mass MEK: Amount that makes the solid content concentration of photosensitive composition Y-2 30%

(Photosensitive composition Y-3)
・Binder polymer B (solid content concentration 30.0% by mass): 53.27 parts by mass ・NK ester BPE-500 (polymerizable compound, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, new Nakamura Chemical Industry Co., Ltd.): 22.5 parts by mass NK ester BPE-200 (polymerizable compound, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, Shin Nakamura Chemical Industry Co., Ltd.): 10 .0 parts by mass・NK ester A-TMPT (polymerizable compound, trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 10 parts by mass・B-CIM (polymerization initiator, 2-(2-chlorophenyl)-4 , 5-diphenylimidazole dimer, Hampford): 3.00 parts by mass SB-PI 701 (sensitizer, 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Boeki): 0.30 parts by mass・Dye N-1 (leuco crystal violet, manufactured by Tokyo Kasei Kogyo Co., Ltd., colored by radicals): 0.60 parts by mass ・Dye N-2 (brilliant green, manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.02 parts by mass 1 -(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole mixture ((hydrogen donating compound, mass ratio 1 :1): 0.10 parts by mass Irganox245 (antioxidant, ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), manufactured by BASF): 0.20 parts by mass N-nitrosophenylhydroxylamine aluminum salt (polymerization inhibitor): 0.01 parts by mass methyl ethyl ketone (manufactured by Sankyo Kagaku Co., Ltd.): The solid content concentration of photosensitive composition Y-3 was 30%.・PGMEA (manufactured by Showa Denko): 50.00 parts by mass ・Methanol (manufactured by Mitsubishi Gas Chemical): 10.00 parts by mass

(Photosensitive composition Y-4)
・Binder polymer C: 52.67 parts by mass (solid content)
・A-NOD-N (1,9-nonanediol diacrylate, Shin Nakamura Chemical Co., Ltd.): 2.73 parts by mass ・A-DCP (tricyclodecane dimethanol diacrylate, Shin Nakamura Chemical Co., Ltd.) ): 17.90 parts by mass Aronix TO-2349 (polyfunctional ethylenically unsaturated compound having a carboxylic acid group, manufactured by Toagosei Co., Ltd.): 2.98 parts by mass DPHA: Dipentaerythritol hexaacrylate ( Toshin Yushi Co., Ltd.): 7.99 parts by mass 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) ( D-1, Irgacure OXE-02, manufactured by BASF): 0.36 parts 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (D-2, Irgacure 907, BASF) ): 0.73 parts Duranate WT32-B75P (E-3, blocked isocyanate compound, manufactured by Asahi Kasei Chemicals Co., Ltd.): 12.50 parts by mass Isonicotinamide: 0.52 parts by mass Benzimidazole: 0 .13 parts by mass N-phenylglycine (manufactured by Junsei Kagaku Co., Ltd.): 0.10 parts by mass Styrene/maleic anhydride = 4:1 (mole ratio) copolymer (acid anhydride value 1.94 mmol/g , weight average molecular weight 10,500) (SMA EF-40, manufactured by Cray Valley): 1.20 parts by mass, BYK-330 (manufactured by BYK): 0.10 parts by mass, PGMEA: 70 parts by mass, MEK: 30 Mass part

(Photosensitive composition Y-5)
・Binder polymer C: 40 parts by mass (solid content)
・Copolymer of benzyl methacrylate/methacrylic acid = 80/20 (mass ratio) (weight average molecular weight 30,000): 12.67 parts by mass (solid content)
・A-NOD-N (1,9-nonanediol diacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.): 2.73 parts by mass ・KAYARAD R-604 (manufactured by Nippon Kayaku): 10 parts by mass ・A-DCP (Tricyclodecane dimethanol diacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.): 7.90 parts by mass. A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.): 2.98 parts by mass. DPHA: dipentaerythritol hexaacrylate (manufactured by Toshin Yushi Co., Ltd.): 8 parts by mass / (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (product name: APi) -307, manufactured by Shenzhen UV-ChemTech Ltd.): 2.1 parts by mass, naphthalenethiol: 0.10 parts by mass, BYK-330 (manufactured by BYK): 0.10 parts by mass, PGMEA: 50 parts by mass, MEK :30 parts by mass

(Photosensitive compositions A to C)
Photosensitive compositions A to C shown in Table 1 below were prepared. In Table 1, the numerical value of each component represents the content (parts by mass) of each component, and the amount of binder polymer means the amount of binder polymer solution (solid content concentration 36.3% by mass).
Note that 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline contained in photosensitive composition B was synthesized by a method according to the following scheme.

Anisaldehyde (20.4 g), acetone (4.4 g), sodium hydroxide (15.0 g), and distilled water (120 mL) were dissolved in ethanol (150 mL) and stirred at room temperature for 3 hours. The resulting solution was filtered, washed with distilled water (500 mL), and the filtrate was dried with air at room temperature to obtain a pale yellow solid (18.7 g).
The obtained pale yellow solid (9.0 g) and phenylhydrazine (3.3 g) were dissolved in acetic acid (100 mL), stirred at room temperature for 3 hours, and then cooled on ice. The obtained solution was filtered and washed with acetic acid (200 mL), distilled water (200 mL), and methanol (200 mL) in this order, and the filtrate was dried with air at room temperature to obtain 1-phenyl- as a pale yellow solid. 4.7 g (yield: 40%) of 3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline was obtained.

[Examples 1 to 14, 16 to 28, 30 and Comparative Examples 1 to 5]
On the temporary support Z-1 obtained above, the photosensitive composition Y-1 was applied using a slit-like nozzle so that the thickness after drying was adjusted to 8.8 μm. After drying at 120°C for 2 minutes, it was further dried at 120°C for 1 minute.
Thereafter, a 16 μm thick polyethylene terephthalate film (16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded as a protective film onto the photosensitive composition layer to obtain the transfer film of Example 1.
Transfer films of Examples 2 to 14, 16 to 28, and 30 and Comparative Examples 1 to 5 were obtained in the same manner as in Example 1, except that each component and the thickness of each layer were changed according to Tables 2 to 3.

[Example 15]
The following refractive index adjusting layer forming composition X-1 was added to the transfer film of Example 1 obtained above and on the photosensitive composition layer so that the thickness after drying was 73 nm. and dried at 80° C. for 1 minute. Thereafter, it was further dried at 110° C. for 1 minute to form a refractive index adjusting layer directly disposed on the photosensitive composition layer, thereby obtaining the transfer film of Example 15.

[Example 29]
On the transfer film of Example 28 obtained above, the following refractive index adjusting layer forming composition X-1 was further added on the photosensitive composition layer so that the thickness after drying was 73 nm. and dried at 80° C. for 1 minute. Thereafter, it was further dried at 110° C. for 1 minute to form a refractive index adjusting layer directly disposed on the photosensitive composition layer, thereby obtaining a transfer film of Example 29.

(Refractive index adjustment layer forming composition)
A composition for forming a refractive index adjustment layer was prepared using the following components.
The composition for forming a refractive index adjusting layer is prepared using a resin having acid groups and an ammonia aqueous solution, and the resin having acid groups is neutralized with an ammonia aqueous solution, and the ammonium of the resin having acid groups is neutralized with the ammonia aqueous solution. It is a water-based resin composition containing salt.

・Metal oxide particles (ZrO ₂ particles, Nanouse OZ-S30M, solid content concentration 30.5% by mass, methanol 69.5% by mass, refractive index 2.2, average particle size approximately 12nm, manufactured by Nissan Chemical Industries, Ltd.): Binder polymer (acrylic resin, ZB-015M, manufactured by Fujifilm Fine Chemical Co., Ltd., copolymer resin of methacrylic acid/allyl methacrylate (composition ratio (molar ratio) = 20/ 80), weight average molecular weight 25,000, solid content concentration 5.00%, ammonia aqueous solution): 14.78 parts by mass in terms of solid content, binder polymer having acid groups (acrylic resin, ARUFON UC3920, manufactured by Toagosei Co., Ltd.) ): 0.53 parts by mass Ethylenically unsaturated compound (polyfunctional ethylenically unsaturated compound having a carboxylic acid group, Aronix TO-2349, manufactured by Toagosei Co., Ltd.): 2.00 parts by mass Surfactant (fluorine-based Surfactant, Megafac F-444, manufactured by DIC): 0.68 parts by mass ・BT-LX (manufactured by Johoku Kagaku Kogyo Co., Ltd.): 2.00 parts by mass ・Methanol, distilled water and mixed solvent (methanol: distilled water =7:3 (mass ratio): Amount that makes the solid content concentration of the composition for forming a refractive index adjustment layer 1.66% by mass

〔evaluation〕
<Patternability>
A copper layer with a thickness of 200 nm was formed on a cycloolefin polymer (COP) film with a thickness of 100 μm by sputtering, thereby producing four COP film substrates with a copper layer. After laminating each transfer film on the copper layer-coated COP film substrate obtained above under lamination conditions of pressure roll temperature: 100°C, linear pressure: 0.6 MPa, and linear speed: 4.0 m/min, Let it stand for a while.
Thereafter, the photosensitive composition layer of the transfer film was exposed to light through a mask (Duty ratio = 1:1) for forming a line-and-space pattern with a line width of 100 μm without peeling off the temporary support. An ultra-high pressure mercury lamp was used as the light source for exposure. The exposure amount was adjusted within a range such that the line width of the resin pattern formed by development was 100 μm.
The temporary support was peeled off from the surface of the photosensitive composition layer after exposure, and the photosensitive composition layer was developed. Specifically, shower development was performed for 45 seconds using a 1.0 mass % sodium carbonate aqueous solution at 33° C. to obtain a laminate having a resin pattern.
The line width at 20 arbitrary points on the obtained resin pattern was measured. The standard deviation σ and the average value α were calculated for the measured line width values at 20 points. Further, the dispersion β was calculated using the following formula, and the patterning properties were evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, A has the best patterning property, and E has the worst patterning property. It is preferably any one of A, B and C, more preferably A or B, and even more preferably A.
Variance β (%) = 100 × (standard deviation σ / average value α)
(Evaluation criteria)
A: Variance β is less than 3% B: Variance β is 3% or more and less than 5% C: Variance β is 5% or more and less than 8% D: Variance β is 8% or more and less than 10% E: Variance β is , 10% or more

<Releasability>
(Peelability between photosensitive composition layer and temporary support)
After peeling off the protective film of each of the transfer films obtained above, the photosensitive composition layer was laminated onto a copper plate. The lamination conditions were a lamination roll temperature of 100° C., a linear pressure of 3 N/cm, and a conveyance speed of 4 m/min. Thereafter, the temporary support was peeled vertically upward at a speed of 0.01 m/min, and the photosensitive composition layer remaining on the copper plate was visually confirmed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, A has the best releasability, and E has the worst releasability. It is preferably any one of A, B and C, more preferably A or B, and even more preferably A.
Remaining area of the photosensitive composition layer on the copper plate (%) = 100 × (Area of the photosensitive composition layer remaining on the copper plate after peeling/Area of the photosensitive composition layer on the copper plate before peeling)
(Evaluation criteria)
A: The remaining area of the photosensitive composition layer on the copper plate is 100%
B: The remaining area of the photosensitive composition layer on the copper plate is 99% or more and less than 100%. C: The remaining area of the photosensitive composition layer on the copper plate is 95% or more and less than 99%. D: The remaining area of the photosensitive composition layer on the copper plate is 95% or more and less than 99%. The remaining area on the copper plate is 90% or more and less than 95%. E: The remaining area of the photosensitive composition layer on the copper plate is less than 90%.

(Peelability between photosensitive composition layer and protective film)
After peeling the protective film vertically upward at a speed of 0.01 m/min, the photosensitive composition layer remaining on the temporary support was visually confirmed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, A has the best releasability, and E has the worst releasability. It is preferably any one of A, B and C, more preferably A or B, and even more preferably A.
Remaining area (%) of the photosensitive composition layer on the temporary support = 100 x (area of the photosensitive composition layer remaining on the temporary support after peeling/photosensitive composition on the temporary support before peeling) layer area)
(Evaluation criteria)
A: The remaining area of the photosensitive composition layer on the temporary support is 100%
B: The remaining area of the photosensitive composition layer on the temporary support is 99% or more and less than 100% C: The remaining area of the photosensitive composition layer on the temporary support is 95% or more and less than 99% D: Photosensitive The remaining area of the composition layer on the temporary support is 90% or more and less than 95%. E: The remaining area of the photosensitive composition layer on the temporary support is less than 90%.

<Evaluation of Kurtosis Rku>
Using New View 6000 manufactured by Zygo, the kurtosis Rku of the surface of the temporary support in contact with the first layer of the photosensitive composition layer was evaluated in accordance with ISO 4287:1997.

In the table, each description indicates the following.
The column "Photosensitive composition layer/temporary support" shows the releasability between the photosensitive composition layer and the temporary support.
The column "Photosensitive composition layer/protective film" shows the releasability between the photosensitive composition layer and the protective film.

From the results in the table, it was confirmed that the desired effects were obtained when the transfer film of the present invention was used.
From a comparison of Examples 1 and 8 to 10 and Examples 7 and 11, it was confirmed that the effects of the present invention are more excellent when the average particle diameter of the first organic particles is 350 to 800 nm.
Further, from a similar comparison, it was confirmed that the effect of the present invention is more excellent when the kurtosis Rku of the surface of the first layer is 2.5 to 10.
From the comparison of Example 1 etc. and Examples 12 and 13, it was found that the effect of the present invention is more excellent when the average particle diameter of the first inorganic particles and the average particle diameter of the second inorganic particles are 10 to 50 nm. confirmed.
From a comparison of Example 1 and the like with Examples 14 and 21, it was confirmed that the effects of the present invention are more excellent when the first inorganic particles and the second inorganic particles contain aluminum oxide.
From the comparison between Example 1 and Example 21, the effects of the present invention are better when the components contained in the first layer and the second layer and the thickness of the first layer and the second layer are the same. This was confirmed.
From the comparison of Example 1 etc. and Examples 7, 11 to 14 and 21, the kurtosis Rku of the surface of the first layer is 3.0 to 5.0, and the first inorganic particles and the second inorganic particles are oxidized. It was confirmed that the effect of the present invention is more excellent when aluminum is included.

1, 11 Temporary support 2, 12 Composition layer 3, 17 Photosensitive composition layer 5 Refractive index adjustment layer 7, 19 Protective film 10, 20 Transfer film 13 Thermoplastic resin layer 15 Intermediate layer

Claims (18)

A transfer film comprising a temporary support, a photosensitive composition layer disposed on the temporary support, and a protective film in this order,
The temporary support includes a temporary support body, a first layer disposed on one surface of the temporary support body, and a second layer disposed on the other surface of the temporary support body. have,
Of the first layer and the second layer, the first layer is arranged on the photosensitive composition layer side,
The first layer includes first organic particles with an average particle diameter of 100 to 1000 nm and first inorganic particles with an average particle diameter of 70 nm or less, and the kurtosis Rku of the surface of the first layer in contact with the photosensitive composition layer is 2.0 to 100,
A transfer film in which the second layer contains second inorganic particles having an average particle diameter of 70 nm or less, or does not contain inorganic particles. The transfer film according to claim 1, wherein the first organic particles include polystyrene resin particles. The transfer film according to claim 1 or 2, wherein the first organic particles have an average particle diameter of 350 to 800 nm. The transfer film according to any one of claims 1 to 3, wherein at least one of the first inorganic particles and the second inorganic particles contains at least one selected from the group consisting of silicon atoms and aluminum atoms. The transfer film according to any one of claims 1 to 4, wherein at least one of the first inorganic particles and the second inorganic particles contains aluminum oxide. The transfer film according to any one of claims 1 to 5, wherein the average particle diameter of the first inorganic particles and the average particle diameter of the second inorganic particles are 10 to 50 nm. The thickness of the temporary support body is 6.0 to 30.0 μm,
The transfer film according to any one of claims 1 to 6, wherein the first layer and the second layer have a thickness of 0.8 to 3.0 μm. The average particle diameter of the first organic particles is 350 to 800 nm,
the first inorganic particles contain aluminum oxide,
The transfer film according to any one of claims 1 to 7, wherein the first inorganic particles have an average particle diameter of 10 to 50 nm. The second layer includes second organic particles with an average particle diameter of 350 to 800 nm,
the second inorganic particles contain aluminum oxide,
The transfer film according to any one of claims 1 to 8, wherein the second inorganic particles have an average particle diameter of 10 to 50 nm. The transfer film according to any one of claims 1 to 9, wherein the kurtosis Rku of the surface of the first layer is 2.5 to 10. The kurtosis Rku of the surface of the first layer is 3.0 to 5.0,
The transfer film according to any one of claims 1 to 10, wherein the first inorganic particles and the second inorganic particles contain aluminum oxide. The transfer film according to any one of claims 1 to 11, wherein the photosensitive composition layer contains a binder polymer, a polymerizable compound, and a polymerization initiator. The transfer film according to any one of claims 1 to 12, further comprising a refractive index adjusting layer between the photosensitive composition layer and the protective film. The transfer film according to any one of claims 1 to 13, wherein the photosensitive composition layer is used for forming an electrode protective film for a touch panel. The transfer film according to claim 1 or 2, wherein the temporary support is in direct contact with the photosensitive composition layer. The transfer film according to claim 1 or 2, wherein a mass ratio of the content of the first inorganic particles to the content of the first organic particles is 1.0 or more and 10.0 or less. The protective film is peeled off from the transfer film according to any one of claims 1 to 16, and the surface opposite to the temporary support is bonded to a substrate having a conductive layer, and the conductive layer and the photosensitive layer are bonded together. a bonding step of obtaining a photosensitive composition layer-coated substrate having a photosensitive composition layer and the temporary support in this order;
an exposure step of exposing the photosensitive composition layer to pattern light;
a developing step of developing the exposed photosensitive composition layer to form a pattern,
Furthermore, between the bonding step and the exposure step, or between the exposure step and the development step, the method further includes a peeling step of peeling off the temporary support from the photosensitive composition layer-coated substrate. , a method for manufacturing a laminate. The protective film is peeled off from the transfer film according to any one of claims 1 to 16, and the surface opposite to the temporary support is bonded to a substrate having a conductive layer, and the conductive layer and the photosensitive layer are bonded together. a bonding step of obtaining a photosensitive composition layer-coated substrate having a photosensitive composition layer and the temporary support in this order;
an exposure step of exposing the photosensitive composition layer to pattern light;
a developing step of developing the exposed photosensitive composition layer to form a pattern;
an etching step of etching the conductive layer in a region where the pattern is not arranged;
Furthermore, between the bonding step and the exposure step, or between the exposure step and the development step, the method further includes a peeling step of peeling off the temporary support from the photosensitive composition layer-coated substrate. , a method of manufacturing circuit wiring .