WO2021172455A1

WO2021172455A1 - Transfer film and method for producing layered body

Info

Publication number: WO2021172455A1
Application number: PCT/JP2021/007172
Authority: WO
Inventors: 大介平木; 佐藤　守正
Original assignee: 富士フイルム株式会社
Priority date: 2020-02-27
Filing date: 2021-02-25
Publication date: 2021-09-02
Also published as: JPWO2021172455A1; CN115136073A

Abstract

The present invention provides: a transfer film that has excellent rollability of a temporary support body and that demonstrates excellent resolution when a photosensitive composition layer is subjected to pattern exposure from the temporary support body side; and a method for producing a layered body using the transfer film. This transfer film comprises a temporary support body and a photosensitive composition layer disposed on the temporary support body. The temporary support body haze is less than 30% and the skewness Rsk of the surface on the photosensitive composition layer side of the temporary support body exceeds 0.40.

Description

Method for manufacturing transfer film and laminate

The present invention relates to a method for producing a transfer film and a laminate.

Since the number of steps for obtaining a predetermined pattern is small, a method of developing a photosensitive composition layer provided on an arbitrary substrate using a transfer film after exposure through a mask is widely used. There is.

For example, Patent Document 1 discloses a transfer film (photosensitive film) having a cushion layer between a support layer and a photosensitive layer (photosensitive composition layer).

Japanese Patent No. 4479450

On the other hand, when the present inventors examined the characteristics of the transfer film described in Patent Document 1, the photosensitive composition layer in the transfer film was bonded onto the substrate by the roll-to-roll method, and then the support layer and the cushion were used. It was found that when the temporary support composed of layers is peeled off and the temporary support is wound and collected, a problem occurs in winding. Specifically, when the temporary support was wound, wrinkles or square winding deformation occurred, and the temporary support could not be wound stably. If such a temporary support cannot be wound stably, the substrate and the transfer film cannot be continuously conveyed in the roll-to-roll method. Hereinafter, the fact that the temporary support peeled from the transfer film can be wound well is said to be excellent in the winding property of the temporary support.
The above-mentioned "square winding deformation" means that the winding surface does not have a beautiful curvature with a circular cross section, and angular deformation parts can be seen in some places.

Further, when forming a pattern using a transfer film, it is often the case that the transfer film is attached onto the transfer target and the photosensitive composition layer is exposed to the pattern from the temporary support side. Even in such an embodiment, it is required to have excellent resolution of the formed pattern.

In view of the above circumstances, it is an object of the present invention to provide a transfer film having excellent take-up property of a temporary support and excellent resolution when a photosensitive composition layer is pattern-exposed from the temporary support side. And.
Another object of the present invention is to provide a method for producing a laminate using the transfer film.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by the following configuration.

(1) It has a temporary support and a photosensitive composition layer arranged on the temporary support.
Temporary support haze is less than 30%
A transfer film having a skewness Rsk of more than 0.40 on the surface of the temporary support on the photosensitive composition layer side.
(2) The transfer film according to (1), wherein the surface roughness Ra of the surface of the temporary support on the photosensitive composition layer side is less than 0.50 μm.
(3) The transfer film according to (1) or (2), wherein the root mean square height RMS of the surface of the temporary support on the photosensitive composition layer side is less than 0.70 μm.
(4) The temporary support has a support and a resin layer arranged on the support.
The resin layer is arranged on the photosensitive composition layer side,
The transfer film according to any one of (1) to (3), wherein the storage elastic modulus of the resin layer at 90 ° C. is 20 MPa or less.
(5) The transfer film according to (4), wherein H / G is more than 0.2 μm / MPa when the storage elastic modulus of the resin layer at 90 ° C. is G and the thickness of the resin layer is H.
(6) The transfer film according to (4) or (5), wherein the thickness of the resin layer is 60 μm or less.
(7) The transfer film according to any one of (4) to (6), wherein the resin layer contains a resin having a repeating unit derived from ethylene.
(8) The transfer film according to any one of (1) to (7), wherein the haze of the temporary support is 2% or more.
(9) The transfer film according to any one of (1) to (8), wherein the surface of the temporary support on the photosensitive composition layer side is embossed.
(10) The photosensitive composition layer of the transfer film according to any one of (1) to (9) is brought into contact with a substrate having a conductive layer and bonded to the temporary support, the photosensitive composition layer, and A bonding step of obtaining a substrate with a photosensitive composition layer having a substrate having a conductive layer in this order, and
An exposure process in which the photosensitive composition layer is pattern-exposed from the temporary support side,
A peeling step of peeling the temporary support from the substrate with the photosensitive composition layer,
A method for producing a laminate, comprising a developing step of developing an exposed photosensitive composition layer to form a pattern.

According to the present invention, it is possible to provide a transfer film having excellent take-up property of a temporary support and excellent resolution when a photosensitive composition layer is pattern-exposed from the temporary support side.
Further, according to the present invention, it is possible to provide a method for producing a laminate using the transfer film.

Hereinafter, the present invention will be described in detail.
The numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

In addition, the term "process" in the present specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term "process" will be used as long as the intended purpose of the process is achieved. included.

In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.
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 the present specification, unless otherwise specified, the content ratio of each structural unit of the polymer is a molar ratio.
Further, as the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure, unless otherwise specified, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) were used. It is a molecular weight converted by using a gel permeation chromatography (GPC) analyzer, THF (tetrahydrofuran), and a differential refractometer, and polystyrene as a standard substance.
In the present disclosure, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
Further, in the present specification, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm unless otherwise specified.

In the present specification, "(meth) acrylic" is a concept that includes both acrylic and methacryl, and "(meth) acryloxy group" is a concept that includes both an acryloxy group and a metaacryloxy group.

The feature of the transfer film of the present invention is that the haze of the temporary support and the skewness Rsk of the surface of the temporary support on the photosensitive composition layer side are adjusted to predetermined ranges.
First, the present inventors examined the problems of the prior art, and found that the resolution was improved by adjusting the haze of the temporary support so as to be within a predetermined range, and the photosensitive composition layer of the temporary support was obtained. It has been found that the take-up property of the temporary support is improved by adjusting the skewness Rsk of the surface on the side so as to be within a predetermined range. The haze and skewness Rsk can be controlled by adjusting the uneven structure on the surface of the temporary support, the thickness of the temporary support (for example, the thickness of the resin layer in the temporary support), and the like. In particular, the uneven structure on the surface of the temporary support can be controlled by, for example, embossing, as will be described later.

The transfer film of the present invention has a temporary support and a photosensitive composition layer arranged on the temporary support.
Hereinafter, each member constituting the transfer film will be described in detail.

<Temporary support>
The transfer film has a temporary support. The temporary support is a member that supports the photosensitive composition layer described later, and is finally removed by a peeling treatment.
The haze of the temporary support is less than 30%. Above all, at least one of the effect of being more excellent in the take-up property of the temporary support and the point of being more excellent in the resolution when the photosensitive composition layer is pattern-exposed from the temporary support side can be obtained (hereinafter, It is also simply referred to as "a point where the effect of the present invention is more excellent"), and 20% or less is preferable, and 15% or less is more preferable. The lower limit is not particularly limited, but 2% or more can be mentioned.
As a method for measuring the haze of the temporary support, a sample of the temporary support cut into 5 cm squares is prepared, and a haze meter (model number: NDH5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) is used to sample the temporary support. A method of measuring haze from the surface side showing a predetermined skewness Rsk described later can be mentioned.

The surface of the temporary support on the photosensitive composition layer side has an uneven structure.
The skewness Rsk of the surface of the temporary support on the photosensitive composition layer side is more than 0.40. Among them, 0.45 or more is preferable, and 0.50 or more is more preferable, in that the effect of the present invention is more excellent. The upper limit is not particularly limited, but is preferably 1.50 or less, and more preferably 1.20 or less.
The surface roughness Ra of the surface of the temporary support on the photosensitive composition layer side is not particularly limited, but it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and 0. It is more preferably 25 μm or less. The lower limit is not particularly limited, but is preferably 0.05 μm or more, and more preferably 0.10 μm or more.
The root mean square height RMS of the surface of the temporary support on the photosensitive composition layer side is not particularly limited, but it is preferably less than 0.70 μm, more preferably 0.50 μm or less in that the effect of the present invention is more excellent. More preferably 0.30 μm or less. The lower limit is not particularly limited, but is preferably 0.05 μm or more, and more preferably 0.10 μm or more.
The skewness Rsk, surface surface Ra, and root mean square height RMS are analyzed after observing the surface of the temporary support with a laser microscope (Keyence Co., Ltd., VK-X100) (objective 50 times). Calculated based on JIS B0601 (2001) using VK-H1XA) manufactured by KEYENCE CORPORATION.

The temporary support is preferably a film, more preferably a resin film. As the temporary support, a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heating can be used.
Examples of such a film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.
Among these, a biaxially stretched polyethylene terephthalate film is preferable as the temporary support.
Further, it is preferable that the film used as the temporary support has no deformation such as wrinkles or scratches.

The temporary support may have a single-layer structure or a multi-layer structure.
Above all, in that the effect of the present invention is more excellent, the temporary support has a support and a resin layer arranged on the support, and the resin layer is arranged on the photosensitive composition layer side. Is preferable. That is, the temporary support preferably has a two-layer structure of a support and a resin layer. When the temporary support has a two-layer structure consisting of a support and a resin layer, the skewness Rsk on the surface of the resin layer opposite to the support side may be more than 0.40. The surface roughness Ra of the surface of the resin layer opposite to the support side and the root mean square height RMS are preferably in the above ranges.

The support is preferably a film, more preferably a resin film. Examples of the resin film include the above-mentioned film.

The resin layer is a layer that functions as a so-called cushion layer.
As the material constituting the resin layer, a thermoplastic resin is preferable. Specifically, for example, polyethylene and polyolefins such as polypropylene; copolymers of ethylene and vinyl acetate and saponified products thereof, copolymers of ethylene and acrylic acid esters and saponified products thereof, and the like. Ethylene copolymer; vinyl chloride copolymer such as polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate and its saponified product; vinylidene chloride copolymer; polystyrene, and styrene and (meth) acrylic acid. A copolymer with an ester and a styrene copolymer such as a saponified product thereof; a polyvinyl toluene and a copolymer of a vinyl toluene and a (meth) acrylic acid ester and a vinyl toluene copolymer such as a saponified product thereof; (Meta) acrylic acid ester and (meth) acrylic acid ester copolymer such as a copolymer of butyl (meth) acrylate and vinyl acetate; vinyl acetate copolymer nylon, copolymer nylon, N-alkoxymethylation Nylons and polyamide resins such as N-dimethylaminoated nylon; can be mentioned.
Among them, a resin having a repeating unit derived from ethylene is preferable, and polyethylene or an ethylene copolymer is preferable because the effect of the present invention is more excellent.

The storage elastic modulus of the resin layer at 90 ° C. is not particularly limited, but 20 MPa or less is preferable, 15 MPa or less is more preferable, and 10 MPa or less is further preferable, in that the effect of the present invention is more excellent. The lower limit is not particularly limited, but 0.01 MPa or more is preferable.
The storage elastic modulus of the resin layer at 90 ° C. is determined by the following method.
First, a material constituting the resin layer (for example, pellets for forming the resin layer) is dissolved in toluene to prepare a solution having a solid content concentration of 30% by mass, and lightly peeled polyethylene terephthalate (25 WZ, manufactured by Toray Co., Ltd.). ) To have a dry thickness of 50 μm, and the dried coating film is peeled off to obtain a measurement film (length: 35 mm, width: 12 mm) having a predetermined size. Using the obtained measuring film, dynamic viscoelasticity measurement under the following conditions is performed to determine the storage elastic modulus at 90 ° C.
Device model number: TA Instrument RSA3
Frequency: 1Hz
Temperature range: The temperature rises from room temperature to 120 ° C (heating rate 5 ° C / min).

When the storage elastic modulus of the resin layer at 90 ° C. is G and the thickness of the resin layer is H, the value of H / G is not particularly limited, but the effect of the present invention is more excellent, and it exceeds 0.2 μm / MPa. Is preferable, and 0.5 μm / MPa or more is more preferable. The upper limit is not particularly limited, but it is often 15 μm / MPa or less.

The thickness of the resin layer is not particularly limited, but 60 μm or less is preferable because the effect of the present invention is more excellent. The lower limit is not particularly limited, but is preferably 1 μm or more.
The thickness of the resin layer can be determined by observing a cross section including the direction perpendicular to the main surface of the layer using a scanning electron microscope (SEM) and determining the thickness of the layer based on the obtained observation image. It is a value obtained by measuring 10 points or more and calculating the average value thereof.

The temporary support preferably has high transparency, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more.
From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign substances and defects contained in the temporary support is small. Diameter 1μm or more particles, the number of foreign matter and defects, preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, more preferably 3/10 mm ² or less, particularly preferably 0/10 mm ² ..

The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, and more preferably 10 to 150 μm from the viewpoint of ease of handling and versatility.

The above-mentioned uneven structure of the temporary support can be formed by a known method. For example, the above-mentioned uneven structure can be formed by embossing the surface of the support.

<Photosensitive composition layer>
The transfer film has a photosensitive composition layer. A pattern can be formed on the transferred body by transferring the photosensitive composition layer onto the transferred body and then exposing and developing the photosensitive composition layer.
As the photosensitive composition layer, a known photosensitive composition layer can be used, and it may be a positive type or a negative type.
The positive photosensitive composition layer is a photosensitive composition layer whose exposed portion becomes highly soluble in a developing solution by exposure, and the negative photosensitive composition layer is a developing solution whose exposed portion is exposed to a developing solution. It is a photosensitive composition layer having reduced solubility in.
Above all, it is preferable to use a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.
Hereinafter, the components contained in the negative photosensitive composition layer will be described in detail.

[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, and a radically polymerizable group is preferable.

The polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as “ethylenically unsaturated compound”).
As the ethylenically unsaturated group, a (meth) acryloxy group is preferable.

The ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound. Here, the "bifunctional or higher functional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.
Examples of the ethylenically unsaturated compound include a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound in terms of film strength after curing. It preferably contains a compound (preferably a trifunctional or higher functional (meth) acrylate compound).

Examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10. -Decandiol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate can be mentioned.

Commercially available products of bifunctional ethylenically unsaturated compounds include, for example, tricyclodecanedimethanol diacrylate [trade name: NK ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], tricyclodecanedimethanol dimethacrylate [ Product name: NK ester DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], 1,9-Nonandiol diacrylate [Product name: NK ester A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], 1,10-decane Didiol diacrylate [trade name: NK ester A-DOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.] and 1,6-hexanediol diacrylate [trade name: NK ester A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.] Made by Co., Ltd.].

Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples thereof include acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and glycerin tri (meth) acrylate.

Here, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. be. Further, "(tri / tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited in the upper limit of the number of functional groups, but may be, for example, 20 functional or less, or 15 functional or less.

Examples of commercially available products of trifunctional or higher functional ethylenically unsaturated compounds include dipentaerythritol hexaacrylate [trade name: KAYARAD DPHA, Shin Nakamura Chemical Industry Co., Ltd.].

Ethylene unsaturated compounds include 1,9-nonanediol di (meth) acrylate or 1,10-decanediol di (meth) acrylate and dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate. It is more preferable to include it.

Examples of the ethylenically unsaturated compound include a caprolactone-modified compound of a (meth) acrylate compound [KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc. ], (Meta) acrylate compound alkylene oxide-modified compound [KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Daicel Ornex Co., Ltd. EBECRYL (registered trademark) 135, etc.] and ethoxylated glycerin triacrylate [NK ester A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.] can also be mentioned.

Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds. As the urethane (meth) acrylate compound, a trifunctional or higher functional urethane (meth) acrylate compound is preferable. Examples of the trifunctional or higher functional urethane (meth) acrylate compound include 8UX-015A [manufactured by Taisei Fine Chemical Co., Ltd.], NK ester UA-32P [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], and NK ester UA-1100H [new]. Nakamura Chemical Industry Co., Ltd.] can be mentioned.

The ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group. Among the above, the carboxy group is preferable as the acid group.

As the ethylenically unsaturated compound having an acid group, a 3- to 4-functional ethylenically unsaturated compound having an acid group [pentaerythritol tri and a compound in which a carboxy group is introduced into a tetraacrylate (PETA) skeleton (acid value: 80 to 80 to). 120 mgKOH / g)] and a 5- to 6-functional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA)) in which a carboxy group is introduced into the skeleton [acid value: 25 to 70 mgKOH / g]. ]). The trifunctional or higher functional ethylenically unsaturated compound having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

As the ethylenically unsaturated compound having an acid group, at least one compound selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof is preferable. When the ethylenically unsaturated compound having an acid group is at least one compound selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof, the developability and developability and The film strength is further increased.

Examples of the bifunctional or higher functional ethylenically unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 [manufactured by Toagosei Co., Ltd.], Aronix (registered trademark) M-520 [manufactured by Toagosei Co., Ltd.], and the like. And, Aronix (registered trademark) M-510 [manufactured by Toagosei Co., Ltd.] can be mentioned.

As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 can be preferably used, and is described in this publication. The contents are incorporated herein by reference.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

Among the ethylenically unsaturated compounds, the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less with respect to the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer. , 25% by mass or less, more preferably 20% by mass or less.

The photosensitive composition layer may contain one kind of ethylenically unsaturated compound alone, or may contain two or more kinds of ethylenically unsaturated compounds.

The content of the ethylenically unsaturated compound is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, and 20 to 20 to 70% by mass with respect to the total mass of the photosensitive composition layer. 50% by mass is particularly preferable.

When the photosensitive composition layer contains a bifunctional or higher functional ethylenically unsaturated compound, it may further contain a monofunctional ethylenically unsaturated compound.

When the photosensitive composition layer contains a bifunctional or higher functional ethylenically unsaturated compound, the bifunctional or higher functional ethylenically unsaturated compound may be the main component of the ethylenically unsaturated compound contained in the photosensitive composition layer. preferable.

When the photosensitive composition layer contains a bifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional or higher functional ethylenically unsaturated compound is the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer. With respect to the amount, 60 to 100% by mass is preferable, 80 to 100% by mass is more preferable, and 90 to 100% by mass is further preferable.

When the photosensitive composition layer contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group or a carboxylic acid anhydride thereof), the ethylenically unsaturated compound having an acid group. The content of the saturated compound is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, still more preferably 1 to 10% by mass, based on the total mass of the photosensitive composition layer.

[Polymerization initiator]
The photosensitive composition layer may contain a polymerization initiator.
As the polymerization initiator, a photopolymerization initiator is preferable.
Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as "oxym-based photopolymerization initiator") and a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, "" α-Aminoalkylphenone-based photopolymerization initiator "), photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as" α-hydroxyalkylphenone-based polymerization initiator "), acylphosphine. A photopolymerization initiator having an oxide structure (hereinafter, also referred to as "acylphosphine oxide-based photopolymerization initiator") and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, "N-phenylglycine-based light"). Also referred to as "polymerization initiator").

The photopolymerization initiator is selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It is preferable to contain at least one of these, and includes at least one 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.

Further, as the photopolymerization initiator, for example, it is described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064]-[0081] of JP-A-2015-014783. A polymerization initiator may be used.

Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio)] phenyl-1,2-octanedione-2- (O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01. , BASF], 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE -02, manufactured by BASF], 8- [5- (2,4,6-trimethylphenyl) -11- (2-ethylhexyl) -11H-benzo [a] carbazoyl] [2- (2,2,3) 3-Tetrafluoropropoxy) phenyl] methanone- (O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-03, manufactured by BASF], 1- [4- [4- (2-benzofuranylcarbonyl)) Phenyl] thio] phenyl-4-methyl-1-pentanone-1- (O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-04, manufactured by BASF], 2- (dimethylamino) -2- [ (4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1- (4-) Methylthiophenyl) -2-morpholinopropan-1-one [trade name: IRGACURE (registered trademark) 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-) Propionyl) benzyl] phenyl} -2-methylpropan-1-one [trade name: IRGACURE (registered trademark) 127, manufactured by BASF], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanon-1 [trade name: IRGACURE (registered trademark) 369, manufactured by BASF], 2-hydroxy-2-methyl-1-phenyl-propane-1-one [trade name: IRGACURE (registered trademark) 1173, manufactured by BASF) ], 1-Hydroxycyclohexylphenyl ketone [trade name: IRGACURE (registered trademark) 184, manufactured by BASF], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: IRGACURE 651, manufactured by BASF] ], And an oxime ester-based compound [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.].

The photosensitive composition layer may contain one kind of photopolymerization initiator alone, or may contain two or more kinds of photopolymerization initiators.

The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit of the content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive composition layer.

[Alkali-soluble resin]
The photosensitive composition layer may contain an alkali-soluble resin.
When the photosensitive composition layer contains an alkali-soluble resin, the solubility of the photosensitive composition layer (non-exposed portion) in the developing solution is improved.
As the alkali-soluble resin, an alkali-soluble acrylic resin is preferable.
Hereinafter, the alkali-soluble acrylic resin will be described in detail.

In the present disclosure, "alkali-soluble" means that the dissolution rate required by the following method is 0.01 μm / sec or more.
A propylene glycol monomethyl ether acetate solution having a concentration of the target compound (for example, resin) of 25% by mass is applied onto a glass substrate, and then heated in an oven at 100 ° C. for 3 minutes to obtain a coating film of the target compound (for example, resin). A thickness of 2.0 μm) is formed. The dissolution rate (μm / sec) of the coating film is determined by immersing the coating film in a 1% by mass aqueous solution of sodium carbonate (liquid temperature 30 ° C.).
When the target compound is not soluble in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent having a boiling point of less than 200 ° C. (for example, tetrahydrofuran, toluene, or ethanol) other than propylene glycol monomethyl ether acetate.

The alkali-soluble acrylic resin is not limited as long as it is the alkali-soluble acrylic resin described above. Here, the "acrylic resin" means a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester.

The total ratio of the constituent units derived from (meth) acrylic acid and the constituent units derived from (meth) acrylic acid ester in the alkali-soluble acrylic resin is preferably 30 mol% or more, preferably 50 mol% or more, based on the total amount of the alkali-soluble acrylic resin. More preferably mol% or more.

In the present disclosure, when the content of "constituent unit" is specified by mole fraction (molar ratio), the above "constituent unit" shall be synonymous with "monomer unit" unless otherwise specified. Further, in the present disclosure, when the resin or polymer has two or more specific structural units, the content of the specific structural units is the total of the two or more specific structural units unless otherwise specified. It shall represent the content.

The alkali-soluble acrylic resin preferably has a carboxy group from the viewpoint of developability. Examples of the method for introducing a carboxy group into an alkali-soluble acrylic resin include a method for synthesizing an alkali-soluble acrylic resin using a monomer having a carboxy group. By the above method, the monomer having a carboxy group is introduced into the alkali-soluble acrylic resin as a structural unit having a carboxy group. Examples of the monomer having a carboxy group include acrylic acid and methacrylic acid.

The alkali-soluble acrylic resin may have one carboxy group or two or more carboxy groups. Further, the constituent unit having a carboxy group in the alkali-soluble acrylic resin may be one kind alone or two or more kinds.

The content of the structural unit having a carboxy group is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 30 mol%, based on the total amount of the alkali-soluble acrylic resin.

The alkali-soluble acrylic resin preferably has a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing. The structural unit having an aromatic ring is preferably a structural unit derived from a styrene compound.
Examples of the monomer forming the structural unit having an aromatic ring include a monomer forming a structural unit derived from a styrene compound and benzyl (meth) acrylate.

Examples of the monomer forming the structural unit derived from the styrene compound include styrene, p-methylstyrene, α-methylstyrene, α, p-dimethylstyrene, p-ethylstyrene, pt-butylstyrene, and t-butoxy. Examples thereof include styrene and 1,1-diphenylethylene, preferably styrene or α-methylstyrene, and more preferably styrene.

The constituent unit having an aromatic ring in the alkali-soluble acrylic resin may be one kind alone or two or more kinds.
When the alkali-soluble acrylic resin has a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5 to 90 mol%, preferably 10 to 80 mol%, based on the total amount of the alkali-soluble acrylic resin. More preferably, 15 to 70 mol% is further preferable.

The alkali-soluble acrylic resin preferably contains a structural unit having an aliphatic cyclic skeleton from the viewpoint of tackiness and strength after curing.

The aliphatic ring in the aliphatic cyclic skeleton may be a monocyclic ring or a polycyclic ring, and examples thereof include a dicyclopentane ring, a cyclohexane ring, an isoborone ring, and a tricyclodecane ring. Among the above, the tricyclodecane ring is preferable as the aliphatic ring in the aliphatic cyclic skeleton.

Examples of the monomer forming a structural unit having an aliphatic cyclic skeleton include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

The constituent unit having an aliphatic cyclic skeleton in the alkali-soluble acrylic resin may be one kind alone or two or more kinds.

When the alkali-soluble acrylic resin has a structural unit having an aliphatic cyclic skeleton, the content of the structural unit having an aliphatic cyclic skeleton is preferably 5 to 90 mol% with respect to the total amount of the alkali-soluble acrylic resin. 10 to 80 mol% is more preferable, and 10 to 60 mol% is further preferable.

The alkali-soluble acrylic resin preferably has a reactive group from the viewpoint of tackiness and strength after curing.

As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the alkali-soluble acrylic resin has an ethylenically unsaturated group, the alkali-soluble acrylic resin preferably has a structural unit having an ethylenically unsaturated group in the side chain.

In the present disclosure, the "main chain" represents a relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain" represents an atomic group branched from the main chain. ..

As the ethylenically unsaturated group, a (meth) acrylic group or a (meth) acryloyl group is preferable, and a (meth) acryloyl group is more preferable.

The constituent unit having an ethylenically unsaturated group in the alkali-soluble acrylic resin may be one kind alone or two or more kinds.

When the alkali-soluble acrylic resin has a structural unit having an ethylenically unsaturated group, the content of the structural unit having an ethylenically unsaturated group is preferably 5 to 70 mol% with respect to the total amount of the alkali-soluble acrylic resin. 10 to 50 mol% is more preferable, and 15 to 40 mol% is further preferable.

As means for introducing a reactive group into an alkali-soluble acrylic resin, a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid or the like, an epoxy compound, a blocked isocyanate compound, etc. Examples thereof include a method of reacting an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride and the like.

A preferred example of a means for introducing a reactive group into an alkali-soluble acrylic resin is that an alkali-soluble acrylic resin having a carboxy group is synthesized by a polymerization reaction and then glycidyl is added to a part of the carboxy groups of the alkali-soluble acrylic resin by a polymer reaction. Examples thereof include means for introducing a (meth) acryloxy group into an alkali-soluble acrylic resin by reacting the (meth) acrylate. By the above means, an alkali-soluble acrylic resin having a (meth) acryloxy group in the side chain can be obtained.

The above polymerization reaction is preferably carried out under a temperature condition of 70 to 100 ° C., and more preferably carried out under a temperature condition of 80 to 90 ° C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferable. Further, the polymer reaction is preferably carried out under temperature conditions of 80 to 110 ° C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

The weight average molecular weight (Mw) of the alkali-soluble acrylic resin is preferably 10,000 or more, more preferably 10,000 to 100,000, and even more preferably 15,000 to 50,000.

From the viewpoint of developability, the acid value of the alkali-soluble acrylic resin is preferably 50 mgKOH / g or more, more preferably 60 mgKOH / g or more, further preferably 70 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more. In the present disclosure, the acid value of the alkali-soluble acrylic resin is a value measured according to the method described in JIS K0070: 1992.
The upper limit of the acid value of the alkali-soluble acrylic resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, from the viewpoint of suppressing dissolution in the developing solution.

The content of the residual monomer of each structural unit of the alkali-soluble resin in the photosensitive composition layer is preferably 1000 mass ppm or less, preferably 500 mass ppm or less, based on the total mass of the alkali-soluble resin from the viewpoint of patterning property and reliability. The following is more preferable, and 100 mass ppm or less is further preferable. The lower limit is not particularly limited, and is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

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

The photosensitive composition layer may contain one kind of alkali-soluble resin alone, or may contain two or more kinds of alkali-soluble resins.

The content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 25 to 70% by mass, based on the total mass of the photosensitive composition layer from the viewpoint of developability. preferable.

[Polymer containing a structural unit having a carboxylic acid anhydride structure]
The photosensitive composition layer may further contain a polymer containing a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer B”) as a binder. When the photosensitive composition layer contains the polymer B, the developability and the strength after curing can be improved.

The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
As the ring having a cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.

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

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

Examples of the substituent represented by ^{RA1a include an alkyl group.}

As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.

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, a plurality of ^RA1a may be the same or different. Further, the plurality of ^RA1a 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.

As the structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable. A structural unit derived from an acid anhydride is more preferable, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.

The structural unit having the carboxylic acid anhydride structure in the polymer B may be one kind alone or two or more kinds.

The content of the structural unit having a carboxylic acid anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 35 mol%, based on the total amount of the polymer B.
The photosensitive composition layer may contain one type of polymer B alone, or may contain two or more types of polymer B.

The content of the residual monomer of each structural unit of the polymer B in the photosensitive composition layer is preferably 1000 mass ppm or less, preferably 500 mass ppm or less, based on the total mass of the polymer B from the viewpoint of patterning property and reliability. The following is more preferable, and 100 mass ppm or less is further preferable. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

When the photosensitive composition layer contains the polymer B, the content of the polymer B is 0.1 to 30 mass with respect to the total mass of the photosensitive composition layer in terms of developability and strength after curing. % Is preferable, 0.2 to 20% by mass is more preferable, 0.5 to 20% by mass is further preferable, and 1 to 20% by mass is particularly preferable.

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

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, and a pyrimidine compound.
Among the above, the heterocyclic compound is at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole compound, and a benzoxazole compound. Species compounds are preferred, and at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazol compounds, thiazole compounds, benzothiazole compounds, benzoimidazole compounds, and benzoxazole compounds is more preferred. ..

A preferable specific example of the heterocyclic compound is shown below. Examples of the triazole compound and the 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 the triazine compound include the following compounds.

Examples of the rhodanine compound include the following compounds.

Examples of the thiazole compound include the following compounds.

Examples of the benzothiazole compound include the following compounds.

Examples of the benzimidazole compound include the following compounds.

Examples of the benzoxazole compound include the following compounds.

The photosensitive composition layer may contain one kind of heterocyclic compound alone, or may contain two or more kinds of heterocyclic compounds.

When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the total mass of the photosensitive composition layer. Is more preferable, 0.3 to 8% by mass is further preferable, and 0.5 to 5% by mass is particularly preferable.

[Aliphatic thiol compound]
The photosensitive composition layer preferably contains an aliphatic thiol compound.
When the photosensitive composition layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an en-thiol reaction with a radically polymerizable compound having an ethylenically unsaturated group, thereby curing and shrinking the formed film. Is suppressed and the stress is relieved.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound) is preferable.

Among the above, as the aliphatic thiol compound, for example, a polyfunctional aliphatic thiol compound is preferable from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).

In the present disclosure, the "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, 2 to 10 functionals are preferable, 2 to 8 functionals are more preferable, and 2 to 6 functionals are further preferable from the viewpoint of adhesion of the formed pattern.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropanthris (3-mercaptobutylate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like. 1,3,5-Tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethanetris (3-mercaptobutyrate) ), Tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) Pionate), Dipentaerythritol hexakis (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis (3-mercaptobutylyloxy) butane, 1,2-ethanedithiol, 1, Examples thereof include 3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio) diethanethiol, meso-2,3-dimercaptosuccinic acid, and di (mercaptoethyl) ether.

Among the above, the polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, and 1,3,5-tris. At least one compound selected from the group consisting of (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferable.

Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and n-. Examples thereof 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. 5 to 30% by mass is more preferable, and 8 to 20% by mass is particularly preferable.

[Blocked isocyanate compound]
The photosensitive composition layer preferably contains a blocked isocyanate compound. The blocked isocyanate compound contributes to the improvement of the strength of the formed pattern.
Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxy group, it is formed, 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 the hydroxyl group and the carboxy group. The hydrophilicity of the polymer tends to decrease, and the function as a protective film tends to be strengthened. 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".

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

In the present disclosure, the "dissociation temperature of a blocked isocyanate compound" is the temperature of 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. As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimetry is not limited to the differential scanning calorimetry described above.

Examples of the blocking agent having a dissociation temperature of 100 to 160 ° C. include active methylene compounds [(dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonate, etc.)], etc. In addition, oxime compounds (compounds having a structure represented by -C (= N-OH)-in the molecule such as formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, cyclohexanone oxime) can be mentioned. Among the above, as the blocking agent having a dissociation temperature of 100 to 160 ° C., for example, an oxime compound is preferable from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred material. The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurate-forming and protecting hexamethylene diisocyanate.

Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is easier to set the dissociation temperature in a preferable range than a compound having no oxime structure, and reduces the development residue. It is preferable because it is easy.

The blocked isocyanate compound preferably has a polymerizable group, and more preferably has a radically polymerizable group, from the viewpoint of the strength of the formed pattern.

Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group, and a styryl group, and a group having 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 surface surface condition, development speed, and reactivity in the obtained pattern.

As the blocked isocyanate compound, a commercially available product can be used. Examples of commercially available blocked isocyanate compounds include, for example, Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) AOI-BP, Karenz (registered trademark) MOI-BP, etc. As mentioned above, Showa Denko Co., Ltd.] and the block type Duranate series [for example, Duranate (registered trademark) TPA-B80E, manufactured by Asahi Kasei Chemicals Co., Ltd.] can be mentioned.

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

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

[Surfactant]
The photosensitive composition layer preferably contains a surfactant.
Examples of the surfactant include the surfactants described in paragraphs [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP2009-237362A.

As the surfactant, a fluorine-based surfactant or a silicon-based surfactant is preferable. Examples of commercially available fluorine-based surfactants include Megafvck (registered trademark) F551A (manufactured by DIC Corporation).
Commercially available products of fluorine-based surfactants include, for example, Megafuck 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-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, MFS-578, MFS-579, MFS-586, MFS -587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS -21 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC -1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Corporation), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), Futergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Co., Ltd.) and the like. ..
Further, as a fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cut and the fluorine atom volatilizes. Can also be preferably used. Examples of such fluorine-based surfactants include Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega. Fuck DS-21 can be mentioned. Further, as the fluorine-based surfactant, 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.
A block polymer can also be used as the fluorine-based surfactant.
The fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). A fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound can also be preferably used.
Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Megafvck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
As the fluorine-based surfactant, from the viewpoint of improving environmental suitability, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are used. It is preferably a surfactant derived from an alternative material.
Commercially available products of silicon-based surfactants include DOWNSIL® 8032 Adaptive.
Specific examples of commercially available silicon-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, and Torre Silicone SH8400 (above, Made by Toray Dow Corning Co., Ltd.), X-22-4952, X-22-2272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642 , KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, Examples thereof include TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like.

The photosensitive composition layer may contain one type of surfactant alone, or may contain two or more types of surfactants.

When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3% by mass, preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. Is more preferable, and 0.1 to 0.8% by mass is further preferable.

[Hydrogen donating compound]
The photosensitive composition layer preferably contains a hydrogen donating compound. The hydrogen donating compound has actions such as further improving the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization inhibition of the polymerizable compound by oxygen.

Examples of the hydrogen donating compound include amines, for example, M.I. R. Sander et al., "Journal of Polymer Society", Vol. 10, p. 3173 (1972), JP-A-44-020189, JP-A-51-081022, JP-A-52-134692, JP-A-59-138205. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 60-084305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, Research Disclosure No. 33825, and the like.

Examples of the hydrogen donating compound include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline.

Examples of the hydrogen donating compound include an amino acid compound (N-phenylglycine, etc.), an organometallic compound (tributyltin acetate, etc.) described in JP-A-48-042965, and hydrogen described in JP-A-55-0344414. Donors and sulfur compounds (Trithian and the like) described in JP-A-6-308727 are also mentioned.

The photosensitive composition layer may contain one kind of hydrogen donating compound alone, or may contain two or more kinds of hydrogen donating compounds.

When the photosensitive composition layer contains a hydrogen donating compound, the content of the hydrogen donating compound is adjusted to the total mass of the photosensitive composition layer in terms of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. On the other hand, 0.01 to 10% by mass is preferable, 0.03 to 5% by mass is more preferable, and 0.05 to 3% by mass is further preferable.

[Other ingredients]
The photosensitive composition layer may contain components other than the components described above (hereinafter, also referred to as “other components”). Other components include, for example, particles (eg, metal oxide particles) and colorants. However, the photosensitive composition preferably does not contain a colorant from the viewpoint of peelability of the cover film.
Examples of other components include the thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent No. 4502784, and other components described in paragraphs [0058] to [0071] of Japanese Patent Application Laid-Open No. 2000-310706. Additives can also be mentioned.

The photosensitive composition layer may contain particles for the purpose of adjusting the refractive index, light transmittance, and the like. Examples of the particles include metal oxide particles.
The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

The average primary particle size of the particles is preferably 1 to 200 nm, more preferably 3 to 80 nm, for example, from the viewpoint of pattern transparency. The average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using a scanning electron microscope (SEM) and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.

The photosensitive composition layer may contain particles of one type alone, or may contain particles of two or more types. When the photosensitive composition layer contains particles, it may contain only one type of particles having different metal species, sizes, etc., or may contain two or more types of particles.

The photosensitive composition layer does not contain particles, or the content of the particles is preferably more than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer, and contains particles. It is more preferable that there is no particle or the content of the particles is more than 0% by mass and 10% by mass or less based on the total mass of the photosensitive composition layer, and the particle is not contained or the content of the particles is contained. Is more preferably more than 0% by mass and 5% by mass or less with respect to the total mass of the photosensitive composition layer, and either does not contain particles or the content of particles is the total mass of the photosensitive composition layer. It is particularly preferable that it exceeds 0% by mass and 1% by mass or less, and it is most preferable that it does not contain particles.

The photosensitive composition layer may contain a trace amount of a colorant (for example, a pigment and a dye), but for example, from the viewpoint of transparency, it is preferable that the photosensitive composition layer contains substantially no colorant.
When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive composition layer.

[Impurities, etc.]
The photosensitive composition layer may contain a predetermined amount of impurities.
Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof. Of these, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.

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

As a method of setting impurities in the above range, a material having a low content of impurities is selected as a raw material of the photosensitive composition layer, and contamination of impurities is prevented during formation of the photosensitive composition layer, and cleaning is performed. Removal is mentioned. By such a method, the amount of impurities can be kept within the above range.

The 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, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive composition layer is Less is preferable. The content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis. The lower limit is based on mass and can be 10 ppb or more, and can be 100 ppb or more. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measurement method.

The water content in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminateability.

[Thickness of photosensitive composition layer]
The thickness of the photosensitive composition layer is not particularly limited, but is preferably 10.0 μm or less, more preferably 8.0 μm or less.
The lower limit of the thickness of the photosensitive composition layer is not limited. The smaller the thickness of the photosensitive composition layer, the better the bending resistance. The lower limit of the thickness of the photosensitive composition layer is preferably 0.05 μm or more from the viewpoint of manufacturing suitability. The lower limit of the thickness of the photosensitive composition layer is preferably 0.5 μm or more, more preferably 1.1 μm or more, from the viewpoint of improving the protection property of the transparent conductive portion.
The thickness of the photosensitive composition layer is calculated as an average value of 5 arbitrary points measured by cross-sectional observation with a scanning electron microscope (SEM).

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

[Color of photosensitive composition layer]
The photosensitive composition layer is preferably achromatic. The a ^* value of the photosensitive composition layer is preferably −1.0 to 1.0, and the b ^* value of the photosensitive composition layer is preferably −1.0 to 1.0.

<Other layers>
The transfer film may include layers other than the temporary support and the photosensitive composition layer described above.

[Protective film]
The transfer film may have a protective film for protecting the photosensitive composition layer on the surface opposite to the temporary support.
The protective film is preferably a resin film, and a resin film having heat resistance and solvent resistance can be used, and examples thereof include a polyolefin film such as a polypropylene film and a polyethylene film. Further, as the protective film, a resin film made of the same material as the above-mentioned temporary support may be used.

The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and preferably 100 μm or less in that it is relatively inexpensive.

<Manufacturing method of transfer film>
The method for producing the transfer film of the present invention is not particularly limited, and a known method can be used.
Above all, from the viewpoint of excellent productivity, a method of applying a photosensitive composition on a temporary support and, if necessary, performing a drying treatment to form a photosensitive composition layer is preferable.
Hereinafter, the above method will be described in detail.

The photosensitive composition preferably contains the components constituting the above-mentioned photosensitive composition layer (for example, a polymerizable compound, an alkali-soluble resin, a photopolymerization initiator, etc.), and a solvent.
As the solvent, an organic solvent is preferable. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. , N-propanol, and 2-propanol. As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.

Further, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 to 250 ° C. can be used, if necessary.
The photosensitive composition may contain one kind of solvent alone, or may contain two or more kinds of solvents.

When the photosensitive composition contains a solvent, the total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, or 5 to 40% by mass, based on the total mass of the photosensitive composition. 30% by mass is more preferable.

When the photosensitive composition contains a solvent, the viscosity of the photosensitive composition at 25 ° C. is preferably 1 to 50 mPa · s, more preferably 2 to 40 mPa · s, and 3 to 30 mPa · s, for example, from the viewpoint of coatability. s is more preferable. Viscosity is measured using a viscometer. As the viscometer, for example, a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TV-22) can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

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

Examples of the method for applying the photosensitive composition include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).

Examples of the drying method include natural drying, heat drying, and vacuum drying. The above methods can be applied alone or in combination of two or more.
In the present disclosure, "drying" means removing at least a portion of the solvent contained in the composition.

When the transfer film has a protective film, the transfer film can be produced by adhering the protective film to the photosensitive composition layer.
The method of attaching the protective film to the photosensitive composition layer is not particularly limited, and known methods can be mentioned.
Examples of the device for adhering the protective film to the photosensitive composition layer include a vacuum laminator and a known laminator such as an auto-cut laminator.
It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.

<Manufacturing method of laminated body>
By using the transfer film described above, the photosensitive composition layer can be transferred to the transfer target.
Among them, the photosensitive composition layer of the transfer film is brought into contact with the substrate having the conductive layer and bonded to each other, and the photosensitive composition having the temporary support, the photosensitive composition layer, and the substrate having the conductive layer in this order. A bonding step for obtaining a layered substrate, an exposure step for pattern-exposing the photosensitive composition layer from the temporary support side, a peeling step for peeling the temporary support from the photosensitive composition layered substrate, and an exposed photosensitive A method for producing a laminate having a developing step of developing a composition layer to form a pattern is preferable.
In the laminate obtained by the above procedure, the pattern is arranged on the substrate having the conductive layer.
Hereinafter, the procedure of each step of the laminated body will be described in detail.

[Lasting process]
In the bonding step, the photosensitive composition layer of the transfer film is brought into contact with the substrate having the conductive layer and bonded, and the temporary support, the photosensitive composition layer, and the substrate having the conductive layer are photosensitive in this order. This is a step of obtaining a substrate with a sex composition layer. By this bonding, the photosensitive composition layer and the temporary support are arranged on the substrate having the conductive layer.
In the bonding, it is preferable that the conductive layer and the surface of the photosensitive composition layer are pressure-bonded so as to be in contact with each other. In the above aspect, the pattern obtained after exposure and development can be suitably used as an etching resist when etching the conductive layer.
The crimping method is not particularly limited, and a known transfer method and laminating method can be used. Above all, it is preferable to superimpose the surface of the photosensitive composition layer on the substrate having the conductive layer, pressurize and heat with a roll or the like.
A known laminator such as a vacuum laminator and an auto-cut laminator can be used for bonding.

The substrate having a conductive layer has a conductive layer on the substrate, and an arbitrary layer may be formed if necessary. That is, the substrate having the conductive layer is a conductive substrate having at least a substrate and a conductive layer arranged on the substrate.
Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
Preferred embodiments of the substrate are described, for example, in paragraph 0140 of WO 2018/155193, the contents of which are incorporated herein.

The conductive layer includes 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 from the viewpoint of conductivity and fine wire forming property. preferable.
Further, only one conductive layer may be arranged on the substrate, or two or more conductive layers may be arranged. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials.
Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of WO 2018/155193, the contents of which are incorporated herein.

[Exposure process]
The exposure step is a step of pattern-exposing the photosensitive composition layer from the temporary support side.
Here, the "pattern exposure" refers to an exposure in a pattern of exposure, that is, a form in which an exposed portion and a non-exposed portion are present.
The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. The pattern formed by the developing step described later preferably contains fine lines having a width of 20 μm or less, and more preferably contains thin lines having a width of 10 μm or less.

As the light source for pattern exposure, any light source in a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used. Above all, the main wavelength of the exposure light for pattern exposure is preferably 365 nm.
The main wavelength is the wavelength having 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.
Exposure is preferably 5 ~ 200mJ / cm ^2, more preferably 10 ~ 200mJ / cm ^2.

Preferred embodiments 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 in the present specification. ..

[Peeling process]
The peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer.
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.

[Development process]
The developing step is a step of developing the exposed photosensitive composition layer to form a pattern.
The development of the photosensitive composition layer can be carried out using a developing solution.
An alkaline aqueous solution is preferable as the developing solution. Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. Do, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

Examples of the development method include paddle development, shower development, spin development, and dip development.

Examples of the developing solution preferably used in the present disclosure include the developing solution described in paragraph [0194] of International Publication No. 2015/093271. Examples of the developing method preferably used include International Publication No. 2015. The developing method described in paragraph [0195] of No. 093271 can be mentioned.

The pattern (cured film of the photosensitive composition layer) formed by the above procedure is preferably achromatic. Specifically, in the L ^* a ^* b ^* color system, the a ^* value of the pattern is preferably -1.0 to 1.0, and the b ^* value of the pattern is -1.0 to 1 It is preferably 0.0.

[Post-exposure process and post-baking process]
The method for producing the laminate may include a step of exposing the pattern obtained by the development step (post-exposure step) and / or a step of heating (post-baking step).
When both the post-exposure step and the post-baking step are included, it is preferable to carry out the post-baking after the post-exposure.

[Etching process]
The method for producing the laminated body may include an etching step of etching the conductive layer in the region where the pattern is not arranged in the obtained laminated body.
In the etching step, the pattern formed from the photosensitive composition layer by the developing step is used as an etching resist, and the conductive layer is etched.
Examples of the etching treatment method include the methods described in paragraphs [0209] to [0210] of JP-A-2017-120435, the methods described in paragraphs [0048]-[0054] of JP-A-2010-152155, and the like. A known method such as a known dry etching method such as plasma etching can be applied.

[Removal process]
The method for producing a laminated body may include a removing step of removing a pattern.
The removal step can be performed as needed, but is preferably performed after the etching step.
The method for removing the pattern is not particularly limited, but a method for removing the pattern by chemical treatment can be mentioned, and it is preferable to use a removing liquid.
As a method for removing the pattern, a method of immersing the laminate having the pattern in the removing liquid being stirred at preferably 30 to 80 ° C., more preferably 50 to 80 ° C. for 1 to 30 minutes can be mentioned.

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

[Other processes]
The method for producing a laminate of the present invention may include any steps (other steps) other than those described above.
For example, a step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089, a new conductive layer is provided on the insulating film described in paragraph [0172] of International Publication No. 2019/022089. Examples thereof include steps of forming, but the process is not limited to these steps.

The laminate produced by the method for producing a laminate of the present invention can be applied to various devices. Examples of the device provided with the laminated body include an input device and the like, and a touch panel is preferable, and a capacitance type touch panel is more preferable. Further, the input device can be applied to a display device such as an organic electroluminescence display device and a liquid crystal display device.
When the laminate is applied to a touch panel, the pattern formed from the photosensitive composition layer is preferably used as a protective film for the touch panel electrodes. That is, the photosensitive composition layer contained in the transfer film is preferably used for forming the touch panel electrode protective film.

The various compounds, compositions, materials and the like used in the present invention preferably do not contain impurities such as metal components, water, isomers, fine particles, aggregates, precipitates and residual monomers. The content of these impurities contained in various materials is preferably 1 mass% or less, more preferably 1 mass ppm or less, further preferably 1 mass ppb or less, and substantially not contained (detection by a measuring device). (Being below the limit) is particularly preferable. As the method for reducing impurities, a method suitable for the object to be removed can be appropriately selected. For example, paragraphs 0321 to 0323 of JP-A-2019-174549, paragraphs 0083 to 097 of Pamphlet of International Publication No. 2019/08868, etc. The methods disclosed in can be used.

The present disclosure will be described in more detail with reference to Examples below. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.
The composition ratio in the polymer is a molar ratio unless otherwise specified.

<Synthesis of polymer A-1>
PGMEA (116.5 parts) was placed in a three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. 90 parts of a solution containing St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts), and PGMEA (116.5 parts). The solution was added dropwise to a three-necked flask solution maintained at ° C. ± 2 ° C. over 2 hours. After completion of the dropping, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain polymer A-1 (solid content concentration 30.0%).
The abbreviations in the above synthesis examples represent the following compounds, respectively.
St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
V-601: Dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

<Preparation of Photosensitive Composition 1>
The following components were mixed to prepare the photosensitive composition 1. The unit of the amount of each component is a mass part.
Polymer A-1 (solid content concentration 30.0%): 21.87 parts D-2 (Aronix M270 (manufactured by Toa Synthetic Co., Ltd.)): 0.51 parts D-1 (NK ester BPE-500 (Shin-Nakamura) Chemical Industry Co., Ltd.)): 4.85 parts C-2 (B-CIM, manufactured by THF): 0.89 parts C-3 (photoradical polymerization initiator (sensitizer), 4,4'-bis (Diethylamino) Benzophenone, manufactured by Tokyo Kasei Co., Ltd.): 0.05 parts Phenothiazine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0.025 parts 1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0.001 part B-2 (LCV, Leuco Crystal Violet, manufactured by Yamada Chemical Industry Co., Ltd.): 0.053 part E-1 (Megafuck F552 (manufactured by DIC Co., Ltd.)): 0.02 part Methyl ethyl ketone (MEK, 3) Kyogaku Co., Ltd.): 30.87 parts propylene glycol monomethyl ether acetate (PGMEA, manufactured by Showa Denko Co., Ltd.): 33.92 parts Tetrahydrofuran (THF, manufactured by Mitsubishi Chemical Co., Ltd.): 6.93 parts

<Example 1>
A resin layer having a thickness of 5 μm made of an ethylene methacrylic acid copolymer (Nucrel AN4214C, manufactured by Mitsui Dow Polychemical Co., Ltd.) is provided on a PET film (16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm by a melt extrusion method. rice field.
The resin layer in the laminate having the obtained PET film and the resin layer was embossed to obtain a temporary support exhibiting the surface characteristics (Rsk, Ra, RMS) shown in Table 1 described later. ..
Next, the photosensitive composition 1 was applied onto the surface of the obtained temporary support on the resin layer side using a slit-shaped nozzle, and passed through a drying zone at 80 ° C. for 40 seconds to a thickness of 3 μm. The photosensitive composition layer of the above was formed.
Next, a PET film (16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was laminated on the photosensitive composition layer as a protective film to prepare a transfer film, which was wound into a roll form.

<Examples 2 to 5, Comparative Examples 1 to 4>
A transfer film was obtained according to the same procedure as in Example 1 except that the thickness of the resin layer, the embossing conditions, and the like were adjusted so as to obtain the characteristics shown in Table 1 described later.
In Comparative Example 4, a temporary support that was not embossed was used.

<Example 6>
An ethylene vinyl acetate copolymer (Evaflex EV550, manufactured by Mitsui Dow Polychemical Co., Ltd.) is used instead of the ethylene methacrylic acid copolymer (Nucrel AN4214C, manufactured by Mitsui Dow Polychemical Co., Ltd.), and the characteristics shown in Table 1 described later are exhibited. A transfer film was obtained according to the same procedure as in Example 1 except that the conditions for embossing were adjusted so as to obtain the film.

<Example 7>
An ethylene methacrylic acid copolymer (Nucrel AN4229C, manufactured by Mitsui Dow Polychemical) was used instead of the ethylene methacrylic acid copolymer (Nucrel AN4214C, manufactured by Mitsui Dow Polychemical), and the properties shown in Table 1 described later were obtained. A transfer film was obtained according to the same procedure as in Example 1 except that the conditions for embossing were adjusted so as to be obtained.

<Rewindability>
A PET base with a thickness of 100 μm and a width of 500 mm is continuously heat-bonded to a support with a transfer film of the same width by roll-to-roll between heat rolls at a temperature of 100 ° C. at a speed of 2 m / min and a pressure of 0.8 MPa. , The photosensitive composition layer and the laminated body laminated with the temporary support were wound up in a roll shape on the support.
Then, while peeling off the temporary support, it was conveyed at a speed of 2 m / min. At that time, the peeled temporary support was wound up in a roll shape with a winding tension of 25N. The takeability was observed from the roll form at the time of winding 100 m, and evaluated according to the following criteria. The results are shown in Table 1 below.
A: No problem in appearance B: Tolerable level of wrinkles or square winding is seen, but there is no effect on transportation.
C: Stable transport is not possible due to wrinkles or square winding.

<Resolution>
A copper layer having a thickness of 500 nm was provided on a glass plate having a thickness of 0.7 mm by a vapor deposition method, and a glass substrate with a copper layer was prepared.
After unwinding the produced transfer film and peeling off the protective film, the copper layer and the photosensitive composition layer come into contact with each other under laminating conditions of a roll temperature of 100 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 2.0 m / min. Was laminated on the glass substrate with a copper layer.
Next, using a photomask having various line width patterns (2 to 20 μm) of line / space = 1/1 ^{, exposure of 80 mJ / cm 2} is performed from the temporary support side, and then the temporary support is peeled off and removed. bottom.
Next, shower development was carried out with a 1% sodium carbonate aqueous solution having a liquid temperature of 25 ° C., washing with water was carried out, and a predetermined pattern was formed on copper.
After that, the minimum line width (using mask dimensional values) with a space was evaluated with an optical microscope. The results are shown in Table 1 below.

The storage elastic modulus, haze, Rsk, Ra and RMS shown in Table 1 were measured by the method described above.
In Table 1, the "haze (%)" column represents the haze (%) of the temporary support.
In Table 1, the “Rsk” column represents the skewness Rsk of the surface of the temporary support on the photosensitive composition layer side.
In Table 1, the “Ra (μm)” column represents the surface roughness Ra of the surface of the temporary support on the photosensitive composition layer side.
In Table 1, the “RMS (μm)” column represents the root mean square roughness RMS of the surface of the temporary support on the photosensitive composition layer side.
In Table 1, ">20" means that all patterns of 2 to 20 μm were not resolved.

As shown in Table 1, the desired effect was obtained by using the transfer film of the present invention.
From the comparison of Examples 1 to 7, it was confirmed that the effect was more excellent when the haze of the temporary support was 20% or less.
From the comparison of Examples 1 to 5, it was confirmed that the effect was more excellent when the skewness Rsk of the surface of the temporary support on the photosensitive composition layer side was 0.45 or more.

Claims

It has a temporary support and a photosensitive composition layer arranged on the temporary support.
The haze of the temporary support is less than 30%
A transfer film having a skewness Rsk of more than 0.40 on the surface of the temporary support on the side of the photosensitive composition layer.
The transfer film according to claim 1, wherein the surface roughness Ra of the surface of the temporary support on the photosensitive composition layer side is less than 0.50 μm.
The transfer film according to claim 1 or 2, wherein the root mean square height RMS of the surface of the temporary support on the side of the photosensitive composition layer is less than 0.70 μm.
The temporary support has a support and a resin layer arranged on the support.
The resin layer is arranged on the photosensitive composition layer side, and the resin layer is arranged on the photosensitive composition layer side.
The transfer film according to any one of claims 1 to 3, wherein the resin layer has a storage elastic modulus of 20 MPa or less at 90 ° C.
The transfer film according to claim 4, wherein the H / G is more than 0.2 μm / MPa when the storage elastic modulus of the resin layer at 90 ° C. is G and the thickness of the resin layer is H.
The transfer film according to claim 4 or 5, wherein the thickness of the resin layer is 60 μm or less.
The transfer film according to any one of claims 4 to 6, wherein the resin layer contains a resin having a repeating unit derived from ethylene.
The transfer film according to any one of claims 1 to 7, wherein the temporary support has a haze of 2% or more.
The transfer film according to any one of claims 1 to 8, wherein the surface of the temporary support on the photosensitive composition layer side is embossed.
The photosensitive composition layer of the transfer film according to any one of claims 1 to 9 is brought into contact with a substrate having a conductive layer and bonded to the temporary support, the photosensitive composition layer, and A bonding step of obtaining a substrate with a photosensitive composition layer having a substrate having a conductive layer in this order, and
An exposure step of pattern-exposing the photosensitive composition layer from the temporary support side,
A peeling step of peeling the temporary support from the substrate with the photosensitive composition layer,
A method for producing a laminate, comprising a developing step of developing the exposed photosensitive composition layer to form a pattern.