TW202236009A - Method for producing laminate, method for producing circuit wiring board, transfer film - Google Patents

Abstract

The present invention addresses the problem of providing a method for manufacturing a laminate with which it is possible to suppress excessive adhesion between a photosensitive layer and a photomask after exposure, and achieve excellent resolution of a pattern formed by the photosensitive layer. This method for manufacturing a laminate comprises: a step for bonding a transfer film having a temporary support, an intermediate layer, and a photosensitive layer and a substrate such that the surface on the opposite side to the intermediate layer side of the photosensitive layer of the transfer film comes into contact with the substrate; a step for peeling the temporary support between the temporary support and the intermediate layer; and a step for forming a pattern by performing exposure processing while the exposed intermediate layer and the mask are brought into contact with each other and further performing development processing after exposure. The surface free energy of the surface on the temporary support side of the intermediate layer is 68.0 mJ/m2 or less.

Description

Manufacturing method of laminate, manufacturing method of circuit wiring board, transfer film

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

Since the number of steps for obtaining a predetermined pattern is small, a pattern forming method using a transfer film is widely used. Specifically, there is a method of arranging a photosensitive layer on an arbitrary substrate using a transfer film, exposing the photosensitive layer through a mask, and then developing it to form a pattern.

For example, in Patent Document 1, it is disclosed that "a method of exposing a photosensitive composition layer is characterized in that a support layer is laminated on the metal-coated surface of a metal-coated insulating board having a metal conductor layer on one or both sides. body (A), a negative photosensitive composition layer (B) with a thickness of 1 to 35 μm, and a photosensitive resin laminate of a protective layer (C), so that the negative photosensitive composition layer (B) and the metal coating The metal-coated surface of the insulating plate is closely bonded, and when the ultraviolet rays are exposed through the photomask, the support is peeled off before exposure, and the image of the photomask is projected through the lens."

[Patent Document 1] Japanese Patent No. 4477077

Referring to the exposure method described in Patent Document 1, the present inventors carried out the process of peeling off the support (pseudo-support) before exposure and contacting the photomask to the photosensitive composition layer (photosensitive layer) exposed by peeling. As a result of research on the exposure method of exposure, it was found that when the photomask was peeled off after exposure, sometimes the photosensitive layer and the photomask were too adhered to make it difficult to peel off. If the detachability between the exposed photosensitive layer and the photomask is poor, problems such as a decrease in operability due to difficulty in detachment and contamination of the mask due to adhesion of the photosensitive layer forming material may occur. Therefore, it was found that it is necessary to suppress excessive adhesion between the photosensitive layer and the photomask after exposure. On the other hand, in order to suppress the excessive adhesion of the photosensitive layer and the photomask, when the dummy support is not peeled off, and the photomask is contacted with the dummy support to perform exposure, the exposure light source is far away from the photosensitive layer due to the existence of the dummy support. layer, so there may be a problem that it is difficult to form a fine pattern in which the residue is suppressed in the area corresponding to the concave part of the pattern (for example, in the case of a negative photosensitive layer, the area corresponding to the non-exposed part) (in other words, analysis easily deteriorated). Therefore, in the study of a method for suppressing excessive adhesion between the exposed photosensitive layer and the photomask, one capable of securing excellent resolution is required.

Therefore, the subject of this invention is to provide the manufacturing method of the laminated body which can suppress excessive adhesion of the photosensitive layer and a photomask after exposure, and is excellent in the resolution of the pattern formed by the photosensitive layer. Moreover, the subject of this invention is providing the manufacturing method of a circuit wiring board. Moreover, the subject of the present invention is also to provide a transfer film suitable for the exposure method of exposing after peeling off the dummy support body, the transfer film can suppress the excessive adhesion of the photosensitive layer and the photomask after exposure, and the resolution is also good. excellent.

The inventors of the present invention found that the above-mentioned problems can be solved by the following configuration.

[1] A method for producing a laminate, comprising: contacting a substrate with a surface of the photosensitive layer opposite to the side of the intermediate layer of a transfer film having a dummy support, an intermediate layer, and a photosensitive layer , the step of attaching the above-mentioned transfer film to the above-mentioned substrate; between the above-mentioned dummy support body and the above-mentioned intermediate layer, the step of peeling the above-mentioned dummy support body; making the exposed above-mentioned intermediate layer contact with a mask to perform exposure treatment, further In the step of performing a development treatment after exposure to form a pattern, the surface free energy of the surface of the intermediate layer on the dummy support side is 68.0 mJ/m ² or less. [2] The method for producing a laminate according to [1], wherein the arithmetic mean roughness Ra of the surface of the intermediate layer on the dummy support side is 50 nm or less. [3] The method for producing a laminate according to [1] or [2], wherein the surface free energy of the pseudo-support on the side of the intermediate layer is 25.0 to 50.0 mJ/m ² . [4] The method for producing a laminate according to any one of [1] to [3], wherein the intermediate layer contains polyvinyl alcohol. [5] The method for producing a laminate according to [4], wherein the content of the polyvinyl alcohol is 5 to 95% by mass relative to the total mass of the intermediate layer. [6] The method for producing a laminate according to any one of [1] to [5], wherein the intermediate layer further contains polyvinylpyrrolidone. [7] The method for producing a laminate according to any one of [1] to [6], wherein the intermediate layer further contains a compound selected from the group consisting of water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerol. One or more compounds X in the group of alcohols. [8] The method for producing a laminate according to [7], wherein the content of the compound X is 0.1% by mass or more and less than 30% by mass relative to the total mass of the intermediate layer. [9] The method for producing a laminate according to [7] or [8], wherein the compound X contains hydroxypropylmethylcellulose. [10] The method for producing a laminate according to any one of [1] to [9], wherein the intermediate layer has a thickness of 3.0 μm or less. [11] The method for producing a laminate according to any one of [1] to [10], wherein the photosensitive layer has a thickness of 2.0 to 20 μm. [12] A method for manufacturing a circuit wiring board, including the method for manufacturing the laminate described in any one of [1] to [11], the method for manufacturing a circuit wiring board comprising: forming a seed layer on a substrate; The step of forming a substrate with a seed layer; using the surface of the photosensitive layer opposite to the side of the intermediate layer having a dummy support, an intermediate layer, and a transfer film of a photosensitive layer with the substrate with a seed layer In the way of contact, the above-mentioned transfer film is bonded to the above-mentioned substrate with a seed crystal layer to obtain a photosensitive layer with the above-mentioned substrate, the above-mentioned seed crystal layer, the above-mentioned photosensitive layer, the above-mentioned intermediate layer and the above-mentioned dummy support in sequence The step of the substrate; between the above-mentioned dummy support and the above-mentioned intermediate layer, the step of peeling the above-mentioned dummy support; making the exposed above-mentioned intermediate layer contact with the mask to perform exposure treatment, and further implement development treatment after exposure to form a pattern the step of forming a metal plating layer by electroplating on the above-mentioned seed layer existing in the region where the above-mentioned pattern is not arranged; the step of forming a protective layer on the above-mentioned metal plating layer; the step of removing the above-mentioned pattern; In the step of obtaining conductive thin wires from the seed layer, the surface free energy of the surface of the intermediate layer on the dummy support side is 68.0 mJ/m ² or less. [13] A transfer film comprising a dummy support, an intermediate layer, and a photosensitive layer, wherein the surface free energy of the surface of the intermediate layer on the dummy support side is 68.0 mJ/m ² or less, and the intermediate layer has The arithmetic mean roughness Ra of the surface on the dummy support side is 50 nm or less. [14] The transfer film according to [13], wherein the surface free energy of the intermediate layer side of the dummy support is 25.0 to 50.0 mJ/m ² . [15] The transfer film according to [13] or [14], wherein the intermediate layer contains polyvinyl alcohol. [16] The transfer film according to [15], wherein the content of the polyvinyl alcohol is 5 to 95% by mass relative to the total mass of the intermediate layer. [17] The transfer film according to any one of [13] to [16], wherein the intermediate layer further contains polyvinylpyrrolidone. [18] The transfer film according to any one of [13] to [17], wherein the intermediate layer comprises a material selected from the group consisting of water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerin. One or more compounds X in the group. [19] The transfer film according to [18], wherein the content of the compound X is 0.1% by mass or more and less than 30% by mass relative to the total mass of the intermediate layer. [20] The transfer film according to [18] or [19], wherein the compound X contains hydroxypropylmethylcellulose. [21] The transfer film according to any one of [13] to [20], wherein the intermediate layer has a thickness of 3.0 μm or less. [22] The transfer film according to any one of [13] to [21], wherein the photosensitive layer has a thickness of 2.0 to 20 μm. [Invention effect]

According to the present invention, it is possible to suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and to form a laminated body with a pattern excellent in resolution of the pattern formed by the photosensitive layer. Furthermore, according to the present invention, it is also possible to provide a method of manufacturing a circuit wiring board. In addition, the present invention can also provide a transfer film suitable for the exposure method of exposing after peeling off the dummy support. The transfer film can suppress excessive adhesion between the photosensitive layer and the photomask after exposure, and can form a film with excellent resolution. The transfer film of the pattern.

Hereinafter, the present invention will be described in detail. In this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In the numerical ranges described step by step in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of other numerical ranges described stepwise. In addition, in the numerical range described in this specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in an Example.

In this specification, the term "step" not only refers to an independent step, but also includes in the term the intended purpose of the step even if it cannot be clearly distinguished from other steps.

In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400-700 nm is 80% or more, preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, for example, can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are obtained by using TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (both are product names manufactured by TOSOH CORPORATION), THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, and polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analysis device And the converted value. In addition, in this specification, unless otherwise specified, the molecular weight of the compound which a molecular weight distribution has is a weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an Inductively Coupled Plasma (ICP: Inductively Coupled Plasma) spectroscopic analyzer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth)acryloxy" is a concept that includes both acryloxy and methacryloxy. , "(meth)acrylamide group" is a concept that includes both acrylamide group and methacrylamide group, "(meth)acrylate" is a concept that includes both acrylate and methacrylate .

In addition, in this specification, "alkali solubility" means that the solubility with respect to 100g of 1 mass % sodium carbonate aqueous solution whose liquid temperature is 22 degreeC is 0.1 g or more. Thus, for example, an alkali-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

In this specification, "water solubility" means that the solubility in 100 g of water of pH7.0 whose liquid temperature is 22 degreeC is 0.1 g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

In this specification, the "solid content" of a composition refers to the components forming the composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components except the solvent. Moreover, if it is a component which forms a composition layer, a liquid component is also regarded as a solid component.

[Method for producing a laminate] The method for producing a laminate of the present invention comprises: using a surface of the photosensitive layer opposite to the side of the intermediate layer of a transfer film having a dummy support, an intermediate layer, and a photosensitive layer, and The method of contacting the substrate is the step of laminating the above-mentioned transfer film to the above-mentioned substrate (hereinafter, also referred to as "transfer film bonding step."); Between the above-mentioned dummy support and the above-mentioned intermediate layer, the above-mentioned dummy support is peeled off (hereinafter also referred to as "pseudo-support stripping step"); exposing the exposed intermediate layer to a mask, and further performing a development process after exposure to form a pattern (hereinafter also referred to as referred to as "pattern forming step."), the surface free energy of the surface of the intermediate layer on the side of the dummy support is 68.0 mJ/m ² or less.

The characteristic points of the method for producing a laminate of the present invention include providing an intermediate layer between the pseudo-support and the photosensitive layer, and setting the surface free energy on the pseudo-support side of the intermediate layer to a predetermined value. scope below this. According to the manufacturing method of the laminated body of this invention, excessive adhesion of the photosensitive layer and a photomask after exposure can be suppressed, and resolution is also excellent.

Although the mechanism by which the method for producing a laminate of the present invention exerts the desired effect is not clear, the present inventors speculate as follows. Firstly, in the method for producing a laminate of the present invention, an intermediate layer is provided between the dummy support and the photosensitive layer, whereby the mask and The photosensitive layers are not in direct contact. As a result, excessive adhesion between the exposed photosensitive layer and the mask is suppressed. As a result of further research by the present inventors on the above-mentioned intermediate layer, it was found that problems such as the following occurred: when the surface free energy of the surface on the pseudo-support side of the intermediate layer exceeds 68.0 mJ/m ² , when performing the pseudo-support stripping step The interface between the intermediate layer and the pseudo-support becomes difficult to peel off, and the interface between the intermediate layer and the pseudo-support does not peel off and a part of the photosensitive layer is exposed and/or the interlayer after the pseudo-support is peeled off The surface becomes rough (the arithmetic mean roughness Ra of the surface of the intermediate layer increases), and the like. Specifically, it has been clarified that when a part of the photosensitive layer is exposed without delamination at the interface between the intermediate layer and the dummy support, excessive adhesion of the exposed photosensitive layer and the mask occurs, and the exposure after exposure The mask does not peel off easily. Also, it has been found that even when the exposure and development treatment is performed after peeling off the dummy support, there are cases where the exposure of the above-mentioned photosensitive layer and/or the roughening of the surface of the intermediate layer (the arithmetic mean of the surface of the intermediate layer The roughness Ra increases) to hinder uniform exposure, and it becomes difficult to form a fine pattern of residues in the region suppressing the concave portion of the pattern.

Hereinafter, each step of the manufacturing method of the laminated body of this invention is demonstrated in detail. In addition, the description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, hereinafter, excessive adhesion between the photosensitive layer and the photomask after exposure can be further suppressed (hereinafter also referred to as "mask non-adhesion is more excellent.") and/or the residue in the region where the recessed part can be patterned is suppressed The fine pattern (hereinafter also referred to as "more excellent resolution") is also referred to as "more excellent effect of the present invention".

[First Embodiment] The first embodiment of the method for producing a laminate includes a transfer film bonding step, a dummy support peeling step, and a pattern forming step shown below in this order. Transfer film bonding step: use the transfer film (hereinafter, also referred to as "transfer film X") having a dummy support, an intermediate layer, and a photosensitive layer on the opposite side of the above-mentioned photosensitive layer and the above-mentioned intermediate layer The surface on the side of the transfer film X (the surface on the side opposite to the pseudo-support side of the transfer film X) is in contact with the above-mentioned substrate, and the step of bonding the above-mentioned transfer film to the above-mentioned substrate. The step of peeling off the dummy support between the intermediate layer and the pattern forming step: exposing the exposed intermediate layer in contact with a mask, and further performing a development process after exposure to form a pattern (hereinafter also referred to as This is the "pattern forming step".) In the transfer film X, the surface free energy of the surface of the intermediate layer on the dummy support side is 68.0 mJ/m ² or less.

＜＜Transfer film lamination process＞＞ ＜Transfer Film X＞ The transfer film X will be described later.

＜Transfer film lamination process＞ The step of attaching the transfer film is to make the transfer film (transfer film X) with a dummy support, an intermediate layer and a photosensitive layer in such a way that the surface of the photosensitive layer opposite to the intermediate layer is in contact with the substrate. The step of attaching the printed film X to the substrate. In addition, in the case where the transfer film X has a structure having a protective film, a bonding step is performed after peeling the protective film.

When laminating, the board|substrate is pressure-bonded so that the surface of the transfer film X opposite to the intermediate|middle layer side of the photosensitive layer may contact. The method of the pressure bonding is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferable to overlay the surface of the transfer film X on the side opposite to the intermediate layer side of the photosensitive layer on the substrate, and to apply pressure and heating with a roller or the like. A known laminator, such as a vacuum laminator and an automatic cutting laminator, can be used for bonding. Although it does not specifically limit as lamination temperature, For example, 70-130 degreeC is preferable.

As the substrate, a conductive substrate having a supporting substrate and a conductive layer arranged on the supporting substrate is preferable. Conductive Substrate Any layer other than the above-mentioned conductive layer may be formed on the supporting substrate as needed. That is, it is preferable that the substrate is a conductive substrate having at least a supporting substrate and a conductive layer arranged on the supporting substrate.

As a supporting substrate, a resin substrate, a glass substrate, and a semiconductor substrate are mentioned, for example. As a preferred aspect of the supporting substrate, for example, it is described in paragraph [0140] of International Publication No. 2018/155193, and this content is incorporated in this specification. Also, when the support substrate is a resin substrate, cycloolefin polymer and polyimide are preferable as the material of the resin substrate, and the thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

As the conductive layer, at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine line formation is better. In addition, only one conductive layer may be arranged on the supporting substrate, or two or more layers may be arranged. When arranging two or more conductive layers, conductive layers having different materials are preferable. As a preferred aspect of the conductive layer, for example, it is described in paragraph [0141] of International Publication No. 2018/155193, and this content is incorporated into this specification.

As a conductive substrate, a substrate having at least one of transparent electrodes and routing wiring is preferable. A conductive substrate having such a structure can be suitably used as a substrate for a touch panel. The transparent electrode can better function as an electrode for a touch panel. The transparent electrodes are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), and thin metal wires such as metal meshes and metal nanowires. Examples of thin metal wires include thin wires such as silver and copper. Among them, silver conductive materials such as silver mesh and silver nanowires are preferred.

As a material of the circuitous wiring, metal is preferable. Examples of the metal used as the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements. As a material of the circuitous wiring, copper, molybdenum, aluminum or titanium are preferable, and copper is particularly preferable.

In addition, in the manufacturing method of the laminated body of this invention, when making the photosensitive layer in the transfer film X function as the electrode protection film for touch panels, in order to protect electrodes etc. (that is, the electrodes for touch panels and at least one of the wiring for the touch panel), it is preferable to provide electrodes or the like directly or covered with another layer.

＜＜Pseudo-support stripping step＞＞ The step of stripping the pseudo-support is a step of stripping the pseudo-support between the pseudo-support and the intermediate layer.

＜Peel processing＞ The method of peeling off the pseudo-support is not particularly limited, and it can be performed based on known methods. For example, the same mechanism as the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.

<Surface Free Energy of the Surface of the Intermediate Layer on the False Support Side> As described above, in the transfer film X, the surface free energy of the surface of the intermediate layer on the pseudo support side is 68.0 mJ/m ² or less. The surface free energy of the surface on the side of the pseudo-support of the intermediate layer (hereinafter, also referred to as "surface free energy E _I ") refers to the pseudo-support of the intermediate layer exposed by peeling off the pseudo-support in the pseudo-support stripping step. Surface free energy in the body-side surface (the surface exposed after peeling off the pseudo-support in the middle layer). The upper limit of the surface free energy E _I is 68.0 ^mJ /m or less. From the viewpoint of more excellent effects of the present invention, 65.0 ^mJ /m or less is preferable, and 63.0 ^mJ /m or less is more preferable. It is further preferably 60.0 mJ/m ² or less. Moreover, as the lower limit value, for example, 45.0 mJ/m ² or more is preferable, 50.0 mJ/m ² or more is more preferable, and 55.0 mJ/m ² or more is still more preferable. In the present specification, the surface free energy E _I of the surface on the pseudo-support side of the intermediate layer is calculated by the following method.

(Measurement and calculation method of surface energy) The surface energy is obtained by using the actual measured contact angles θ _H2O and θ _CH2I2 of pure water H ₂ O and diiodomethane CH ₂ I ₂ , and the Owens formula (continuous Formulas (A) and (B)) to obtain. In addition, in measuring the following surface energy, the support peeling method and the kind of base material are not particularly limited.

(Contact angle of water (θ _H2O )) First, the contact angle of water (θ _H2O ) was measured by the following method. After laminating the transfer film on the substrate, the dummy support is peeled off. Next, in an environment with a room temperature of 25°C and a relative humidity of 50%, 12 μL of pure water was dripped onto the surface of the intermediate layer on the side of the pseudo-support (the surface exposed after peeling off the pseudo-support), and after 20 seconds, use Contact angle meter CA-D type (Kyowa Interface Science Co., Ltd) was used to measure the contact angle. The above measurement was performed 5 times in total. Furthermore, the arithmetic mean of 3 measured values excluding the maximum value and the minimum value among 5 measured values was made into the contact angle of water (θ _H2O ).

(Contact angle of diiodomethane (θ _CH2I2 )) Next, the contact angle of diiodomethane (θ _CH2I2 ) was measured by the following method. The dummy support is peeled off after laminating the transfer film to the substrate. Next, in an environment where the room temperature is 25° C. and the relative humidity is 50%, diiodomethane (manufactured by FUJIFILM Wako Pure Chemical Corporation) is dropped on the surface of the pseudo-support side of the intermediate layer (the surface exposed after peeling off the pseudo-support). ) 12 μL, and after 20 seconds, the contact angle was measured using a contact angle meter CA-D type (Kyowa Interface Science Co., Ltd). The above measurement was performed 5 times in total. Furthermore, the arithmetic mean of three measured values excluding the maximum and minimum values among five measured values was set as the contact angle of diiodomethane (θ _CH2I2 ).

(Calculation of surface energy based on Owens formula) The values of θ _H2O and θ _CH2I2 measured by the above-mentioned method and the value of γ shown in Table 1 below were put into the continuous formulas (A) and (B) shown below The obtained "value of γs ^d + γs ^h " is defined as the surface energy. In addition, in the following tables, when L is H ₂ O, for example, γ _L ^d is represented by γ _H2O ^d . Also, when L is CH ₂ I ₂ , for example, γ _L ^d is represented by γ _CH2I2 ^d .

[Table 1] L γ _L ^d γ _L ^h γ _LV H ₂ O 21.8 51.0 72.8 CH ₂ I ₂ 49.5 1.3 50.8

〔Continuous program〕 (A): 1+cosθ _H2O =2√γ _S ^d (√γ _H2O ^d /γ _H2O,V )+2√γ _S ^h (√γ _H2O ^h /γ _H2O,V ) (B): 1+cosθ _CH2I2 =2√γ _S ^d ( _{√γ CH2I2} ^d /γ _CH2I2,V )+2√γ _S ^h ( _{√γ CH2I2} ^h /γ _CH2I2,V )

<Arithmetic mean roughness Ra of the surface on the pseudo-support side of the intermediate layer> The arithmetic mean roughness Ra of the surface on the pseudo-support side of the intermediate layer refers to the surface on the pseudo-support side of the intermediate layer exposed by peeling off the pseudo-support in the pseudo-support stripping step (in the intermediate layer, the surface on the pseudo-support side of the stripped pseudo-support is The arithmetic mean roughness Ra of the surface exposed after the support. The upper limit value of the arithmetic average roughness Ra of the surface of the pseudo-support side of the intermediate layer is preferably 50 nm or less, more preferably 30 nm or less, and still more preferably 20 nm or less, from the viewpoint of more excellent effects of the present invention. . Moreover, as its lower limit, for example, 0 nm or more is preferable, and 1 nm or more is more preferable. In this specification, the arithmetic mean roughness Ra of the surface of the pseudo-support side of an intermediate|middle layer is the value measured by the following method.

The arithmetic mean roughness Ra of the surface on the pseudo-support side of the intermediate layer was measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation), the surface profile of the object to be measured was obtained under the following conditions. As measurement and analysis software, Microscope Application of MetroPro ver8.3.2 was used. Then, use the above-mentioned software to display the Surface Map screen, and obtain the histogram data in the Surface Map screen. The arithmetic mean roughness Ra of the surface of the object to be measured is obtained from the obtained histogram data.

＜Thickness of middle layer＞ The thickness of the intermediate layer is not particularly limited, but the upper limit is, for example, preferably 10 μm or less, more preferably 5.0 μm or less, and still more preferably 4.0 μm or less, from the viewpoint of more excellent effects of the present invention. , 3.0 μm or less is particularly preferred. In addition, as the lower limit value, from the viewpoint of more excellent oxygen permeability, for example, 50 nm or more is preferable, and 100 nm or more is more preferable. The thickness of the intermediate layer is calculated as an average value of arbitrary 5 points measured by SEM (Scanning Electron Microscope: Scanning Electron Microscope) cross-sectional observation.

<Surface free energy on the intermediate layer side of the pseudo-support> The surface free energy of the surface on the intermediate layer side of the pseudo-support (hereinafter, also referred to as "surface free energy E _S ") refers to the , the surface free energy of the surface on the side of the intermediate layer of the pseudo-support exposed by peeling off the pseudo-support (in the pseudo-support, the surface exposed after separation from the intermediate layer). The upper limit of the surface free energy _ES is, for example, preferably not more than 60.0 mJ/m ² , more preferably not more than 54.0 mJ/m ² , and still more preferably not more than 50.0 mJ/m ² . Also, as the lower limit value, for example, 20.0 mJ/m ² or more is preferable, and from the viewpoint of more excellent effects of the present invention, 25.0 mJ/m ² or more is more preferable. In this specification, the surface free energy E _S of the surface of the intermediate layer side of the pseudo-support is a value obtained by the same method as the surface free energy E _I of the surface of the pseudo-support side of the intermediate layer.

In addition, as the surface free energy _{E I} and the surface free energy ES , it is also preferable to satisfy the following relationship (1) and/or (2). (1) Surface free energy E _I (mJ/m ² ) > Surface free energy E _S (mJ/m ² ) (2) Surface free energy E _I (mJ/m ² ) and surface free energy E _S (mJ/m ² ) The difference is 3.0 to 40 mJ/m ² (preferably 3.0 to 30 mJ/m ² ).

＜＜Pattern Formation Step＞＞ The pattern forming step is a step of exposing the exposed intermediate layer in contact with a mask, and further implementing a developing process to form a pattern.

＜Exposure processing＞ Exposure treatment is a process of exposing a pattern to the photosensitive layer of the laminate in which the intermediate layer is exposed by peeling off the dummy support. In addition, "pattern exposure" refers to exposure in a pattern-like form, that is, exposure in a form in which an exposed portion and a non-exposed portion exist. The positional relationship between the exposed portion and the non-exposed portion in the pattern exposure is not particularly limited, and can be appropriately adjusted. In the exposure process, on the intermediate layer exposed by peeling off the dummy support, a mask having openings at predetermined positions is placed in close contact with each other, and the exposure process is performed. For example, in the case where the photosensitive layer is a negative photosensitive layer, by performing the above-mentioned exposure treatment, it is possible to generate the light contained in the photosensitive layer in the exposed part (corresponding to the position of the opening of the mask) of the photosensitive layer. The hardening reaction of the ingredients. The non-exposed portion of the photosensitive layer is removed by performing development treatment (in particular, alkali development treatment) after the exposure treatment, and a pattern is formed.

Also, when the photosensitive layer is a negative photosensitive layer, as a light source for pattern exposure, it can be appropriately selected as long as it can irradiate at least light in the wavelength range obtained by hardening the photosensitive layer (for example, 365 nm or 405 nm). use. Among them, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. In addition, the dominant wavelength means the wavelength with the highest intensity. Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 to 200 mJ/cm ² , more preferably 10 to 200 mJ/cm ² .

As a preferred aspect of the light source, exposure amount, and exposure method used for exposure, for example, it is described in paragraphs [0146] to [0147] of International Publication No. 2018/155193, and these contents are incorporated into this document in the manual.

In the first embodiment of the method for producing a laminate, it is preferable to peel off the mask (reticle) used in the exposure process after the exposure process and before the development process.

＜Development treatment＞ The development treatment is a treatment for forming a pattern by developing the pattern-exposed photosensitive layer obtained by the exposure treatment. The image development of the said photosensitive layer can be implemented using a developing solution. For example, when the photosensitive layer is a negative-type photosensitive layer, the non-exposed portion of the photosensitive layer is removed by developing treatment using an alkali developing solution, and as a result, a masked opening can be formed as a convex portion. The pattern.

In the developing treatment, an alkaline aqueous solution is preferable as a developing solution. As the basic compound that can be contained in the alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethyl hydroxide Ammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide and Choline (2-Hydroxyethyltrimethylammonium Hydroxide).

As a system of image development, systems, such as flood image development, shower image development, spin image development, and dip-coat image development, are mentioned, for example.

As a developing solution that can be preferably used in this specification, for example, the developing solution described in paragraph [0194] of International Publication No. 2015/093271 can be mentioned. As a developing method that can be used preferably, for example, The developing method described in paragraph [0195] of International Publication No. 2015/093271 is mentioned.

<<Post-exposure step and post-baking step>> The first embodiment of the method for producing a laminate may include a step of exposing the pattern obtained by the development treatment (post-exposure step) and/or a step of heating ( post-bake step). In the case of including both the post-exposure step and the post-baking step, it is preferable to perform post-baking after the post-exposure. The exposure amount of the post-exposure is preferably 100 to 5000 mJ/cm ² , more preferably 200 to 3000 mJ/cm ² . The post-baking temperature is preferably from 80 to 250°C, more preferably from 90 to 160°C. The post-baking time is preferably from 1 to 180 minutes, more preferably from 10 to 60 minutes.

The position and size of the pattern formed on the substrate through the above steps are not particularly limited. The pattern is preferably in the shape of a thin line, and its width is preferably 20 μm or less, more preferably 15 μm or less. In addition, the lower limit value is not particularly limited, and is preferably 1 μm or more, preferably 5 μm or more, for example.

<Transfer Film X> Next, the transfer film X will be described. The transfer film X has a dummy support, an intermediate layer, and a photosensitive layer, and as long as it is a transfer film whose surface free energy on the dummy support side of the intermediate layer is 68.0 mJ/ ^m2 or less, there is no Particularly limited, known transfer films can be used. Hereinafter, an embodiment of the transfer film X will be described.

Although it does not specifically limit as a structure of the transfer film X, For example, the following structures are mentioned. (1) "pseudo-support/intermediate layer/photosensitive layer/protective film" (2) "pseudo-support/intermediate layer/photosensitive layer/refractive index adjustment layer/protective film" In addition, in each of the above structures, it is preferable that the photosensitive layer is a negative photosensitive layer. Moreover, it is also preferable that a photosensitive layer is a colored resin layer. In addition, in the above (1) transfer film X, the intermediate layer may be formed of two layers. Specifically, the structure of "dummy support/second intermediate layer/first intermediate layer/photosensitive layer/protective film". Moreover, as for the pattern obtained by the manufacturing method of the laminated body of this invention, as mentioned later, the seed layer protection pattern in the manufacturing method of circuit wiring, the wiring protective film pattern in the manufacturing method of a wiring protective film, etc. can be applied. Therefore, the transfer film X may be a transfer film for an etching resist or a transfer film for a wiring protective film. Moreover, when the transfer film X is a transfer film for etching resists, as a structure of the transfer film X, for example, the structure of said (1) is preferable. When the transfer film X is a transfer film for wiring protection films, as a structure of the transfer film X, for example, the structure of said (1) or (2) is preferable.

From the viewpoint of suppressing generation of air bubbles in the bonding step in the above-mentioned method for producing a laminate, the maximum width of the ripples of the transfer film X is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 60 μm or less. In addition, the lower limit of the maximum width of the corrugation is 0 μm or more, preferably 0.1 μm or more, more preferably 1 μm or more. The maximum width of the ripples of the transfer film X is a value measured by the following procedure. First, the transfer film X was cut into a size of 20 cm long by 20 cm wide in a direction perpendicular to the main surface to prepare a test sample. In addition, when the transfer film X has a protective film, the protective film is peeled off. Next, the above-mentioned test sample was left still on a stage with a smooth and horizontal surface so that the surface of the dummy support faced the stage. After standing still, use a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) to scan the surface of the test sample to obtain a three-dimensional surface image of the center of the test sample within a 10 cm square area. From the obtained three-dimensional surface image The maximum convex height observed in the image minus the lowest concave height. The above-mentioned operation was performed on 10 test samples, and the arithmetic mean thereof was taken as "the maximum width of the ripples of the transfer film X".

Hereinafter, first, the intermediate layer and the dummy support will be described, and then, an example of a specific embodiment will be given to describe the overall structure of the transfer film X. In addition, the transfer film X1 of the first embodiment described later as a specific embodiment of the transfer film X has a structure that can be preferably used for a transfer film for etching resist, and the transfer film X1 of the second embodiment As the transfer film X2, a structure that can be preferably used for a transfer film for wiring protective films can be preferably used.

(Intermediate Layer) Regarding the intermediate layer of the transfer film X, the surface free energy (surface free energy E _I ) of the surface on the pseudo-support side is 68.0 mJ/m ² or less. In addition, the surface free energy E _I refers to the surface free energy in the surface of the dummy support side of the intermediate layer exposed from the transfer film X by peeling off the dummy support. The preferred aspect and measurement method of the surface free energy E _I are as described above.

In addition, the upper limit value of the arithmetic average roughness Ra of the surface of the intermediate layer of the transfer film X on the dummy support side is preferably 50 nm or less from the viewpoint that the effect of the present invention is more excellent. In addition, the arithmetic average roughness Ra of the surface of the intermediate layer on the dummy support side refers to the arithmetic average roughness Ra of the surface of the intermediate layer exposed by peeling off the dummy support from the transfer film X. A preferred aspect and measurement method of the arithmetic mean roughness Ra of the surface of the intermediate layer are as described above.

In addition, the upper limit of the thickness of the intermediate layer of the transfer film X is preferably 10 μm or less from the viewpoint that the effect of the present invention is more excellent. The preferred aspects and measuring methods of the thickness of the intermediate layer are as described above.

As the intermediate layer, a water-soluble resin layer containing a water-soluble resin is preferable. Also, as an intermediate layer, it is preferable to have an oxygen barrier capability. Since the sensitivity at the time of exposure improves and the time load of an exposure machine reduces and productivity improves because an intermediate layer has an oxygen barrier capability, it is preferable. In addition, when the photosensitive layer in the transfer film X is a negative photosensitive layer containing a radically polymerizable compound, there is also an advantage that oxygen hindrance hardly occurs in the polymerization reaction at the time of exposure. As the intermediate layer, among them, a layer exhibiting low oxygen permeability, and being dispersed or dissolved in water or an aqueous alkali solution (a 1 mass % aqueous solution of sodium carbonate at 22° C.) is preferable.

It is preferable that the intermediate layer contains resin. It is preferable that the above-mentioned resin contains a water-soluble resin as part or all of it. As resins that can be used as water-soluble resins, for example, polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins (such as hydroxypropyl cellulose and hydroxypropyl methylcellulose, etc.) water-soluble cellulose derivatives), acrylamide-based resins, polyether-based resins (such as polyalkylene oxide-based resins such as polyethylene glycol and polypropylene glycol), gelatin, vinyl ether-based resins, polyamide resins, and Resins such as these copolymers. Moreover, as a water-soluble resin, the copolymer of (meth)acrylic acid/vinyl ester compound etc. can also be used. As a copolymer of (meth)acrylic acid/vinyl ester compound, a copolymer of (meth)acrylic acid/allyl (meth)acrylate is preferable, and a copolymer of methacrylic acid/allyl methacrylate is more preferable. good. In the case of a water-soluble resin-based (meth)acrylic acid/vinyl compound copolymer, the respective composition ratios (mol %) are, for example, preferably 90/10 to 20/80, and 80/20 to 30/70 for better.

The lower limit of the weight average molecular weight of the water-soluble resin is preferably at least 5,000, more preferably at least 7,000, and still more preferably at least 10,000. Moreover, as the upper limit value, 200,000 or less are preferable, 100,000 or less are more preferable, 50,000 or less are still more preferable. The degree of dispersion (Mw/Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5.

As the water-soluble resin, it is preferable to contain at least one kind of polyvinyl alcohol and polyvinylpyrrolidone from the viewpoint of more excellent effects of the present invention and/or more excellent oxygen barrier ability, and it is more preferable to contain polyvinyl alcohol. Preferably, any one of polyvinyl alcohol and polyvinylpyrrolidone is further preferably included. In addition, it is also preferable to use one or more kinds of polyvinyl alcohol and polyvinylpyrrolidone and one or more kinds of water-soluble cellulose derivatives and polyethers in combination, and to use together one or more kinds of polyvinyl alcohol and polyvinylpyrrolidone and Water-soluble cellulose derivatives are more preferred.

The water-soluble cellulose derivative is not particularly limited, and examples thereof include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, and ethylcellulose. Polyethylene glycol, polypropylene glycol, etc. are mentioned as a polyether.

The water-soluble resin may be used alone or in combination of two or more. The content of the water-soluble resin is not particularly limited, but it is preferably 50% by mass or more, 70% by mass relative to the total mass of the intermediate layer, from the standpoint of a better effect of the present invention and/or a better oxygen barrier capability. The above is better. In addition, the upper limit is not particularly limited, for example, 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, still more preferably 99% by mass or less.

In addition, the intermediate layer may have other components than the above-mentioned resins. In addition, the upper limit of the molecular weight of the above-mentioned other components is not particularly limited, but it is preferably less than 5,000, more preferably 4,000 or less, still more preferably 3,000 or less, still more preferably 2,000 or less, and particularly preferably 1,500 or less. . Moreover, as a lower limit, it is 60 or more, for example.

As the above-mentioned other components, among them, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, or amide compounds are selected from the viewpoint of easy adjustment of the surface free energy E _I of the pseudo-support side of the intermediate layer. Preferably, polyols or phenol derivatives are more preferred. The number of hydroxyl groups contained in polyols is not particularly limited, for example, 2 to 10 are preferable. As polyhydric alcohols, glycerol, diglycerol, diethylene glycol, etc. are mentioned, for example. Examples of the alkylene oxide adducts of polyols include compounds obtained by adding ethylene oxide, propylene oxide, and the like to the above-mentioned polyols. Moreover, the average addition number is not specifically limited, For example, it is 1-100, Preferably it is 2-50, More preferably, it is 2-20. Bisphenol A, bisphenol S, etc. are mentioned as a phenol derivative. Examples of the amide compound include N-methylpyrrolidone and the like.

When the intermediate layer contains the above-mentioned other components, the above-mentioned other components may be used alone or in combination of two or more. The content of the above-mentioned other components is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more based on the total mass of the intermediate layer. Further better. In addition, the upper limit is not particularly limited. For example, less than 30% by mass is preferable, 10% by mass or less is more preferable, and 5% by mass or less is still more preferable.

As an intermediate layer, it contains one or more of polyvinyl alcohol and polyvinylpyrrolidone and is selected from the group consisting of water-soluble cellulose from the viewpoint of more excellent effect of the present invention and/or more excellent oxygen barrier ability. Compound X in the group of derivatives, polyethers, phenol derivatives and glycerol is preferred. When the intermediate layer has the above composition, the compound X tends to exist more unevenly on the surface of the pseudo-support side of the intermediate layer and/or it is difficult to form a WBL (weak boundary layer: Weak boundary layer) layer, the surface free energy E _I of the pseudo-support side of the intermediate layer and the arithmetic mean roughness Ra of the same surface can be easily adjusted to more appropriate values. If the surface free energy E _I of the pseudo-support side of the intermediate layer and the arithmetic mean roughness Ra of the same surface are adjusted to a more appropriate value, then when the pseudo-support is peeled off, the cohesion failure of the intermediate layer will not occur and the pseudo-support The interface between the body and the intermediate layer is easy to peel off, and it is easy to form a pattern with excellent resolution. In particular, the composition of the intermediate layer includes at least one of polyvinyl alcohol and polyvinylpyrrolidone, and at least one of water-soluble cellulose derivatives and polyethers as the compound X, so that the intermediate layer can be more easily suppressed. From the viewpoint of the plasticization of polyvinyl alcohol and polyvinylpyrrolidone, it is more preferable to include at least one of polyvinyl alcohol and polyvinylpyrrolidone and a water-soluble cellulose derivative as the compound X, and from the viewpoint of better detachability of the pseudo-support, It is particularly preferable to include at least one of polyvinyl alcohol and polyvinylpyrrolidone and hydroxypropylmethylcellulose as the compound X. Moreover, it is preferable to use both polyvinyl alcohol and polyvinylpyrrolidone together. When the intermediate layer has the above composition, the total content of polyvinyl alcohol and polyvinylpyrrolidone is preferably 50% by mass or more based on the total mass of the intermediate layer from the viewpoint of more excellent effects of the present invention. More than 70% by mass is more preferable. In addition, the upper limit is not particularly limited, for example, 100% by mass or less, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, still more preferably 99% by mass or less. Moreover, when the intermediate layer has the above-mentioned composition, it is preferable that the content of polyvinyl alcohol is 5 to 95 mass % with respect to the total mass of the intermediate layer. Also, when the intermediate layer has the above composition, the compounding ratio (mass ratio) of polyvinyl alcohol and polyvinylpyrrolidone is preferably 5/95 to 95/5, and 20/80 to 80/20 is still more preferable. Excellent, 25/75-70/25 is more preferred, 60/40-75/25 is particularly preferred. In addition, when the intermediate layer has the above-mentioned composition, the content of the compound X is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 0.1% by mass or more, and 0.5% by mass relative to the total mass of the intermediate layer Above is more preferable, and 1 mass % or more is still more preferable. As an upper limit, less than 30 mass % is preferable, and 15 mass % or less is more preferable. When the content of the compound X is less than 30% by mass relative to the total mass of the intermediate layer, since the phase separation of the intermediate layer forming components is easily suppressed, and the roughening of the surface of the intermediate layer due to this is less likely to occur, the resolving power is improved. excellent.

(pseudo-support) The transfer film X has a dummy support. The member of the pseudo support system supporting the photosensitive layer is finally removed by peeling treatment.

The pseudo-support can be a single-layer structure or a multi-layer structure. The pseudo-support is preferably a film, more preferably a resin film. As the pseudo-support, a film that is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat is preferred. As the above-mentioned film, for example, polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film and polycarbonate film. Among them, polyethylene terephthalate film is preferred as the pseudo-support. In addition, it is preferable that the film used as a pseudo-support has no deformation such as wrinkles or scratches.

From the viewpoint of enabling pattern exposure through the dummy support, the dummy support is preferably highly transparent, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. It is preferable that the haze of the dummy support is small from the viewpoint of the pattern formability and the transparency of the dummy support when pattern exposure is performed through the dummy support. Specifically, the haze value of the pseudo-support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. From the viewpoint of the pattern formation property and the transparency of the pseudo-support when pattern exposure is performed through the pseudo-support, it is preferable that the number of fine particles, foreign substances and defects contained in the pseudo-support is small. The number of particles, foreign matter, and defects with a diameter of ¹ μm or more in the pseudo-support is preferably 50 pieces/10mm2 or less, more preferably ¹⁰ pieces/10mm2 or less, more preferably ³ pieces/10mm2 or less, and 0 pcs/10mm ² is especially good.

The thickness of the pseudo-support is not particularly limited, but is preferably 5-200 μm, more preferably 5-150 μm, further preferably 5-50 μm, and most preferably 5-25 μm from the viewpoint of ease of handling and versatility. The thickness of the pseudo-support was calculated by the average value of arbitrary 5 points measured by the cross-sectional observation of SEM (Scanning Electron Microscope: Scanning Electron Microscope).

As the pseudo support, for example, a biaxially stretched polyethylene terephthalate film with a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 μm biaxially stretched polyethylene terephthalate film.

As a preferred form of the pseudo-support, for example, paragraphs [0017] to [0018] of Japanese Patent Application Laid-Open No. 2014-085643, paragraphs [0019] to [0026] of Japanese Patent Laid-Open No. 2016-027363, international The descriptions in paragraphs [0041] to [0057] of Publication No. 2012/081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370 are incorporated into this specification.

From the viewpoint of imparting workability, a layer containing fine particles (a lubricant layer) may be provided on the surface of the pseudo-support. The lubricant layer may be provided on one side or both sides of the dummy support. The diameter of the particles contained in the lubricant layer is preferably 0.05-0.8 μm. Also, the film thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

The surface free energy (surface free energy E _S ) of the surface on the side of the intermediate layer as the pseudo-support is preferably 60.0 mJ/m ² or less. In addition, the surface free energy E _S refers to the surface free energy of the surface of the intermediate layer side of the dummy support exposed by peeling off the dummy support from the transfer film X. The preferred aspect and measurement method of the surface free energy E _S are as described above.

Examples of commercially available pseudo-supports include Lumirror 16KS40, Lumirror 16FB40 (manufactured by TORAY INDUSTRIES, INC.), Cosmo Shine A4100, Cosmo Shine A4300, and Cosmo Shine A8300 (manufactured by Toray Industries, Inc.).

(Overall structure of transfer film X) Next, an example of a specific embodiment is given, and the overall structure of the transfer film X will be described. In addition, as described above, the transfer film X1 of the first embodiment can preferably be used as a transfer film for etching resist, and the transfer film X2 of the second embodiment can be preferably used for wiring protection. The structure of transfer film for film. In addition, the thickness of the photosensitive layer is not particularly limited, but in most cases, it is 30 μm or less. From the viewpoint of more excellent effects of the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, more preferably 10 μm or less, and 5.0 μm The following are excellent. The lower limit is preferably at least 0.60 μm, more preferably at least 1.5 μm, and still more preferably at least 2.0 μm, from the viewpoint of excellent strength of a film obtained by curing the photosensitive layer. The thickness of the photosensitive layer is calculated by the average value of arbitrary 5 points measured by the cross-sectional observation of SEM (Scanning Electron Microscope: Scanning Electron Microscope).

・Transfer film X1 of the first embodiment Hereinafter, an example of an embodiment of the transfer film X1 according to the first embodiment will be described. The transfer film 10 shown in FIG. 1 has a dummy support 1 , a composition layer 7 including an intermediate layer 3 and a photosensitive layer 5 , and a protective film 9 in this order. In addition, although the transfer film 10 shown in FIG. 1 is the form in which the protective film 9 was arrange|positioned, the protective film 9 may not be arrange|positioned. In addition, in FIG. 1 , each layer other than the protective film 9 that can be disposed on the dummy support 1 is referred to as a composition layer 7 . Hereinafter, each element which comprises the transfer film X1 is demonstrated. In addition, the respective structures of the intermediate layer and the dummy support constituting the transfer film X1 are as described above.

··Photosensitive layer A pattern can be formed on a to-be-transferred body by exposing and developing after transferring a photosensitive layer to a to-be-transferred body. As the photosensitive layer, a negative photosensitive layer is preferable. In addition, the negative photosensitive layer is a photosensitive layer in which the solubility of an exposed portion to a developing solution decreases by exposure. When the photosensitive layer is a negative photosensitive layer, the formed pattern corresponds to a cured layer.

When the photosensitive layer is a negative photosensitive layer, it is preferable that the negative photosensitive layer contains a resin, a polymerizable compound, and a polymerization initiator. Moreover, when the photosensitive layer is a negative photosensitive layer, it is also preferable to contain an alkali-soluble resin (alkali-soluble resin, polymer A etc.) as a part or all of resin as mentioned later. That is, in one aspect, it is preferable that the photosensitive layer contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. This photosensitive layer (negative photosensitive layer) contains resin: 10-90 mass %; polymerizable compound: 5-70 mass %; polymerization initiator: 0.01-20 mass %, based on the total mass of the photosensitive layer % is better. Hereinafter, each component is demonstrated sequentially.

···Polymer A (resin) When the photosensitive layer is a negative photosensitive layer, especially the resin contained in the photosensitive layer is called polymer A. Polymer A series alkali-soluble resin is preferred. From the standpoint of better resolution by suppressing the swelling of the negative photosensitive layer caused by the developer, the acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and less than 190 mgKOH /g is more preferable. The lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, still more preferably 150 mgKOH/g or more, and 170 mgKOH/g or more. G or above is especially good.

In addition, the acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. An acid value can be calculated|required according to the method of JISK0070:1992, for example. What is necessary is just to adjust the acid value of polymer A according to the kind of the structural unit which comprises polymer A, and content of the structural unit containing an acid group.

The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably at most 100,000, further preferably at most 60,000. On the other hand, when the weight-average molecular weight is 5,000 or more, it is considered from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as edge melting and dicing chip properties when it is a negative photosensitive resin laminate. is better. The weight average molecular weight is more preferably at least 10,000, further preferably at least 20,000, and particularly preferably at least 30,000. The edge melting property refers to the extent to which the negative photosensitive layer tends to protrude from the end surface of the roll when the negative photosensitive resin laminate is wound up in a roll shape. Cutting chipping property refers to the degree of easy flying of chips in the case of cutting an unexposed film with a cutter. When this swarf adheres to the upper surface and the like of the negative photosensitive resin laminate, it will be transferred to the mask in the subsequent exposure step and the like to cause a defective product. The degree of dispersion of the polymer A is preferably 1.0-6.0, more preferably 1.0-5.0, still more preferably 1.0-4.0, and particularly preferably 1.0-3.0. In the present invention, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight). In the present invention, the weight average molecular weight and the number average molecular weight are values measured using gel permeation chromatography.

In the negative photosensitive layer, it is preferable that the polymer A contains a structural unit based on a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing a thickening of the line width and deterioration of resolution when the focal position shifts during exposure. Moreover, as such an aromatic hydrocarbon group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group are mentioned, for example. The content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A. The upper limit is not particularly limited, but is preferably at most 95% by mass, more preferably at most 85% by mass. Moreover, when including several types of polymer A, it is preferable that the average value based on the content of the structural unit of the monomer which has an aromatic hydrocarbon group exists in the said range.

As monomers having an aromatic hydrocarbon group, for example, monomers having an aralkyl group, styrene and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tertiary butoxybenzene Ethylene, acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer, etc.). Among them, monomers having aralkyl groups or styrene are preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content of the structural unit based on styrene is 20 to 70% by mass relative to the total mass of the polymer A. It is more preferable, 25-65 mass % is more preferable, 30-60 mass % is still more preferable, 30-55 mass % is especially preferable. Moreover, when the photosensitive layer contains several types of polymer A, the content rate of the structural unit which has an aromatic hydrocarbon group was calculated|required as a weight average.

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

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

As a monomer having a benzyl group, (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, Examples include vinyl benzyl chloride and benzyl alcohol. Among them, benzyl (meth)acrylate is preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, based on the composition of benzyl (meth)acrylate relative to the total mass of polymer A The content of the units is preferably from 50 to 95% by mass, more preferably from 60 to 90% by mass, still more preferably from 70 to 90% by mass, and particularly preferably from 75 to 90% by mass.

Polymer A comprising a constituent unit based on a monomer having an aromatic hydrocarbon group is obtained by combining the monomer having an aromatic hydrocarbon group with at least one of the first monomers described below and/or at least one of the second monomers described below Polymerization is better.

It is preferable that the polymer A not containing a constituent unit based on a monomer having an aromatic hydrocarbon group is obtained by polymerizing at least one of the first monomers described later, by combining at least one of the first monomers described later with It is more preferably obtained by copolymerizing at least one of the second monomers.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid. Acid half esters etc. Among these, (meth)acrylic acid is preferable. Relative to the total mass of the polymer A, the content of the constituent units based on the first monomer in the polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% by mass. better. From the viewpoint of expressing favorable developability, control of edge melting property, etc., it is preferable to make the said content into 5 mass % or more. From the viewpoint of high resolution and edge shape of the photoresist pattern, and further from the viewpoint of chemical resistance of the photoresist pattern, the above content is preferably 50% by mass or less.

The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid n-butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic acid esters such as cyclohexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, etc. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferable, and methyl (meth)acrylate is more preferable. Relative to the total mass of the polymer A, the content of the constituent units based on the second monomer in the polymer A is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and still more preferably 17 to 45% by mass. better.

In the case where the polymer A contains a structural unit based on an aralkyl-containing monomer and/or a structural unit based on a styrene monomer, the line width becomes thicker when shifting from the focus position at the time of exposure, and the resolution decreases. The viewpoint of deterioration is considered to be better. For example, a copolymer comprising a structural unit based on methacrylic acid, a structural unit based on benzyl methacrylate, and a structural unit based on styrene, a structural unit based on methacrylic acid, a structural unit based on methyl methacrylate, Copolymers of structural units based on benzyl methacrylate and structural units based on styrene are preferred. In one aspect, polymer A contains 25 to 55% by mass of structural units based on monomers having aromatic hydrocarbon groups, 20 to 35% by mass of structural units based on first monomers, and 15 to 45% by mass of A polymer based on a constituent unit of the second monomer is preferable. Also, in another aspect, a polymer containing 70 to 90 mass % of structural units based on a monomer having an aromatic hydrocarbon group and 10 to 25 mass % of structural units based on a first monomer is preferable.

Polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A . A group having an alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched chain structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, second-butyl (meth)acrylate, Tert-butyl (meth)acrylate, isopentyl (meth)acrylate, third-pentyl (meth)acrylate, second-pentyl (meth)acrylate, 2-octyl (meth)acrylate, ( 3-octyl methacrylate and tertiary octyl (meth)acrylate, etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred. . Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Moreover, (meth)acrylate which has an alicyclic hydrocarbon group with 5-20 carbon atoms is mentioned. As more specific examples, (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl base ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3- Ethyl adamantyl ester, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate Base ester, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (methyl) 2-Ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5-(meth)acrylate base, octahydro-4,7-menthol-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, (meth) ) Acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1 .0] Heptyl ester, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenzyl (meth)acrylate, 2,2,5-trimethyl (meth)acrylate Cyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenzyl (meth)acrylate, 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate are preferred, (meth) Cyclohexyl acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferable.

The polymer A may be used alone or in combination of two or more. When using two or more types, use a mixture of two polymers A containing constituent units based on monomers having an aromatic hydrocarbon group, or use a mixture of polymers A containing constituent units based on monomers having an aromatic hydrocarbon group and Polymer A which does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferable. In the latter case, with respect to the total mass of the polymer A, the usage ratio of the polymer A comprising a constituent unit based on a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more , more than 80% by mass is better, and more than 90% by mass is more preferred.

Regarding the synthesis of Polymer A, an appropriate amount of free radicals such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the above singular or plural monomers with solvents such as acetone, methyl ethyl ketone, and isopropanol. It is preferable to carry out the polymerization initiator and heat and stir. In some cases, the synthesis is performed while a part of the mixture is added dropwise to the reaction liquid. In some cases, after completion of the reaction, a solvent is further added to adjust to a desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can be used.

The glass transition temperature Tg of the polymer A is preferably 30-135°C. By using the polymer A which has Tg of 135 degreeC or less, it can suppress that a line width becomes thick and the deterioration of a resolution at the time of focus position shift at the time of exposure is suppressed. From this point of view, the Tg of the polymer A is preferably 130°C or lower, further preferably 120°C or lower, and particularly preferably 110°C or lower. Moreover, it is preferable to use the polymer A which has Tg of 30 degreeC or more from a viewpoint of edge melting resistance improvement. From this point of view, the Tg of the polymer A is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, most preferably 70°C or higher.

The negative photosensitive layer contains other resins than the above as the polymer A. Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycol.

As the polymer A, an alkali-soluble resin described in the description of the thermoplastic resin layer described later can be used.

The content of the polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass, based on the total mass of the negative photosensitive layer. Excellent. From the viewpoint of controlling the developing time, it is preferable to make the content of the polymer A 90% by mass or less. On the other hand, from the viewpoint of improving edge melting resistance, the content of the polymer A is preferably 10% by mass or more.

···polymeric compound When the photosensitive layer is a negative photosensitive layer, it is preferable that the negative photosensitive layer contains a polymerizable compound having a polymerizable group. In addition, in this specification, a "polymerizable compound" is a compound which polymerizes by the action of the polymerization initiator mentioned later, and means a compound different from the said polymer A.

The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group related to the polymerization reaction, for example, vinyl group, acryl group, methacryl group, styryl group and cis A group having an ethylenically unsaturated group such as a butenedilimide group; and a group having a cationic polymerizable group such as an epoxy group and an oxetanyl group. As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryl group or a methacryl group is more preferable.

As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compounds) is preferred from the viewpoint of better photosensitivity of the negative photosensitive layer, and one molecule has two or more ethylenically unsaturated groups. The above ethylenically unsaturated compound (polyfunctional ethylenically unsaturated compound) is more preferable. Also, from the standpoint of better resolving properties and exfoliation properties, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less. for further improvement.

From the viewpoint of a better balance between photosensitivity, resolution and release properties of the negative photosensitive layer, bifunctional or trifunctional ethylenically unsaturated compounds having 2 or 3 ethylenically unsaturated groups in one molecule More preferably, it contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound relative to the total mass of the negative photosensitive layer is preferably 20% by mass or more, and more than 40% by mass, based on the total solid content of the composition. It is more preferable, and it is still more preferable that it is 55 mass % or more. The upper limit is not particularly limited, and may be 100% by mass. That is, all polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Also, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryl group as a polymerizable group is preferable.

····polymerizable compound B1 It is also preferable that the negative photosensitive layer contains the polymerizable compound B1 which has an aromatic ring and 2 ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule of the above-mentioned polymerizable compound B.

From the viewpoint of better resolution, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compound in the negative photosensitive layer is preferably 40% or more, more preferably 50% by mass or more, 55 mass % or more is more preferable, and 60 mass % or more is especially preferable. The upper limit is not particularly limited, but from the viewpoint of releasability, for example, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less. For the best.

Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, aromatic rings such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings. Aromatic heterocycles and their condensed rings, aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. In addition, the above-mentioned aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

It is preferable that polymerizable compound B1 has a bisphenol structure from a viewpoint of improving resolution by suppressing the swelling of the photosensitive layer by a developing solution. As the bisphenol structure, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl) hydroxyphenyl) methane) and bisphenol B structure from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), bisphenol A structure is better.

Examples of the polymerizable compound B1 having a bisphenol structure include those having a bisphenol structure and two polymerizable groups (preferably (meth)acryl groups) bonded to both ends of the bisphenol structure. compound. Both ends of the bisphenol structure may be directly bonded to two polymerizable groups, or may be bonded via one or more alkyleneoxy groups. As the alkoxyl group added to both ends of the bisphenol structure, ethoxyl or propoxyl is preferred, and ethoxyl is more preferred. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the content described in the publication is incorporated into this specification.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is better. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethyl) Oxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2 ,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methyl 2,2-bis(4-(methacryloxydecamethacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd. Pentaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) .

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

[chemical formula 1]

In the general formula B1, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents C ₂ H ₄ . B represents C ₃ H ₆ . n1 and n3 are each independently an integer of 1-39, and n1+n3 is an integer of 2-40. n2 and n4 are each independently an integer of 0-29, and n2+n4 is an integer of 0-30. The sequence of the constituent units of -(AO)- and -(BO)- may be random or block. And, in the case of a block, both -(AO)- and -(BO)- may be on the side of the bisphenyl group. In one aspect, n1+n2+n3+n4 is preferably 2-20, more preferably 2-16, and still more preferably 4-12. Also, n2+n4 is preferably 0-10, more preferably 0-4, still more preferably 0-2, and particularly preferably 0.

The polymerizable compound B1 may be used individually by 1 type, and may use 2 or more types. From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably at least 10% by mass, more preferably at least 20% by mass, based on the total mass of the negative photosensitive layer. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive resin bleeds from the edge of the transfer material).

The negative photosensitive layer may contain polymerizable compounds other than the above-mentioned polymerizable compound B1. The polymerizable compound other than the polymerizable compound B1 is not particularly limited, and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds not having an aromatic ring, and trifunctional or higher ethylenically unsaturated compounds. compound.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloxyethylsuccinate, polyethylene glycol Glycol Mono(meth)acrylate, Polypropylene Glycol Mono(meth)acrylate and Phenoxyethyl(meth)acrylate.

Examples of bifunctional ethylenically unsaturated compounds not having an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di( Meth)acrylate and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), Methanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate and new Pentylene glycol di(meth)acrylate. Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. )Acrylate. Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, ethylene oxide and propylene oxide modified urethane di(meth)acrylate ester. As a commercial item, for example, 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO,. LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co. ., Ltd.).

Examples of ethylenically unsaturated compounds having a trifunctional or higher function include diperythritol (tri/tetra/penta/hexa) (meth)acrylate, neopentylthritol (tri/tetra) (methyl) Acrylates, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate (meth)acrylates, glycerol tri(meth)acrylates and their alkylene oxide modified substances. Here, "(three/four/five/hexa)(meth)acrylate" refers to tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate ) the concept of acrylate, "(three/four) (meth)acrylate" is a concept including three (meth)acrylate and tetra(meth)acrylate. In one aspect, it is also preferable that the negative photosensitive layer contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional or higher ethylenically unsaturated compounds. compound is more preferred. At this time, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound is (the total mass of the polymerizable compound B1): (the total mass of the trifunctional or higher ethylenically unsaturated compound)=1:1～ 5:1 is preferable, 1.2:1-4:1 is more preferable, and 1.5:1-3:1 is still more preferable. Moreover, in one aspect, it is preferable that the negative photosensitive layer contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. , A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura ATM-35E and A-9300 manufactured by Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAI-CELL-ALLNEX LTD., etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co. ., Ltd., A-GLY-9E, etc.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

Moreover, as a polymeric compound, the polymeric compound which has an acidic group (carboxyl group etc.) can be used. The above-mentioned acid groups may form acid anhydride groups. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX ( registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.). As the polymerizable compound having an acid group, for example, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

A polymeric compound may be used individually by 1 type, and may use 2 or more types. The content of the polymerizable compound is preferably from 10 to 70% by mass, more preferably from 15 to 70% by mass, and still more preferably from 20 to 70% by mass with respect to the total mass of the negative photosensitive layer.

The molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200.

···polymerization initiator When the photosensitive layer is a negative photosensitive layer, it is also preferable that the negative photosensitive layer contains a polymerization initiator. A polymerization initiator can be selected according to the form of a polymerization reaction, For example, a thermal polymerization initiator and a photopolymerization initiator are mentioned. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

It is preferable that a negative photosensitive layer contains a photoinitiator. A photopolymerization initiator is a compound that starts polymerization of a polymerizable compound upon receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. As a photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example, A photoradical polymerization initiator is preferable.

Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, and photopolymerization initiators having an α-hydroxyalkylphenone structure. A photopolymerization initiator with a structure, a photopolymerization initiator with an acyl phosphine oxide structure, and a photopolymerization initiator with an N-phenylglycine structure.

In addition, from the viewpoint of photosensitivity, visibility and resolution of exposed and non-exposed parts, the negative photosensitive layer contains a compound selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof. At least one of them is preferred as a photoradical polymerization initiator. In addition, the structures of two 2,4,5-triarylimidazoles in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl )-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl) -4,5-diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

As the photoradical polymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 can be used.

Examples of photoradical polymerization initiators include dimethylaminobenzoic acid ethyl ester (DBE, CAS No. 10287-53-3), benzoin methyl ether, methoxyphenyl (p,p'-di methoxybenzyl ester), TAZ-110 (product name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (product name: manufactured by Midori Kagaku Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF Corporation), Omnirad651 and 369 (product name: manufactured by IGM Resins B.V.), and 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (product Name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1 -(O-acetyloxime) (product name: IRGACURE OXE-02, manufactured by BASF Corporation), IRGACURE OXE-03 (manufactured by BASF Corporation), IRGACURE OXE-04 (manufactured by BASF Corporation), 2-(dimethylamino )-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-Methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one (product name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4 -(2-Hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2- Dimethylamino-1-(4-morpholinephenyl)butanone-1 (product name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropane-1- Ketone (product name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenyl Ethan-1-one (product name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins B.V. ), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester photopolymerization initiator (product name: Lunar 6 , manufactured by DKSH Management Ltd.), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (product name: Omnirad 907FF, manufactured by IGM Resins B.V.), 2 -Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one (product name: Omnirad 379, manufactured by IGM Resins B.V.), 2, 2'-bis(2-chlorophenyl)-4,4',5, 5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (product name: B-CIM, manufactured by Hampford Research Inc.) and 2-(o- Chlorophenyl)-4,5-diphenylimidazole dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclo Amyl propane-1,2-dione-2-(O-benzoyl oxime) (product name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), 1,2-propane di Ketone, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (product name: TR -PBG-326, manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexyl)-9-ethyl -9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (product name: TR-PBG-391, Changzhou Tronly New Electronic Materials CO.,LTD. manufacture).

Photocationic polymerization initiators (photoacid generators) are compounds that generate acid upon receiving actinic rays. As the photocationic polymerization initiator, a compound that responds to actinic rays with a wavelength of 300 nm or more, preferably 300-450 nm and generates acid is preferred, but its chemical structure is not particularly limited. Also, as for the photocationic polymerization initiator that does not directly respond to actinic rays with a wavelength of 300 nm or more, if it is a compound that generates an acid by using a sensitizer in combination with actinic rays with a wavelength of 300 nm or more, it can also be combined with the sensitizer. It is better to use in combination. As a photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less The photocatalytic polymerization initiator of acid is especially preferred. The lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.

As a photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator are mentioned. As an ionic photocationic polymerization initiator, for example, onium salt compounds such as diaryliodonium salts and triaryliumium salts, and quaternary ammonium salts are mentioned. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-085643 can be used.

Examples of nonionic photocationic polymerization initiators include trichloromethyl-symmetrical trisulfones, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be used as the trichloromethyl-symmetric trisulfones, the diazomethane compound, and the imidesulfonate compound. In addition, as the oxime sulfonate compound, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be used.

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

A polymerization initiator may be used individually by 1 type, and may use 2 or more types. The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass relative to the total mass of the negative photosensitive layer. It is still more preferable that it is more than mass %. The upper limit is not particularly limited, but is preferably 20% by mass or less, further preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total mass of the negative photosensitive layer.

···pigment From the viewpoint of the visibility of the exposed part and the non-exposed part, the visibility of the pattern after development, and the resolution, the photosensitive layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm during color development and is affected by acid and alkali. A pigment whose maximum absorption wavelength is changed by free radicals (also referred to as "pigment N") is also preferable. When the pigment N is contained, the detailed mechanism is not clear, but the adhesion with the adjacent layer (such as the pseudo-water-soluble resin layer) is improved, and the resolution is more excellent.

In this specification, the pigment "changes the maximum absorption wavelength due to acid, alkali or free radical" may refer to the state in which the pigment in the color-developing state is decolorized by acid, alkali or free radicals, or in the achromatic state. Any of the state in which the pigment in the pigment develops color by acid, alkali or free radicals and the state in which the pigment in the color state changes to another color state. Specifically, the dye N may be a compound that develops color by changing from a color-absorbing state to light exposure, or may be a compound that loses color by changing from a color-developing state to light exposure. In this case, it may be a dye that generates an acid, an alkali, or a radical in the photosensitive layer by exposure to act to change the state of color development or decolorization, or may be a pigment that is activated by an acid, an alkali, or a radical. A pigment that changes the state of color development or decolorization by changing the state (for example, pH) in the photosensitive layer. In addition, it may be a pigment that is directly stimulated by an acid, an alkali, or a free radical without exposure to light to change the state of color development or decolorization.

Among them, dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and a dye whose maximum absorption wavelength is changed by a radical from the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion. for better. In the case where the photosensitive layer is a negative photosensitive layer, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part, the negative photosensitive layer contains a dye whose maximum absorption wavelength changes due to radicals and Both are preferable as a photoradical polymerization initiator. Moreover, from the viewpoint of the visibility of an exposed part and a non-exposed part, it is preferable that the dye N is a dye that develops color with an acid, an alkali, or a radical.

As an example of the color development mechanism of the dye N, the following aspect can be mentioned: adding a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator to the photosensitive layer, exposing Radical-reactive dyes, acid-reactive dyes or base-reactive dyes (such as leuco dyes) due to free radicals, acids or bases generated by photoradical polymerization initiators, photocationic polymerization initiators or photobase generators color.

Regarding the pigment N, from the viewpoint of the visibility of the exposed part and the non-exposed part, the maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or more, more preferably 550 to 700 nm, and 550 to 650 nm. Further better. In addition, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the color development wavelength range of 400 to 780 nm, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

Regarding the maximum absorption wavelength of dye N, the transmission spectrum of a solution (liquid temperature: 25°C) containing dye N is measured in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION) in the atmospheric atmosphere , and obtained by detecting the wavelength at which the intensity of light reaches a minimum (maximum absorption wavelength).

As a coloring matter which develops or loses color by exposure, a colorless compound is mentioned, for example. Examples of dyes that are decolorized by exposure include colorless compounds, diarylmethane-based dyes, 㗁𠯤-based dyes, Kuchi Yamaguchi-based dyes, iminonaphthoquinone-based dyes, and azomethine-based dyes. and anthraquinone pigments. As the dye N, a colorless compound is preferable from the viewpoint of the visibility of the exposed portion and the non-exposed portion.

As the colorless compound, for example, a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a helicopyran skeleton (helicopyran-based dye), and a colorless compound having a fluorescent yellow mother skeleton (fluorescent yellow matrix pigment), colorless compound with diarylmethane skeleton (diarylmethane pigment), colorless compound with rhodamine lactamide skeleton (rhodamine lactamide pigment), indole A colorless compound with an indolylphthalide skeleton (indolylphthalide pigment) and a colorless compound with a white gold amine skeleton (white gold amine pigment). Among them, triarylmethane-based pigments or fluorescent yellow parent system pigments are preferred, and colorless compounds (triphenylmethane-based pigments) with triphenylmethane skeletons or fluorescent yellow parent system pigments are more preferred.

As a colorless compound, it is preferable to have a lactone ring, a sultine ring, or a sultone ring from the viewpoint of the visibility of an exposure part and a non-exposure part. Thereby, the lactone ring, sultine ring or sultone ring of the colorless compound can react with the free radical generated by the photoradical polymerization initiator or the acid generated by the photocationic polymerization initiator to make the colorless compound The compound is changed to a ring-closed state to lose color, or the colorless compound is changed to a ring-opened state to develop color. As a colorless compound, a compound having a lactone ring, a sultine ring or a sultone ring, and having a lactone ring, a sultine ring or a sultone ring that develops color due to free radicals or acids is preferred, and a compound having a lactone ring , and the compound that develops color due to the opening of the lactone ring by free radicals or acids is more preferable.

Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes in the dye N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, methyl quinoline red, rose bengal, and metasamine yellow. , bromophenol blue, xylenol blue, methyl orange, p-methyl red, Congo red, benzene red violet 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, Magenta, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Powder #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (Orient Chemical Co., Ltd.), Oil Scarlet #308 (Orient Chemical Co., Ltd.), Oil Red OG (Orient Chemical Co., Ltd.) , Oil Red RR (manufactured by Orient Chemical Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Co., Ltd.), SPIRON Red BEH SPECIAL (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol violet, formazan Phenol Red, Rhodamine B, Rhodamine 6G, Sulphonyl Rhodamine B, Gold Ammonium, 4-p-Diethylaminophenyliminonaphthoquinone, 2-Carboxyanilino-4-p-Diethylamino Phenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl- 4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthalene-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the colorless compound in Dye N include p,p',p''-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal Violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow Parent, 2-anilino-3-methyl-6-(N-ethyl-p-toluidine) fluorescent yellow precursor, 3,6-dimethoxy fluorescent yellow precursor, 3-(N,N-di Ethylamino)-5-methyl-7-(N,N-dibenzylamino) fluorescent yellow precursor, 3-(N-cyclohexyl-N-methylamino)-6-methyl- 7-anilino fluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-anilino fluorescent yellow precursor, 3-(N,N-diethylamino) -6-Methyl-7-amino-fluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow precursor, 3-(N,N- Diethylamino)-6-methoxy-7-amino fluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino) fluorescent yellow precursor, 3-(N,N-diethylamino)-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow precursor, 3-( N,N-diethylamino)-7,8-benzofluorescent yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-stibamido fluorescent yellow precursor, 3-piperidinyl-6-methyl-7-anilino fluorescent yellow precursor, 3 -Pyrrolidinyl-6-methyl-7-anilinofluorescent yellow precursor, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-( 4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4- Diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzo Furan-1(3H), 9'-[9H]koukousing-3-one.

From the viewpoint of the visibility of the exposed part and the non-exposed part, the visibility of the pattern after development, and the resolution, the dye N is preferably a dye whose maximum absorption wavelength changes due to free radicals, and a dye that develops color by free radicals for better. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate are preferable.

One type of dye N may be used alone, or two or more types may be used. From the viewpoint of the visibility of the exposed portion and the non-exposed portion, the visibility of the pattern after development, and the resolution, the content of the pigment N is preferably 0.1% by mass or more, and 0.1 to 10% by mass relative to the total mass of the photosensitive layer. % is more preferred, 0.1 to 5% by mass is still more preferred, and 0.1 to 1% by mass is particularly preferred.

The content of the dye N means the content of the dye when all the dye N contained in the total mass of the photosensitive layer is in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described by taking a dye that develops color by radicals as an example. A solution in which 0.001 g and 0.01 g of a dye were dissolved in 100 mL of methyl ethyl ketone was prepared. A photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Ltd.) was added to each of the obtained solutions, and 365nm light was irradiated to generate free radicals to bring all the pigments into a color-developed state. Then, under the air atmosphere, using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION), the absorbance of each solution at a liquid temperature of 25° C. was measured to prepare a calibration curve. Next, except having dissolved the photosensitive layer 3g in methyl ethyl ketone instead of a dye, the absorbance of the solution which color-developed all the dyes was measured by the method similar to the above. Based on the obtained absorbance of the solution containing the photosensitive layer, the content of the pigment contained in the photosensitive layer is calculated according to the calibration curve. In addition, 3 g of photosensitive layers are the same as 3 g of total solids in a photosensitive composition.

···Heat-crosslinkable compounds When the photosensitive layer is a negative photosensitive layer, it is preferable to include a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In addition, in this specification, the heat-crosslinkable compound which has the ethylenically unsaturated group mentioned later is not regarded as a polymeric compound, but is regarded as a heat-crosslinkable compound. Examples of the heat-crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. The blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group. Therefore, for example, in the case of a resin and/or a polymerizable compound having at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film decreases, and the negative type is strengthened. The tendency of the function of the film formed by hardening the photosensitive layer to be used as a protective film. In addition, the blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so called masking) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter". As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

As an end-capping agent with a dissociation temperature of 100 to 160°C, active methylene compounds [malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, Malonate (2-ethylhexyl, etc.)], oxime compounds (formaldoxime, acetaldehyde oxime, acetyloxime, methyl ethyl ketone oxime and cyclohexanone oxime, etc. have -C (=N-OH)- in the molecule compounds of the structure). Among them, as a blocking agent having a dissociation temperature of 100 to 160° C., for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.

For example, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoints of improving the brittleness of the film, improving the adhesive force with the transfer target, and the like. A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among the blocked isocyanate compounds having an isocyanurate structure, the compound containing the oxime structure having an oxime compound as a blocking agent can easily set the dissociation temperature within a preferable range compared with the compound not having the oxime structure, and It is preferable from the viewpoint of being easy to reduce image development residue.

The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, and radically polymerizable groups are preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group. Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is still more preferable.

As a blocked isocyanate compound, a commercial item can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (the above are manufactured by SHOWA DENKO K.K.) . Block-type DURANATE series (for example, DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation.). Moreover, the compound of the following structure can also be used as a block isocyanate compound.

[chemical formula 2]

A heat-crosslinkable compound may be used individually by 1 type, and may use 2 or more types. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, relative to the total mass of the photosensitive layer.

···Other additives The photosensitive layer may contain well-known additives other than the said component as needed. Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (triazoles, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonia Alkaline amide, etc.), purine bases (adenine, etc.) and surfactants. Each additive may be used individually by 1 type, and may use 2 or more types.

The photosensitive layer may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenothiazine or 4-methoxyphenol are preferred. Examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, and the like. In order not to impair the sensitivity of the photosensitive layer, it is preferable to use nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor. The preferred content of the radical polymerization inhibitor is the same as the content of the same components in the photosensitive layer of the transfer film X2 of the second embodiment.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)amino Methylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl base) aminomethylene-1,2,3-benzotriazole, etc.

As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N- Di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N, N-di-2-ethylhexyl)aminoethylenylcarboxybenzotriazole, etc. As carboxybenzotriazoles, for example, commercial items such as CBT-1 (JOHOKU CHEMICAL CO., LTD, product name) can be used.

The total content of benzotriazoles and carboxybenzotriazoles is preferably from 0.01 to 3% by mass, more preferably from 0.05 to 1% by mass, relative to the total mass of the photosensitive layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and the suppression of decolorization of the dye are more excellent.

Moreover, as a radical polymerization inhibitor, for example, a hindered phenol compound is also preferable. As the hindered phenol compound, for example, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid][ethylenebis(oxyethylene)]2,4-bis[ (Stearylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4 -tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butyl Anilino)-1,3,5-tri-3-(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and so on.

The photosensitive layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, tiostatone compounds, and acridone compounds. , azole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, trioxazole compounds, thiophene compounds, naphthalene dicarboxamides Amine compounds, triarylamine compounds and aminoacridine compounds. As a commercial item of a sensitizer, "SB-PI 701" (4,4'-bis (diethylamino) benzophenone) etc. by Sanyo Trading Co., Ltd. are mentioned, for example.

A sensitizer may be used individually by 1 type, and may use 2 or more types. When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the hardening speed based on the balance between the polymerization speed and chain transfer, relatively In the total mass of the photosensitive layer, 0.01-5 mass % is preferable, and 0.05-1 mass % is more preferable.

The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International Publication No. 2018/179640.

It is preferable that the photosensitive layer contains a surfactant. Examples of the surfactant include the same ones as those that may be contained in the photosensitive layer of the transfer film X2 according to the second embodiment described later, and preferred aspects are also the same.

In addition, the photosensitive layer may contain metal oxide particles, antioxidants, rust inhibitors, dispersants, acid multiplying agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic Known additives such as anti-precipitation agents. Also, as a chain transfer agent, it is also preferable to include N-phenylaminoformylmethyl-N-methylolaniline and/or N,N-tetraethyl-4,4-diaminobenzophenone . About the additive contained in a photosensitive layer, it describes in paragraphs 0165-0184 of Unexamined-Japanese-Patent No. 2014-085643, and the content of this publication is incorporated in this specification.

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

In addition, from the viewpoint of better adhesion, the transmittance of light having a wavelength of 365 nm of the photosensitive layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

···Impurities etc. The photosensitive layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, since halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, it is preferable to set them to the following content.

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

As a method of keeping the impurities within the above-mentioned ranges, there may be mentioned: selecting a raw material of the composition with a low content of impurities; preventing contamination of impurities during production of the photosensitive layer; and removing them by washing. By this method, the amount of impurities can be set within the above-mentioned range.

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

Benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and It is preferable that the content of compounds such as hexane is small. The content of these compounds with respect to the total mass of the photosensitive layer is preferably at most 100 ppm, more preferably at most 20 ppm, and still more preferably at most 4 ppm, on a mass basis. On a mass basis, the lower limit can be 10 ppb or more, and can be 100 ppb or more with respect to the total mass of the photosensitive layer. Regarding these compounds, the content can be suppressed by the same method as the impurities of the above-mentioned metals. In addition, it can be quantified by a known measurement method.

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

···pigment The photosensitive layer may be a colored resin layer containing a pigment. In recent years, a cover glass in which a black frame-shaped light-shielding layer is formed on the back peripheral portion of a transparent glass substrate or the like may be attached to a liquid crystal display window of an electronic device to protect the liquid crystal display window. In order to form such a light-shielding layer, a colored resin layer can be used. As a pigment, what is necessary is just to select suitably according to desired hue, and can select from black pigment, white pigment, and color pigments other than black and white. Among them, in the case of forming a black-based pattern, a black pigment can be preferably selected as the pigment.

Known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as the black pigment within the range that does not impair the effects of the present invention. Among them, from the viewpoint of optical density, examples of the black pigment preferably include carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, black lead, and the like, and carbon black is particularly preferred. Carbon black having at least a part of the surface covered with a resin is preferable from the viewpoint of surface resistance.

The particle size of the black pigment is preferably from 0.001 to 0.1 μm, more preferably from 0.01 to 0.08 μm, in terms of the number average particle size from the viewpoint of dispersion stability. Here, the particle diameter refers to the diameter of a circle when the area of the pigment particle is calculated from the photo image of the pigment particle taken with an electron microscope and a circle having the same area as the area of the pigment particle is considered, and the number average particle diameter is calculated for any 100 particles. Particles The average value obtained by calculating the above-mentioned particle size and averaging the calculated particle sizes of 100 particles.

As pigments other than black pigments, white pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as white pigments. Specifically, among white pigments, as inorganic pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate are preferred, and titanium oxide or zinc oxide is more preferred. , titanium oxide is further preferred. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable. In addition, silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment may be performed on the surface of titanium oxide, or two or more treatments may be performed. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance, delustering properties, and the like are improved. From the viewpoint of reducing the thickness of the photosensitive layer after heating, as the surface treatment on the surface of titanium oxide, at least one of alumina treatment and zirconia treatment is preferable, alumina treatment and zirconia treatment Both are excellent.

Moreover, when a photosensitive layer is a colored resin layer, it is preferable that a photosensitive layer further contains color pigments other than a black pigment and a white pigment from a transferable viewpoint. When a color pigment is included, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. Examples of color pigments include Victoria Pure Blue BO (Color Index: Color Index (C.I.) 42595), Goldamine (C.I. 41000), Fat Black HB (C.I. 26150), Monoright Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Magenta FBB (C.I. Pigment Red 146), Master Yeast Red ESB (C.I. C.I. Pigment Red 11), Fastel Powder B Supra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monoright Black B (C.I. Pigment Black 1) Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, C.I. Pigment Violet 23, etc. Among them, C.I. Pigment Red 177 is preferred.

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

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

In addition, when the photosensitive layer contains a black pigment and the photosensitive layer is formed of a photosensitive composition, it is preferable to introduce the black pigment (preferably carbon black) into the photosensitive composition in the form of a pigment dispersion. The dispersion liquid may be one prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle), and dispersing using a disperser. What is necessary is just to select a pigment dispersant according to a pigment and a solvent, For example, a commercially available dispersant can be used. In addition, the vehicle refers to the part of the medium in which the pigment is dispersed in the case of a pigment dispersion liquid, and is liquid, and contains a binder component that maintains the black pigment in a dispersed state and a solvent component that dissolves and dilutes the binder component. (Organic solvents).

The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, roll mill, attritor, supermill, dissolver, homomixer, and sand mixer. Furthermore, fine pulverization can be performed by mechanical grinding using frictional force. For the disperser and fine pulverization, refer to the records in "Encyclopedia of Pigments" (by Kunizo Asakura, first edition, Asakura Publishing Co., Ltd., 2000, pages 438 and 310).

In addition, the thickness of the photosensitive layer is not particularly limited, but in most cases, it is 30 μm or less. From the viewpoint of more excellent effects of the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, more preferably 10 μm or less, and 5.0 μm The following are excellent. The lower limit is preferably at least 0.60 μm, more preferably at least 1.5 μm, and still more preferably at least 2.0 μm, from the viewpoint of excellent strength of a film obtained by curing the photosensitive layer. The thickness of the photosensitive layer is calculated by the average value of arbitrary 5 points measured by the cross-sectional observation of SEM (Scanning Electron Microscope: Scanning Electron Microscope).

··Protective film The transfer film X1 may have a protective film. As the protective film, a heat-resistant and solvent-resistant resin film can be used, for example, polyolefin films such as polypropylene film and polyethylene film, polyester film such as polyethylene terephthalate film, polycarbonate film, etc. film and polystyrene film. Moreover, as a protective film, the resin film which consists of the same material as the above-mentioned dummy support body can also be used. Among these, as a protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is still more preferable.

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

In addition, in the protective film, it is preferable that the number of fish eyes with a diameter of 80 μm or more included in the protective film is 5 or less/m ² . In addition, "fish eye" refers to the foreign matter, undissolved matter, and oxidative deterioration of the material when the film is produced by thermal melting, kneading, extrusion, biaxial stretching, and casting methods. Incorporated into the thin film.

The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, still more preferably 5 particles/mm ² or less. Thereby, it is possible to suppress the defects caused by the transfer of the unevenness caused by the particles contained in the protective film to the photosensitive layer or the conductive layer.

From the viewpoint of imparting windability, the arithmetic mean roughness Ra of the surface opposite to the surface in contact with the composition layer of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and 0.03 μm or more. Further better. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface of the protective film in contact with the composition layer is preferably at least 0.01 μm, more preferably at least 0.02 μm, and still more preferably at least 0.03 μm. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less. The arithmetic mean roughness Ra of each surface of the protective film is implemented in the same manner as the measurement method of the already described "arithmetic mean roughness Ra of the intermediate layer side of the pseudo-support".

··Pseudo-support body, photosensitive layer and protective film of the best relationship between the physical properties Hereinafter, regarding the transfer film X1, it is preferable that the respective physical properties of the dummy support, the photosensitive layer, and the protective film show the following aspects. It is preferable that the transfer film X1 satisfies one or more of the preferred aspect 1, the preferred aspect 2, the preferred aspect 3, the preferred aspect 4, and the preferred aspect 5, and it is more preferable to satisfy all of them.

"The elongation at break of the cured film with the photosensitive layer hardened" is measured by tensile test on the cured film, which is cured by exposing the photosensitive layer with a thickness of 20 μm with an ultra-high pressure mercury lamp at 120 mJ/cm ² Thereafter, the cured film was additionally exposed at 400 mJ/cm ² using a high-pressure mercury lamp, and heated at 145° C. for 30 minutes. About the measurement method of "the arithmetic mean roughness Ra of the intermediate|middle layer side of a pseudo-support body", it is as above-mentioned. The measurement method of "the arithmetic mean roughness Ra of the surface of the photosensitive layer side of a protective film" is carried out in the same manner as the measurement method of the already described "arithmetic mean roughness Ra of the intermediate layer side of the dummy support body".

···Better Form 1 In the transfer film X1, it is preferable that each physical property of the dummy support, the photosensitive layer, and the protective film satisfy each of the following conditions (P1) to (P3). (P1) The elongation at break at 120°C of the cured film obtained by curing the photosensitive layer is 15% or more. (P2) The arithmetic average roughness Ra of the surface of the intermediate layer side of the pseudo support is 50 nm or less. (P3) The arithmetic average roughness Ra of the surface of the photosensitive layer side of a protective film is 150 nm or less.

···The best form 2 It is preferable that each physical property of the pseudo-support of the transfer film X1 and the photosensitive layer satisfy the following formula (1). X×Y＜1500 Formula (1) Among them, in the formula (1), X represents the value (%) of the elongation at break of the cured film formed by curing the photosensitive layer at 120°C, and Y represents the arithmetic mean roughness of the surface on the side of the intermediate layer of the pseudo-support Ra value (nm). In the above formula (1), the value represented by X×Y is preferably 750 or less.

···The best form 3 It is preferable that the physical properties of the photosensitive layer of the transfer film X1 satisfy the following condition (P4). (P4) The elongation at break at 120° C. is twice or more larger than the elongation at break at 23° C. of the cured film obtained by curing the photosensitive layer.

···Better Form 4 It is preferable that each physical property of the pseudo-support of transfer film X1 and a photosensitive layer satisfy|fills following formula (2). Y≤Z formula (2) Wherein, in the formula (2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the intermediate layer side of the pseudo-support body, and Z represents the value of the arithmetic mean roughness Ra of the surface of the photosensitive layer side of the protective film (nm).

・Manufacturing method of the transfer film X1 of the first embodiment The manufacturing method of the transfer film X1 of 1st Embodiment is not specifically limited, A well-known method can be used. As a method for producing the above-mentioned transfer film 10, for example, a method including the steps of applying a composition for forming an intermediate layer on the surface of the dummy support 1 to form a coating film, and further drying the coating film to form an intermediate layer The step of layer 3; and the step of coating the photosensitive composition on the surface of the intermediate layer 3 to form a coating film, and further drying the coating film to form the photosensitive layer 5. In addition, in this specification, "drying" means removing at least a part of the solvent contained in the composition. As a drying method, natural drying, heat drying, and reduced-pressure drying are mentioned, for example. The above-mentioned methods can be applied individually or in combination of plural kinds.

The transfer film 10 is manufactured by crimping the protective film 9 on the photosensitive layer 5 of the laminate manufactured by the above-mentioned manufacturing method. As the method of manufacturing the transfer film according to the first embodiment, the film provided with the dummy support 1 is manufactured by including the step of providing the protective film 9 so as to be in contact with the surface of the photosensitive layer 5 opposite to the side having the dummy support 1 . , the intermediate layer 3, the photosensitive layer 5 and the transfer film 10 of the protective film 9 are preferred. After the transfer film 10 is produced by the above-mentioned production method, the transfer film 10 is wound up, whereby the transfer film in the form of a roll can be produced and stored. The transfer film in the form of a roll can be provided as it is in a step of bonding to a substrate in the roll-to-roll system described later.

··Composition for forming an intermediate layer and method for forming an intermediate layer It is preferable that the composition for forming an intermediate layer contains various components and a solvent for forming the above-mentioned intermediate layer. In addition, in the composition for forming an intermediate layer, the preferable range of the content of each component relative to the total solid content of the composition is the same as the preferable range of the content of each component relative to the total mass of the above-mentioned intermediate layer. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin. At least one selected from the group consisting of water and water-miscible organic solvents is preferred. Water or a mixture of water and water-miscible organic solvents A solvent is more preferred. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, among which alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. One type of solvent may be used alone, or two or more types of solvents may be used. The content of the solvent is preferably from 50 to 2,500 parts by mass, more preferably from 50 to 1,900 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The formation method of the intermediate layer is not particularly limited as long as it is a method capable of forming a layer comprising the above-mentioned components, for example, known coating methods (slit coating, spin coating, curtain coating and ink-jet coating) cloth, etc.).

As a drying method of the coating film of the intermediate layer forming composition, heat drying and reduced-pressure drying are preferable. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. Moreover, as its upper limit, it is preferable that it is 130 degreeC or less, and it is more preferable that it is 120 degreeC or less. Drying can also be performed by continuously changing the temperature. Moreover, as a drying time, 20 seconds or more are preferable, 40 seconds or more are more preferable, and 60 seconds or more are still more preferable. The upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

··Photosensitive composition and method for forming photosensitive layer From the viewpoint of excellent productivity, it is desirable to use a photosensitive composition containing components (for example, binder polymer, polymerizable compound, and polymerization initiator, etc.) and a solvent that constitute the above-mentioned photosensitive layer and form it by a coating method .

As a photosensitive composition, it is preferable to contain various components and a solvent which form the said photosensitive layer. In addition, in the photosensitive composition, the preferable range of content of each component with respect to the total solid content of a composition is the same as the preferable range of content of each component with respect to the total mass of the said photosensitive layer. The solvent is not particularly limited as long as it can dissolve or disperse components other than the solvent, and known solvents can be used. Specifically, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents And a mixed solvent containing two or more of them.

As the solvent, it is preferable to contain at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents The mixed solvent is more preferably a mixed solvent comprising at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents, and cyclic ether solvents. for further improvement.

Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and diethylene glycol monoalkyl ether acetate. Propylene Glycol Monoalkyl Ether Acetate. As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvents described in paragraph 0014 of JP-A-2018-177889 can be used, and these contents are incorporated in this specification. One type of solvent may be used alone, or two or more types of solvents may be used. The content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1200 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

As the coating method of the photosensitive composition, for example, a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method) can be mentioned. .

As a method of drying the coating film of the photosensitive composition, heat drying and reduced-pressure drying are preferable. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. Moreover, as its upper limit, it is preferable that it is 130 degreeC or less, and it is more preferable that it is 120 degreeC or less. Drying can also be performed by continuously changing the temperature. Moreover, as a drying time, 20 seconds or more are preferable, 40 seconds or more are more preferable, and 60 seconds or more are still more preferable. The upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

Furthermore, the transfer film X1 of 1st Embodiment can be manufactured by bonding a protective film to a photosensitive layer. The method of bonding a protective film to a photosensitive layer is not specifically limited, A well-known method is mentioned. Well-known laminators, such as a vacuum laminator and an automatic cutting laminator, are mentioned as an apparatus which bonds a protective film to a photosensitive layer. It is preferable that the laminator is equipped with any heatable roll such as a rubber roll, and can be pressurized and heated.

The transfer film X1 of the first embodiment is used, for example, in the production process film of a semiconductor package, a printed circuit board, and a rewiring layer of an interposer, for circuit wiring arranged on a support substrate such as a sheet, a metal substrate, a ceramic substrate, and a glass. form better.

・Transfer film X2 of the second embodiment Hereinafter, an example of an embodiment of the transfer film X2 according to the second embodiment will be described. The transfer film 20 shown in FIG. 2 has a dummy support 11 , a composition layer 19 including an intermediate layer 13 , a photosensitive layer 15 , and a refractive index adjustment layer 17 , and a protective film 21 in this order. In addition, although the transfer film 20 shown in FIG. 2 is the form in which the protective film 21 was arrange|positioned, the protective film 21 may not be arrange|positioned. In addition, although the transfer film 20 shown in FIG. 2 is the form which arrange|positioned the refractive index adjustment layer 17, the refractive index adjustment layer 17 may not be arrange|positioned. In addition, in FIG. 2 , each layer other than the protective film 21 that can be disposed on the dummy support 11 is referred to as a composition layer 17 . Hereinafter, each element which comprises the transfer film X2 is demonstrated. In addition, the respective structures of the intermediate layer and the dummy support constituting the transfer film X2 are as described above. Moreover, about the structure of a protective film, it is the same as that of the transfer film X1.

··Photosensitive layer The transfer film X2 of the second embodiment has a photosensitive layer. A pattern can be formed on a to-be-transferred body by exposing and developing after transferring a photosensitive layer to a to-be-transferred body. As the photosensitive layer, a negative photosensitive layer is preferable. In addition, the negative photosensitive layer is a photosensitive layer in which the solubility of an exposed portion to a developing solution decreases by exposure. When the photosensitive layer is a negative photosensitive layer, the formed pattern corresponds to a cured layer.

Hereinafter, components that can be contained in the photosensitive layer will be described in detail.

···Binder Polymers The photosensitive layer may contain a binder polymer. Examples of the binder polymer include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, Epoxy acrylate resin obtained by reaction of epoxy resin and (meth)acrylic acid and acid-modified epoxy acrylate resin obtained by reaction of epoxy acrylate resin with acid anhydride.

As one of the preferable aspects of the binder polymer, a (meth)acrylic resin is mentioned from the viewpoint of being excellent in alkali developability and film formability. In addition, in this specification, a (meth)acrylic resin means resin which has a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from the (meth)acrylic compound is preferably at least 50% by mass, more preferably at least 70% by mass, and still more preferably at least 90% by mass, based on all the structural units of the (meth)acrylic resin. good. A (meth)acrylic resin may consist only of the structural unit derived from a (meth)acrylic compound, and may have the structural unit derived from a polymerizable monomer other than a (meth)acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth)acrylic compound is 100% by mass or less with respect to all the structural units of the (meth)acrylic resin.

Examples of (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylates, (meth)acrylamide, and (meth)acrylonitrile. Examples of (meth)acrylates include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylates, dimethylaminoethyl (meth)acrylates, (meth) Diethylaminoethyl acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate and 2,2 (meth)acrylate , 3,3-tetrafluoropropyl ester and alkyl (meth)acrylate are preferred. Examples of (meth)acrylamide include acrylamide such as diacetone acrylamide.

The alkyl group of the alkyl (meth)acrylate may be linear or branched. As specific examples, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, ( Hexyl (meth)acrylate, Heptyl (meth)acrylate, Octyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, Nonyl (meth)acrylate, Decyl (meth)acrylate Alkyl (meth)acrylates having an alkyl group having 1 to 12 carbons, such as undecyl (meth)acrylate and dodecyl (meth)acrylate. As the (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.

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

Moreover, it is preferable that a (meth)acrylic resin contains the structural unit which has an acid group from a viewpoint of making alkali developability more favorable. As an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group are mentioned, for example. Among them, it is more preferable that the (meth)acrylic resin has a structural unit having a carboxyl group, and it is still more preferable that it has a structural unit derived from the above-mentioned (meth)acrylic acid.

From the viewpoint of better developability, the content of structural units having acid groups (preferably those derived from (meth)acrylic acid) in the (meth)acrylic resin is higher than the total amount of the (meth)acrylic resin. Quality, more than 10% by mass is better. Also, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, and more preferably 40% by mass or less.

Moreover, it is more preferable that a (meth)acrylic resin has the structural unit derived from the said alkyl (meth)acrylate. The content of the constituent units derived from the alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50 to 90% by mass, and 60 to 90% by mass relative to all the constituent units of the (meth)acrylic resin. % is more preferable, and 65 to 90% by mass is still more preferable.

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

In addition, from the viewpoint that the effects of the present invention are more excellent, the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates. It is preferable to have both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate. From the point of view that the effect of the present invention is more excellent, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate in the (meth)acrylic resin relative to the (meth)acrylic resin The content of all the constituent units of the compound is preferably 40% by mass or more, and more preferably 60% by mass or more. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

In addition, from the viewpoint that the effects of the present invention are more excellent, the (meth)acrylic resin has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates. And at least one selected from the group consisting of a structural unit derived from acrylic acid and a structural unit derived from an alkyl acrylate is also preferable. From the viewpoint that the effect of the present invention is more excellent, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate is higher than the content of the structural unit derived from acrylic acid and alkyl acrylate. The total content of the constituent units is preferably 60/40 to 80/20 in mass ratio.

From the viewpoint of being excellent in the developability of the photosensitive layer after transfer, it is preferable that the (meth)acrylic resin has an ester group at the terminal. In addition, the terminal portion of the (meth)acrylic resin is constituted by a portion derived from a polymerization initiator used for synthesis. A (meth)acrylic resin having an ester group at the terminal can be synthesized by using a radical-generating polymerization initiator having an ester group.

Moreover, alkali-soluble resin is mentioned as another preferable aspect of a binder polymer. For example, it is preferable that the binder polymer is a binder polymer having an acid value of 60 mgKOH/g or more from the viewpoint of developability. Also, for example, from the viewpoint of thermally crosslinking with a crosslinking component by heating to easily form a firm film, the binder polymer is a resin having a carboxyl group with an acid value of 60 mgKOH/g or more (so-called carboxyl group-containing resin) ) is more preferable, and a (meth)acrylic resin having a carboxyl group (so-called carboxyl group-containing (meth)acrylic resin) having an acid value of 60 mgKOH/g or more is still more preferable. If the binder polymer is a resin having a carboxyl group, for example, by adding a thermally crosslinkable compound such as a blocked isocyanate compound to perform thermal crosslinking, the three-dimensional crosslinking density can be increased. Moreover, when the carboxyl group of the resin which has a carboxyl group is dehydrated and hydrophobized, heat-and-moisture resistance can be improved.

The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the above acid value conditions, and can be appropriately selected from known (meth)acrylic resins. [ 0033] to [0052] paragraphs of polymers described in the acid value of 60mgKOH/g or more carboxyl group-containing acrylic resin, etc.

A styrene-acrylic acid copolymer is mentioned as another preferable aspect of a binder polymer. In addition, in this specification, a styrene-acrylic acid copolymer refers to the resin which has the structural unit derived from a styrene compound and the structural unit derived from a (meth)acrylic compound, and the structural unit derived from the said styrene compound and The total content of the structural units derived from the above-mentioned (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, relative to all the structural units of the above-mentioned copolymer. Moreover, the content of the structural unit derived from a styrene compound is preferably 1 mass % or more, more preferably 5 mass % or more, and still more preferably 5-80 mass % with respect to all the structural units of the said copolymer. Furthermore, the content of the structural units derived from the above-mentioned (meth)acrylic compound is preferably at least 5% by mass, more preferably at least 10% by mass, and further preferably 20 to 95% by mass, based on all the structural units of the above-mentioned copolymer. better.

From the viewpoint that the effects of the present invention are more excellent, it is preferable that the binder polymer has an aromatic ring structure, and it is more preferable that it contains a structural unit having an aromatic ring structure. As a monomer forming a constituent unit having an aromatic ring structure, monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxy styrene, acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer, etc.). Among them, monomers having aralkyl groups or styrene are preferred. Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (benzyl group is removed) and a substituted or unsubstituted benzyl group, among which a substituted or unsubstituted benzyl group is preferred.

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

As a monomer having a benzyl group, (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, Examples include vinyl benzyl chloride and benzyl alcohol. Among them, benzyl (meth)acrylate is preferred.

Moreover, it is more preferable that the binder polymer has a structural unit (structural unit derived from styrene) represented by the following formula (S) from the viewpoint that the effects of the present invention are more excellent.

[chemical formula 3]

In the case where the binder polymer contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure relative to all the structural units of the binder polymer is 5 to 90 mass % is preferable, 10-70 mass % is more preferable, and 20-60 mass % is still more preferable. Also, from the standpoint of more excellent effects of the present invention, the content of the structural units having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer. 10-60 mol% is more preferable, and 20-60 mol% is still more preferable. Furthermore, from the point of view that the effects of the present invention are more excellent, the content of the structural unit represented by the above formula (S) in the binder polymer is 5 to 70 mol % with respect to all the structural units of the binder polymer. Preferably, 10-60 mol% is more preferred, 20-60 mol% is still more preferred, and 20-50 mol% is particularly preferred. In addition, in this specification, when content of a "constituent unit" is prescribed|regulated by molar ratio, the said "constitutive unit" is synonymous with a "monomeric unit". In addition, in this specification, the above-mentioned "monomer unit" may be modified after being polymerized by a polymer reaction or the like. The same applies below.

From the viewpoint that the effect of the present invention is more excellent, it is preferable that the binder polymer has an aliphatic hydrocarbon ring structure. That is, it is preferable that the binder polymer contains a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. Among them, the binder polymer preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the constituent unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborane ring. Among them, from the point of view that the effect of the present invention is more excellent, aliphatic hydrocarbon rings having two or more rings are preferable, and tetrahydrodicyclopentadiene rings (tricyclo[5.2.1.0 ^2,6 ]decane Ring) is better. As a monomer which forms the structural unit which has an aliphatic hydrocarbon ring structure, dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate are mentioned. Also, from the viewpoint of more excellent effects of the present invention, it is more preferable that the binder polymer has a structural unit represented by the following formula (Cy), and has a structural unit represented by the above formula (S) and the following formula (Cy ) The constituent unit represented by ) is more preferable.

[chemical formula 4]

In the formula (Cy), R ^M represents a hydrogen atom or a methyl group, and R ^Cy represents a group having a valency of an aliphatic hydrocarbon ring structure.

R ^M in formula (Cy) is preferably methyl. From the point of view that the effects of the present invention are more excellent, R ^Cy in the formula (Cy) is preferably a valent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbons, and an aliphatic hydrocarbon with 6 to 16 carbons A valent group having an aliphatic hydrocarbon ring structure is more preferable, and a valent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms is still more preferable. Also, from the viewpoint that the effect of the present invention is more excellent, the aliphatic hydrocarbon ring structure in R ^Cy of the formula (Cy) is a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, The norbornane ring structure or the isoborane ring structure is preferable, the cyclohexane ring structure or the tetrahydrodicyclopentadiene ring structure is more preferable, and the tetrahydrodicyclopentadiene ring structure is still more preferable. From the point of view that the effect of the present invention is more excellent, the aliphatic hydrocarbon ring structure in the R ^Cy of formula (Cy) is preferably a ring structure formed by condensation of two or more aliphatic hydrocarbon rings, from 2 to 4 The ring formed by condensing the aliphatic hydrocarbon ring of the ring is more preferable. Furthermore, from the viewpoint that the effects of the present invention are more excellent, the R ^Cy in the formula (Cy) is a group in which the oxygen atom of -C(=O)O- in the formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure Group, that is, an aliphatic hydrocarbon ring group is preferred, cyclohexyl or dicyclopentyl is more preferred, and dicyclopentyl is still more preferred.

The binder polymer may have one kind of structural unit having an aliphatic hydrocarbon ring structure alone, or may have two or more kinds. When the binder polymer contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure relative to all the structural units of the binder polymer is considered to be more excellent in the effect of the present invention. , 5-90 mass % is more preferable, 10-80 mass % is more preferable, 20-70 mass % is still more preferable. Also, from the viewpoint of more excellent effect of the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is 5 to 70 mol% relative to all the structural units of the binder polymer. Preferably, 10-60 mol % is more preferable, 20-50 mol % is still more preferable. Furthermore, from the point of view that the effects of the present invention are more excellent, the content of the structural unit represented by the above formula (Cy) in the binder polymer is 5 to 70 mol % with respect to all the structural units of the binder polymer. Preferably, 10-60 mol % is more preferable, and 20-50 mol % is still more preferable.

In the case where the binder polymer contains a constituent unit having an aromatic ring structure and a constituent unit having an aliphatic hydrocarbon ring structure, the constituent units having an aromatic ring structure and a constituent unit having an aliphatic hydrocarbon ring The total content of the constituent units of the structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass, relative to all the constituent units of the binder polymer. Also, from the viewpoint of more excellent effects of the present invention, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the binder polymer relative to all the structural units of the binder polymer, 10-80 mol% is preferable, 20-70 mol% is more preferable, and 40-60 mol% is still more preferable. Furthermore, from the point of view that the effect of the present invention is more excellent, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer relative to the content of the binder polymer 10-80 mol% is preferable for all constituent units, 20-70 mol% is more preferable, and 40-60 mol% is still more preferable. Also, from the viewpoint of more excellent effects of the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer It is preferable to satisfy the relationship shown in the following formula (SCy), it is more preferable to satisfy the following formula (SCy-1), and it is still more preferable to satisfy the following formula (SCy-2). 0.2≤nS/(nS+nCy)≤0.8 Formula (SCy) 0.30≤nS/(nS+nCy)≤0.75 Formula (SCy-1) 0.40≤nS/(nS+nCy)≤0.70 Formula (SCy-2)

From the viewpoint that the effect of the present invention is more excellent, it is preferable that the binder polymer contains a structural unit having an acid group. Examples of the above-mentioned acid groups include carboxyl groups, sulfonic acid groups, phosphonic acid groups, and phosphoric acid groups, and carboxyl groups are preferred. As a structural unit which has the said acidic group, the structural unit derived from (meth)acrylic acid shown below is preferable, and the structural unit derived from methacrylic acid is more preferable.

[chemical formula 5]

The binder polymer may have one type of structural unit having an acid group alone, or may have two or more types. In the case where the binder polymer contains a structural unit having an acid group, the content of the structural unit having an acid group is 5 to 50% by mass relative to all the structural units of the binder polymer, from the viewpoint that the effects of the present invention are more excellent. % is more preferable, 5-40 mass % is more preferable, and 10-30 mass % is still more preferable. Also, from the viewpoint of more excellent effects of the present invention, the content of the structural units having acid groups in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer, and 10 -50 mol% is more preferable, and 20-40 mol% is still more preferable. Furthermore, from the point of view that the effect of the present invention is more excellent, the content of the structural unit derived from (meth)acrylic acid in the binder polymer is 5 to 70 mol % with respect to all the structural units of the binder polymer. Preferably, 10-50 mol % is more preferable, 20-40 mol % is still more preferable.

From the viewpoint that the effect of the present invention is more excellent, it is preferable that the binder polymer has a reactive group, and it is more preferable that it contains a structural unit having a reactive group. As the reactive group, a radical polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. Moreover, when a binder polymer has an ethylenically unsaturated group, it is preferable that a binder polymer contains the structural unit which has an ethylenically unsaturated group in a side chain. In this specification, "main chain" means the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and "side chain" means an atomic group branched from the main chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable. As an example of the structural unit which has a reactive group, what is shown below is mentioned, However, It is not limited to these.

[chemical formula 6]

A binder polymer may contain the structural unit which has a reactive group individually, and may have 2 or more types. In the case where the binder polymer contains a structural unit having a reactive group, the content of the structural unit having a reactive group relative to all the structural units of the binder polymer is from 5 to 70 mass % is preferable, 10-50 mass % is more preferable, and 20-40 mass % is still more preferable. Also, from the viewpoint of more excellent effects of the present invention, the content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer. 10-60 mol% is more preferable, and 20-50 mol% is still more preferable.

As a method for introducing reactive groups into the binder polymer, there may be mentioned compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinylidene compounds, aldehyde compounds, methylol compounds, and carboxylic anhydrides with hydroxyl groups. , carboxyl group, primary amino group, secondary amino group, acetoacetyl group (acetoacetyl group) and sulfonic acid group and other functional groups to react. As a preferable example of the method of introducing a reactive group into the binder polymer, it is possible to synthesize glycidyl (meth)acrylate by polymer reaction after synthesizing a polymer having a carboxyl group by a polymerization reaction. A method of introducing a (meth)acryloxy group into a polymer by reacting with a part of the carboxyl group of the obtained polymer. By this method, a binder polymer having a (meth)acryloxy group in a side chain can be obtained. The above polymerization reaction is preferably carried out at a temperature of 70-100°C, more preferably at a temperature of 80-90°C. As the polymerization initiator used in the above-mentioned polymerization reaction, an azo-based initiator is preferable, for example, V-601 (product name) or V-65 (product name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferable. The above polymer reaction is preferably carried out at a temperature of 80-110°C. In the above polymer reaction, it is better to use catalysts such as ammonium salts.

As the binder polymer, polymers X1 to X4 shown below are preferable from the viewpoint that the effect of the present invention is more excellent. In addition, the content ratio (a-d) and weight average molecular weight Mw etc. of each structural unit shown below can be changed suitably according to the objective, but the following structure is preferable from a viewpoint of the effect of this invention being more excellent among them. (Polymer X1) a: 20-60 mass %, b: 10-50 mass %, c: 5.0-25 mass %, d: 10-50 mass %. (Polymer X2) a: 20-60 mass %, b: 10-50 mass %, c: 5.0-25 mass %, d: 10-50 mass %. (Polymer X3) a: 30-65 mass %, b: 1.0-20 mass %, c: 5.0-25 mass %, d: 10-50 mass %. (Polymer X4) a: 1.0-20 mass %, b: 20-60 mass %, c: 5.0-25 mass %, d: 10-50 mass %.

[chemical formula 7]

In addition, the binder polymer may contain a polymer (hereinafter also referred to as "polymer X") containing a structural unit having a carboxylic anhydride structure. The carboxylic acid anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but a cyclic carboxylic anhydride structure is preferable. As the ring of the cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is still more preferable.

The constituent unit having a carboxylic acid anhydride structure is a constituent unit comprising a divalent group obtained by removing 2 hydrogen atoms from a compound represented by the following formula P-1 in the main chain or a constituent unit derived from the compound represented by the following formula P-1. In the compounds shown, a monovalent group obtained by removing one hydrogen atom is preferably a structural unit bonded to the main chain directly or via a divalent linking group.

[chemical formula 8]

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

As a substituent represented by R ^A1a , an alkyl group is mentioned, for example. As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is still more preferable. n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and more preferably 0. When n ^1a represents an integer of 2 or more, R ^A1a that exists in plural may be the same or different. In addition, a plurality of R ^A1a may be bonded to each other to form a ring, but it is preferable to bond to each other without forming a ring.

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

Hereinafter, although the specific example of the structural unit which has a carboxylic anhydride structure is mentioned, the structural unit which has a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group or a CF ₃ group, and Me represents a methyl group.

[chemical formula 9]

[chemical formula 10]

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

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

The photosensitive layer may contain only 1 type of polymer X, and may contain 2 or more types. When the photosensitive layer contains polymer X, the content of polymer X is preferably 0.1 to 30% by mass, 0.2 to 20% by mass relative to the total mass of the photosensitive layer, from the viewpoint of more excellent effects of the present invention. It is more preferable, 0.5-20 mass % is still more preferable, and 1-20 mass % is still more preferable.

From the viewpoint of more excellent effects of the present invention, the weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and most preferably 20,000 to 30,000.

The acid value of the binder polymer is preferably 10-200 mgKOH/g, more preferably 60-200 mgKOH/g, still more preferably 60-150 mgKOH/g, and particularly preferably 70-125 mgKOH/g. In addition, the acid value of a binder polymer can be measured according to the method of JISK0070:1992, for example. From the viewpoint of developability, the degree of dispersion of the binder polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

The photosensitive layer may contain only 1 type of binder polymer, and may contain 2 or more types. From the viewpoint that the effect of the present invention is more excellent, the content of the binder polymer relative to the total mass of the photosensitive layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 70% by mass. Further better.

···polymeric compound The photosensitive layer may contain a polymerizable compound. A polymeric compound is a compound having a polymeric basis. Examples of the polymerizable group include a radical polymerizable group and a cation polymerizable group, and a radical polymerizable group is preferred.

It is preferable that the polymerizable compound contains a radically polymerizable compound (hereinafter, also simply referred to as "ethylenically unsaturated compound") having an ethylenically unsaturated group. As the ethylenically unsaturated group, a (meth)acryloxy group is preferable. In addition, the ethylenically unsaturated compound in this specification is a compound other than the said binder polymer, and it is preferable that a molecular weight is less than 5,000.

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

Q ¹ and Q ² in the ^formula (M ⁾ are preferably the same group from the viewpoint of ease of synthesis. Also, Q ¹ and Q ² in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity. As R ¹ in the formula (M), from the viewpoint of more excellent effect of the present invention, an alkylene group, an alkylene group (-L ¹ -OL ¹ -) or a polyalkylene group (- (L ¹ -O) _p -L ¹ -) is preferred, a hydrocarbon group or a polyalkoxyalkylene group with 2 to 20 carbons is more preferred, an alkylene group with 4 to 20 carbons is further preferred, and carbon A straight chain alkylene group having a number of 6 to 18 is particularly preferred. The above-mentioned hydrocarbon group is not particularly limited as long as at least a part thereof has a chain structure, and the part other than the above-mentioned chain structure is not particularly limited. Arylylene group, ether bond, and any combination thereof. An alkylene group or a group formed by combining two or more alkylene groups with one or more arylylene groups is preferred. The alkylene group is More preferably, a straight-chain alkylene group is further more preferable. In addition, the above L ¹ each independently represent an alkylene group, preferably an ethylene group, a propylidene group or a butylene group, and more preferably an ethylene group or a 1,2-propylidene group. p represents an integer of 2 or more, preferably an integer of 2-10.

Also, from the viewpoint of more excellent effects of the present invention, the number of atoms in the shortest connecting chain between Q1 and ^Q2 in compound M is preferably ³ to 50, more preferably 4 to 40, and 6 -20 is further preferred, and 8-12 is particularly preferred. ^In this specification, "the number ^of atoms of the shortest connecting chain between Q1 and ^Q2 " refers to the shortest chain connecting the atom ^of R1 connected to Q1 to the atom ^of R1 connected to ^Q2 . number of atoms.

Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate ester, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1, 9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F Di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol/propylene glycol) di(meth)acrylate and polybutylene Ethylene glycol di(meth)acrylate. The above-mentioned ester monomers can also be used in the form of a mixture. Among the above-mentioned compounds, from the viewpoint that the effects of the present invention are more excellent, those selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1 , At least one compound from the group of 10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate is preferred, selected from the group consisting of 1,6-hexanediol di(meth)acrylate More preferably, at least one compound selected from the group consisting of acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate, selected from the group consisting of 1 At least one compound selected from the group of ,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate is still more preferable.

Moreover, as one of the preferable aspects of a polymeric compound, a bifunctional or more ethylenically unsaturated compound is mentioned. In this specification, a "difunctional or more ethylenically unsaturated compound" means a compound which has two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryl group is preferable. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferable.

The bifunctional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds. Examples of the bifunctional ethylenically unsaturated compound other than the above compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (product name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane Decane dimethanol dimethacrylate (product name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (product name: NK Ester A-NOD- N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (product name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

It does not specifically limit as a trifunctional or more ethylenically unsaturated compound, It can select suitably from well-known compounds. Examples of ethylenically unsaturated compounds having trifunctional or higher functions include dipenteoerythritol (tri/tetra/penta/hexa)(meth)acrylate, neopentylthritol (tri/tetra)(meth)acrylate , trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate and glycerol tri(meth)acrylate Skeleton (meth)acrylate compound.

Here, "(three/four/five/hexa)(meth)acrylate" refers to tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate ) the concept of acrylate, "(three/four) (meth)acrylate" is a concept including three (meth)acrylate and tetra(meth)acrylate.

Examples of polymerizable compounds include caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd. .manufactured A-9300-1CL, etc.), (meth)acrylic ester compound's alkylene oxide modified compound (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co. , Ltd. ATM-35E, A-9300, DAICEL-ALLNEX LTD. EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., Ltd. NK Ester A-GLY-9E, etc.).

Urethane (meth)acrylate compounds are also mentioned as a polymeric compound. Urethane (meth)acrylates include urethane di(meth)acrylates, for example, propylene oxide modified urethane di(meth)acrylates, ethylene oxide and epoxy Propane modified urethane di(meth)acrylate. Moreover, as urethane (meth)acrylate, the urethane (meth)acrylate more than trifunctional can also be mentioned. The lower limit of the number of functional groups is more preferably hexafunctional or higher, and further preferably octafunctional or higher. In addition, as the upper limit of the number of functional groups, 20 functional groups or less is preferable. Examples of trifunctional or higher urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (product name) manufactured by Kyoeisha Chemical Co., Ltd., and UA -306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

One of the preferable aspects of the polymerizable compound includes an ethylenically unsaturated compound having an acidic group. A phosphoric acid group, a sulfonic acid group, and a carboxyl group are mentioned as an acidic group. Among these, as the acid group, a carboxyl group is preferable. Examples of the ethylenically unsaturated compound having an acid group include 3-4 functional ethylenically unsaturated compounds having an acid group [those having a carboxyl group introduced into the skeleton of neopentylitol tri- and tetraacrylate (PETA) (acid value : 80-120mgKOH/g)] and 5-6 functional ethylenically unsaturated compounds with acid groups [those with carboxyl groups introduced into the skeleton of diperythritol pentaacrylate and diperythritol hexaacrylate (DPHA) [Acid value: 25~70mgKOH/g)], etc. Such a trifunctional or higher ethylenically unsaturated compound having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group as needed.

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 having a carboxyl group and a carboxylic anhydride thereof is preferable. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher-functional ethylenically unsaturated compound having a carboxyl group and its carboxylic anhydride, developability and film strength are further improved. The difunctional or more ethylenically unsaturated compound having a carboxyl group is not particularly limited, and can be appropriately selected from known compounds. Examples of ethylenically unsaturated compounds having a difunctional or higher carboxyl group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD. Manufactured), ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO.,LTD.).

As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of Japanese Patent Application Laid-Open No. 2004-239942 is preferable, and the The contents are incorporated into this manual.

Examples of ethylenically unsaturated compounds include compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, and compounds obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound. The obtained compounds, amine ester monomers such as (meth)acrylate compounds with amine ester bonds, γ-chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl-phthalate Formate, β-Hydroxyethyl-β'-(meth)acryloxyethyl-phthalate and β-Hydroxypropyl-β'-(meth)acryloxyethyl - Phthalate-based compounds such as phthalates and alkyl (meth)acrylates. These are used alone or in combination of two or more.

Examples of compounds obtained by reacting α,β-unsaturated carboxylic acids with polyhydric alcohols include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl) Propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolyethoxypolypropylene) Bisphenol A-based (meth)acrylate compounds such as oxy)phenyl)propane, polyethylene glycol di(meth)acrylate with 2 to 14 ethylene oxide groups, number of propylene oxide groups Polypropylene glycol di(meth)acrylate with 2 to 14, polyethylene glycol with 2 to 14 oxirane groups and 2 to 14 propylene glycol (polyethylene polypropylene glycol) di (meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane Methylolpropane Diethoxytri(meth)acrylate, Trimethylolpropane Triethoxytri(meth)acrylate, Trimethylolpropane Tetraethoxytri(meth)acrylate, Trimethylolpropane pentaethoxytri(meth)acrylate, bis(trimethylolpropane)tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate base) acrylate, diperythritol tetra(meth)acrylate, diperythritol penta(meth)acrylate and diperythritol hexa(meth)acrylate. Among them, ethylenically unsaturated compounds with tetramethylolmethane structure or trimethylolpropane structure are preferred, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate , trimethylolpropane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate is more preferred.

Examples of polymerizable compounds include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd. .manufactured A-9300-1CL, etc.), alkylene oxide modified compounds of ethylenically unsaturated compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., manufactured by Shin-Nakamura Chemical Co., Ltd. ATM-35E, A-9300, EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd. wait.

As a polymeric compound (especially an ethylenic unsaturated compound), what contains an ester bond among these is also preferable from a viewpoint of the excellent developability of the photosensitive layer after transfer. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the viewpoint of excellent effects of the present invention, those having a tetramethylolmethane structure or a trimethylol Ethylenically unsaturated compounds with a propane structure are preferred, such as tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate or Di(trimethylolpropane) tetraacrylate is more preferred. From the viewpoint of imparting reliability, the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the aforementioned ethylene having a tetramethylolmethane structure or a trimethylolpropane structure. Unsaturated compounds are preferred. Examples of ethylenically unsaturated compounds having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and Tricyclodecane dimethanol di(meth)acrylate.

One of the preferable aspects of the polymerizable compound includes a polymerizable compound (preferably a bifunctional ethylenically unsaturated compound) having an aliphatic hydrocarbon ring structure. As the above-mentioned polymerizable compound, a polymer having a ring structure (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) formed by condensing two or more aliphatic hydrocarbon rings Sexual compounds are preferred, and 2-functional ethylenically unsaturated compounds having a ring structure formed by ring condensation of more than 2 aliphatic hydrocarbon rings are more preferred, and tricyclodecane dimethanol di(meth)acrylate is further preferred. better. As the above-mentioned aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects of the present invention, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborane structure is better.

The molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, still more preferably from 280 to 2,200, and most preferably from 300 to 2,200. Among the polymerizable compounds contained in the photosensitive layer, the ratio of the content of the polymerizable compound with a molecular weight of 300 or less to the content of all the polymerizable compounds contained in the photosensitive layer is preferably 30% by mass or less , 25% by mass or less is more preferred, and 20% by mass or less is still more preferred.

As one of the preferred aspects of the photosensitive layer, the photosensitive layer preferably contains ethylenically unsaturated compounds with more than two functions, more preferably contains ethylenically unsaturated compounds with three or more functions, and contains three or more functional ethylenically unsaturated compounds. Ethylenically unsaturated compounds are further preferred.

Also, as one of the preferred aspects of the photosensitive layer, it is preferable that the photosensitive layer contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer containing a constituent unit having an aliphatic hydrocarbon ring. .

Also, as one of the preferred aspects of the photosensitive layer, the photosensitive layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, including 1,9-nonanediol diacrylic acid Esters, tricyclodecane dimethanol diacrylate and polyfunctional ethylenically unsaturated compounds with carboxylic acid groups are more preferred, including 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and A succinic-acid modified body of dipenteoerythritol pentaacrylate is still more preferable.

Also, as one of the preferred aspects of the photosensitive layer, it is preferable that the photosensitive layer contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a heat-crosslinkable compound described later, including the compound represented by the formula The compound represented by (M), an ethylenically unsaturated compound having an acidic group, and a blocked isocyanate compound described later are more preferable.

Also, as one of the preferred aspects of the photosensitive layer, the photosensitive layer contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (methyl) Acrylate compound) and a trifunctional or higher ethylenically unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound) are preferred. The mass ratio of the content of the bifunctional ethylenically unsaturated compound to the trifunctional or higher ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30. The content of the bifunctional ethylenically unsaturated compound relative to the total amount of all the ethylenically unsaturated compounds is preferably 20 to 80% by mass, more preferably 30 to 70% by mass. The content of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably from 10 to 60% by mass, more preferably from 15 to 40% by mass.

Moreover, as one of the preferable aspects of the photosensitive layer, it is preferable that the photosensitive layer contains compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. Also, as one of the preferred aspects of the photosensitive layer, it is preferable that the photosensitive layer contains the compound M and an ethylenically unsaturated compound having an acidic group from the viewpoints of substrate adhesion, development residue suppression, and rust prevention. , including compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acidic group are more preferred, including compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure Compounds, trifunctional or higher ethylenically unsaturated compounds and ethylenically unsaturated compounds having acid groups are further preferred, including compound M, bifunctional ethylenically unsaturated compounds having aliphatic hydrocarbon ring structures, trifunctional or higher ethylenically unsaturated compounds Especially preferred are unsaturated compounds, ethylenically unsaturated compounds having acid groups, and urethane (meth)acrylate compounds. Also, as one of the preferred aspects of the photosensitive layer, the photosensitive layer contains 1,9-nonanediol diacrylate and Polyfunctional ethylenically unsaturated compounds with carboxylic acid groups are preferred, including 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and polyfunctional ethylenically unsaturated compounds with carboxylic acid groups Compounds are preferred, including 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, diperythritol hexaacrylate and ethylenically unsaturated compounds with carboxylic acid groups are further preferred Preferably, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, ethylenically unsaturated compounds having carboxylic acid groups, and acrylate amine ester compounds are particularly preferred.

The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound. The content of the ethylenically unsaturated compound having more than two functions in the above-mentioned ethylenically unsaturated compound is preferably 60-100% by mass, 80-100% by mass relative to the total content of all the ethylenically unsaturated compounds contained in the photosensitive layer. 100 mass % is more preferable, and 90-100 mass % is further more preferable.

A polymeric compound (especially an ethylenic unsaturated compound) may be used individually by 1 type, and may use 2 or more types together. The content of the polymerizable compound (especially an ethylenically unsaturated compound) in the photosensitive layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, and 5 to 60% by mass based on the total mass of the photosensitive layer. % is more preferable, and 5-50 mass % is especially preferable.

···polymerization initiator The photosensitive layer may contain a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferable. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Examples of photopolymerization initiators include photopolymerization initiators having an oxime ester structure (hereinafter, also referred to as "oxime-based photopolymerization initiators"), and photopolymerization initiators having an α-aminoalkylphenone structure. Polymerization initiators (hereinafter also referred to as "α-aminoalkylphenone-based photopolymerization initiators"), photopolymerization initiators having an α-hydroxyalkylphenone structure (hereinafter also referred to as "α-Hydroxyalkylphenone-based polymerization initiator."), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and A photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiator") and the like.

The photopolymerization initiator comprises oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based polymerization initiators and N-phenyl At least one of the group of glycine-based photopolymerization initiators is preferred, including oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-benzene At least one of the group of glycine-based photopolymerization initiators is more preferred.

In addition, as the photopolymerization initiator, for example, those in paragraphs [0031] to [0042] of JP-A-2011-95716 and paragraphs [0064]-[0081] of JP-A-2015-014783 can also be used. The described polymerization initiator.

Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) [product name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-( O-acetyl oxime) [product name: IRGACURE (registered trademark) OXE-02, manufactured by BASF Corporation], IRGACURE (registered trademark) OXE03 (manufactured by BASF Corporation), IRGACURE (registered trademark) OXE04 (manufactured by BASF Corporation), 2- (Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Product name: Omnirad (registered trademark ) 379EG, manufactured by IGM Resins B.V.], 2-methyl-1-(4-methylthiophenyl)-2-morpholine propan-1-one [product name: Omnirad (registered trademark) 907, manufactured by IGM Resins B.V. ], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [product name: Omnirad (registered trademark) 127, manufactured by IGM Resins B.V.], 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl) butanone-1 [product name: Omnirad (registered trademark) 369, IGM Resins B.V. Manufactured], 2-Hydroxy-2-methyl-1-phenylpropan-1-one [product name: Omnirad (registered trademark) 1173, manufactured by IGM Resins B.V.], 1-hydroxycyclohexylphenyl ketone [product name : Omnirad (registered trademark) 184, manufactured by IGM Resins B.V.], 2,2-dimethoxy-1,2-diphenylethan-1-one [product name: Omnirad (registered trademark) 651, manufactured by IGM Resins B.V. ], etc., oxime ester [product name: Lunar (registered trademark) 6, manufactured by DKSH MANAGEMENT LTD.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2- Diketone-2-(O-benzoyl oxime) (product name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), 1,2-propanedione, 3-cyclohexyl-1 -[9-Ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (product name: TR-PBG-326, Changzhou Tronly New Manufactured by Electronic Materials CO.,LTD. ), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2 -Diketone-2-(O-benzoyl oxime) (product name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), APi-307 (1-(biphenyl-4-yl )-2-methyl-2-morpholin-1-one, manufactured by Shenzhen UV-ChemTech Ltd.), etc.

A photoinitiator may be used individually by 1 type, and may use 2 or more types. In the case of using two or more kinds in combination, use an oxime-based photopolymerization initiator and at least one selected from the group consisting of α-aminoalkylphenone-based photopolymerization initiators and α-hydroxyalkylphenone-based polymerization initiators is better. When the photosensitive layer contains a photopolymerization initiator, the content of the photopolymerization initiator relative to the total mass of the photosensitive layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more. Further better. Moreover, as its upper limit, it is preferable that it is 10 mass % or less with respect to the total mass of a photosensitive layer, and it is more preferable that it is 5 mass % or less.

···Heterocyclic compounds The photosensitive layer may contain a heterocyclic compound. The heterocyclic ring possessed by the heterocyclic compound may be any of monocyclic and polycyclic heterocyclic rings. Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazole compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, and benzimidazole compounds. , benzoxazole compounds and pyrimidine compounds. Among the above, the heterocyclic compound is selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazole compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds and benzo At least one compound in the group of oxazole compounds is preferably selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and At least one compound of the group of benzoxazole compounds is more preferred.

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

[chemical formula 11]

[chemical formula 12]

As the tetrazole compound, the following compounds can be exemplified.

[chemical formula 13]

[chemical formula 14]

As the thiadiazole compound, the following compounds can be illustrated.

[chemical formula 15]

As the trisulfide compound, the following compounds can be exemplified.

[chemical formula 16]

As the rhodanine compound, the following compounds can be exemplified.

[chemical formula 17]

As the thiazole compound, the following compounds can be exemplified.

[chemical formula 18]

As the benzothiazole compound, the following compounds can be exemplified.

[chemical formula 19]

As the benzimidazole compound, the following compounds can be exemplified.

[chemical formula 20]

[chemical formula 21]

As the benzoxazole compound, the following compounds can be exemplified.

[chemical formula 22]

One type of heterocyclic compound may be used alone, or two or more types may be used in combination. When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, further preferably 0.30 to 8.0% by mass relative to the total mass of the photosensitive layer. More preferably, 0.50 to 5.0% by mass is particularly preferred.

···Aliphatic Thiol Compounds The photosensitive layer may contain an aliphatic thiol compound. By containing the aliphatic thiol compound in the photosensitive layer and the ene-thiol reaction between the aliphatic thiol compound and the radically polymerizable compound having an ethylenically unsaturated group, the hardening shrinkage of the formed film is suppressed, And the stress is relieved.

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

Among the above, polyfunctional aliphatic thiol compounds are preferred from the viewpoint of the adhesiveness of the pattern to be formed (especially the adhesiveness after exposure) as the aliphatic thiol compound.

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

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

As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, from the viewpoint of the adhesiveness of the formed pattern, 2-10 functional groups are preferable, 2-8 functional groups are more preferable, and 2-6 functional groups are still more preferable. good.

Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, neopentyl tetra Alcohol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H )-triketone, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3- mercaptopropionate), neopentylthritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipenteoerythritol hexa(3-mercaptopropionate), ethyl Diol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylene Methyldithiol, 2,2'-(ethylenedithio)diethanethiol, meso 2,3-dimercaptosuccinic acid, and bis(mercaptoethyl)ether.

Among the above, the polyfunctional aliphatic thiol compound is selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and 1 , at least one compound from the group of 3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione is better.

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

The photosensitive layer may contain a single type of aliphatic thiol compound, or may contain two or more types of aliphatic thiol compounds.

When the photosensitive layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, and 5 to 30% by mass based on the total mass of the photosensitive layer. % is more preferable, and 8-20 mass % is especially preferable.

···Heat-crosslinkable compounds From the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained, it is preferable that the photosensitive layer contains a heat-crosslinkable compound. In addition, in this specification, the heat-crosslinkable compound which has an ethylenically unsaturated group mentioned later is not handled as an ethylenically unsaturated compound, but is handled as a heat-crosslinkable compound. Examples of the thermally crosslinkable compound include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Since a blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of the hydroxyl group and the carboxyl group, it tends to The hydrophilicity of the formed film decreases, and the function as a protective film is enhanced. In addition, the blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so called masking) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C. The dissociation temperature of blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter". As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

As an end-capping agent with a dissociation temperature of 100 to 160°C, active methylene compounds [malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, Malonate (2-ethylhexyl, etc.)], oxime compounds (formaldoxime, acetaldehyde oxime, acetyloxime, methyl ethyl ketone oxime and cyclohexanone oxime, etc. have -C (=N-OH)- in the molecule compounds of the structure). Among them, as a blocking agent having a dissociation temperature of 100 to 160° C., for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.

For example, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoints of improving the brittleness of the film, improving the adhesive force with the transfer target, and the like. A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among the blocked isocyanate compounds having an isocyanurate structure, the compound containing the oxime structure having an oxime compound as a blocking agent can easily set the dissociation temperature within a preferable range compared with the compound not having the oxime structure, and It is preferable from the viewpoint of being easy to reduce image development residue.

The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, and radically polymerizable groups are preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group. Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is still more preferable.

As a blocked isocyanate compound, a commercial item can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (the above are manufactured by SHOWA DENKO K.K.) . Block-type DURANATE series (for example, DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation.).

A heat-crosslinkable compound may be used individually by 1 type, and may use 2 or more types together. When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, relative to the total mass of the photosensitive layer.

···Surfactant The photosensitive layer may contain a surfactant. Examples of the surfactant include those described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of Japanese Patent Application Laid-Open No. 2009-237362.

As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable. Moreover, as a surfactant, a nonionic surfactant is preferable. Examples of commercially available fluorine-based surfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F -144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557 , F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, EXP.MFS-578, EXP .MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41 -LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above are manufactured by DIC CORPORATION), Fluorad FC430, FC431, FC171 (the above are manufactured by Sumitomo 3M Limited), SurflonS-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 , KH-40 (manufactured by AGC INC. above), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc. above), FTERGENT 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by NEOS Corporation), U-120E (UNICHEM CO., LTD.), etc. Also, as a fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and the functional group containing a fluorine atom being partially cut off when heat is applied can also be preferably used. And the fluorine atom volatilizes. Examples of such fluorine-based surfactants include MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Out of MEGAFACE DS-21. Furthermore, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. Moreover, a block polymer can also be used as a fluorine-type surfactant. Also, as a fluorine-based surfactant, a fluorine-containing polymer compound comprising a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a structure unit derived from a (meth)acrylate compound having two A constituent unit of the (meth)acrylate compound of the above (preferably 5 or more) alkoxyl groups (preferably ethylenyloxy, propoxyl). In addition, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in a side chain can also be used. Examples thereof include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (the above are manufactured by DIC Corporation) and the like. From the viewpoint of improving environmental adaptability, it is preferable to use a compound having a linear perfluoroalkyl group having 7 or more carbon atoms as a fluorine-based surfactant instead of PFOA or PFOS.

As the nonionic surfactant, glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate , glycerol ethoxylate, etc.), polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl Ether, polyethylene glycol distearate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Specific examples include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (the above are manufactured by BASF Corporation), TETRONIC 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 ( The above are manufactured by BASF Corporation), SOLSPERSE 20000 (the above are manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (the above are manufactured by FUJIFILM Wako Pure Chemical Corporation), Pionin D-1105, D-6112, D -6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT Co., Ltd. above), OLFINE E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd. above), etc.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Specific examples of surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (manufactured by DIC CORPORATION), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are manufactured by BYK-Chemie GmbH), and X-22-4952, X 22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF- 6004, KP-341, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP- 121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (以上為Momentive Performance Materials Inc.製造）、BYK300、BYK306、BYK307、BYK310、BYK320、BYK323、BYK325、BYK330、BYK313、BYK315N、BYK331、BYK333、BYK345、BYK347、BYK348、BYK349、BYK370、BYK377、BYK378、BYK323（ The above are manufactured by BYK Chemie GmbH), etc.

Surfactants may be used alone or in combination of two or more. When the photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and further preferably 0.05 to 0.80% by mass relative to the total mass of the photosensitive layer. better.

···polymerization inhibitor The photosensitive layer may contain a polymerization inhibitor. The polymerization inhibitor refers to a compound that has the function of delaying or inhibiting the polymerization reaction. As the polymerization inhibitor, for example, known compounds used as polymerization inhibitors can be used.

As polymerization inhibitors, for example, phenanthrene compounds such as phenanthrene, bis-(1-dimethylbenzyl) phenanthrene, and 3,7-dioctyl phenanthrene; bis[3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(stearylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di Methylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-tri-butanilo and new Pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) acrylate and other hindered phenolic compounds; 4-nitrosophenol, N-nitrosodiphenylamine, N-nitroso Nitroso compounds such as cyclohexyl hydroxylamine and N-nitrosophenylhydroxylamine or their salts; methyl hydroquinone, tertiary butyl hydroquinone, 2,5-di-tertiary butyl hydroquinone and 4-benzoquinone Quinone compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tertiary butylcatechol and other phenolic compounds; copper dibutyl dithiocarbamate, diethyl dithiocarbamate Metal salt compounds such as copper carbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among them, from the viewpoint that the effects of the present invention are more excellent, as a polymerization inhibitor, at least one selected from the group consisting of phenthiazine compounds, nitroso compounds or their salts, and hindered phenolic compounds is preferred. 𠯤, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [vinylbis(oxyethylene)]2,4-bis[(stearylthio )methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), p-methoxyphenol and N-nitrosophenylhydroxylamine aluminum salt for better.

A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together. When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.02 to 2.0% by mass, based on the total mass of the photosensitive layer. better. The content of the polymerization inhibitor is preferably from 0.005 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, and still more preferably from 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound.

···Hydrogen Donating Compounds The photosensitive layer may contain a hydrogen donating compound. The hydrogen-donating compound has the functions of further increasing the sensitivity of the photopolymerization initiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

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

As the amines, for example, "Journal of Polymer Society (" Vol. 10, p. 3173 (1972) by M.R. Sander et al., Japanese Patent Publication No. 44-020189, Japanese Patent Laid-Open No. 51-082102, Japanese JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104 and Research Compounds described in Disclosure No. 33825, etc. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane ( Alias: colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyl dimethyl aniline and p-methylthio dimethyl aniline. Among them, from the viewpoint that the effects of the present invention are more excellent, the amines are selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane At least one of the group is preferred.

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, N-phenylglycine is preferred as the amino acid compound from the viewpoint of more excellent effects of the present invention.

In addition, as the hydrogen-donating compound, for example, organometallic compounds (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, etc. and sulfur compounds (trithiane, etc.) described in JP-A-6-308727.

The hydrogen-donating compound may be used alone or in combination of two or more. When the photosensitive layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is 0.01 to 10.0 mass by mass relative to the total mass of the photosensitive layer from the viewpoint of increasing the curing rate by balancing the polymerization growth rate and chain transfer % is more preferable, 0.01-8.0 mass % is more preferable, and 0.03-5.0 mass % is still more preferable.

···Impurities etc. The photosensitive layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, since halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, it is preferable to set them to the following content.

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

As a method of keeping the impurities within the above-mentioned range, selection of a raw material for the photosensitive layer with a low content of impurities, prevention of contamination of impurities during formation of the photosensitive layer, and removal of impurities by washing are mentioned. By this method, the amount of impurities can be set within the above-mentioned range.

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

Benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and It is preferable that the content of compounds such as hexane is small. The content of these compounds in the photosensitive layer is preferably at most 100 ppm on a mass basis, more preferably at most 20 ppm, and still more preferably at most 4 ppm. On a mass basis, the lower limit can be set at 10 ppb or more, and can be set at 100 ppb or more. Regarding these compounds, the content can be suppressed by the same method as the impurities of the above-mentioned metals. In addition, it can be quantified by a known measurement method.

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

···Residual monomer A photosensitive layer may contain the residual monomer of each structural unit of the said alkali-soluble resin. From the viewpoint of patternability and reliability, the residual monomer content is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, based on the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but it is preferably at least 1 mass ppm, more preferably at least 10 mass ppm. From the viewpoint of patternability and reliability, the residual monomer of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and 100 mass ppm with respect to the total mass of the photosensitive layer The following are further preferred. The lower limit is not particularly limited, but is preferably at least 0.1 mass ppm, more preferably at least 1 mass ppm.

It is also preferable that the residual monomer amount of the monomer when synthesizing the alkali-soluble resin by a polymer reaction be within the above-mentioned range. For example, when a carboxylic acid side chain reacts glycidyl acrylate to synthesize alkali-soluble resin, it is preferable to make content of glycidyl acrylate into the said range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

···Other ingredients The photosensitive layer may contain components (hereinafter also referred to as "other components") other than the above-described components. Examples of other components include colorants, antioxidants, and particles (eg, metal oxide particles). In addition, as other components, other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706 can also be mentioned.

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

When the photosensitive layer contains particles, it may contain only one type of particles different in metal type and size, or may contain two or more types. When the photosensitive layer does not contain particles, or when the photosensitive layer contains particles, the content of the particles is preferably more than 0% by mass and not more than 35% by mass based on the total mass of the photosensitive layer. No particles or the content of the particles is relatively In the total mass of the photosensitive composition, it is more preferably more than 0% by mass and not more than 10% by mass, excluding particles, or the content of particles is more than 0% by mass and not more than 5% by mass relative to the total mass of the photosensitive layer. Preferably, no particles are included, or the content of particles is more than 0% by mass and 1% by mass or less with respect to the total mass of the photosensitive layer. More preferably, no particles are included.

-Colorant- The photosensitive layer may contain a trace amount of coloring agent (pigment, dye, etc.), For example, it is preferable not to contain a coloring agent substantially from a transparent viewpoint. When the photosensitive layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the photosensitive layer.

-Antioxidants- Examples of antioxidants include 1-phenyl-3-pyrazolidone (alias: phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolone 3-pyrazolones such as oxazolinone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; hydroquinone, catechol, gallol, methylhydroquinone and Chlorohydroquinone and other polyhydroxybenzenes; p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine and p-phenylenediamine. Among them, 3-pyrazolones are preferred as antioxidants, and 1-phenyl-3-pyrazolones are more preferred from the viewpoint that the effects of the present invention are more excellent.

When the photosensitive layer contains an antioxidant, the content of the antioxidant is preferably at least 0.001% by mass, more preferably at least 0.005% by mass, and still more preferably at least 0.01% by mass, based on the total mass of the photosensitive layer. The upper limit is not particularly limited, but is preferably 1% by mass or less.

··Thickness of photosensitive layer In addition, the thickness of the photosensitive layer is not particularly limited, but in most cases, it is 30 μm or less. From the viewpoint of more excellent effects of the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, more preferably 10 μm or less, and 5.0 μm The following are excellent. The lower limit is preferably at least 0.60 μm, more preferably at least 1.5 μm, and still more preferably at least 2.0 μm, from the viewpoint of excellent strength of a film obtained by curing the photosensitive layer. The thickness of the photosensitive layer is calculated by the average value of arbitrary 5 points measured by the cross-sectional observation of SEM (Scanning Electron Microscope: Scanning Electron Microscope).

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

Color of the photosensitive layer It is preferable that the photosensitive layer is colorless. Specifically, in the CIE1976 (L _* , a _* , b _* ) color space of total reflection (incident angle 8°, light source: D-65 (2° field of view)), an L ^* value of 10 to 90 is relatively low. Good, more preferably a ^* value of -1.0 to 1.0, more preferably b ^* value of -1.0 to 1.0.

Moreover, it is preferable that the pattern obtained by hardening a photosensitive layer (cured film of a photosensitive layer) is colorless. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) in the CIE1976 (L _* , a _* , b _* ) color space, the L ^* value of the pattern is 10 to 90 Preferably, the a ^* value of the pattern is preferably -1.0 to 1.0, and the b ^* value of the pattern is preferably -1.0 to 1.0.

··The moisture permeability of the photosensitive layer is considered from the viewpoint of rust prevention, and the moisture permeability of the pattern obtained by curing the photosensitive layer (cured film of the photosensitive layer) at a film thickness of 40 μm is 500g/m ² /24hr Below is preferable, below 300g/m ² /24hr is more preferred, and below 100g/m ² /24hr is still more preferred. In addition, the moisture permeability is measured using a cured film that hardens the photosensitive layer by exposing the photosensitive layer to i-rays at an exposure dose of 300 mJ/cm ² and then performing post-baking at 145° C. for 30 minutes. get.

··Refractive index adjustment layer It is preferable that the transfer film X2 of the second embodiment has a refractive index adjustment layer. As the refractive index adjustment layer, known refractive index adjustment layers can be applied. Examples of materials contained in the refractive index adjusting layer include binder polymers, polymerizable compounds, metal salts, and particles. The method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, for example, a method of using a resin with a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin.

As a binder polymer and a polymeric compound, the binder polymer and polymeric compound demonstrated in the said "photosensitive layer" section are mentioned, for example.

Examples of the particles include metal oxide particles and metal particles. The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. Metals in the metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.

For example, from the viewpoint of the transparency of the cured film, the average primary particle diameter of the particles is preferably from 1 to 200 nm, more preferably from 3 to 80 nm. The average primary particle diameter of the particles is calculated by measuring the particle diameters of 200 random particles using an electron microscope, and calculating the arithmetic mean of the measurement results. In addition, when the shape of a particle is not spherical, let the longest side be a particle diameter.

Specifically, the metal oxide particles are selected from zirconia particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles), silicon dioxide particles (SiO ₂ particles), and the like. At least one of the group of composite particles is preferred. Among them, as the metal oxide particles, at least one selected from the group consisting of zirconia particles and titanium oxide particles is more preferable, for example, from the viewpoint of easy adjustment of the refractive index.

Commercially available metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (Nanouse OZ- S30M, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.) and zirconia particles (Nanouse OZ-S30K, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.).

The particles may be used alone or in combination of two or more. The content of the particles in the refractive index adjusting layer is preferably from 1 to 95% by mass, more preferably from 20 to 90% by mass, and still more preferably from 40 to 85% by mass, based on the total mass of the refractive index adjusting layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and 40 to 85% by mass relative to the total mass of the refractive index adjusting layer. Further better.

The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive layer. The refractive index of the refractive index adjusting layer is preferably at least 1.50, more preferably at least 1.55, still more preferably at least 1.60, and particularly preferably at least 1.65. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, and still more preferably 1.78 or less.

The thickness of the refractive index adjusting layer is preferably from 50 to 500 nm, more preferably from 55 to 110 nm, and still more preferably from 60 to 100 nm. The thickness of the refractive index adjustment layer is calculated as the average value of five arbitrary points measured by cross-sectional observation with a scanning electron microscope (SEM).

・The method of manufacturing the transfer film of the second embodiment The manufacturing method of the transfer film of 2nd Embodiment is not specifically limited, A well-known method can be used. As a method for producing the above-mentioned transfer film 20, for example, a method including the steps of applying a composition for forming an intermediate layer on the surface of the dummy support 11 to form a coating film, and further drying the coating film to form an intermediate layer The step of layer 13; the step of coating the photosensitive composition on the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form the photosensitive layer 15; and coating the surface of the photosensitive layer 15 to adjust the refractive index The layer-forming composition is used to form a coating film, and the coating film is further dried to form the refractive index adjustment layer 17 .

The transfer film 20 is produced by crimping the protective film 21 on the refractive index adjustment layer 17 of the laminate produced by the above-described production method. As the method of manufacturing the transfer film of the second embodiment, By including the step of providing protective film 21 so as to be in contact with the surface of refractive index adjustment layer 17 on the side opposite to the side having dummy support 11, a device with dummy support 11, intermediate layer 13, photosensitive layer 15, refractive index adjustment layer 17 is manufactured. The transfer film 20 of the rate adjustment layer 17 and the protective film 21 is preferable. After the transfer film 20 is produced by the above-mentioned production method, the transfer film 20 is wound up, whereby the transfer film in the form of a roll can be produced and stored. The transfer film in the form of a roll can be provided as it is in a step of bonding to a substrate in the roll-to-roll system described later.

Also, as the manufacturing method of the above-mentioned transfer film 20, the intermediate layer 13 and the photosensitive layer 15 can be formed on the dummy support 11, the refractive index adjustment layer 17 can be formed on the protective film 21 separately, and the photosensitive layer 15 A method of forming the refractive index adjustment layer 17 by attaching it on top.

··Composition for forming an intermediate layer and method for forming an intermediate layer The composition for forming an intermediate layer and the method for forming the intermediate layer are the same as those for the composition for forming an intermediate layer and the method for forming the intermediate layer in the transfer film X1 of the first embodiment.

··Photosensitive composition and method for forming photosensitive layer From the standpoint of excellent productivity, it is desirable that the photosensitive layer in the transfer film X2 be coated with components that constitute the photosensitive layer (for example, a binder polymer, a polymerizable compound, and a polymerization initiator, etc. ) and a photosensitive composition of a solvent. The manufacturing method of the transfer film as the second embodiment is specifically a method of coating a photosensitive composition on a dummy support to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive layer. good.

An organic solvent is preferable as a solvent which can be contained in a photosensitive composition. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alternative name: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclic Hexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol and 2-propanol.

Moreover, as a solvent, the organic solvent (high boiling point solvent) with a boiling point of 180-250 degreeC can also be used as needed.

A solvent may be used individually by 1 type, and may use 2 or more types together. The total solid content of the photosensitive composition is preferably from 5 to 80% by mass, more preferably from 5 to 40% by mass, and still more preferably from 5 to 30% by mass, relative to the total mass of the photosensitive composition. That is, the content of the solvent in the photosensitive composition is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and still more preferably 70 to 95% by mass relative to the total mass of the photosensitive composition. good.

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

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

As the coating method of the photosensitive composition, for example, a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method) can be mentioned. .

As a method of drying the coating film of the photosensitive composition, heat drying and reduced-pressure drying are preferable. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. Moreover, as its upper limit, it is preferable that it is 130 degreeC or less, and it is more preferable that it is 120 degreeC or less. Drying can also be performed by continuously changing the temperature. Moreover, as a drying time, 20 seconds or more are preferable, 40 seconds or more are more preferable, and 60 seconds or more are still more preferable. The upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

・Composition for forming a refractive index adjusting layer and method for forming a refractive index adjusting layer The composition for forming the refractive index adjusting layer preferably contains various components and a solvent for forming the above-mentioned refractive index adjusting layer. In addition, in the composition for forming a refractive index adjusting layer, the preferred ranges of the content of each component relative to the total solid content of the composition are the same as the preferred ranges of the content of each component relative to the total mass of the above-mentioned refractive index adjusting layer. The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer. At least one selected from the group including water and water-miscible organic solvents is preferred, and water or water and water A mixed solvent of mixed organic solvents is more preferable. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, among which alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. A solvent may be used individually by 1 type, and may use 2 or more types. The content of the solvent is preferably from 50 to 2,500 parts by mass, more preferably from 50 to 1,900 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, for example, known coating methods (slit coating, spin coating, curtain coating and spray coating) can be mentioned. ink coating, etc.).

As a drying method of the coating film, heat drying and reduced-pressure drying are preferable. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. Moreover, as its upper limit, it is preferable that it is 130 degreeC or less, and it is more preferable that it is 120 degreeC or less. Drying can also be performed by continuously changing the temperature. Moreover, as a drying time, 20 seconds or more are preferable, 40 seconds or more are more preferable, and 60 seconds or more are still more preferable. The upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

Moreover, the transfer film of 2nd Embodiment can be manufactured by bonding a protective film to a refractive index adjustment layer. The method of bonding the protective film to the refractive index adjustment layer is not particularly limited, and known methods can be used. As an apparatus for bonding the protective film to the refractive index adjustment layer, known laminators such as a vacuum laminator and an automatic cutting laminator can be mentioned. It is preferable that the laminator is equipped with any heatable roll such as a rubber roll, and can be pressurized and heated.

··Pseudo-support body, photosensitive layer and protective film of the best relationship between the physical properties Regarding the transfer film X2 of the second embodiment, like the transfer film X1 of the first embodiment described above, the physical properties of the dummy support, the photosensitive layer, and the protective film satisfy the preferred aspect 1 and the preferred aspect. 2. One or more of the preferred aspects 3, 4, and 5 are preferred, and it is better to satisfy all of them. Each of the preferred aspect 1, the preferred aspect 2, the preferred aspect 3, the preferred aspect 4, and the preferred aspect 5 is as described above.

[Method of Manufacturing Circuit Wiring (Method of Manufacturing Circuit Wiring 1)] The present invention also relates to a manufacturing method of circuit wiring. The pattern formed by the above-mentioned method for producing a laminate of the present invention can be used as a protective pattern for the seed layer during plating in the process of producing circuit wiring using the semi-additive method (SAP).

The manufacturing method of the circuit wiring of the present invention includes the manufacturing method of the above-mentioned laminated body of the present invention, and the manufacturing method of the circuit wiring includes: a step of forming a seed layer on a substrate to form a substrate with a seed layer (hereinafter also referred to as is the "seed layer forming step".); In such a way that the side of the transfer film having a pseudo-support, an intermediate layer and a photosensitive layer opposite to the side of the pseudo-support is in contact with the above-mentioned substrate with a seed layer. The step of attaching the above-mentioned transfer film to the above-mentioned substrate with a seed crystal layer to obtain a substrate with a photosensitive layer with the above-mentioned substrate, the above-mentioned seed crystal layer, the above-mentioned photosensitive layer, the above-mentioned intermediate layer and the above-mentioned dummy support transfer film bonding step); between the above-mentioned pseudo-support and the above-mentioned intermediate layer, the step of peeling the above-mentioned pseudo-support (pseudo-support stripping step); making the exposed above-mentioned intermediate layer contact with the mask to perform exposure treatment, A step of further performing a development treatment after exposure to form a pattern (pattern forming step); a step of forming a metal plating layer by electroplating on the above-mentioned seed layer existing in a region where the above-mentioned pattern is not arranged (hereinafter, also referred to as "Metal plating layer forming step."); Step of forming a protective layer on the above metal plating layer (hereinafter, also referred to as "protective layer forming step".); Step of removing the above pattern (hereinafter, also referred to as "pattern removal step".); and the step of removing the exposed seed layer to obtain conductive thin lines (hereinafter also referred to as "conductive thin line forming step".) The surface free energy of the surface of the above-mentioned dummy support side of the above-mentioned intermediate layer is 68.0 mJ/ ^m2 or less.

Hereinafter, each step of the manufacturing method of the circuit wiring of this invention is demonstrated in detail. In addition, the description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[First Embodiment] The first embodiment of the manufacturing method of circuit wiring has a seed layer forming step, a transfer film bonding step, a dummy support peeling step, a pattern forming step, a metal plating layer forming step, and a protective layer forming step in this order. step, the pattern removing step, and the conductive thin line forming step, the surface free energy of the surface of the intermediate layer on the side of the dummy support is 68.0 mJ/m ² or less. In addition, the step of laminating the transfer film, the step of detaching the dummy support, and the step of forming the pattern are the same as those of the first embodiment of the above-mentioned method for producing a laminate except that the substrate is a substrate with a seed layer attached thereto, and are preferred. The pattern is also the same.

＜＜Seed layer formation process＞＞ The seed layer forming step is a step of forming a seed layer on the substrate. Examples of the substrate used in this step include the substrate described in the transfer film bonding step in the first embodiment of the above-mentioned method for producing a laminate.

＜Seed layer＞ The metal contained in the seed layer is not particularly limited, and known metals can be used. Examples of main components (so-called main metals) contained in the seed layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. In addition, the above-mentioned main component refers to the metal with the largest content among the metals contained in the seed layer.

The thickness of the seed layer is not particularly limited, but is preferably at least 50 nm, more preferably at least 100 nm. The upper limit is not particularly limited, and is preferably 2 μm or less.

The method for forming the seed layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion liquid in which fine metal particles are dispersed and firing a coating film, a sputtering method, and a vapor deposition method.

＜＜Metal plating formation process＞＞ The metal plating layer forming step is a step of forming a metal plating layer by electroplating on the seed layer existing in a region where no pattern is arranged. Examples of the plating treatment include an electroplating method and an electroless plating method, and the electroplating method is preferred from the viewpoint of productivity.

The metal contained in the metal plating layer is not particularly limited, and known metals can be used. The metal plating layer may include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals, for example. Among these, it is preferable that the metal plating layer contains copper or an alloy thereof from the viewpoint that the electroconductivity of the electroconductive thin wire is more excellent. In addition, from the viewpoint that the electroconductivity of the electroconductive thin wire is more excellent, it is preferable that the main component of the metal plating layer is copper.

The lower limit of the thickness of the metal plating layer is not particularly limited, but it is preferably 0.1 μm or more, and more preferably 1 μm. In addition, there is no particular limitation on the upper limit, but it is preferably 20 μm or less.

＜＜Protective layer formation process＞＞ The protective layering step is a step of forming a protective layer on the metal plating layer. As a material of the protective layer, a material resistant to a removal solution or an etching solution in the removal step or the conductive thin line formation step is preferable. For example, metals, such as nickel, chromium, tin, zinc, magnesium, gold, silver, these alloys, and resin are mentioned. Among them, nickel or chromium is preferable as the material of the protective layer.

As a formation method of a protective layer, an electroless plating method, an electroplating method, etc. are mentioned, for example, An electroplating method is preferable.

The lower limit of the thickness of the protective layer is not particularly limited, but it is preferably 0.3 μm or more, more preferably 0.5 μm or more. The upper limit is not particularly limited, but is preferably 3.0 μm or less, more preferably 2.0 μm or less.

＜＜Pattern Removal Step＞＞ The pattern removing step is a step of removing the pattern. The method of removing the pattern is not particularly limited, but a method of removing it by chemical treatment is mentioned, and a method of removing it using a removing liquid is preferable. As liquid temperature of a removal liquid, 30-80 degreeC is preferable, and 50-80 degreeC is more preferable. As a preferred aspect of the removal method, a method of immersing a substrate having a pattern to be removed in a removal solution having a liquid temperature of 50 to 80° C. under stirring for 1 to 30 minutes is mentioned.

Examples of the removal liquid include those obtained by dissolving an inorganic basic component or an organic basic component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof. As an inorganic basic component, sodium hydroxide and potassium hydroxide are mentioned, for example. Examples of the organic basic component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Moreover, it can remove by well-known methods, such as a spray method, a shower method, and a immersion method, using a remover.

＜＜Seed Layer Removal Step＞＞ The step of removing the seed crystal layer is a step of obtaining thin conductive lines by removing the exposed seed crystal layer. In addition, in the seed layer removal step, the metal plating layer formed by the metal plating layer forming step is used as an etching resist, and the seed layer located in the non-pattern formation region (in other words, the region not protected by the metal plating layer) is performed. etching treatment.

The method of removing a part of the seed layer is not particularly limited, and it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, copper chloride solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixed solution, phosphoric acid-hydrogen peroxide mixed solution, and the like.

The upper limit of the line width of the formed conductive fine wire is preferably 8 μm or less, and more preferably 6 μm or less. The lower limit is not particularly limited, but it is often 2 μm or more.

＜＜Other steps＞＞ The first embodiment of the manufacturing method of circuit wiring may include arbitrary steps (other steps) other than the above-mentioned steps. For example, the step of reducing the reflectance of visible light described in paragraph [0172] of International Publication No. 2019/022089, and the step of forming a new light on the insulating film described in paragraph [0172] of International Publication No. 2019/022089 can be mentioned. steps of the conductive layer, etc., but these steps are not limited.

＜Steps to reduce the reflectance of visible light＞ The first embodiment of the method of manufacturing circuit wiring may include the step of performing a process of reducing the visible light reflectance of a part or all of the plurality of conductive layers included in the substrate. Oxidation treatment can be mentioned as a treatment for lowering the reflectance of visible light. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer. Regarding the treatment of reducing the reflectance of visible light, it is described in paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315, and these The contents described in the gazette are incorporated into this manual.

<Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> It is also preferable that the first embodiment of the method of manufacturing circuit wiring includes the step of forming an insulating film on the surface of the circuit wiring and the step of forming a new conductive layer on the surface of the insulating film. Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed. The step of forming an insulating film is not particularly limited, and a known method of forming a permanent film can be mentioned. In addition, an insulating film having a desired pattern can be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited. For example, a photosensitive material with conductivity can be used to form a new conductive layer with a desired pattern by photolithography.

〔Use of circuit wiring〕 The circuit wiring produced by the first embodiment of the production method of the circuit wiring is used, for example, to be arranged on a sheet, a metal substrate, a ceramic substrate, and a glass in a manufacturing process film of a semiconductor package, a printed circuit board, an interposer, and a wiring layer. The circuit wiring on the supporting base material is better.

[Method for Manufacturing Circuit Wiring (Method 2 for Manufacturing Circuit Wiring)] In addition, although the method of forming a conductive fine line pattern on a substrate by the semi-additive method was described in the above section, this The manufacturing method of the circuit wiring of the manufacturing method of the laminated body of this invention is not limited to this. As another manufacturing method of circuit wiring, the following manufacturing method can be mentioned, which includes the manufacturing method of the above-mentioned laminated body of the present invention, and the manufacturing method of the circuit wiring includes: The surface of the above-mentioned photosensitive layer of the thin film opposite to the above-mentioned intermediate layer side and the conductive substrate (the conductive substrate refers to a substrate composed of at least a supporting substrate and a conductive layer arranged on the supporting substrate as described above. .) contact method, the above-mentioned transfer film is bonded to the above-mentioned substrate to obtain the substrate with the above-mentioned conductive substrate, the above-mentioned photosensitive layer, the above-mentioned intermediate layer and the above-mentioned dummy support in sequence (wherein, the above-mentioned The conductive substrate is arranged in such a way that the above-mentioned conductive layer and the above-mentioned photosensitive layer are facing each other.) step (transfer film bonding step); between the above-mentioned dummy support body and the above-mentioned intermediate layer, the step of peeling the above-mentioned dummy support body ( Pseudo-support stripping step); exposing the exposed intermediate layer to a mask, and further performing a development process after exposure to form a pattern (pattern forming step); In an etching step (etching step) in which the conductive layer is etched, the surface free energy of the surface of the intermediate layer on the side of the dummy support is 68.0 mJ/m ² or less. In addition, the step of laminating the transfer film, the step of detaching the dummy support, and the step of forming the pattern are the same as those in the first embodiment of the above-mentioned method for producing a laminate except that the substrate is a substrate having a conductive layer, and are preferably The pattern is also the same.

The etching step is a step of etching the conductive layer in the area where no pattern is arranged. As the method of etching treatment, known methods can be applied, for example, the method described in paragraphs [0209] to [0210] of Japanese Patent Application Laid-Open No. 2017-120435 and [ [0048] to [0054], the method described in the paragraphs, the wet etching method immersed in an etching solution, and the method based on dry etching such as plasma etching.

As a device provided with the circuit wiring manufactured by the said manufacturing method, an input device is mentioned, for example, Preferably it is a touch panel, More preferably, it is a capacitive type touch panel. In addition, the input device described above can be applied to display devices such as organic EL display devices and liquid crystal display devices. In the second embodiment of the method of manufacturing circuit wiring, it is also preferable to form circuits sequentially or simultaneously on both surfaces of the substrate. With such a structure, it is possible to form circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a board|substrate by roll-to-roll.

[Transfer film] The invention also relates to a transfer film. Hereinafter, the transfer film of this invention is demonstrated.

The transfer film of the present invention has a pseudo-support, an intermediate layer, and a photosensitive layer, wherein the surface free energy of the surface of the intermediate layer on the side of the pseudo-support is 68.0 mJ/m ² or less, and the pseudo-support of the intermediate layer is The arithmetic mean roughness Ra of the side surface is 50 nm or less. The above-mentioned transfer film is suitable for an exposure method in which exposure is performed after peeling off the dummy support, which can suppress excessive adhesion between the exposed photosensitive layer and the photomask, and is also excellent in resolution.

The transfer film of the present invention corresponds to one aspect of the transfer film X described above. The structure and preferred aspects of the transfer film X are as described above. [Example]

Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps and the like 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 should not be limitedly interpreted by the Examples shown below. In addition, "parts" and "%" are based on mass unless otherwise specified. In addition, in the following examples, the weight average molecular weight of resin is the weight average molecular weight calculated|required based on the polystyrene conversion of gel permeation chromatography (GPC). In addition, the theoretical acid value was used for the acid value.

[Various Components of Transfer Film] Hereinafter, first, various components used when producing the transfer film will be described.

〔middle layer〕 ＜＜Various ingredients of the middle layer＞＞ Various components of the intermediate layer shown in Table 4 are shown below. PVA: (polyvinyl alcohol: product name "KURARAY POVALPVA-205" (manufactured by Kuraray Co., Ltd.)) PVP: (polypyrrolidone: product name "polyvinylpyrrolidone K-30" (manufactured by NIPPON SHOKUBAI CO., LTD.)) HPMC: (Hydroxypropyl methylcellulose: product name "METOLOSE 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.) PEG: (polyethylene glycol: product name "polyethylene glycol 1,000" (molecular weight: 900 to 1000), manufactured by FUJIFILM Wako Pure Chemical Corporation) HPC: (Hydroxypropylcellulose: product name "HPC-SSL", manufactured by NISSO CORPORATION) Glycerol: Product name "Glycerol" (molecular weight: 92.09), manufactured by FUJIFILM Wako Pure Chemical Corporation Bisphenol A: Product name "4,4'-isopropenol" (molecular weight: 228.29), manufactured by FUJIFILM Wako Pure Chemical Corporation

＜＜Composition for intermediate layer＞＞ After mixing the components as described in Table 4, add a solvent (solvent: ion-exchanged water and methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.) and mix so that the mixing ratio (mass ratio) becomes 40/ 60 mixed solvent) to produce a composition for forming an intermediate layer. In addition, the numerical value corresponding to each component described in the column of "composition of the intermediate layer (type and compounding amount (mass %) of components)" in Table 4 represents content of each component with respect to the total mass of the intermediate layer.

〔Photosensitive layer〕 Table 2 shows the composition of the photosensitive layers 1-4 shown in Table 4.

[Table 2] photosensitive layer 1 photosensitive layer 2 photosensitive layer 3 photosensitive layer 4 Components (Numerical value of each component: parts by mass) polymer Polymer 1 50.90 56.23 54.23 Polymer 2 57.22 polymeric compound BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 37.00 37.00 37.00 30 M-270 (manufactured by TOAGOSEI CO., LTD.) 4.00 4.00 4.00 A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 polymerization initiator B-CIM (manufactured by Hampford) 6.90 2 Irgacure OXE-02 (manufactured by BASF JAPAN) 0.30 Omnirad 907FF (manufactured by IGM Resins BV) 0.70 1.35 Omnirad 379 (manufactured by IGM Resins BV) 1.65 Sensitizer SB-PI 701 (manufactured by SANYO TRADING CO., LTD.) 0.10 0.50 0.50 0.1 chain transfer agent Colorless crystal violet (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.40 0.40 0.40 0.4 N,N-tetraethyl-4,4-diaminobenzophenone (HODOGAYA CHEMICAL CO.,LTD.) 0.1 N-Phenylaminoformylmethyl-N-carbonylmethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation) 0.14 0.14 0.14 Colorant Bright green (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.08 Rust inhibitor CBT-1 (manufactured by JOHOKU CHEMICAL CO.,LTD) 0.10 0.10 0.10 polymerization inhibitor TDP-G (manufactured by Kawaguchi Chemical Industry Co., LTD.) 0.13 0.30 0.30 Irganox 245 (manufactured by BASF) 0.1 Antioxidants 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 0.01 0.01 0.01 Surfactant MEGAFACE F-552 (manufactured by DIC Corporation) 0.32 0.32 0.32

＜＜Various components of the photosensitive layer＞＞ Each component of the photosensitive layer shown in Table 2 is as follows. ＜Polymer＞ Polymer P-1 and polymer P-2 were synthesized by known methods. In addition, the weight average molecular weight (Mw) of the synthesized polymer was measured by gel permeation chromatography (GPC: Gel Permeation Chromatography) under the following conditions.

(GPC conditions) Device: Manufactured by TOSOH CORPORATION, TOSOH CORPORATION high-speed GPC device HLC-8420GPC (product name) Guard column: manufactured by TOSOH CORPORATION, HZ-L Separation column: Manufactured by TOSOH CORPORATION, three columns are connected in series with TSK gel Super HZM-N (product name) Measuring temperature: 40°C Eluent: THF (tetrahydrofuran) Flow rate: sampling pump 0.35mL/min, reference pump 0.175mL/min Injection volume: 10μL Detector: Differential refractometer Standard substance solution for GPC column calibration: Standard polystyrene manufactured by TOSOH CORPORATION

(polymer synthesis) In the following synthesis examples, the following abbreviations represent the following compounds, respectively. St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation) MAA: methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation) MMA: methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) BA: Butyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) PGMEA: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.) MEK: methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.) V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

· Synthesis of Polymer P-1 PGMEA (116.5 parts) was put into the three-necked flask, and it heated up to 90 degreeC under nitrogen atmosphere. After 2 hours, add the solution of St (52.0 parts), MAA (29.0 parts), MMA (19.0 parts), V-601 (4.0 parts) and PGMEA (116.5 parts) dropwise to a temperature maintained at 90°C±2°C solution in the above flask. After the dropwise addition, the solution in the flask was stirred at 90° C.±2° C. for 2 hours to obtain a polymer P-1 (solid content concentration: 30.0 mass %).

· Synthesis of Polymer P-2 A solution containing polymer P-2 was obtained in the same manner as polymer P-1 with regard to other conditions, such as changing the type and compounding amount of the monomers used. The solid content concentration of the solution containing the polymer P-2 was set to 30% by mass.

The types of monomers used for synthesizing each polymer, the content (% by mass) and weight average molecular weight of constituent units derived from each monomer in each polymer are shown below. In addition, resins P-1 to P-2 all correspond to alkali-soluble resins.

[table 3] P-1 P-2 St. 52 20 MAA 29 25 MMA 19 30 BA 25 Weight average molecular weight (Mw) 60,000 70,000

＜Other ingredients＞ Hereinafter, other components contained in the photosensitive layer shown in Table 2 are shown. (polymeric compound) ・BPE-500: 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. ・M-270: Polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO., LTD. A-TMPT: trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

(polymerization initiator) B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford ・Irgacure OXE-02 (oxime ester-based photopolymerization initiator, manufactured by BASF JAPAN Corporation) Omnirad 907FF: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, manufactured by IGM Resins B.V. Omnirad 379: 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, manufactured by IGM Resins B.V.

(sensitizer) ・SB-PI 701: 4,4'-bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO., LTD.

(chain transfer agent) ・Colorless crystal violet: manufactured by Tokyo Chemical Industry Co., Ltd. ・N,N-Tetraethyl-4,4-diaminobenzophenone: Manufactured by HODOGAYA CHEMICAL CO.,LTD. ・N-Phenylaminoformylmethyl-N-carbonylmethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

(Colorant) Bright green: manufactured by Tokyo Chemical Industry Co., Ltd. (Rust inhibitor) ・CBT-1: carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO.,LTD (polymerization inhibitor) ・TDP-G: Phytothiophene, manufactured by Kawaguchi Chemical Industry Co., LTD. ・Irganox245: hindered phenolic antioxidant, manufactured by BASF Corporation

(Antioxidants) 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation) (surfactant) ・MEGAFACE F-552: Surfactant, manufactured by DIC Corporation

＜＜Photosensitive composition 1～4＞＞ After mixing the respective components according to the description in Table 2, photosensitive compositions 1 to 4 in which the solid content concentration was adjusted to 25% by mass were produced by adding methyl ethyl ketone. In addition, the numerical value corresponding to each component described in the component column in Table 2 shows the mass part of solid content. That is, each numerical value mentioned above means the compounding quantity of solvents, such as a diluent solvent, not included.

〔Pseudo-support body〕 The pseudo-supports (pseudo-supports A to F) in Table 4 are shown below. Pseudo-support A: Lumirer16KS40 (manufactured by TORAY INDUSTRIES, INC.) Pseudo-support B: The one produced by the method mentioned later was used. Pseudo support C: TOYOBO ESTER FILM E5000 (manufactured by TOYOBO CO., LTD.) Pseudo-support D: UNIPEEL TR-1 (manufactured by UNITIKA LTD.) Pseudo-support E: Therapy25WZ (manufactured by TORAY INDUSTRIES, INC.) Pseudo support F: Cosmo Shine A4300 (manufactured by TOYOBO CO., LTD.)

<Manufacturing method of pseudo-support B> (Preparation of Particle-Containing Layer Forming Composition 1) The components were mixed in the formulation shown below to obtain a particle-containing layer-forming composition 1 . After preparing the particle-containing layer-forming composition 1, it was filtered with a 6 μm filter (F20, manufactured by Mahle Filter Systems Japan Corp.), and then membrane degassed using 2×6 RADIAL FLOW SUPERPHOBIC (manufactured by Polypore International, Inc.) .

・Propylene polymer (AS-563A, manufactured by DAICEL FINECHEM LTD., solid content 27.5% by mass) 167 parts ・Nonionic surfactant (Naro Acty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass) 0.7 parts ・Anionic surfactant (Rapisol A-90, manufactured by NOF CORPORATION, diluted with water to a solid content of 1% by mass) 114.4 parts ・Palm wax dispersion (Cerozol 524, manufactured by CHUKYO YUSHI CO.,LTD., solid content 30% by mass) 7 parts Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Chemical Inc., diluted with water to a solid content of 10% by mass) 20.9 parts ・Matting agent (SNOWTEX XL, manufactured by Nissan Chemical Industries, LTD., solid content 40% by mass, average particle diameter 50nm) 2.8 parts ·Water 690.2 parts

(extrusion molding) After drying the particles of polyethylene terephthalate using the citric acid chelated organotitanium complex described in Japanese Patent No. 5575671 as a polymerization catalyst to a moisture content of 50ppm or less, they are put into a single shaft with a diameter of 30mm. In the hopper of the kneading extruder, it was melted and extruded at 280°C. This molten body (melt) was passed through a filter (pore size: 3 μm), and extruded from a die to a cooling roll at 25° C. to obtain an unstretched film. In addition, the extruded melt was brought into close contact with the cooling roll by using an electrostatic application method.

(extension, coating) Extruded onto a cooling roll by the above method, and sequentially biaxially stretched the solidified unstretched film by the following method, a pseudo-support having a polyester film with a thickness of 16 μm and a particle-containing layer with a thickness of 40 nm was obtained .

(a) Longitudinal extension The unstretched film is passed between two pairs of nip rollers with different peripheral speeds, and stretched in the longitudinal direction (transport direction). In addition, the preheating temperature was set to 75° C., the stretching temperature was set to 90° C., the stretching ratio was set to 3.4 times, and the stretching speed was set to 1300%/sec.

(b) coating The particle-containing layer-forming composition 1 was coated on one side of the longitudinally stretched film with a bar coater so that the film had a thickness of 40 nm after film formation.

(c) Horizontal extension The above-mentioned longitudinally stretched and coated film was laterally stretched using a tenter under the following conditions. -Transverse extension condition- Preheating temperature: 110°C Extension temperature: 120°C Extension ratio: 4.2 times Extension speed: 50%/second

(heat fixation, heat relaxation) Next, the biaxially stretched film after completion|finish of longitudinal stretching and lateral stretching was heat-set under the following conditions. After further heat fixing, the width of the tenter was shortened, and heat relaxation was performed under the following conditions. -Heat Fixation Conditions- Heat Fixing Temperature: 227°C Heat fixation time: 6 seconds -Heat relaxation conditions- Heat relaxation temperature: 190°C Heat mitigation rate: 4%

(coiled) After heat fixing and heat relaxation, both ends were trimmed, and the ends were extruded (knurled) with a width of 10 mm, and wound up at a tension of 40 kg/m. In addition, the width was 1.5 m, and the coiling length was 6300 m. The obtained film roll was used as a dummy support B.

[Production of photosensitive transfer film] [Examples 1-48, Comparative Examples 5-7] The photosensitive transfer film composed of the dummy support, the intermediate layer and the photosensitive layer was fabricated into the structures shown in Table 4, respectively. Specifically, it is as follows. First, on the dummy support shown in Table 4, the intermediate layer-forming composition for forming the intermediate layer shown in Table 4 was dried using a slit-shaped nozzle, and then coated so that the coating width It became 1.0m, and the film thickness became the value shown in Table 4, and it passed through the drying zone of 80 degreeC for 40 seconds, and formed the intermediate layer. Furthermore, on the intermediate layer, after drying the photosensitive composition for forming the photosensitive layer shown in Table 4 using a slit-shaped nozzle, it was coated so that the coating width became 1.0 m and the film thickness became Table 4. 4, and passed through a drying zone at 80°C for 40 seconds to form a negative photosensitive layer. A polyethylene film (manufactured by Tredegar Corporation, OSM-N) was pressure-bonded thereon as a protective film to prepare a photosensitive transfer film, which was wound up into a roll form.

In addition, as the transfer film used in Example 1, for example, a dummy support: type A, an intermediate layer: type 1, and a photosensitive layer: type 1 transfer film were produced through the above steps.

[Comparative examples 1 to 4] The photosensitive transfer film composed of the dummy support and the photosensitive layer was fabricated into the structures shown in Table 4, respectively. In addition, it produced by the method similar to the transfer film used in Example 1 except not forming an intermediate layer.

[Surface free energy E ₁ in the surface of the pseudo-support side of the intermediate layer, Surface free energy E _s in the surface of the pseudo-support side of the intermediate layer, Arithmetic mean roughness in the surface of the pseudo-support side of the intermediate layer Ra] The pseudo-support of the prepared transfer film was peeled off by any method, and the surface free energy E _s (mJ/cm ² ) of the surface of the intermediate layer side of the pseudo-support and the E s (mJ/cm 2 ) of the pseudo-support side of the intermediate layer were measured The surface free energy E _I (mJ/cm ² ) of the surface, and the arithmetic mean roughness Ra of the surface on the pseudo-support side of the intermediate layer. In addition, about the measurement method, it is as above-mentioned. Table 4 shows the measurement results.

[Various evaluations] [Evaluation 1: Pseudo-support peelability] On a PET substrate with a thickness of 0.1mm, a copper layer with a thickness of 200nm was formed by vapor deposition to prepare a PET substrate with a copper layer. After peeling off the protective film of the produced transfer film, it was laminated to the PET substrate with copper layer above under the lamination conditions of roll temperature 100°C, line pressure 1.0MPa, and line speed 4.0m/min. , so that the copper layer and the photosensitive layer are in contact. After peeling off the dummy support at a gradient of 180°, the dummy support and the surface of the photosensitive layer were visually observed and evaluated based on the following evaluation criteria. Table 4 shows the measurement results. (evaluation criteria) "A": The pseudo-support can be peeled off smoothly "B": The false support can be peeled off, but there is a sound when peeling off "C": When the pseudo-support is peeled off, the interlayer is peeled off, and the pseudo-support is torn and/or cohesively broken.

[Evaluation 2: Mask non-adhesiveness] After the said exposure operation, the photosensitive layer surface was observed visually, and it evaluated based on the following evaluation criteria. Table 4 shows the measurement results. (evaluation criteria) "A": The photosensitive layer is not attached to the mask "B": The photosensitive layer is not attached to the mask, but there is a sound when it is peeled off "C": The photosensitive layer is attached to the mask (the mask can be peeled off, but the peeling of the photosensitive layer occurs)

[Evaluation 3: Analysis] On a PET substrate with a thickness of 0.1mm, a copper layer with a thickness of 200nm was formed by vapor deposition to prepare a PET substrate with a copper layer. After peeling off the protective film of the produced transfer film, it was laminated to the PET substrate with copper layer above under the lamination conditions of roll temperature 100°C, line pressure 1.0MPa, and line speed 4.0m/min. , so that the copper layer and the photosensitive layer are in contact. Next, using a mask having a predetermined line (μm)/space (μm) pattern, exposure was performed by bringing the dummy support into contact with the mask after peeling. For exposure, a high-pressure mercury lamp with i-rays (365nm) as the main wavelength of exposure was used. The exposure amount was arbitrarily set so that the top shape of each pattern matched the opening of the mask. Next, spray image development was performed using a 1% sodium carbonate aqueous solution at a liquid temperature of 25° C., and water washing was performed to form a predetermined pattern on copper. Next, the resolving power was evaluated based on the following evaluation criteria. Table 4 shows the measurement results. In addition, in the following, "analysis without residue between patterns" means that analysis without residue can be performed in the concave region of the pattern (position corresponding to the unexposed portion). (evaluation criteria) "AA": L/S=3μm/3μm can be resolved without residue between patterns "A": L/S=6μm/6μm can be resolved without residue between patterns "B": L/S=8μm/8μm can be resolved without residue between patterns "C": L/S=8μm/8μm cannot be resolved

[Comprehensive evaluation of evaluations 1 to 3] Based on the evaluation results of evaluations 1 to 3, comprehensive evaluation was implemented by the following evaluation criteria. ＜Evaluation criteria＞ "AA": The resolving power is AA evaluation, and the non-adhesiveness of the mask and the detachment of the pseudo-support are both A evaluations "A": The resolving power is an A evaluation, and the non-adhesiveness of the mask and the detachment of the pseudo-support are both A evaluations "B": The resolving property is evaluated as A, and any one of mask non-adhesiveness and false support peelability is evaluated as A, and the other is evaluated as B "C": Resolubility is evaluated as B, and mask non-adhesiveness and pseudo-support peelability are evaluated as any of A and B. "D": A C rating for resolution or a C rating for mask non-stickiness. In addition, the pseudo-support evaluation may be any evaluation.

Table 4 is shown below. In Table 4, "the kind of photosensitive layer" corresponds to the number of the photosensitive layer shown in Table 2 as above-mentioned. In addition, "whether the dummy support peeling step is performed" in Table 4 indicates whether the dummy support peeling step is performed. "A" indicates the case where the dummy support peeling step was performed in the method for producing the laminate, and "B" indicates the case where the dummy support peeling step was not performed in the method for producing the laminate. In addition, in Comparative Examples 1 to 4 (without an intermediate layer), the surface free energy in the "type and physical properties of the pseudo-support" represents the surface free energy of the surface of the pseudo-support on the photosensitive layer side.

[Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Structural transitivity of the middle layer Film thickness of intermediate layer [μm] 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2.0 3.0 5.0 1.1 Types of middle layer 1 1 1 1 1 1 2 3 1 4 5 1 1 1 6 Composition of the middle layer (type and amount of ingredients (mass %)) PVA 67.5 67.5 67.5 67.5 67.5 67.5 67.75 60.5 67.5 67.95 58 67.5 67.5 67.5 67.5 pvp 31.5 31.5 31.5 31.5 31.5 31.5 31.75 24.5 31.5 31.95 twenty two 31.5 31.5 31.5 31.5 HPMC 1 1 1 1 1 1 0.5 15 1 0.1 20 1 1 1 - PEG - - - - - - - - - - - - - - 1 HPC - - - - - - - - - - - - - - - other - - - - - - - - - - - - - - - Physical properties of the middle layer Arithmetic mean roughness Ra 2nm 2nm 2nm 2nm 2nm 2nm 2nm 5nm 2nm 2nm 23nm 2nm 2nm 2nm 2nm Surface free energy E _I (mJ/cm ² ) 60.1 60.1 60.1 60.1 60.1 60.1 62.1 58.8 60.1 65.1 56.0 60.1 60.1 60.1 60.0 Structure transitivity of photosensitive layer Film thickness of photosensitive layer [μm] 15 2.4 3.0 5.0 10 20 15 15 25 15 15 15 15 15 15 Types of photosensitive layer 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Types and properties of pseudo-supports Types and properties of pseudo-supports type A A A A A A A A A A A A A A A Surface free energy Es (mJ/cm ² ) 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 Whether to implement the pseudo-support stripping step A A A A A A A A A A A A A A A Evaluation results Evaluation 1 Pseudo-support peelability A A A A A A A A A B A A A A A Evaluation 2 mask non-adhesive A A A A A A A A A A A A A A B Evaluation 3 analytical A AAA AAA AAA AAA A A A B A B A A B A Comprehensive evaluation of evaluations 1 to 3 A AAA AAA AAA AAA A A A C B C A A C B

[table 5] Table 4 (continued) Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Structural transitivity of the middle layer Film thickness of intermediate layer [μm] 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Types of middle layer 7 8 9 10 11 12 13 14 15 16 17 18 Composition of the middle layer (type and amount of ingredients (mass %)) PVA 60.5 67.5 60.5 65.5 65.5 53 53 53 68 5 50 95 pvp 24.5 31.5 24.5 29.5 29.5 17 17 17 32 95 50 5 HPMC - - - - - 30 - - - - - - PEG 15 - - - - - 30 - - - - - HPC - 1 15 - - - - 30 - - - - other - - - Glycerol 5 Bisphenol A 5 - - - - - - - Physical properties of the middle layer Arithmetic mean roughness Ra 5nm 2nm 2nm 2nm 2nm 39nm 35nm 31nm 2nm 2nm 2nm 2nm Surface free energy E _I (mJ/cm ² ) 58.5 59.8 57.2 58.9 58.7 55.7 54.9 56.1 65.5 67.4 66.1 65.2 Structure transitivity of photosensitive layer Film thickness of photosensitive layer [μm] 15 15 15 15 15 15 15 15 15 15 15 15 Types of photosensitive layer 1 1 1 1 1 1 1 1 1 1 1 1 Types and properties of pseudo-supports Types and properties of pseudo-supports type A A A A A A A A A A A A Surface free energy Es (mJ/cm ² ) 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 Whether to implement the pseudo-support stripping step A A A A A A A A A A A A Evaluation results Evaluation 1 Pseudo-support peelability A B B A A A A A B B B B Evaluation 2 mask non-adhesive B A A B B A A A A A A A Evaluation 3 analytical A A A A A B B B A A A A Comprehensive evaluation of evaluations 1 to 3 B B B B B C C C B B B B

[Table 6] Table 4 (continued) Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Structural transitivity of the middle layer Film thickness of intermediate layer [μm] 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2.5 5.0 1.1 1.1 1.1 Types of middle layer 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 28 28 1 1 1 Composition of the middle layer (type and amount of ingredients (mass %)) PVA 68 5 50 68 5 50 3 98 100 - - - 67.5 67.5 67.5 pvp - - - - - - 97 2 0 100 100 100 31.5 31.5 31.5 HPMC 32 95 50 - - - - - - - - - 1 1 1 PEG - - - 32 95 50 - - - - - - - - - HPC - - - - - - - - - - - - - - - other - - - - - - - - - - - - - - - Physical properties of the middle layer Arithmetic mean roughness Ra 15nm 2nm 39nm 5nm 5nm 5nm 2nm 2nm 2nm 2nm 2nm 2nm 4nm 26nm 22nm Surface free energy E _I (mJ/cm ² ) 65.1 66.6 65.4 67.2 67.9 67.5 67.2 65.1 63.2 67.8 67.8 67.8 60.1 60.1 60.1 Structure transitivity of photosensitive layer Film thickness of photosensitive layer [μm] 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Types of photosensitive layer 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Types and properties of pseudo-supports Types and properties of pseudo-supports type A A A A A A A A A A A A B C D. Surface free energy Es (mJ/cm ² ) 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 43.7 53.7 40.5 38.3 Whether to implement the pseudo-support stripping step A A A A A A A A A A A A A A A Evaluation results Evaluation 1 Pseudo-support peelability B B B B B B B B B B B B A A A Evaluation 2 mask non-adhesive A A A A A A B A A B B B A A A Evaluation 3 analytical B B B B B B B A A B B B A A A Comprehensive evaluation of evaluations 1 to 3 C C C C C C C B B C C C A A A

[Table 7] Table 4 (continued) Example 43 Example 44 Example 45 Example 46 Example 47 Example 48 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Structural transitivity of the middle layer Film thickness of intermediate layer [μm] 1.1 1.1 1.1 1.1 1.1 1.1 none none none none 1.1 1.1 1.1 Types of middle layer 1 1 1 1 1 1 - - - - 1 R1 R2 Composition of the middle layer (type and amount of ingredients (mass %)) PVA 67.5 67.5 67.5 67.5 67.5 67.5 - - - - 67.5 - - pvp 31.5 31.5 31.5 31.5 31.5 31.5 - - - - 31.5 - - HPMC 1 1 1 1 1 1 - - - - 1 100 - PEG - - - - - - - - - - - - - HPC - - - - - - - - - - - - 100 other - - - - - - - - - - - - - Physical properties of the middle layer Arithmetic mean roughness Ra 21nm 32nm 2nm 2nm 2nm 2nm - - - - 2nm 40nm 50nm Surface free energy E _I (mJ/cm ² ) 60.1 60.1 60.1 60.1 60.1 60.1 (photosensitive layer: 50.2) (photosensitive layer: 50.2) (photosensitive level: 52.5) (photosensitive level: 52.5) 65.5 72.7 69.2 Structure transitivity of photosensitive layer Film thickness of photosensitive layer [μm] 15 15 15 15 15 15 15 15 15 15 15 15 15 Types of photosensitive layer 1 1 2 3 4 1 4 4 1 1 1 1 1 Types and properties of pseudo-supports Types and properties of pseudo-supports type E. f f f f f A A A A A A A Surface free energy Es (mJ/cm ² ) 24.4 55.2 55.2 55.2 55.2 55.2 43.7 43.7 43.7 43.7 43.7 43.7 43.7 Whether to implement the pseudo-support stripping step A A A A A A A C A C C A A Evaluation results Evaluation 1 Pseudo-support peelability B B B B B B A - A - - C C Evaluation 2 mask non-adhesive A A A A A A C A C A A C C Evaluation 3 analytical A A B B B B C C C C C C C Comprehensive evaluation of evaluations 1 to 3 B B C C C C D. D. D. D. D. D. D.

From the results in Table 4, it is clear that in the case of the manufacturing method of the laminated body of the embodiment, the excessive adhesion of the photosensitive layer and the photomask after exposure can be suppressed (in other words, the mask non-adhesion is excellent) and it is possible to form a suppressed A fine pattern of residues in the concave region of the pattern (in other words, excellent resolution).

On the other hand, in Comparative Examples 1 to 7, the desired effect was not obtained. As shown in Comparative Examples 1 and 3, when exposure was performed by directly adhering the photosensitive layer and the mask without forming the intermediate layer, the mask non-adhesion was poor. Also, as shown in Comparative Examples 3 and 4, it was a result that the resolution was poor when exposure was performed through the dummy support in a state where no intermediate layer was formed and no dummy support peeling step was performed. Also, as shown in Comparative Example 5, when the intermediate layer was formed, the dummy support peeling step was not performed, and the exposure was performed through the dummy support, the resolution was poor. Also, as shown in Comparative Examples 6 and 7, the result was that when the surface free energy E _I of the surface of the intermediate layer on the pseudo-support side exceeded 68.0 mJ/cm ² , mask non-adhesion and resolution were both Difference.

Moreover, it was confirmed from the result of Examples 1-6, 9 that when the thickness of a photosensitive layer is 2.0-20 micrometers (preferably 2.0-10 micrometers), resolution is more excellent. Also, from the results of Examples 1, 7, 8, 10, 11, and 21 to 23, it was confirmed that the upper limit of the content of compound X in the intermediate layer was less than 30% by mass (compared to the total mass of the intermediate layer). (preferably 15% by mass or less), the resolving power is more excellent. In addition, it was confirmed that when the upper limit of the content of the compound X in the intermediate layer is 0.5% by mass or more relative to the total mass of the intermediate layer, the dummy support release property is more excellent. Also, from the results of Examples 1 and 12 to 14, it was confirmed that the resolution was more excellent when the thickness of the intermediate layer was 3.0 μm or less. Also, from the comparison of Example 1 and Example 15, and the comparison of Example 1 and Example 19, it is confirmed that when Compound X is a polymer (preferably a water-soluble cellulose derivative), due to further inhibition of the film Therefore, the non-adhesiveness of the mask is more excellent (the compound X used in Examples 15 and 19 can be easily plasticized into a film with a small molecular weight). In addition, it was confirmed from the comparison between Example 1 and Example 17 that, among the water-soluble cellulose derivatives, when it is hydroxypropylmethylcellulose, the detachability of the pseudo-support is more excellent. From the comparison of Example 1 and Examples 24 to 27, it was confirmed that when the intermediate layer contained the compound X, the dummy support release property was more excellent. From the comparison of Example 1 and Examples 28 to 33, it was confirmed that when polyvinyl alcohol, polyvinylpyrrolidone, and Compound X were used in combination, the detachability and resolution of the pseudo-support were more excellent (presumably polyvinyl alcohol and Compound X has low compatibility, and the compatibility is improved by using polyvinylpyrrolidone in combination, and the deterioration of resolution due to phase separation is suppressed). From the comparison of Example 1 and Examples 34 to 39, it is confirmed that the intermediate layer contains polyvinyl alcohol and polyvinyl pyrrolidone, and the compounding ratio (mass ratio) of polyvinyl alcohol to polyvinyl pyrrolidone is 5/95 to 95 In the case of /5, the non-adhesiveness of the mask and the detachment of the pseudo-support are more excellent. From the comparison between Example 1 and Examples 43 and 44, it was confirmed that when the surface free energy of the surface of the intermediate layer side of the pseudo support is 25.0 to 50.0 mJ/m ² , the detachment of the pseudo support is more excellent. From the comparison of Examples 44 to 46, it was confirmed that when the material of the photosensitive layer contains at least one selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof, the analytical performance was improved. more excellent. Also, from the results of Example 47, it was confirmed that when the content of the structural units derived from styrene in the polymer is 30% by mass or more with respect to the total mass of the polymer, the resolution is more excellent.

[Example 49: Manufacturing method of printed wiring board] The transfer film of Example 48 shown in Table 4 was used as a photoresist pattern forming material in paragraph 0050 of JP-A-2019-121740, and the method of manufacturing a printed wiring board disclosed in the above-mentioned patent publication was implemented. , as a result, a substrate with good wiring without erosion was obtained. It was confirmed that the transfer film of the example is also suitable for obtaining a photoresist pattern for the semi-additive method.

10,20: transfer film 1,11: Pseudo-support 3,13: middle layer 5,15: photosensitive layer 7,19: Composition layer 17: Refractive index adjustment layer 9,21: Protective film

FIG. 1 is a schematic diagram showing an example of a transfer film X1. FIG. 2 is a schematic diagram showing an example of the transfer film X2.

1: Pseudo-support

3: middle layer

5: Photosensitive layer

7: Composition layer

9: Protective film

10: Transfer film

Claims (22)

A method for producing a laminate comprising: placing the above-mentioned photosensitive layer in contact with a substrate so that the surface of the photosensitive layer of a transfer film having a dummy support, an intermediate layer, and a photosensitive layer is in contact with a substrate. The step of attaching the transfer film to the aforementioned substrate; the step of peeling off the aforementioned dummy support between the aforementioned dummy support and the aforementioned intermediate layer; exposing the exposed aforementioned intermediate layer to a mask, and further exposing In the step of performing a development treatment to form a pattern, the surface free energy of the surface of the intermediate layer on the dummy support side is 68.0 mJ/m ² or less. The manufacturing method of the laminated body as described in claim 1, wherein The arithmetic average roughness Ra of the surface of the intermediate layer on the pseudo-support side is 50 nm or less. The method for producing a laminate according to claim 1 or claim 2, wherein the surface free energy of the dummy support on the side of the intermediate layer is 25.0 to 50.0 mJ/m ² . The method for manufacturing a laminate according to Claim 1 or Claim 2, wherein The aforementioned intermediate layer contains polyvinyl alcohol. The manufacturing method of the laminated body as described in claim 4, wherein Content of the said polyvinyl alcohol is 5-95 mass % with respect to the gross mass of the said intermediate layer. The method for manufacturing a laminate according to Claim 1 or Claim 2, wherein The aforementioned intermediate layer further contains polyvinylpyrrolidone. The method for manufacturing a laminate according to Claim 1 or Claim 2, wherein The intermediate layer further contains at least one compound X selected from the group consisting of water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerol. The manufacturing method of the laminated body as described in claim 7, wherein The content of the compound X is 0.1% by mass or more and less than 30% by mass relative to the total mass of the intermediate layer. The manufacturing method of the laminated body as described in claim 7, wherein The aforementioned compound X contains hydroxypropylmethylcellulose. The method for manufacturing a laminate according to Claim 1 or Claim 2, wherein The thickness of the aforementioned intermediate layer is 3.0 μm or less. The method for manufacturing a laminate according to Claim 1 or Claim 2, wherein The thickness of the said photosensitive layer is 2.0-20 micrometers. A method for manufacturing a circuit wiring board, which includes a method for manufacturing a laminate according to any one of claim 1 to claim 11, the method for manufacturing a circuit wiring board includes: forming a seed layer on a substrate to form an attached crystal The step of the substrate of the seed layer; the surface of the aforementioned photosensitive layer of the transfer film having the dummy support, the intermediate layer and the photosensitive layer, which is opposite to the aforementioned intermediate layer, is in contact with the aforementioned substrate with the seed layer bonding the aforementioned transfer film to the aforementioned substrate with a seed crystal layer to obtain the substrate with the aforementioned substrate, the aforementioned seed crystal layer, the aforementioned photosensitive layer, the aforementioned intermediate layer, and the aforementioned pseudo-support with a photosensitive layer of the substrate step; between the aforementioned dummy support body and the aforementioned intermediate layer, the step of peeling off the aforementioned dummy support body; making the exposed aforementioned intermediate layer contact with a mask to perform exposure treatment, and further implement a development treatment to form a pattern after exposure; A step of forming a metal plating layer by electroplating treatment on the aforementioned seed layer existing in a region where the aforementioned pattern is not arranged; a step of forming a protective layer on the aforementioned metal plating layer; a step of removing the aforementioned pattern; and removing the exposed aforementioned crystal layer In the step of obtaining conductive thin wires in the seed layer, the surface free energy of the surface of the intermediate layer on the side of the dummy support is 68.0 mJ/m ² or less. A transfer film, which is a transfer film having a pseudo-support, an intermediate layer, and a photosensitive layer, wherein the surface free energy of the surface of the intermediate layer on the pseudo-support side is 68.0 mJ/m ² or less, and the intermediate layer is The arithmetic average roughness Ra of the surface on the side of the aforementioned dummy support is 50 nm or less. The transfer film according to claim 13, wherein the surface free energy of the intermediate layer side of the pseudo-support is 25.0-50.0 mJ/m ² . The transfer film as described in Claim 13 or Claim 14, wherein The aforementioned intermediate layer contains polyvinyl alcohol. The transfer film as described in claim 15, wherein Content of the said polyvinyl alcohol is 5-95 mass % with respect to the gross mass of the said intermediate layer. The transfer film as described in Claim 13 or Claim 14, wherein The aforementioned intermediate layer further contains polyvinylpyrrolidone. The transfer film as described in Claim 13 or Claim 14, wherein The intermediate layer contains at least one compound X selected from the group consisting of water-soluble cellulose derivatives, polyethers, phenol derivatives, and glycerin. The transfer film as described in Claim 18, wherein The content of the compound X is 0.1% by mass or more and less than 30% by mass relative to the total mass of the intermediate layer. The transfer film as described in Claim 18, wherein The aforementioned compound X contains hydroxypropylmethylcellulose. The transfer film as described in Claim 13 or Claim 14, wherein The thickness of the aforementioned intermediate layer is 3.0 μm or less. The transfer film as described in Claim 13 or Claim 14, wherein The thickness of the said photosensitive layer is 2.0-20 micrometers.

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