JP7094372B2 - Transfer film, laminate, and pattern forming method - Google Patents

Description

The present disclosure relates to transfer films, laminates, and pattern forming methods.

In recent years, in electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals, tablet-type input devices are arranged on the surface of liquid crystal devices and the like. There is a device that can input information corresponding to an instruction image by touching a place where the instruction image is displayed with a finger or a stylus while referring to the instruction image displayed in the image display area of the liquid crystal device.
The input device (hereinafter, also referred to as a touch panel) includes a resistance film type and a capacitance type. In the case of a capacitance type input device, there is an advantage that a translucent conductive film may be simply formed on a single substrate.

As the wiring board in which the conductive film is formed in a pattern, a double-sided printed wiring board in which metal wiring patterns are arranged on both sides of the substrate tends to be used.
In a wiring board in which metal wiring is arranged on a substrate, a patterned resist film is formed on the metal film formed on the substrate by a photoresist method, and the metal film is etched using the resist film as a mask. Can be made. Then, in the case of a double-sided printed wiring board, the work of etching the patterned resist film as a mask is performed on both sides of the board.

As a technique related to the above, there is a disclosure regarding a method of patterning on both sides of a transparent substrate (see, for example, Japanese Patent Application Laid-Open No. 2011-154080). Specifically, in pattern formation of a transparent metal film provided on both the front and back surfaces of a transparent base material, an opaque layer that shields exposure light is formed on at least one of the transparent metal films of the transparent metal film to form a transparent base material. It is described that a photoresist film can be formed by applying a photoresist on both the front and back surfaces, and different pattern exposures can be performed on both sides having the photoresist film to form a resist pattern.

Further, as a material useful for manufacturing a printed wiring board, a first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on a support, and light relatively higher than the light sensitivity of the first photosensitive layer. A photosensitive transfer sheet in which a second photosensitive layer exhibiting sensitivity is laminated in this order is disclosed (see, for example, Japanese Patent Application Laid-Open No. 2005-331695).

As described above, forming wiring patterns on both sides of the transparent substrate has been conventionally performed. However, when photosensitive resist patterns are provided on both sides of the transparent substrate and exposed to each other to form different patterns on both sides of the transparent substrate, for example, the light emitted from one side of the transparent substrate is transparent. It easily penetrates the substrate and reaches the other side. Therefore, even if a good pattern can be formed on one side irradiated with light, the shape of the pattern may be significantly impaired on the other side due to the influence of the transmitted light.

Among the prior arts, in the above-mentioned Japanese Patent Application Laid-Open No. 2011-154080, an opaque layer is provided to prevent light irradiated to one side from being transmitted to the other side. However, since a metal such as aluminum is used for the opaque layer, when the wiring pattern is etched after the resist pattern is formed, the work of etching the opaque layer in advance is performed separately from the etching for forming the metal wiring. There is a problem that the number of steps must be increased. Further, since the opaque layer is not removed during the developing process of the photoresist, it is also impossible to etch both sides of the transparent substrate at the same time as it is after the developing process.
Moreover, in the technique described in Japanese Patent Application Laid-Open No. 2011-154080, since the light at the time of pattern exposure is easily reflected by the opaque layer, the reflected light tends to impair the pattern accuracy and the fineness of the pattern.

The present disclosure has been made in view of the above.
The problem to be solved by one embodiment of the present invention is that the influence of the irradiation light from one side of the transparent substrate on the pattern formation property on the other side at the time of pattern exposure after transfer is suppressed. It is an object of the present invention to provide a transfer film or a laminate capable of easily forming a fine pattern.
The problem to be solved by another embodiment of the present invention is to suppress the influence on the pattern formation property of the other side due to the irradiation light from one side of the transparent substrate at the time of pattern exposure after transfer. At the same time, it is an object of the present invention to provide a pattern forming method capable of easily forming a fine pattern.

Specific means for solving the problem include the following aspects.
<1> A temporary support, a first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator, and a light-shielding layer containing at least a binder polymer and having an optical density of 0.5 or more. It is a transfer film having in this order.
<2> The transfer film according to <1>, wherein the light-shielding layer further contains an ultraviolet absorbing material.
<3> The transfer film according to <2>, wherein the ultraviolet absorbing material contains carbon black.
<4> The transfer film according to any one of <1> to <3>, wherein the light-shielding layer further contains a polymerizable compound.
<5> The transfer film according to any one of <1> to <4>, wherein the content of the photopolymerization initiator is 1% by mass or less with respect to the total solid content of the light-shielding layer.
<6> The transfer film according to any one of <1> to <5>, which has an intermediate layer between the first photosensitive layer and the light-shielding layer.
<7> The transfer film according to <6>, wherein the intermediate layer contains a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms.
<8> The transfer film according to <6> or <7>, wherein the intermediate layer further contains a polymerizable compound and a photopolymerization initiator.
<9> A laminate having a transparent substrate and the transfer film according to any one of <1> to <8>.
<10> The laminate according to <9>, which has a second photosensitive layer on the side of the transparent substrate opposite to the side on which the transfer film is laminated.
<11> The laminate according to <10>, wherein the second photosensitive layer contains a binder polymer, a polymerizable compound, and a photopolymerization initiator.

<12> The step of attaching the transfer film according to any one of <1> to <8> to one side of the transparent base material, and the binder polymer and the polymerizable compound on the other side of the transparent base material. , And a step of forming a second photosensitive layer containing a photopolymerization initiator, a step of irradiating both sides of the transparent substrate with different patterns, and a transparent group after irradiation. It is a pattern forming method including a step of forming different patterns on both sides of a transparent substrate by developing both sides of the material.
<13> The pattern forming method according to <12>, wherein the transparent substrate has at least one of a metal electrode and a metal wiring on both surfaces.
<14> The pattern forming method according to <12> or <13>, which is used for forming at least one of a touch panel electrode and a touch panel wiring.

According to one embodiment of the present invention, the influence of the irradiation light from one side of the transparent substrate on the pattern formation property on the other side at the time of pattern exposure after transfer is suppressed, and it is simple and fine. Transfer films or laminates capable of forming patterns are provided.
According to another embodiment of the present invention, it is easy to suppress the influence of the irradiation light from one side of the transparent substrate on the pattern formation property of the other side at the time of pattern exposure after transfer. A pattern forming method capable of forming a fine pattern is provided.

FIG. 1 is a cross-sectional configuration diagram showing an embodiment of the transfer film of the present disclosure. FIG. 2 is a cross-sectional configuration diagram showing an embodiment of the laminated body of the present disclosure. FIG. 3 is a cross-sectional configuration diagram showing another embodiment of the laminated body of the present disclosure. FIG. 4 is a process diagram for explaining how different patterns are simultaneously formed on both sides of the transparent substrate by the pattern forming method of the present disclosure.

Hereinafter, the contents of the present disclosure will be described in detail.
The description of the constituents described below may be based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.

In the present disclosure, "-" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

In the notation of a group (atomic group) in the present disclosure, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Further, in the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. do.

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

In the present disclosure, "(meth) acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth) acrylate" is a concept that includes both acrylate and methacrylate, and "(meth) acrylate" is a concept. ) Acryloyl group ”is a concept that includes both acryloyl group and methacrylic acid group.

In the present disclosure, the ratio of the constituent units in the resin represents the mass ratio unless otherwise specified.
In the present disclosure, the molecular weight when there is a molecular weight distribution represents a weight average molecular weight (Mw) unless otherwise specified.

Hereinafter, the transfer film of the present disclosure and the laminate and the pattern forming method using the transfer film of the present disclosure will be described in detail.

<Transfer film>
The transfer film of the present disclosure contains a temporary support, a first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator, and at least a binder polymer, and has an optical density of 0.5 or more. The layers may be provided in this order, and if necessary, another layer such as an intermediate layer may be further provided.

Conventionally, a technique for forming a wiring pattern or the like by an etching method using a resist pattern formed by a photoresist method as a mask has been known. A method using a photosensitive transfer film as an example of a resist material is also widely used.
In recent years, there has been known a technique in which photosensitive resin compositions are provided on both sides of a transparent base material and exposed to each other to form different patterns on both sides of the transparent base material, for example. When light is irradiated from both sides of the transparent substrate, the light emitted from one side of the transparent substrate tends to pass through the transparent substrate and reach the other side. Therefore, even if a good pattern is formed on one side where light irradiation is performed, the latent image is disturbed on the other side due to the influence of the light transmitted from one side, and the shape of the pattern formed after development. May be significantly impaired.

As in the technique described in JP-A-2011-154080, a layer structure is provided in which an opaque layer is provided between layers so that light irradiated on one side of the transparent substrate does not pass through to the other side. Is prevented from transmitting the light irradiated to one side of the transparent substrate, and is unlikely to disturb the photosensitive state (latent image) on the other side. However, in the technique described in JP-A-2011-154080, a metal such as aluminum is used for the opaque layer. Therefore, when the wiring pattern is formed by etching using the resist pattern as a mask, an etching process for the opaque layer must be provided in advance in addition to the etching process for forming the wiring pattern. Therefore, the number of processes is large, which is disadvantageous in terms of cost.
Moreover, when the opaque layer arranged between the layers is a metal layer as in the invention described in Japanese Patent Application Laid-Open No. 2011-154080, the metal layer is accompanied by light reflection to some extent, so that the light at the time of pattern exposure is emitted. It is reflected by the opaque layer to produce an unnecessary exposure effect, and as a result, it contributes to impairing the fineness of the pattern.
Further, since the opaque layer cannot be developed and removed at the same time as the photoresist by the developing process after light irradiation, for example, the opaque layer remains as it is at the time of developing the photoresist film formed on both sides of the transparent substrate. Therefore, it is not possible to form a state in which etching is possible at the same time as development.

In view of the above, in the transfer film of the present disclosure, a first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator and a binder polymer are contained on the temporary support, and the optical density is 0.5. The above-mentioned light-shielding layer and the above-mentioned light-shielding layer are laminated in this order to form a laminated structure. As a result, for example, as shown in FIG. 2, the transfer film 41 is attached to one side of the transparent base material 21 to have a laminated structure of the transparent base material 21 / light-shielding layer 13 / first photosensitive layer 17 / temporary support 19. In the case of a laminated body, the irradiation light emitted from one side (for example, the temporary support 19 side of the laminated body) is blocked by the light-shielding layer 13 and blocked by the other side (for example, the transparent base material 21 side of the laminated body). ) Is suppressed, and the light from the other side is also blocked by the light-shielding layer 13 to suppress the transmission to one side. In such a layer structure, the first photosensitive layer 17 and the light-shielding layer 13 are not only the first photosensitive layer 17 but also the region other than the region exposed to the first photosensitive layer 17 by the irradiation light from one side. The light-shielding layer 13 is also satisfactorily developed and removed, a state in which etching is possible at the same time as development is obtained, and the light-shielding layer 13 is unlikely to remain on the transparent substrate 21. As a result, a highly accurate pattern is formed on the transparent substrate 21.
In this respect, for example, as shown in FIG. 3, the transfer film 41 is attached to one side of the transparent substrate 21, and another transfer film 43 having the second photosensitive layer 27 is attached to the other side. This is more noticeable when the laminated body 101 has a laminated structure of the temporary support 19 / first photosensitive layer 17 / light-shielding layer 13 / transparent base material 21 / second photosensitive layer 27 / temporary support 19a. That is, the irradiation light emitted from one side (for example, the temporary support 19 side of the laminated body) is blocked by the light-shielding layer 13 and is blocked by the other side (for example, the temporary support 19a side of the laminated body in FIG. 3). The irradiation light emitted from the other side is also blocked by the light-shielding layer 13, and the transmission to one side (for example, the temporary support 19 side of the laminated body of FIG. 3) is suppressed. It is suppressed. In such a layer structure, the first photosensitive layer and the light-shielding layer are good not only in the first photosensitive layer 17 but also in the light-shielding layer 13 in the region where the first photosensitive layer is not exposed to the irradiation light from one side. It is developed and removed, and a state that can be etched at the same time as development is obtained. Further, since the residual light-shielding layer 13 and the residual second photosensitive layer on the transparent substrate 21 are unlikely to occur, a highly accurate pattern is formed on the transparent substrate 21 with a small amount of residue.
As described above, in the transfer film of the present disclosure, the light-shielding layers arranged between the layers easily absorb the irradiation light and hardly reflect the irradiated light, so that the unnecessary exposure effect caused by the reflected light is suppressed. The fineness of the pattern is further enhanced. Further, since the light-shielding layer in the present disclosure is a layer that can be removed during development of the first photosensitive layer, it can be removed in the process of developing to reveal the pattern and can form an etchable state. Therefore, it is possible to perform etching processing on both sides as it is after development.

(First photosensitive layer)
The first photosensitive layer is a photosensitive negative layer arranged on a temporary support, and contains at least a binder polymer, a polymerizable compound, and a photopolymerization initiator. The first photosensitive layer may further contain other components such as a surfactant, a solvent, and an additive, if necessary.

-Binder polymer-
The first photosensitive layer contains at least one kind of binder polymer.
The binder polymer is preferably a resin (so-called alkali-soluble resin) that can be dissolved by contact with an alkaline solvent.
The acid value of the binder polymer is not particularly limited, but is preferably 60 mg / KOH or more from the viewpoint of developability. Specifically, the binder polymer is preferably a binder polymer having an acid value of 60 mgKOH / g or more, more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and contains a carboxy group having an acid value of 60 mgKOH / g or more. Acrylic resin is particularly preferable.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more (hereinafter, may be referred to as a specific polymer) is not particularly limited as long as the above acid value conditions are satisfied, and is appropriately selected from known resins. Can be used.
For example, a binder polymer which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0025 of JP-A-2011-95716, described in paragraphs 0033 to 0052 of JP-A-2010-237589. Among the polymers of the above, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used as the specific polymer in the present embodiment.
Here, the (meth) acrylic resin refers to 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 structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in the (meth) acrylic resin is preferably 30 mol% or more, more preferably 50 mol% or more.

The preferable range of the copolymerization ratio of the monomer having a carboxy group in the specific polymer is 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, based on 100% by mass of the specific polymer. More preferably, it is in the range of 10% by mass to 20% by mass.
The specific polymer may have a reactive group.
As a means for introducing a reactive group into a specific polymer, a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone, etc. Examples thereof include a method of reacting a compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride and the like.
Among these, the reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group, and particularly preferably a (meth) acryloxy group.

Further, the binder polymer (particularly the specific polymer) may have a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing.
Examples of the monomer forming a structural unit having an aromatic ring include styrene, tert-butoxystyrene, 4-methylstyrene, α-methylstyrene, benzyl (meth) acrylate and the like.
Further, the structural unit having an aromatic ring is preferably a structural unit derived from styrene.

When the binder polymer contains a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5% by mass to 90% by mass, preferably 10% by mass or more, based on the total mass of the binder polymer. It is more preferably 70% by mass, and even more preferably 20% by mass to 50% by mass.

Further, the binder polymer, particularly the specific polymer, preferably has a structural unit having an aliphatic cyclic skeleton from the viewpoint of tackiness and strength after curing.
Specific examples of the monomer forming a structural unit having an aliphatic cyclic skeleton include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Preferred examples of the aliphatic ring contained in the constituent unit having an aliphatic cyclic skeleton include a dicyclopentane ring, a cyclohexane ring, an isovoron ring, and a tricyclodecane ring. Among them, the tricyclodecane ring is particularly preferable.

When the binder polymer contains a structural unit having an alicyclic skeleton, the content of the structural unit having an alicyclic skeleton may be 5% by mass to 90% by mass with respect to the total mass of the binder polymer. It is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass.

Further, the binder polymer, particularly the specific polymer, preferably has a structural unit having an ethylenically unsaturated group from the viewpoint of tackiness and strength after curing. As the ethylenically unsaturated group, a (meth) acrylic group is preferable, and a (meth) acryloyl group is more preferable.
When the binder polymer contains a structural unit having an ethylenically unsaturated group, the content of the structural unit having an ethylenically unsaturated group may be 5% by mass to 70% by mass with respect to the total mass of the binder polymer. It is preferably 10% by mass to 50% by mass, more preferably 20% by mass to 40% by mass.

As the binder polymer, for example, the following compound A (Me represents a methyl group) is preferably mentioned. The content ratio of each structural unit shown below can be appropriately changed according to the purpose.
As the binder polymer, commercially available products on the market may be used, for example, Acribase (registered trademark) FFS-6058, FF187 of Fujikura Kasei Co., Ltd., Acrit (registered trademark) 8KB-001 of Taisei Fine Chemical Co., Ltd., etc. The 8KB series can be mentioned.

The acid value of the binder polymer is preferably 60 mgKOH / g to 250 mgKOH / g, and more preferably 70 mgKOH / g to 180 mgKOH / g.

In the present disclosure, the acid value is a value measured according to the method described in JIS K0070 (1992). The same applies hereinafter.

When the binder polymer contains a binder polymer having an acid value of 60 mgKOH / g or more, in addition to the above-mentioned advantages, the light-shielding layer described later contains an acrylic resin having an acid group, so that the first photosensitive layer and the light-shielding layer are combined. It is possible to improve the adhesion between the two.

In addition to the above polymers, any film-forming resin can be appropriately selected and used as the binder polymer according to the purpose.

The weight average molecular weight of the binder polymer is not particularly limited, but is preferably more than 3,000, more preferably more than 3,000 and not more than 60,000, and preferably 5,000 to 50,000. More preferred.
The weight average molecular weight can be measured by a gel permeation chromatograph (GPC) under the same method and conditions as those for measuring the weight average molecular weight of the binder polymer used for the light-shielding layer described later.

The binder polymer may be used alone or may contain two or more kinds.
The content of the binder polymer in the first photosensitive layer is preferably 10% by mass to 90% by mass, preferably 15% by mass or more and 80% by mass, based on the total mass of the first photosensitive layer from the viewpoint of photosensitive and the strength of the cured film. It is more preferably 20% by mass or more and 70% by mass or less, more preferably 20% by mass or less.

-Polymerizable compound-
The first photosensitive layer contains at least one kind of polymerizable compound.
The polymerizable compound is a component that contributes to the photosensitivity (that is, photocurability) of the first photosensitive layer and the strength of the cured film. The polymerizable compound in the present disclosure is a compound having one or more ethylenically unsaturated groups (hereinafter, also referred to as “ethylenically unsaturated compound”). Among them, the polymerizable compound is preferably a radically polymerizable compound that emits a radical as an active species by irradiation with light.

The first photosensitive layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound as the 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 group, a (meth) acryloyl group is more preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The first photosensitive layer is a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably) from the viewpoint of curability after curing. It is particularly preferable to contain (3 functional or higher) (meth) acrylate compound).

The bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexane. Examples thereof include diol di (meth) acrylate.
Specific examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, new). Nakamura Chemical Industry Co., Ltd.), 1,9-Nonandiol diacrylate (A-NOD-N, Shin Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, new) Nakamura Chemical Industry Co., Ltd.) and the like.

The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
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 (meth) acrylate compound having a glycerintri (meth) acrylate skeleton.

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

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (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 RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Ornex Co., Ltd. 135 Etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like.

Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds (preferably trifunctional or higher functional urethane (meth) acrylate compounds).
Examples of the trifunctional or higher functional urethane (meth) acrylate compound include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). Co., Ltd.) and the like.

Further, 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, and a carboxy group is preferable.
Examples of the ethylenically unsaturated compound having an acid group include a 3- to tetrafunctional ethylenically unsaturated compound having an acid group (pentaerythritol tri and tetraacrylate (PETA)) having a carboxy group introduced into the skeleton (acid value =). 80-120 mgKOH / g)), 5-6-functional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA)) with a carboxy group introduced into the skeleton (acid value = 25-70 mgKOH / g) )), Etc. can be mentioned.
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group and a carboxylic acid anhydride thereof is preferable. This enhances the developability and the strength of the cured film.
The bifunctional or higher functional unsaturated compound containing a carboxy group is not particularly limited and can be appropriately selected from known compounds.
Examples of the bifunctional or higher functional unsaturated compound containing a carboxy group include Aronix (registered trademark) TO-2349ME (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), or , Aronix M-510 (manufactured by Toagosei Co., Ltd.) can be preferably used.

The ethylenically unsaturated compound having an acid group is also preferably a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The contents of this publication are incorporated herein by reference.

The weight average molecular weight (Mw) of the ethylenically unsaturated compound used in the present disclosure is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and 300 to 2, 200 is particularly preferred.
Further, among the ethylenically unsaturated compounds used in the first photosensitive layer, the ratio of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is the same as that of all the ethylenically unsaturated compounds contained in the first photosensitive layer. 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.

The ethylenically unsaturated compound may be used alone or in combination of two or more.
The content of the ethylenically unsaturated compound in the first photosensitive layer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, and 20% by mass to 20% by mass, based on the total mass of the first photosensitive layer. 60% by mass is more preferable, and 20% by mass to 50% by mass is particularly preferable.

When the first photosensitive layer contains a bifunctional ethylenically unsaturated compound and a trifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional ethylenically unsaturated compound is contained in the first photosensitive layer. It is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, still more preferably 30% by mass to 80% by mass, based on all the ethylenically unsaturated compounds.
Further, in this case, the content of the trifunctional or higher functional ethylenically unsaturated compound is preferably 10% by mass to 90% by mass, preferably 15% by mass or more, based on all the ethylenically unsaturated compounds contained in the first photosensitive layer. 80% by mass is more preferable, and 20% by mass to 70% by mass is further preferable.
Further, in this case, the content of the bifunctional or higher functional ethylenically unsaturated compound is 40% by mass or more 100 with respect to the total content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher ethylenically unsaturated compound. It is preferably less than mass%, more preferably 40% by mass to 90% by mass, further preferably 50% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass. ..

When the first photosensitive layer contains a bifunctional or higher functional ethylenically unsaturated compound, the first photosensitive layer may further contain a monofunctional ethylenically unsaturated compound.
Further, when the first photosensitive layer contains a bifunctional or higher ethylenically unsaturated compound, the ethylenically unsaturated compound contained in the first photosensitive layer contains a bifunctional or higher functional ethylenically unsaturated compound as a main component. Is preferable.
Specifically, when the first photosensitive layer contains a bifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional or higher ethylenically unsaturated compound is the ethylenically unsaturated compound contained in the first photosensitive layer. With respect to the total content of the saturated compound, 40% by mass to 100% by mass is preferable, 50% by mass to 100% by mass is more preferable, and 60% by mass to 100% by mass is particularly preferable.

When the first photosensitive layer contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group or a carboxylic acid anhydride thereof), the acid group is used. The content of the ethylenically unsaturated compound is preferably 0.5% by mass to 50% by mass, more preferably 0.5% by mass to 20% by mass, and 0.5% by mass with respect to the total mass of the first photosensitive layer. % To 10% by mass is more preferable.

-Photopolymerization initiator-
The first photosensitive layer contains at least one kind of photopolymerization initiator.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
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 oxide structure. Photopolymerization initiator (hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”), photopolymerization initiator having an N-phenylglycine structure (hereinafter, “N-phenylglycine-based photopolymerization initiator””. Also known as)) and the like.

The photopolymerization initiator is at least 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 include 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. ..

Further, as the photopolymerization initiator, for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-014783 may be used.

Commercially available photopolymerization initiators include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE® OXE-01, BASF). (Manufactured by), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF) , 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2- Methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2) -Methyl-propionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (trade name: IRGACURE 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (trade name: IRGACURE 1173, manufactured by BASF), 1-hydroxycyclohexylphenylketone (trade name: IRGACURE 1173, manufactured by BASF) Product name: IRGACURE 184, manufactured by BASF, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF), oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd., etc. can be mentioned.

The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the first photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the first photosensitive layer. 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 first photosensitive layer.

-Surfactant-
The first photosensitive layer can contain at least one of the surfactants.
As the surfactant, for example, the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP2009-237362A, known fluorosurfactants and the like can be used.
As the surfactant, a fluorine-based surfactant is preferable.
Examples of commercially available fluorosurfactants include Megafuck (registered trademark) F-551A (manufactured by DIC Corporation).

When the first photosensitive layer contains a surfactant, the content of the surfactant in the first photosensitive layer is preferably 0.01% by mass to 3% by mass with respect to the total mass of the first photosensitive layer. , 0.05% by mass to 1% by mass, more preferably 0.1% by mass to 0.8% by mass.

-Other ingredients-
The first photosensitive layer may contain other components such as additives, if necessary, in addition to the above-mentioned components.

(Blocked isocyanate compound)
The photosensitive layer can further contain a blocked isocyanate compound from the viewpoint of hardness after curing.
The blocked isocyanate compound means "a compound having a structure in which the isocyanate group of isocyanate is protected (masked) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is preferably 100 ° C. to 160 ° C., more preferably 130 ° C. to 150 ° C.
The dissociation temperature of blocked isocyanate in the present specification refers to the deprotection reaction of blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis with a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Co., Ltd.). It means the temperature of the accompanying heat absorption peak.

Examples of the blocking agent having a dissociation temperature of 100 ° C to 160 ° C include pyrazole compounds (3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4-nitro-3,5-dimethyl). Pyrazole, etc.), active methylene compounds (malonate diesters (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonate, etc.), etc.), triazole compounds (1,2,4-triazole, etc.), Examples thereof include oxime compounds (compounds having a structure represented by -C (= N-OH)-in the molecule such as formaldehyde, acetaldoxime, acetoxime, methylethylketoxime, cyclohexanoneoxime) and the like. Among them, an oxime compound or a pyrazole compound is preferable, and an oxime compound is particularly preferable, from the viewpoint of storage stability.

Further, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body. The blocked isocyanate compound having an isocyanurate structure can be prepared, for example, by converting hexamethylene diisocyanate into isocyanurate and protecting it.
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 it is easy to reduce the development residue. It is preferable from.

The blocked isocyanate compound used in the present disclosure preferably has a radically polymerizable group from the viewpoint of hardness after curing.
The radically polymerizable group is not particularly limited, and a known polymerizable group can be used. For example, an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group or a styryl group, a glycidyl group or the like can be used. Examples thereof include a group having an epoxy group of. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloxy group, from the viewpoint of the surface surface condition, development speed and reactivity of the obtained cured film.

Examples of the blocked isocyanate compound used in the present disclosure include commercially available blocked isocyanate compounds. For example, Karenz AOI-BM, Karenz MOI-BM, Karenz MOI-BP (all manufactured by Showa Denko KK), block type Duranate series (manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like can be mentioned.

The blocked isocyanate compound used in the present disclosure preferably has a molecular weight of 200 to 3,000, more preferably 250 to 2,600, and particularly preferably 280 to 2,200.

In the present disclosure, one type of blocked isocyanate compound may be used alone, or two or more types may be used in combination.
The content of the blocked isocyanate compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the first photosensitive layer.

(Polymerization inhibitor)
The first photosensitive layer may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, the thermal polymerization inhibitor (also referred to as a polymerization inhibitor) described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

When the first photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, preferably 0.01% by mass or more, based on the total mass of the first photosensitive layer. 1% by mass is more preferable, and 0.01% by mass to 0.8% by mass is further preferable.

(Hydrogen donating compound)
The first photosensitive layer can further contain a hydrogen donating compound.
The hydrogen donating compound has an action of further improving the sensitivity of the photopolymerization initiator to the active light, or suppressing the inhibition of the polymerization of the polymerizable compound by oxygen.
Examples of hydrogen donating compounds include amines such as M. et al. R. Sander et al., "Journal of Polymer Society", Vol. 10, pp. 3173 (1972), JP-A-44-20189, JP-A-51-82102, JP-A-52-134692, JP-A-59-138205. Japanese Patent Laid-Open No. 60-84305, Japanese Patent Application Laid-Open No. 62-18537, Japanese Patent Application Laid-Open No. 64-33104, compounds described in Japanese Patent Laid-Open No. 64-33425, Research Disclosure 33825, and the like, and specific examples thereof include triethanolamine. , P-Dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Further, as yet another example of the hydrogen donating compound, an amino acid compound (eg, N-phenylglycine, etc.), an organometallic compound described in JP-A-48-4-2965 (eg, tributyltin acetate, etc.), JP-G Examples thereof include a hydrogen donor described in JP-A-344414, a sulfur compound described in JP-A-6-308727 (eg, Trithian, etc.) and the like.

The content of these hydrogen donating compounds is in the range of 0.1% by mass or more and 30% by mass or less with respect to the total mass of the first photosensitive layer from the viewpoint of improving the curing rate by balancing the polymerization growth rate and the chain transfer. The range of 1% by mass or more and 25% by mass or less is more preferable, and the range of 0.5% by mass or more and 20% by mass or less is further preferable.

(Other ingredients)
The first photosensitive layer may contain other components other than the above-mentioned components.
Examples of other components include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784, and other additives described in paragraphs 0058 to 0071 of Japanese Patent Application Laid-Open No. 2000-310706.

Further, the first photosensitive layer may contain at least one kind of particles (for example, metal oxide particles) as other components for the purpose of adjusting the refractive index and light transmittance.
The metal constituting the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te. From the viewpoint of the transparency of the cured film, the average primary particle size of the particles (for example, metal oxide particles) is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm. The average primary particle size is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particle is not spherical, the longest side is the particle size.
The content of the particles is preferably 0% by mass to 35% by mass, more preferably 0% by mass to 10% by mass, still more preferably 0% by mass to 5% by mass, and 0% by mass with respect to the total mass of the first photosensitive layer. It is more preferably mass% to 1% by mass, and particularly preferably 0% by mass (that is, the first photosensitive layer does not contain particles).

Further, the first photosensitive layer may contain a trace amount of a colorant (pigment, dye, etc.) as another component, but from the viewpoint of transparency, it is preferable that the first photosensitive layer does not substantially contain the colorant.
Specifically, the content of the colorant in the first photosensitive layer is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the first photosensitive layer.

(impurities)
The first photosensitive layer preferably has a low content of impurities.
Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof, as well as free halogens and halide ions (chlorides). Material ions, bromide ions, iodide ions, etc.) and the like.
The content of impurities in the first photosensitive layer is preferably 1000 ppm or less, more preferably 200 ppm or less, still more preferably 40 ppm or less on a mass basis. Although the lower limit is not particularly defined, it can be 10 ppb or more and 100 ppb or more on a mass basis from the viewpoint of the limit that can be reduced realistically and the measurement limit.
Examples of the method for reducing impurities to the above range include selecting a resin and additive raw materials that do not contain impurities, and preventing impurities from being mixed during layer formation. By such a method, the amount of impurities can be kept within the above range.
Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy and atomic absorption spectroscopy.

In addition, 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 first photosensitive layer is low. Is preferable. The content of these compounds in the first photosensitive layer is preferably 1000 ppm or less, more preferably 200 ppm or less, still more preferably 40 ppm or less on a mass basis. Although the lower limit is not particularly defined, it can be 10 ppb or more and 100 ppb or more on a mass basis from the viewpoint of the limit that can be reduced realistically and the measurement limit.
The content of impurities can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.

The thickness of the first photosensitive layer is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 12 μm or less. When the thickness of the first photosensitive layer is 20 μm or less, the entire transfer film is thinned, the transmittance of the first photosensitive layer or the obtained cured film is improved, and the yellow coloring of the first photosensitive layer or the obtained cured film is suppressed. It is advantageous in terms of such things.
From the viewpoint of manufacturing suitability, the thickness of the first photosensitive layer is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more.

The refractive index of the first photosensitive layer is preferably 1.47 to 1.56, more preferably 1.50 to 1.53, further preferably 1.50 to 1.52, and 1.51 to 1.52. Especially preferable.
In the present disclosure, "refractive index" refers to the refractive index at a wavelength of 550 nm.
Unless otherwise specified, the "refractive index" in the present disclosure means a value measured by ellipsometry with visible light having a wavelength of 550 nm at a temperature of 23 ° C.

-Formation of the first photosensitive layer-
The method for forming the first photosensitive layer is not particularly limited, and a known method can be used.
As an example of the method for forming the first photosensitive layer, a composition for forming the first photosensitive layer (composition for the first photosensitive layer) containing a solvent is applied onto the temporary support by a method such as coating, and it is necessary. A method of forming by drying according to the above can be mentioned.
The composition for the first photosensitive layer is mixed with at least a binder polymer, a polymerizable compound, a photopolymerization initiator and a solvent (particularly an organic solvent), and if necessary, other components such as a surfactant and an additive. Can be prepared by.

As a coating method, a known method can be used, and for example, a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, a die coating method (that is, a slit coating method) and the like can be used. The die coat method is preferable.
As a drying method, known methods such as natural drying, heat drying, and vacuum drying can be applied alone or in combination of two or more.

As the solvent used in the composition for the first photosensitive layer, a commonly used solvent can be used without particular limitation. 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, 2-propanol and the like.
Further, the solvent may be used as a mixed solvent in which two or more kinds of organic solvents are mixed.
As the mixed 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.

When a solvent is used, the solid content of the composition for the first photosensitive layer is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 40% by mass, based on the total amount of the composition for the first photosensitive layer. 5% by mass to 30% by mass is particularly preferable.

When a solvent is used, the viscosity (25 ° C.) of the composition for the first photosensitive layer is preferably 1 mPa · s to 50 mPa · s, more preferably 2 mPa · s to 40 mPa · s, and 3 mPa · s from the viewpoint of coatability. -S to 30 mPa · s is more preferable.
The viscosity is a value measured using, for example, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.).
When the composition for the first photosensitive layer contains a solvent, the surface tension (25 ° C.) of the composition for the first photosensitive layer is preferably 5 mN / m to 100 mN / m, preferably 10 mN / m to m, from the viewpoint of coatability. 80 mN / m is more preferable, and 15 mN / m to 40 mN / m is particularly preferable.
The surface tension is a value measured using, for example, Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

As the solvent, the solvent described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073 can also be used, and the contents of this specification are incorporated herein by reference.
Further, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 ° C. to 250 ° C. can be used, if necessary.

(Shading layer)
The light-shielding layer is a layer having a light-blocking property arranged on the side opposite to the side having the temporary support of the first photosensitive layer, contains at least a binder polymer, and is formed with an optical density of 0.5 or more. It is a thing. The light-shielding layer preferably contains an ultraviolet absorbing material in addition to the binder polymer, and may contain a curing component if necessary, and may contain other components such as a surfactant, a solvent, and an additive. May be good.
Curing components include polymerizable compounds, photopolymerization initiators and the like.

The light-shielding layer has an optical density of 0.5 or more.
When the optical density is 0.5 or more, it is easy to absorb light over a wide wavelength region, and the amount of light transmitted from one side of the light-shielding layer to the other side can be suppressed to a small value. This makes it possible to reduce the influence of light from the other side on the photosensitive layer arranged on one side of the transparent substrate.
From the above viewpoint, the higher the optical density is, the more preferable, 1.5 or more is preferable, 2.0 or more is more preferable, 2.5 or more is further preferable, and 3.0 or more is further preferable.
Although the upper limit of the optical density is not set, the optical density can be set to 6.0 or less or 5.0 or less, for example, from the viewpoint of ease of formulation design of the light-shielding layer.

For the optical density in the present disclosure, a laminate having a laminated structure of a temporary support / a light-shielding layer / a glass substrate is prepared, and the optical density of the laminate is measured using a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.). Measure. Further, the optical densities of the temporary support and the glass substrate used for the laminated body are measured by the same method. Then, the optical density of the temporary support and the glass substrate is subtracted from the optical density of the laminated body to obtain the optical density of the light-shielding layer.

-Binder polymer-
The light-shielding layer contains at least one of the binder polymers.
The binder polymer is preferably a resin (so-called alkali-soluble resin) that can be dissolved by contact with an alkaline solvent.

Examples of the binder polymer include the resins described in paragraphs 0025 of JP2011-95716A and paragraphs 0033 to 0052 of JP2010-237589A.

The light-shielding layer preferably contains a binder polymer having a carboxy group, and particularly preferably contains a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, from the viewpoint of improving the pattern forming property.
The acid value of the binder polymer is preferably 60 mgKOH / g or more and 250 mgKOH / g or less, and 70 mgKOH / g or more and 180 mgKOH / g or less is preferable.
By containing the binder polymer having a carboxy group, the linearity of the formed pattern end portion becomes better, and the so-called edge roughness tends to be improved.
The edge roughness means that the edge of the pattern is observed with a laser microscope (for example, VK-9500, KEYENCE Co., Ltd., objective lens 50x), and the most bulging part of the pattern edge in the field of view (for example). The difference between the peak (mountain top) and the most constricted part (valley bottom) is taken as the absolute value, the absolute value is obtained for 5 different points, and the average value of the 5 points is calculated, which means the calculated value.

Specific examples of the binder polymer include a random copolymer of benzyl (meth) acrylate / (meth) acrylic acid, a random copolymer of styrene / (meth) acrylic acid, and cyclohexyl (meth) acrylate / (meth) acrylic. Acid / methyl (meth) acrylate copolymer, cyclohexyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer glycidyl (meth) acrylate adduct, benzyl (meth) acrylate / (meth) ) Glycidyl (meth) acrylate adduct of copolymer of acrylic acid, allyl (meth) acrylate / copolymer of (meth) acrylic acid, benzyl (meth) acrylate / (meth) acrylic acid / hydroxyethyl (meth) acrylate Examples thereof include the copolymer of.
Of these, a random copolymer of benzyl (meth) acrylate / (meth) acrylic acid is preferable from the viewpoint of developability.

As the binder polymer, commercially available products on the market may be used, for example, Acribase (registered trademark) FFS-6058, FF187 of Fujikura Kasei Co., Ltd., Acrit (registered trademark) 8KB-001 of Taisei Fine Chemical Co., Ltd., etc. The 8KB series can be mentioned.

The weight average molecular weight (Mw) of the binder polymer is preferably 4000 to 25000, more preferably 4000 to 20000, and even more preferably 5000 to 18000.
When the weight average molecular weight of the binder polymer is 4000 or more, the removability of the first photosensitive layer during development becomes good. Furthermore, since the tackiness of the formed pattern is suppressed, when the transfer film has a protective film, the peelability of the protective film when the protective film is peeled off is improved. On the other hand, when the weight average molecular weight of the binder polymer is 25,000 or less, the heat dripping property is improved and the generation of development residue is suppressed.

The weight average molecular weight of the binder polymer can be measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A". It is made from 8 samples of "-2500", "A-1000" and "n-propylbenzene".
<Condition>
-GPC: HLC (registered trademark) -8020GPC (manufactured by Tosoh Corporation)
-Column: TSKgel (registered trademark), Super Multipole HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) 3 bottles-Eluent: THF (tetrahydrofuran)
-Sample concentration: 0.45% by mass
-Flow velocity: 0.35 ml / min
-Sample injection volume: 10 μl
・ Measurement temperature: 40 ° C
-Detector: Differential refractometer (RI)

The acid value of the binder polymer is a value obtained according to the method described in JIS K0070 (1992).

The content of the binder polymer in the light-shielding layer is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 60% by mass, still more preferably 20% by mass to 50% by mass, based on the total solid content of the light-shielding layer. ..

-UV absorbing material-
The light-shielding layer preferably further contains at least one type of UV-absorbing material.
The ultraviolet light here refers to light having a wavelength in the range of 250 nm to 400 nm.
The ultraviolet absorbing material is not limited as long as it is a material that absorbs ultraviolet rays, and examples thereof include pigments (particularly black pigments) and materials called ultraviolet absorbers having an absorption maximum between 250 nm and 400 nm. Be done.

(Black pigment)
The black pigment is not particularly limited as long as it can exhibit light-shielding properties in the light-shielding layer.
As the black pigment, known black pigments, for example, organic pigments and black pigments selected from inorganic pigments can be preferably used. Inorganic pigments include pigments containing metal compounds such as metal pigments and metal oxide pigments.
From the viewpoint that the optical density of the formed light-shielding layer is good, examples of the black pigment include carbon black, titanium carbon, titanium oxide pigments such as iron oxide and titanium black, and graphite.

The light-shielding layer in the present disclosure preferably contains carbon black as an ultraviolet absorbing material.
Carbon black is also available as a commercially available product, and examples thereof include FDK-911 [trade name: FDK-911], which is a black pigment dispersion manufactured by Tokyo Ink Co., Ltd.
The carbon black is preferably a carbon black whose surface is coated with a resin (hereinafter, also referred to as a resin-coated carbon black) in that the uniform dispersibility of the carbon black in the light-shielding layer becomes better. The carbon black may be coated with the resin as long as at least a part of the surface of the carbon black is covered, and the entire surface may be covered.
The resin-coated carbon black can be produced, for example, by the method described in paragraphs 0036 to 0042 of Japanese Patent No. 5320652. It is also available as a commercially available product, and examples thereof include SF Black GB4051 manufactured by Sanyo Dye Co., Ltd.

From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 μm to 0.3 μm, more preferably 0.01 μm to 0.2 μm in terms of number average particle size.
The "particle size" refers to the diameter when the electron micrograph image of the particles is made into a circle of the same area, and the "number average particle size" is the particle size obtained for any 100 particles, and this particle size is obtained. The average value of.
The number average particle size of the black pigment contained in the light-shielding layer is included in the viewing angle using a photograph of the light-shielding layer containing the black pigment taken with a transmission electron microscope (JEOL) at a magnification of 300,000. The particle size can be measured for any 100 particles and calculated as the average value of the measured values.

(Pigments other than black)
Examples of the pigment other than black include the pigments described in JP-A-2008-224982, paragraphs 0030 to 0044, which exhibit a hue other than black, C.I. I. Pigment Green 58, C.I. I. Examples thereof include pigments in which the chloro group (Cl) of Pigment Blue 79 is changed to a hydroxyl group (OH).

Above all, C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; C.I. I. Pigment Orange 36, 38, 62, 64; C.I. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255; C.I. I. Pigment Violet 19, 23, 29, 32; C.I. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; C.I. I. Pigment Green 7, 36, 37, and 58 are preferred. However, the pigment that can be contained in the light-shielding layer is not limited to the above pigments.

Specific examples of the ultraviolet absorber having an absorption maximum between 250 nm and 400 nm include Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (all manufactured by Taiwan Eiko Chemical Industry Co., Ltd.), and Tomisorb 800 (AP). Benzophenone compounds such as SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (all manufactured by Sipro Chemical Co., Ltd.); (Above, manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (above, manufactured by Johoku Chemical Industry Co., Ltd.), TINUVIN PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130 (above, BASF) EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB77, EVERSORB78, EVERSORB80, Benzotriazole compounds such as SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (all manufactured by Sumitomo Chemical Co., Ltd.); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.) Hydroxyphenyltriazine compounds such as TINUVIN460, TINUVIN477DW, and TINUVIN479 (above, manufactured by BASF); and the like can be mentioned.

The content of the ultraviolet absorbing material in the light-shielding layer (the content of the black pigment when the light-shielding layer contains only the black pigment, and the total mass of both the black pigment and the non-black pigment when the light-shielding layer contains the black pigment) is the total solid of the light-shielding layer. It is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and further preferably 20% by mass to 45% by mass with respect to the amount.
When the content of the ultraviolet absorbing material is 10% by mass or more, the optical density of the light-shielding layer can be increased while keeping the film thickness thin. When the content of the ultraviolet absorbing material is 70% by mass or less, the curing sensitivity when patterning the light-shielding layer becomes good.

-Polymerizable compound-
The light-shielding layer preferably further contains at least one type of polymerizable compound as a curing component. When the light-shielding layer contains a polymerizable compound, it has excellent solubility during development. The polymerizable compound is a compound having at least one polymerizable group in the molecule, and may be either a monomer or a polymer, but is a monomer (that is, polymerizable) in terms of solubility during development. Monomer) is more preferred. The type of polymerizable group is not particularly limited.

Examples of the polymerizable group include an ethylenically unsaturated group and an epoxy group, and an ethylenically unsaturated group is preferable, and a (meth) acryloyl group is more preferable.

The polymerizable compound is preferably a bifunctional or higher (polyfunctional) polymerizable monomer having two or more polymerizable groups, and more preferably a bifunctional polymerizable monomer. By using the polyfunctional polymerizable monomer, it is possible to suppress the generation of development residue when developing the light-shielding layer. By using a bifunctional polymerizable monomer, it is possible to suppress the generation of development residue even in development with a weak alkaline developer (for example, an aqueous sodium carbonate solution).

Examples of the polymerizable compound include monofunctional acrylates or monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate and polypropylene glycol. Di (meth) acrylate, trimethylol ethanetriacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropanetri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) ) Cyanurate, glycerin tri (meth) acrylate; polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin and then (meth) acrylated can be mentioned. ..
Further, urethane-based monomers such as urethane (meth) acrylate compounds can also be preferably used.

Further, the urethane acrylates described in JP-A-48-41708, JP-B-50-6034, and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, and JP-B. Polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Urethane (meth) acrylate compounds are preferred from the viewpoint of layer bendability.

As the polymerizable compound, a commercially available product on the market may be used.
Examples of commercially available products include tricyclodecanedimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Industry Co., Ltd., bifunctional, molecular weight 304), tricyclodecanedimenanol dimethacrylate (DCP, Shin-Nakamura Chemical Industry Co., Ltd.). , Bifunctional, molecular weight 332), 1,9-nonandiol diacrylate (A-NOD-N, Shin-Nakamura Chemical Industry Co., Ltd., bifunctional, molecular weight 268), 1,6-hexanediol diacrylate (A) -HD-N, Shin-Nakamura Chemical Industry Co., Ltd., Bifunctional, Molecular Weight 226), 9,9-Bis [4- (2-acryloyloxyethoxy) phenyl] Fluolen (A-BPEF, Shin-Nakamura Chemical Industry Co., Ltd.) , Bifunctional, molecular weight 546), urethane acrylate (UA-160TM, Shin-Nakamura Chemical Industry Co., Ltd., bifunctional, molecular weight 1600), 1,6-hexanediol diacrylate (V # 230, Osaka Organic Chemical Industry Co., Ltd.) , Bifunctional, molecular weight 226), 1,3-adamantyldiacrylate (ADDA, Mitsubishi Gas Chemicals Co., Ltd., bifunctional, molecular weight 276), trimethyl propantriacrylate (A-TMPT, Shin-Nakamura Chemical Industry Co., Ltd.), Trifunctional, molecular weight 296), trimethylolpropaneethylene oxide (EO) modified (n≈1) triacrylate (M-350, Toa Synthetic Co., Ltd., trifunctional), pentaerythritol tetraacrylate (A-TMMT, Shin-Nakamura Chemical) Industrial Co., Ltd., 4-functional, molecular weight 352), dipentaerythritol hexaacrylate (A-DPH, Shin-Nakamura Chemical Industry Co., Ltd., 6-functional, molecular weight 578), pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (UA- 306H, Kyoeisha Chemical Co., Ltd., 6-functional), Pentaerythritol triacrylate toluenediisocyanate urethane prepolymer (UA306T, Kyoeisha Chemical Co., Ltd., 6-functional), Dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.), 6-functionality, molecular weight 579), urethane acrylate (UA-32P, Shin-Nakamura Chemical Industry Co., Ltd., 9-functionality), urethane acrylate (8UX-015A, Taisei Fine Chemicals Co., Ltd., 15-functionality) and the like are preferably mentioned.

The polymerizable compound preferably has a molecular weight of 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and particularly preferably 500 or less.
When the molecular weight of the polymerizable compound is 500 or less, heat dripping is likely to occur in the heat treatment at a low temperature. In particular, a bifunctional polymerizable monomer having a molecular weight of 500 or less is preferable.

The molecular weight of the polymerizable compound is determined by mass spectrometry (eg, liquid chromatograph (LC / MS) analysis, gas chromatograph (GC / MS) analysis, fast atom bombardment chromatograph (FAB / MS analysis), etc.). , Can be obtained from the molecular formula.

The polymerizable compound may be used alone or in combination of two or more.
Above all, it is preferable to use two or more kinds of polymerizable compounds in combination in terms of removability during development. Further, from the viewpoint of suppressing residues during development (preferably carbonic acid development) and film strength, it is preferable to use a bifunctional polymerizable compound and a non-bifunctional polymerizable compound in combination.

The content of the polymerizable compound contained in the light-shielding layer is preferably 0% by mass to 50% by mass, more preferably 0% by mass to 40% by mass, and 0% by mass to 30% by mass with respect to the total solid content of the composition. % Is more preferable.

When a bifunctional polymerizable compound and a non-bifunctional polymerizable compound are used in combination, the bifunctional polymerizable property with respect to the total mass of the polymerizable compound (the total amount of the bifunctional polymerizable compound and the non-bifunctional polymerizable compound). The ratio of the mass of the compound (bifunctional polymerizable compound / total weight of the polymerizable compound) is preferably 50% by mass or more.
When (the total mass of the bifunctional polymerizable compound / the polymerizable compound) is 50% by mass or more, it is advantageous in terms of suppressing the development residue by the weak alkaline developer (for example, an aqueous sodium carbonate solution) and the film strength.

-Quantitative relationship between binder polymer and polymerizable compound-
In the light-shielding layer, the mass ratio (M / B ratio) of the content (M) of the above-mentioned polymerizable compound to the content (B) of the above-mentioned binder polymer is preferably 0.50 or less. When the M / B ratio is 0.50 or less, the linearity of the formed pattern becomes better.

-Photopolymerization initiator-
The light-shielding layer can further contain at least one kind of photopolymerization initiator as a curing component.
It is effective in improving the pattern shape after development.
On the other hand, if too much photopolymerization initiator is contained, for example, when the light irradiated from the other side reaches one side, the polymerization reaction of the light-shielding layer proceeds, and the polymerization reaction is in the vicinity of the transparent substrate. In some cases, the residue of the light-shielding layer after development (remaining removal of the light-shielding layer during development (so-called fog) is likely to occur.
Therefore, the content of the photopolymerization initiator in the light-shielding layer is preferably 1% by mass or less with respect to the total solid content of the light-shielding layer from the viewpoint of suppressing deterioration of the residue of the light-shielding layer in the light irradiation region. For the above reasons, the content of the photopolymerization initiator is more preferably less than 0.5% by mass, further preferably 0% by mass (not contained).

Examples of the photopolymerization initiator include the photopolymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-95716 and the oxime-based photopolymerization initiator described in paragraphs 0064 to 0081 of JP-A-2015-014783. Be done.
As the photopolymerization initiator, a commercially available product on the market may be used.
Examples of commercially available products include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (trade name: IRGACURE OXE-01, BASF), 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] Etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), 2- (dimethylamino)- 2-[(4-Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropane-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Phenyl} -2-methyl-propane-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name:) IRGACURE 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (trade name: IRGACURE 1173, manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name:) IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF), trade name of oxime ester-based photopolymerization initiator: Lunar 6 (trade name: DKSH Japan Co., Ltd.), 2,4-diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.), DFI-091 and DFI-020, which are fluorene oxime-based photopolymerization initiators. (Both manufactured by Daito Kemix Co., Ltd.) are preferable.

-Surfactant-
The light-shielding layer can contain at least one of the surfactants.
Examples of the surfactant include the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362. Above all, from the viewpoint of improving the film property at the time of forming the light-shielding layer coating, a fluorine-based surfactant (for example, Megafuck (registered trademark) F-784-F, F-780F, F-555A, etc. manufactured by DIC Corporation), etc. ) Is preferably used.

When the light-shielding layer contains a surfactant, the content of the surfactant in the light-shielding layer is preferably 0.01% by mass to 3% by mass, preferably 0.05% by mass, based on the total mass of the light-shielding layer. ~ 1% by mass is more preferable, and 0.1% by mass to 0.8% by mass is further preferable.

-Other ingredients-
The light-shielding layer may contain other components such as a polymerization inhibitor, a dye, and an additive, if necessary, in addition to the above-mentioned components.

(Polymerization inhibitor)
The light-shielding layer preferably contains at least one polymerization inhibitor.
When the light-shielding layer contains a polymerization inhibitor, the generation of development residue is further suppressed. As the polymerization inhibitor, for example, the thermal polymerization inhibitor (also referred to as a polymerization inhibitor) described in paragraph 0018 of Japanese Patent No. 4502784 can be used. Among them, as the polymerization inhibitor, phenothiazine, hydroquinone monomethyl ether and the like can be preferably used.

(dye)
The light-shielding layer may contain a dye from the viewpoint of exhibiting antireflection ability.
The dyes that can be contained in the light-shielding layer are not particularly limited, and are known dyes, for example, known dyes described in documents such as "Handbook of Dyes" (edited by the Society of Synthetic Organic Chemistry, published in 1970), or Dyes available as commercially available products can be appropriately selected and used.
Specific examples of the dye include azo dye, metal complex salt azo dye, pyrazolone azo dye, naphthoquinone dye, anthraquinone dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine dye, cyanine dye, squarylium dye, pyrylium salt, metal thiolate complex and the like. Dyes can be mentioned.

When the light-shielding layer contains a dye, the content of the dye is preferably 1 part by mass to 40 parts by mass with respect to 100 parts by mass of the above-mentioned pigment from the viewpoint of exhibiting antireflection ability. It is more preferably 20 parts by mass to 20 parts by mass. When the content of the dye is in the above range, the antireflection effect in the formed light-shielding layer, that is, the effect of visually suppressing glare becomes good.

(Additive)
Examples of the additive include other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

(impurities)
The light-shielding layer preferably has a low content of impurities.
The details of the impurities in the light-shielding layer and the details such as the preferred embodiment are the same as in the case of the first photosensitive layer described above, and thus the description thereof will be omitted here.

The thickness of the light-shielding layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the light-shielding layer is 20 μm or less, it is advantageous in terms of thinning the entire transfer film. The thickness of the light-shielding layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of manufacturing suitability.

~ Formation of light-shielding layer ~
The method for forming the light-shielding layer is not particularly limited, and a known method can be used.
As an example of the method for forming the light-shielding layer, for example, a composition for a light-shielding layer containing a solvent on the surface of the first photosensitive layer described above, or on the surface of the intermediate layer when the intermediate layer is provided on the first photosensitive layer. Is applied by a method such as coating, and if necessary, it is dried to form the mixture.
The composition for a light-shielding layer can be prepared by mixing at least a binder polymer and a solvent (particularly an organic solvent), and if necessary, other components such as a curing component, a surfactant and an additive.

The method of coating and the method of drying are the same as in the case of the first photosensitive layer described above, and known methods can be applied, and are used, for example, for coating and drying the first photosensitive layer described above. A method similar to the method can be mentioned.

When a black pigment is used as an ultraviolet absorbing material for the light-shielding layer, it is desirable that the black pigment is used in the composition for the light-shielding layer as a dispersion liquid in which the black pigment is dispersed.
The dispersion liquid can be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent or a vehicle described later and dispersing the mixture. The vehicle refers to a medium portion in which a pigment is dispersed, and includes a binder component that is liquid and forms a layer by binding to a black pigment, and a medium such as an organic solvent that dissolves and dilutes the binder component.
The disperser used to disperse the black pigment is not particularly limited, and for example, the kneader described in "Encyclopedia of Pigments" (First Edition, Kunizo Asakura, Asakura Shoten, 2000, p. 438). Known dispersers such as roll mills, attritors, super mills, dissolvers, homomixers, and sand mills can be mentioned. Further, the black pigment which is a dispersoid may be finely pulverized by using the frictional force by the mechanical grinding described on page 310.
The pigment dispersant may be selected according to the type of the pigment and the organic solvent, and for example, a commercially available dispersant can be used.

-solvent-
As the solvent used in the composition for a light-shielding layer, a commonly used organic solvent can be used without particular limitation, and examples thereof include esters, ethers, ketones, aromatic hydrocarbons and the like.
Further, as the solvent, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PEGMEA), cyclohexanone, cyclohexanol, and methyl isobutyl, as in Solvent described in paragraphs 0054 and 0055 of US Patent Publication No. 2005/282073. Ketone, ethyl lactate, methyl lactate and the like can be used.
Among them, as the solvent, 1-methoxy-2-propyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, etc. Cyclohexanone, diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate, methyl ethyl ketone and the like are suitable.
The solvent may be used alone or in combination of two or more.
Further, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 ° C. to 250 ° C. can be used, if necessary.

When a solvent is used, the solid content of the light-shielding layer composition is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 40% by mass, and 5% by mass, based on the total amount of the light-shielding layer composition. ~ 30% by mass is particularly preferable.

(Middle layer)
It is preferable to have an intermediate layer between the first photosensitive layer and the light-shielding layer.
By arranging the intermediate layer between the first photosensitive layer and the light-shielding layer, it is possible to suppress the movement of the photopolymerization initiator in the first photosensitive layer to the light-shielding layer during storage after coating. When the photopolymerization initiator moves from the first photosensitive layer to the light-shielding layer and mixes, and the content ratio of the photopolymerization initiator in the light-shielding layer increases, the light from the side of the transparent substrate that does not have the light-shielding layer becomes a transparent group. When the material is transmitted and incident on the light-shielding layer, the polymerization reaction in the light-shielding layer tends to proceed, and since the polymerization reaction proceeds in the vicinity of the transparent substrate, the residue of the light-shielding layer after development (light-shielding during development). Layer removal residue (so-called fog) is likely to occur.

The intermediate layer preferably contains a binder polymer, more preferably contains a binder polymer that is soluble in water or a lower alcohol having 1 to 4 carbon atoms, and may contain a binder polymer and a polymerizable compound. More preferred.

-Binder polymer-
The intermediate layer preferably contains a binder polymer that is soluble in water or a lower alcohol having 1 to 4 carbon atoms as a main component. When such a binder polymer is contained, it is easy to remove it at the time of development and it is easy to form a good pattern.

In the present disclosure, "containing as a main component" is a binder polymer contained most in the binder component contained in the intermediate layer, or a content ratio of the binder component contained in the intermediate layer to the whole. Is a binder polymer of 50% by mass or more.

The binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms can be appropriately selected from known ones, and examples thereof include polyvinyl alcohol and polyvinylpyrrolidone. Above all, as the binder polymer used for the intermediate layer, a combination of polyvinyl alcohol and polyvinylpyrrolidone is preferable.

In addition, "having solubility in water or a lower alcohol having 1 to 4 carbon atoms" means a property of dissolving 5 g or more in 100 ml of water or a lower alcohol having 1 to 4 carbon atoms at 25 ° C.
Here, examples of water include ion-exchanged water and distilled water.
Examples of the lower alcohol having 1 to 4 carbon atoms include methanol, ethanol, propanol, isopropanol, and butanol.

The content of the binder polymer contained in the intermediate layer is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total solid content of the intermediate layer. The upper limit value is not particularly limited and may be adjusted within the range of 100% by mass or less.

-Polymerizable compound-
The intermediate layer further preferably contains at least one polymerizable compound.
The inclusion of a polymerizable compound is preferable in terms of suppressing residues during development (preferably carbonic acid development).

As the polymerizable compound that can be used for the intermediate layer, the same polymerizable compound that can be used for the first photosensitive layer or the light-shielding layer can be appropriately selected and used, and a polymerizable monomer is preferable. Among them, acrylamide monomers (for example, FAM-401, FAM-301, FAM-201, FAM-402, etc. manufactured by FUJIFILM Corporation) are preferable from the viewpoint of solubility in water.
The polymerizable compound may be used alone or in combination of two or more.
The content of the polymerizable compound contained in the intermediate layer is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total solid content of the intermediate layer.

-Photopolymerization initiator-
The intermediate layer may further contain at least one of the photopolymerization initiators.
As the photopolymerization initiator that can be used for the intermediate layer, for example, the same photopolymerization initiator that can be used for the first photosensitive layer or the light-shielding layer can be appropriately selected and used.
When the intermediate layer contains a photopolymerization initiator, it is effective in improving the pattern shape after development.
The content of the photopolymerization initiator contained in the intermediate layer is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the intermediate layer.

-Surfactant-
The intermediate layer can contain at least one of the surfactants.
As the surfactant, a fluorine-containing surfactant (for example, Megafuck (registered trademark) F-784F, F-780F, F manufactured by DIC Corporation) is used from the viewpoint of improving the film property when the intermediate layer is applied and formed. -444 etc.) and the like.
The content of the surfactant contained in the intermediate layer is preferably 0.001% by mass to 1% by mass, more preferably 0.001% by mass to 0.5% by mass, based on the total solid content of the intermediate layer. It is more preferably 0.001% by mass to 0.1% by mass.

-Other ingredients-
The intermediate layer may contain other components such as additives, if necessary. The additives are the same as those that can be added to the light-shielding layer.

The thickness of the intermediate layer is preferably 0.2 μm to 5 μm, more preferably 0.5 μm to 3 μm, and even more preferably 0.8 μm to 2 μm.

～ Formation of middle layer ～
The method for forming the intermediate layer is not particularly limited, and a known method can be used.
As a method for forming the intermediate layer, for example, a method of applying a solvent-containing composition for an intermediate layer to the surface of the first photosensitive layer described above by a method such as coating and drying the intermediate layer as necessary can be mentioned. Be done.
The composition for the intermediate layer can be prepared by mixing at least a binder polymer and an aqueous solvent, and if necessary, other components such as a curing component, a surfactant and an additive. For the preparation of the composition for the intermediate layer, it is preferable to use a solvent different from that of the first photosensitive layer and the light-shielding layer, and an aqueous solvent is preferably used. Examples of the aqueous solvent include water, a mixed solvent of water and a possible organic solvent in water, and the like. The composition for the intermediate layer is preferably an aqueous composition.

The method of coating and the method of drying are the same as in the case of the first photosensitive layer described above, and known methods can be applied, and are used, for example, for coating and drying the first photosensitive layer described above. A method similar to the method can be mentioned.

(Protective film)
The transfer film of the present disclosure may have a protective film on the surface of a light-shielding layer laminated on a temporary support. By attaching a protective film, it is possible to protect the exposed surface from contamination by impurities such as foreign substances during storage.

The protective film is preferably one that can be easily peeled off from the light-shielding layer, and a base material that is the same as or similar to the temporary support described later can be used.
Examples of the protective film include a polyolefin film (for example, polypropylene (PP) film, polyethylene (PE) film, etc.), polyethylene terephthalate (PET) film, silicon paper, polytetrafluoroethylene film, and the like.
Further, the protective film described in paragraphs 0083 to 0087 and 093 of JP-A-2006-259138 can be appropriately used.

The thickness of the protective film is preferably 0.2 μm to 40 μm, more preferably 0.5 μm to 30 μm.

(Temporary support)
The temporary support is preferably a base material made of resin in terms of peeling from the transfer film, and more preferably a base material using a material that exhibits flexibility after molding. The base material may be either a film or a sheet.
Further, the temporary support may have transparency or may be colored (for example, colored by containing silicon dyed, alumina sol, chromium salt, zirconium salt and the like).

Examples of the temporary support include a cycloolefin copolymer base material, a polyethylene terephthalate (PET) base material, a cellulose triacetate base material, a polystyrene base material, a polycarbonate base material, and the like, and among them, a PET base material from the viewpoint of handling. Is particularly preferable.

As the temporary support, a temporary support to which conductivity is imparted is also suitable, and the conductivity may be imparted by, for example, the method described in Japanese Patent Application Laid-Open No. 2005-221726.

The thickness of the temporary support is preferably 5 μm to 60 μm, more preferably 5 μm to 40 μm.

An example of the transfer film of the present disclosure will be described with reference to FIG.
The transfer film of the present disclosure may have at least a first photosensitive layer and a light-shielding layer on the temporary support, and may have an intermediate layer between the first photosensitive layer and the light-shielding layer.
As shown in FIG. 1, the transfer film 10 has a laminated structure in which a first photosensitive layer 17, an intermediate layer 15, a light-shielding layer 13, and a protective film 11 are laminated in this order from the temporary support side on the temporary support 19. Have. By providing the intermediate layer 15 between the first photosensitive layer 17 and the light-shielding layer 13, the movement of the photopolymerization initiator from the first photosensitive layer 17 to the light-shielding layer 13 is suppressed. As a result, the polymerization reaction in the light-shielding layer when the laminate is produced and irradiated with light from both sides of the transparent substrate is suppressed, and the generation of development residue is suppressed. Further, the protective film 11 is peeled off and removed when the laminated body is produced as described later.
The transfer film is not limited to the laminated structure shown in FIG. 1, and may be a laminated structure having no intermediate layer as shown in the laminated body of FIG.

The transfer film according to the embodiment of the present disclosure can be used, for example, as a transfer film for forming a wiring pattern of a metal wiring board arranged in an image display device such as a touch panel.
A method of transferring a first photosensitive layer, a light-shielding layer, or the like to a transparent substrate using the transfer film of the present disclosure to form a pattern will be described later.

The transfer film can be stored by a known method.
At the time of storage, the atmosphere can be the atmosphere or nitrogen.
The storage temperature can be a known temperature, and examples thereof include room temperature (20 ° C to 25 ° C), refrigeration temperature (0 ° C to 5 ° C), and freezing temperature (-50 ° C to -10 ° C). .. The storage temperature is preferably a freezing temperature or a refrigerating temperature from the viewpoint of preventing unexpected deterioration of the transfer film. Specifically, the storage temperature may be 5 ° C, −10 ° C, −20 ° C, or −30 ° C.
The storage period is not particularly limited, and examples thereof include a mode in which the transfer film is used after being stored at 5 ° C. for 20 days, and a mode in which the transfer film is stored at −20 ° C. for 50 days.

<Laminated body>
The laminate of the present disclosure has a transparent substrate and the above-mentioned transfer film of the present disclosure laminated on the transparent substrate, and may further have another layer, if necessary.

The details of the transfer film of the present disclosure are as described above, and the details and preferred embodiments of the temporary support, the first photosensitive layer, the light-shielding layer, and the intermediate layer constituting the transfer film are as described above. be.

(Transparent substrate)
The transparent base material is a base material having transparency, and is preferably a material that is not optically distorted and has high transparency. In addition, transparency in the present disclosure is intended to have a transmittance of 85% or more for all visible light, and is preferably 90% or more, more preferably 95% or more.

As the transparent base material in the present disclosure, a glass base material or a resin base material is preferable.
Among them, a resin base material is preferable because it is lightweight and is not easily damaged. Examples of the resin base material include a transparent base material made of a resin such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate (PC), triacetyl cellulose (TAC), and cycloolefin polymer (COP).

The transparent substrate preferably has a refractive index of 1.6 to 1.78 and a thickness of 50 μm to 200 μm from the viewpoint of further improving the visibility of the displayed image.

The transparent substrate may have a single-layer structure or a laminated structure of two or more layers.
When the transparent substrate has a laminated structure of two or more layers, the refractive index means the refractive index of all the layers of the transparent substrate.
The thickness of the transparent substrate means the total thickness of all the layers when the transparent substrate has a laminated structure of two or more layers.

As the transparent substrate, a substrate having a conductive member (for example, an electrode and wiring) on at least one surface is preferable, and a substrate having at least one of an electrode and wiring on both surfaces is more preferable.
In the present disclosure, it is preferable that the transparent base material is a base material having at least one of a touch panel electrode and a touch panel wiring.

As the conductive material used for the conductive member, a transparent conductive material and a metal material are preferable. As the transparent conductive material, for example, a metal oxide film such as ITO (indium tin oxide) or IZO (zinc oxide) is preferable. Examples of the metallic material include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, and alloys composed of two or more of these metallic elements.

In the case of a touch panel application, examples of the touch panel electrode include a transparent electrode pattern arranged at least in an image display area of the touch panel. The touch panel electrode may extend from the image display area to the frame portion of the touch panel.
Further, as the touch panel wiring, for example, a routing wiring (take-out wiring) arranged in the frame portion of the touch panel can be mentioned, and a metal material is suitable. As the material of the routing wiring, copper, molybdenum, aluminum or titanium is preferable, and copper is particularly preferable.

(Second photosensitive layer)
The laminate of the present disclosure has the above-mentioned first photosensitive layer on one side of the transparent substrate, and the transfer film of the present disclosure of the transparent substrate is laminated on the other side of the transparent substrate (that is, the transfer film of the present disclosure of the transparent substrate is laminated. It is preferable to further have a second photosensitive layer on the side opposite to the side).
When the laminate of the present disclosure has a second photosensitive layer, resist patterns (preferably resist patterns having different patterns from each other) can be attached to both sides of the transparent substrate, and fine details can be provided on both sides of the transparent substrate. Wiring patterns (preferably wiring patterns having different patterns from each other) can be formed.

The second photosensitive layer may be the same layer as the first photosensitive layer described above, or may be different layers from each other. The second photosensitive layer is preferably a layer having the same component composition as the first photosensitive layer.
In this case, the first photosensitive layer is provided on one side of the transparent substrate, and the second photosensitive layer is provided on the other side, so that it is possible to simultaneously irradiate light using the same light source. The first photosensitive layer and the second photosensitive layer may be irradiated using different light sources, and the wavelength of the irradiated light may be different.

The second photosensitive layer can be a layer containing at least a binder polymer, a polymerizable compound, and a photopolymerization initiator, and further contains other components such as a surfactant, a solvent, and an additive, if necessary. But it may be.
The details and preferred embodiments of other components such as the binder polymer, the polymerizable compound, the photopolymerization initiator, the surfactant, the solvent, and the additive in the second photosensitive layer are the same as in the case of the first photosensitive layer.
The second photosensitive layer preferably contains a binder polymer, a polymerizable compound, and a photopolymerization initiator.

The thickness of the second photosensitive layer is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 12 μm or less. When the thickness of the second photosensitive layer is 20 μm or less, the entire transfer film is thinned, the transmittance of the second photosensitive layer or the obtained cured film is improved, and the yellow coloring of the second photosensitive layer or the obtained cured film is suppressed. It is advantageous in that.
From the viewpoint of manufacturing suitability, the thickness of the second photosensitive layer is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more.

-Formation of the second photosensitive layer-
The method for forming the second photosensitive layer is not particularly limited, and a known method can be used.
The second photosensitive layer is, for example, a method of applying a coating liquid for forming a second photosensitive layer (coating liquid for a second photosensitive layer) on a transparent substrate, or a above-mentioned book on a transparent substrate. It can be formed by a method of laminating a transfer material different from the disclosed transfer film.
In the latter, as the transfer material, for example, a transfer film having a temporary support and a second photosensitive layer formed by applying a coating liquid for a second photosensitive layer on the temporary support and drying can be used. A transfer film having another layer (for example, the intermediate layer described above) between the temporary support and the second photosensitive layer may be used.
The method of applying and drying the coating liquid for the second photosensitive layer is the same as that of the first photosensitive layer described above, and a known method can be applied. For example, the first photosensitive layer described above can be applied. Examples thereof include methods similar to those used for coating and drying.

<Pattern formation method>
The pattern forming method of the present disclosure includes a step of bonding the transfer film of the present disclosure described above to one side of the transparent base material (hereinafter referred to as a bonding step), and a binder polymer on the other side of the transparent base material. Both sides of the step of forming the second photosensitive layer containing the polymerizable compound and the photopolymerization initiator (hereinafter referred to as the step of forming the second photosensitive layer) and the transparent substrate are irradiated with light in different patterns. (Hereinafter, light irradiation step) and a step of forming different patterns on both sides of the transparent base material by developing the transparent base material after irradiation (hereinafter, light irradiation step). It has a patterning process).
Further, the pattern forming method of the present disclosure may further include other steps, if necessary.

(Lasting process)
In the bonding step, the transfer film of the present disclosure described above is bonded to one side of the transparent substrate.
In this step, the transfer film of the present disclosure can be bonded to one side of a transparent substrate (for example, the side on which an electrode or the like is arranged) by, for example, laminating.
Lamination can be performed using a known laminator such as a vacuum laminator or an auto-cut laminator.

As the laminating condition, general conditions can be applied.
The laminating temperature is preferably 80 ° C. to 150 ° C., more preferably 90 ° C. to 150 ° C., and particularly preferably 100 ° C. to 150 ° C. The laminating temperature refers to the surface temperature of the roll of the laminator provided with the roll (hereinafter referred to as the roll temperature).
The temperature of the transparent substrate at the time of laminating is not particularly limited. The temperature of the transparent substrate at the time of laminating is preferably 10 ° C to 150 ° C, more preferably 20 ° C to 150 ° C, still more preferably 30 ° C to 150 ° C.
The linear pressure at the time of laminating is preferably 0.5 MPa to 10 MPa, more preferably 0.5 MPa to 5 MPa, and particularly preferably 0.5 MPa to 1 MPa.
The transport speed (lamination speed) at the time of laminating is preferably 0.5 m / min to 5 m / min, more preferably 1.5 m / min to 3 m / min.

When a transfer film having a laminated structure of a protective film / light-shielding layer / intermediate layer / first photosensitive layer / temporary support is used, first, the protective film is peeled off from the transfer film to expose the light-shielding layer. Next, the transfer film and the transparent base material are bonded so that the exposed light-shielding layer and the surface on the side where the electrodes of the transparent base material are arranged are in contact with each other.
As a result, the light-shielding layer of the transfer film is brought into close contact with the transparent base material, and a laminated body having a laminated structure of a temporary support / first photosensitive layer / intermediate layer / light-shielding layer / electrode or the like / transparent base material is formed.
In this laminated structure, electrodes and the like are a part of a transparent base material, and are used, for example, as a touch panel substrate.
Then, if necessary, the temporary support is peeled off from the laminated body.

(Second photosensitive layer forming step)
In the second photosensitive layer forming step, a second photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator is formed on the other side of the transparent substrate, that is, the side having no first photosensitive layer and a light-shielding layer. do.
As described above, the second photosensitive layer is formed by, for example, a method of applying a coating liquid for forming a second photosensitive layer (coating liquid for a second photosensitive layer) on a transparent substrate, or a transparent substrate. On top of this, a transfer material different from the transfer film of the present disclosure described above may be bonded by any method.

As for the method of applying and drying the coating liquid for the second photosensitive layer, a known method can be applied in the same manner as in the case of forming the first photosensitive layer described above. Examples thereof include methods similar to those used for drying.
The method of bonding the transfer materials can be performed in the same manner as in the above-mentioned bonding step.

(Light irradiation process)
In the light irradiation step, both sides of the transparent substrate are irradiated with light in different patterns. That is, in this step, pattern exposure is performed in such a manner that the exposed portion and the non-exposed portion are present.
In this step, the exposed portion of the first photosensitive layer exposed to the pattern is cured by the light irradiated from the side where the first photosensitive layer is arranged on the transparent substrate, and finally becomes a cured film. .. Further, also in the second photosensitive layer, the exposed portion of the second photosensitive layer exposed to the pattern is cured by the light irradiated from the side where the second photosensitive layer is arranged on the transparent substrate, and finally. It becomes a hardened film.
On the other hand, of the first photosensitive layer and the second photosensitive layer, the non-exposed portion in the pattern exposure is not cured and is removed (dissolved) by the developing solution in the next patterning step. The unexposed portion may form an opening in the cured film after the developing step.
The pattern exposure may be an exposure through a mask or a digital exposure using a laser or the like.

As the light source for pattern exposure, any light source in a wavelength range capable of curing the photosensitive layer (for example, 365 nm or 405 nm) can be appropriately selected and used.
Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 mJ / cm ² to 200 mJ / cm ² , and more preferably 10 mJ / cm ² to 200 mJ / cm ² .

When the first photosensitive layer and the second photosensitive layer are formed on the transparent substrate using the transfer film, the temporary support may be exposed to a pattern before the temporary support is peeled off, and then the temporary support may be peeled off. The pattern may be exposed after the body is peeled off.
Further, in this step, even if the first photosensitive layer and the second photosensitive layer are heat-treated (so-called PEB (Post Exposure Bake)) after the pattern exposure and before the patterning step (that is, before development). good.

(Patterning process)
In the patterning step, different patterns are formed on both sides of the transparent base material by developing both sides of the transparent base material after the light irradiation is performed in the above light irradiation step.

Development can be performed using a developer.
The developer is not particularly limited, and a known developer such as the developer described in JP-A-5-72724 can be used. The developer is preferably a developer capable of dissolving an unexposed photosensitive resin layer, and for example, a compound having pKa = 7 to 13 (for example, sodium carbonate, potassium hydroxide, etc.) is added at 0.05 mol / L to 5 mol /. A developer containing a concentration of L is preferable. More specifically, an aqueous solution of sodium carbonate, an aqueous solution of potassium hydroxide and the like can be mentioned.
A small amount of an organic solvent miscible with water may be further added to the developing solution. Organic solvents that are miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As the development method, any method such as paddle development, shower development, combination of shower development and spin development, and dip development may be used.
In the case of shower development, a patterned cured product can be formed by removing the uncured portion by spraying the developing solution on the first photosensitive layer and the second photosensitive layer after exposure by a shower. Further, after the development, it is preferable to spray a cleaning agent or the like with a shower and rub it with a brush or the like to remove the development residue.
The liquid temperature of the developing solution is preferably 20 ° C. to 40 ° C., and the pH of the developing solution is preferably 8 to 13.

Hereinafter, an example of the pattern forming method of the present disclosure will be described with reference to FIG.
First, as shown in FIG. 4A, the transfer film 41 of the present disclosure is bonded to one side of the transparent base material 21 (bonding step), and then transferred to the other side of the transparent base material 21. Another transfer film 43 different from the film 41 is bonded (second photosensitive layer forming step), for example, a laminated body having a laminated structure shown in FIG. 3 is prepared.
Then, as shown in FIG. 4B, the first photomask 31 is arranged on the side having the transfer film 41 of the laminated body and the first photomask 31 is arranged on the side having the transfer film 43 of the laminated body when viewed from the transparent base material 21. A second photomask 33 having a pattern different from that of the photomask 31 of the above is arranged, and light is irradiated from both sides of the laminated body through each photomask (light irradiation step). At this time, different pattern exposures are performed on the first photosensitive layer 17 and the second photosensitive layer 27.
Subsequently, the first photomask 31 and the second photomask 33 are removed, and the temporary supports 19 and 19a arranged on both sides of the laminated body are further peeled off, respectively. Then, the first photosensitive layer 17 and the second photosensitive layer 27 exposed on both sides of the laminated body are subjected to a developing process (patterning step). As a result, the region of the first photosensitive layer 17 that has not been pattern-exposed by the first photomask 31 is developed and removed. Further, the region of the light-shielding layer 19 located below the region not exposed to the pattern is also removed. As a result, as shown in FIG. 4C, a pattern is formed by the pattern-exposed first photosensitive layer 17a and the light-shielding layer 13a which is a layer below the first photosensitive layer 17a. Similarly, the portion of the second photosensitive layer 27 that has not been pattern-exposed by the second photomask 33 is developed and removed. As a result, a pattern is formed by the second photosensitive layer 27a that has been exposed to the pattern.
By irradiating both sides of the laminated body with light in this way, the influence of the light irradiated on one side invading the other side and affecting the photosensitive layer on the other side is effectively suppressed. , Patterns having different pattern shapes can be formed finely on both sides of the transparent substrate.

The pattern forming method of the present disclosure is suitably used for forming at least one of a touch panel electrode and a touch panel wiring.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, 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 invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
Unless otherwise specified, "parts" are based on mass.

(Example 1)
<Preparation of transfer film A>
The first photosensitive layer forming composition B-1 having the following composition was applied onto a temporary support (Lumirror (registered trademark) 16QS62 (thickness 16 μm), Toray Industries, Inc .; polyethylene terephthalate film) using a slit-shaped nozzle. It was dried with hot air at 100 ° C. for 2 minutes to form a first photosensitive layer having a dry thickness of 6 μm.
In Table 1, the "polymer" is the binder polymer in the present disclosure, and the "radical polymerizable compound" is the polymerizable compound in the present disclosure.

-Composition for forming the first photosensitive layer B-1-

The ratio of each structural unit in the above polymer A-1 and Acrybase FF187 is a molar ratio. Me represents a methyl group.

Next, the composition C-1 for forming an intermediate layer having the following composition is applied onto the first photosensitive layer using a slit-shaped nozzle, and dried with hot air at 100 ° C. for 2 minutes to form an intermediate layer having a dry thickness of 1 μm. Formed.

-Composition for forming an intermediate layer C-1-

Next, the composition A-1 for forming a light-shielding layer having the composition shown in Table 3 below is applied onto the intermediate layer using a slit-shaped nozzle, dried with hot air at 100 ° C. for 2 minutes, and has a dry thickness of 3 μm. Formed a layer.

Further, a protective film (Trefan (registered trademark) 12KW37 (thickness 12 μm), Toray Industries, Inc .; polypropylene film) is laminated on the light-shielding layer, and a temporary support / first photosensitive layer / intermediate layer / light-shielding layer / protective film is attached. A transfer film A having a laminated structure of the above was produced.

<Preparation of transfer film B>
Next, the same first photosensitive layer forming composition B-1 as described above was applied onto a temporary support (Lumirror (registered trademark) 16QS62 (thickness 16 μm), Toray Industries, Inc.) using a slit-shaped nozzle, and 100 It was dried with hot air at ° C. for 2 minutes to form a second photosensitive layer having a dry thickness of 6 μm. A protective film (Trefan (registered trademark) 12KW37 (thickness 12 μm), Toray Industries, Inc.) is further bonded onto the formed second photosensitive layer to form a laminated structure of a temporary support / second photosensitive layer / protective film. A transfer film B having the above was produced.

<Pattern formation>
-Preparation of laminated body-
First, a laminate was prepared as follows.
A film piece obtained by cutting the transfer film A (= temporary support / first photosensitive layer / intermediate layer / light-shielding layer / protective film; the transfer film of the present disclosure) produced as described above into a size of 5 cm × 5 cm square. Then, the protective film of the film piece was peeled off. Then, the film piece is placed on one surface of the COP substrate so that the surface of the light-shielding layer exposed by the peeling of the protective film is in contact with the cycloolefin resin film substrate (thickness: 50 μm; hereinafter also referred to as “COP substrate”). And laminated under the following conditions (bonding process).
<Laminating conditions>
・ Roll temperature: 110 ℃
・ Linear pressure: 0.6MPa
-Line speed (lamination speed): 2.0 m / min

Subsequently, the transfer film B (= temporary support / second photosensitive layer / protective film; transfer material other than the transfer film of the present disclosure) produced as described above is reduced to a size of 5 cm × 5 cm square in the same manner as described above. It was cut into a film piece, and the protective film of the film piece was peeled off. Then, the film pieces were laminated on the other surface of the COP substrate so that the surface of the second photosensitive layer exposed by the peeling of the protective film was in contact with the COP substrate, and laminated under the same conditions as above (second photosensitive layer forming step). ).
As described above, a laminated body having a laminated structure of a temporary support / first photosensitive layer / intermediate layer / light-shielding layer / COP substrate / second photosensitive layer / temporary support was produced.

-Pattern formation-
Next, with respect to the produced laminated body, the exposure amount was 120 mJ from both sides of the laminated body by an ultra-high pressure mercury lamp via a mask pattern having different patterns without peeling off the temporary support of the laminated body. Light irradiation was performed at / cm ² (light irradiation step). After light irradiation, it was left for 1 hour. Then, the temporary supports provided on both sides of the laminated body were peeled off, and development treatment was performed on both sides of the COP base material (patterning step).
In this way, the first photosensitive layer, the intermediate layer and the light-shielding layer on one side of the COP substrate and the second photosensitive layer on the other side are developed, and patterns different from each other on both sides of the COP substrate are developed. Was formed respectively.
The development was carried out by shower development for 45 seconds using a 0.7 mass% potassium carbonate aqueous solution having a temperature of 29 ° C. and a pH of 11.2 as a developing solution.

<Evaluation>
Next, the following evaluation was performed on the laminated body before and after development. The results of measurement and evaluation are shown in Table 3 below.

-1. Residue after exposure (fog)-
When the stacking direction of the laminate is viewed from the transparent substrate, the unirradiated region (1000 μm × 1000 μm square) of the laminate that was not irradiated with light from the first photosensitive layer side was viewed from the first photosensitive layer side with an optical microscope. The area of the residue was determined from the micrograph by observing at a magnification of 5 times, and the area ratio of the residue (fog) on the transparent substrate of the first photosensitive layer and the light-shielding layer was calculated. Then, the evaluation was made according to the following evaluation criteria based on the calculated value.
When a residue is observed, it indicates that the first photosensitive layer or the light-shielding layer has been cured by the irradiation light from the second photosensitive layer side (that is, exposure fog has occurred).
Here, as for the residue of the first photosensitive layer, the residue of the first photosensitive layer remaining on the surface of the light-shielding layer was confirmed, and the area ratio occupied in the unirradiated region, which is the observation region, was determined. When the light-shielding effect of the light-shielding layer is low, the first photosensitive layer is exposed to the irradiation light from the second photosensitive layer side, and a residue is likely to be generated.
As for the residue of the light-shielding layer, the residue of the light-shielding layer remaining on the surface of the transparent substrate was confirmed, and the area ratio occupied in the unirradiated area, which is the observation area, was determined. Even if the light-shielding effect of the light-shielding layer is ensured, if the light-shielding layer itself has photosensitivity, the light-shielding layer itself is exposed to light, and a residue is likely to be generated.
<Evaluation criteria>
A: No residue is found.
B: The residue can be confirmed, and the area ratio of the residue is 5% or less with respect to the area of the unirradiated area.
C: The residue can be confirmed, and the area ratio of the residue is more than 5% and 10% or less with respect to the area of the unirradiated area.
D: The residue can be confirmed, and the area ratio of the residue is more than 10% and 30% or less with respect to the area of the unirradiated area.
E: The residue can be confirmed, and the area ratio of the residue exceeds 30% with respect to the area of the unirradiated area.

-2. Optical density (OD) of the light-shielding layer-
A light-shielding layer forming composition A-1 is applied onto a temporary support (Lumirer 16QS62; thickness 16 μm) using a slit-shaped nozzle and dried in a convection oven at a temperature of 100 ° C. for 2 minutes to form a light-shielding layer having a thickness of 3 μm. After that, a protective film (Trefan 12KW37) was further laminated on the light-shielding layer to prepare a transfer film having a laminated structure of a temporary support / light-shielding layer / protective film.
This transfer film was cut into a size of 5 cm × 5 cm to be used as a measuring film piece, and the protective film was peeled off from the measuring film piece. Then, a piece of the measuring film is laminated on the glass so that the surface of the light-shielding layer exposed by peeling of the protective film comes into contact with the glass substrate, and the glass substrate (Eagle XG (thickness 0.7 mm)) under the same conditions as above. , Made by Corning Inc.) to obtain a laminated body having a laminated structure of a temporary support / light-shielding layer / glass base material.
The optical density of the light-shielding layer of this laminated body was measured using a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.).
Further, the optical densities of the temporary support and the glass substrate used for producing the laminated body were measured by the same method as described above.
Then, the optical densities of the temporary support and the glass substrate were subtracted from the optical densities of the laminated body to obtain the optical densities of the light-shielding layer. The measurement results are shown in Table 3 below.

(Examples 2 to 4, Comparative Example 1)
In Example 1, the same as in Example 1 except that the light-shielding layer-forming composition A-1 was replaced with the light-shielding layer-forming compositions A-2 to A-4 or AA-1 shown in Table 3. Then, a transfer film was prepared, and the same measurement and evaluation were performed. The results of measurement and evaluation are shown in Table 3 below.

As shown in Table 3, in Examples 1 to 4 using the transfer film of the present disclosure, the light-shielding effect was obtained by attaching the light-shielding layer having a constant optical density, so that both sides of the transparent substrate were irradiated with light. Even if this was done, one side was not easily affected by the irradiation light of the other side, and a fine pattern could be formed on both sides of the transparent substrate. Among these, in Example 3, since the light-shielding layer contained a photopolymerization initiator, the first photosensitive layer was not exposed to light due to the light-shielding effect of the light-shielding layer, and the residue was suppressed to a small amount, but the polymerization reaction of the light-shielding layer was slight. As a result, some residue of the light-shielding layer was observed.
On the other hand, in Comparative Example 1 provided with a light-shielding layer having a low optical density, the light-shielding effect was insufficient, and when light was irradiated on both sides of the transparent substrate, the irradiation light on one side was transmitted to the other side. This resulted in one side being affected by the irradiation light of the other side, and significant residues were generated on both sides of the transparent substrate.

(Examples 5 to 6)
In Example 1, the transfer film is the same as in Example 1 except that the intermediate layer forming composition C-1 is replaced with the intermediate layer forming compositions C to 2 or C to 3 shown in Table 4. Was prepared, and similar measurements and evaluations were performed. The results of measurement and evaluation are shown in Table 5 below.

-Compositions for forming an intermediate layer C-2, C-3-

As shown in Table 5, in Examples 5 to 6 using the transfer film of the present disclosure, the light-shielding effect was obtained by attaching the light-shielding layer having a constant optical density, so that both sides of the transparent substrate were irradiated with light. Even if this was done, one side was not easily affected by the irradiation light of the other side, and a fine pattern could be formed on both sides of the transparent substrate.

The disclosure of Japanese patent application 2018-156419 filed on August 23, 2018 is incorporated herein by reference in its entirety. Also, all documents, patent applications and technical standards described herein are to the same extent as if the individual documents, patent applications and technical standards were specifically and individually stated to be incorporated by reference. , Incorporated by reference herein.

Claims (12)

Temporary support and
A first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator,
A light-shielding layer containing a binder polymer and a polymerizable compound and having an optical density of 0.5 or more.
In this order ,
A transfer film in which the light-shielding layer does not contain a photopolymerizable initiator . The transfer film according to claim 1, wherein the light-shielding layer further contains an ultraviolet absorbing material. The transfer film according to claim 2, wherein the ultraviolet absorbing material contains carbon black. The transfer film according to any one of claims 1 to 3 , which has an intermediate layer between the first photosensitive layer and the light-shielding layer. The transfer film according to claim 4 , wherein the intermediate layer contains a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms. The transfer film according to claim 4 or 5 , wherein the intermediate layer further contains a polymerizable compound and a photopolymerization initiator. With a transparent base material,
The transfer film according to any one of claims 1 to 6 , and the transfer film.
Laminated body having. The laminate according to claim 7 , wherein the transparent substrate has a second photosensitive layer on the side opposite to the side on which the transfer film is laminated. The laminate according to claim 8 , wherein the second photosensitive layer contains a binder polymer, a polymerizable compound, and a photopolymerization initiator. The step of adhering the transfer film according to any one of claims 1 to 6 to one side of the transparent substrate,
A step of forming a second photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator on the other side of the transparent substrate.
A step of irradiating both sides of the transparent substrate with different patterns, and a step of irradiating the transparent substrate with different patterns.
A step of forming different patterns on both sides of the transparent substrate by developing both sides of the transparent substrate after the irradiation is performed.
A pattern forming method having. The pattern forming method according to claim 10 , wherein the transparent substrate has at least one of a metal electrode and a metal wiring on both surfaces. The pattern forming method according to claim 10 or 11 , which is used for forming at least one of a touch panel electrode and a touch panel wiring.

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